WO2016141765A1

WO2016141765A1 - Novel lithium-air battery based on high-density solid electrolyte

Info

Publication number: WO2016141765A1
Application number: PCT/CN2015/100232
Authority: WO
Inventors: 郭向欣; 赵宁; 孙继杨; 李忆秋; 李泓
Original assignee: 中国科学院上海硅酸盐研究所
Priority date: 2015-03-06
Filing date: 2015-12-31
Publication date: 2016-09-15
Also published as: CN104701588A

Abstract

Disclosed is a novel lithium-air battery based on a high-density solid electrolyte. The lithium-air battery comprises: a negative electrode, a porous oxygen electrode, and a solid electrolyte layer sandwiched between the negative electrode and the porous oxygen electrode. The negative electrode material comprises lithium, a lithium alloy and/or a lithium-metal-containing composite. A porous conductive carrier, a catalyst, ion conductor material, lithium salts and/or an adhesive are uniformly mixed and dried to obtain the porous oxygen electrode. The solid electrolyte layer material comprises a lithium lanthanum zirconium oxide-based ceramic, a lithium lanthanum titanium oxide-based ceramic, a lithium aluminum titanium phosphate-based ceramic and/or a lithium silicophosphate-based ceramic.

Description

一种基于高致密度固体电解质的新型锂空气电池技术领域 Novel lithium air battery based on high density solid electrolyte

[0001] 本发明涉及一种固态电解质体系的锂空气电池，属于电池领域。 [0001] The present invention relates to a lithium air battery of a solid electrolyte system, which belongs to the field of batteries.

背景技术 Background technique

[0002] 二次锂空气电池 (Lithium-air battery)具有高出锂离子电池 5- 10倍的理论比能量，因而有望成为下一代高性能化学电源。二次锂空气电池一般采用金属锂或含锂材料作为负极，空气作为氧电极，以不含水的有机电解质或水与非水体系共存的非对称电解质、水系电解质或固体电解质作为工作电解质，电解质、电极也可以为流动相。其中，基于非水有机电解质体系的锂空气电池的理论能量密度高达 3500 Wh kg i，受到工业和科研界的广泛关注。若将成功用于电动汽车电池且***能量密度达到 800 Wh kg 1，则汽车一次充电可以行驶 800km，可以达到目前燃油汽车水平。 [0002] A lithium-ion battery (Lithium-air battery) has a theoretical specific energy of 5-10 times higher than that of a lithium-ion battery, and is expected to become the next-generation high-performance chemical power source. Secondary lithium air batteries generally use lithium metal or lithium-containing materials as negative electrodes, air as oxygen electrodes, non-aqueous organic electrolytes or asymmetric electrolytes, water-based electrolytes or solid electrolytes in which water and non-aqueous systems coexist as electrolytes, electrolytes, electrolytes, The electrode can also be a mobile phase. Among them, the theoretical energy density of lithium-air batteries based on non-aqueous organic electrolyte systems is as high as 3,500 Wh kg i, which has received extensive attention from industry and scientific research. If it is successfully used in electric vehicle batteries and the system energy density reaches 800 Wh kg 1, the car can travel 800km on a single charge, which can reach the current fuel car level.

[0003] 然而，作为一种新的电池体系，能否成功应用需要综合考虑其能量密度,功率密度以及成本、安全性、能量效率、自放电、循环寿命、服役寿命、环境适应性、环境污染等诸多因素。而这些问题正是基于非水有机电解质体系的锂空气电池所面临且难以在现阶段克服的。因此锂空气电池的进步亟待发展新的电解质体系来解决这些困难。 [0003] However, as a new battery system, successful application requires comprehensive consideration of its energy density, power density and cost, safety, energy efficiency, self-discharge, cycle life, service life, environmental adaptability, environmental pollution. And many other factors. These problems are faced by lithium-air batteries based on non-aqueous organic electrolyte systems and are difficult to overcome at this stage. Therefore, the advancement of lithium-air batteries urgently needs to develop new electrolyte systems to solve these difficulties.

技术问题 technical problem

[0004] 本发明目的在于针对目前基于非水有机电解质体系锂空气电池存在的上述问题，提出了一种新型固态电解质体系的锂空气电池。 [0004] The object of the present invention is to provide a lithium air battery of a novel solid electrolyte system for the above problems existing in a lithium air battery based on a nonaqueous organic electrolyte system.

问题的解决方案 Problem solution

技术解决方案 Technical solution

[0005] 本发明提供了一种锂空气电池，所述锂空气电池包括负极、多孔氧电极、以及夹在负极和多孔氧电极之间的固态电解质层，其中，负极材质包括锂、锂合金和 /或含金属锂的复合物，多孔氧电极采用多孔导电载体、催化剂、离子导体材料、锂盐和 /或粘接剂均匀混合后干燥得到，固态电解质层的材质包括锂镧锆氧基陶瓷、锂镧钛氧基陶瓷、磷酸钛铝锂基陶瓷和 /或硅磷酸锂基陶瓷。 [0005] The present invention provides a lithium air battery including a negative electrode, a porous oxygen electrode, and a solid electrolyte layer sandwiched between the negative electrode and the porous oxygen electrode, wherein the negative electrode material includes lithium, a lithium alloy, and / or a metal lithium-containing composite, the porous oxygen electrode is uniformly mixed and dried by using a porous conductive carrier, a catalyst, an ion conductor material, a lithium salt and/or a binder, and the material of the solid electrolyte layer includes lithium lanthanum zirconium oxide. Base ceramics, lithium niobium titanyl oxide ceramics, lithium aluminum aluminum phosphate ceramics and/or lithium silicon phosphate ceramics.

[0006] 较佳地，锂合金中，锂的含量至少 20 wt<¾，锂合金还含有 Mg、 Ca、 [0006] Preferably, in the lithium alloy, the content of lithium is at least 20 wt<3⁄4, and the lithium alloy further contains Mg, Ca,

B、 Al、 Ga、 In、 Si、 Ge、 Sn、 Pb、 Sb中的至少一种；含金属锂的复合物含有至少 20 wt%的金属锂，还包含碳颗粒、碳纳米管、碳纤维、石墨烯、石墨片、多孔金属、多孔碳、惰性氧化物和 /或铜粉；所述锂空气电池的氧气源包括纯氧、含有氧气的混合气体、自然存在的空气。 At least one of B, Al, Ga, In, Si, Ge, Sn, Pb, and Sb; the lithium metal-containing composite contains at least 20 wt% of metallic lithium, and further includes carbon particles, carbon nanotubes, carbon fibers, and graphite. An olefin, a graphite sheet, a porous metal, a porous carbon, an inert oxide, and/or a copper powder; the oxygen source of the lithium air battery includes pure oxygen, a mixed gas containing oxygen, and naturally occurring air.

[0007] 较佳地，多孔氧电极中，催化剂包括过渡金属氧化物、过渡金属氮化物、 Pt、[0007] Preferably, in the porous oxygen electrode, the catalyst comprises a transition metal oxide, a transition metal nitride, Pt,

Pd和 /或 Au，过渡金属氧化物优选氧化锰、氧化亚锰、氧化铁、氧化镍、氧化钴Pd and / or Au, transition metal oxides are preferably manganese oxide, manganese oxide, iron oxide, nickel oxide, cobalt oxide

、氧化钌、氧化铱、氧化钼和 /或氧化铈，过渡金属氮化物优选氮化锰、氮化铁, cerium oxide, cerium oxide, molybdenum oxide and/or cerium oxide, transition metal nitrides, preferably manganese nitride, iron nitride

、氮化镍、氮化钛和 /或氮化钴。 , nickel nitride, titanium nitride and/or cobalt nitride.

[0008] 较佳地，多孔氧电极中，离子导体材料为锂镧锆氧基陶瓷粉体、锂镧钛氧基陶瓷粉体、磷酸钛铝锂基陶瓷粉体和 /或硅磷酸锂基陶瓷粉体，粉体粒径为 lO nm-5 μηι。 [0008] Preferably, in the porous oxygen electrode, the ionic conductor material is lithium lanthanum zirconium oxide ceramic powder, lithium lanthanum titanyl oxide ceramic powder, lithium aluminum silicate ceramic powder and/or lithium silicon silicate ceramic. Powder, powder particle size is lO nm-5 μηι.

[0009] 较佳地，多孔氧电极中，锂盐选自 LiN03、 Li2S04、 LiCl、 Li2C03、 LiBOB、 LiC(S02CF3)3、 Li[(FS02)(n-C4F9S02)N]、 LiN(S02CF3)2、 LiFNFSI、 LiCF3SO [0009] Preferably, in the porous oxygen electrode, the lithium salt is selected from the group consisting of LiN03, Li2S04, LiCl, Li2C03, LiBOB, LiC(S02CF3)3, Li[(FS02)(n-C4F9S02)N], LiN(S02CF3)2 , LiFNFSI, LiCF3SO

3中的至少一种。 At least one of 3.

[0010] 较佳地，多孔氧电极中，粘接剂包括聚偏氟乙烯、聚四氟乙烯、聚酰胺酰亚胺 [0010] Preferably, in the porous oxygen electrode, the adhesive comprises polyvinylidene fluoride, polytetrafluoroethylene, polyamideimide

、聚酰亚胺、海藻酸钠、羧甲基纤维素中的至少一种。 And at least one of polyimide, sodium alginate, and carboxymethyl cellulose.

[0011] 较佳地，多孔氧电极中，孔导电载体包括多孔碳、乙炔黑、石墨、石墨烯、氧化石墨烯、碳纳米管、碳纤维、氮惨杂碳中的至少一种、和 /或导电氧化物。 [0011] Preferably, in the porous oxygen electrode, the porous conductive support comprises at least one of porous carbon, acetylene black, graphite, graphene, graphene oxide, carbon nanotubes, carbon fibers, nitrogen miscellaneous carbon, and/or Conductive oxide.

[0012] 较佳地，固态电解质层的 100ηηι-500μιη。 [0012] Preferably, the solid electrolyte layer is 100 ηηι - 500 μηη.

[0013] 较佳地，所述锂空气电池还包括封装负极、多孔氧电极、固态电解质层的电池封装材料，以及能够在工作温度使用的导电极耳、极柱。 [0013] Preferably, the lithium air battery further includes a battery encapsulating material encapsulating a negative electrode, a porous oxygen electrode, a solid electrolyte layer, and a lead electrode pole and a pole capable of being used at an operating temperature.

[0014] 较佳地，所述锂空气电池的工作温度为室温到 250°C，优选工作温度为 80-250°C[0014] Preferably, the lithium air battery has an operating temperature of room temperature to 250 ° C, preferably an operating temperature of 80-250 ° C.

，更优选工作温度为 180-220°C。 More preferably, the working temperature is 180-220 °C.

发明的有益效果 Advantageous effects of the invention

有益效果 Beneficial effect

[0015] 1、该电池体系的氧电极直接面对空气、正极可稳定从空气中获取，不需要配备专门的高效过滤膜对空气进行过滤。 [0015] 1. The oxygen electrode of the battery system directly faces the air, and the positive electrode can be stably obtained from the air, and does not need to be matched. A special high-efficiency filter membrane is used to filter the air.

[0016] 2、氧电极端界面得到优化：该电池的氧电极由活性物质、锂盐、导电添加剂和高温粘结剂复合混合后干燥制备而成。氧电极的制备过程相比于之前关于全固态电池的制备方法 (一般是将固态电解质粉与活性物质混合后再在高温下进行烧结)，更加简单，节能环保。 [0016] 2. The oxygen electrode end interface is optimized: the oxygen electrode of the battery is prepared by compounding and mixing the active material, the lithium salt, the conductive additive and the high temperature binder. The preparation process of the oxygen electrode is simpler, energy-saving and environmentally friendly than the previous preparation method of the all-solid-state battery (generally, the solid electrolyte powder is mixed with the active material and then sintered at a high temperature).

[0017] 3、负极端界面得到优化：该电池在 200摄氏度下工作，负极金属锂为熔融态，即优化了金属锂和锂镧锆氧基陶瓷电解质片之间的界面问题，又解决了金属锂在有机电解质中存在的锂枝晶问题。 [0017] 3. The interface of the negative electrode end is optimized: the battery operates at 200 degrees Celsius, and the lithium metal of the negative electrode is in a molten state, that is, the interface problem between the metal lithium and the lithium lanthanum zirconium ceramic electrolyte sheet is optimized, and the metal is solved. Lithium dendrite problems in the presence of lithium in organic electrolytes.

[0018] 4、该电池体系在室温的干燥空气中放电吋可以吸收空气中二氧化碳 (C02)作为氧电极反应活性物质，将其转化为碳酸锂，可作为一次电池使用。因此该电池体系除了可以作为未来的一种重要储能器件，还可以作为未来解决温室效应 (减少大气中的二氧化碳含量)的潜在方案。 [0018] 4. The battery system is discharged in a dry air at room temperature, and can absorb carbon dioxide (C02) in the air as an oxygen electrode reactive material, and convert it into lithium carbonate, which can be used as a primary battery. Therefore, in addition to being an important energy storage device in the future, the battery system can also serve as a potential solution for solving the greenhouse effect (reducing the carbon dioxide content in the atmosphere) in the future.

[0019] 5、能量密度高：电池体系具有超过目前商业化钴酸锂电池将近 5-10倍的比容量。室温下的放电比容量高达 650 mAh/g; 在 100摄氏度下，比容量高达 1250 mAh/g, 并且此吋的电池充电效率高达 100 %; 在 200摄氏度下，容量高达 1400 mAh/g, 对应的能量密度为 4000Wh/kg。 [0019] 5. High energy density: The battery system has a specific capacity of nearly 5-10 times that of the current commercial lithium cobalt oxide battery. The specific discharge capacity at room temperature is up to 650 mAh/g; at 100 degrees Celsius, the specific capacity is up to 1250 mAh/g, and the battery charging efficiency of this battery is as high as 100%; at 200 degrees Celsius, the capacity is up to 1400 mAh/g, corresponding The energy density is 4000 Wh/kg.

[0020] 能量效率高：该体系的放电最终产物主要为碳酸锂，该电池在充电吋碳酸锂可以大部分解，并且充放电之间的过电压差约为 0.4 V，对应的能量效率约为 87.6% [0020] High energy efficiency: The final product of the discharge of the system is mainly lithium carbonate, the battery can be mostly solved in charging lithium carbonate, and the overvoltage difference between charge and discharge is about 0.4 V, and the corresponding energy efficiency is about 87.6%

[0021] 6、得益于氧电极和负极端与固态电解质界面的优化，该电池体系充放电倍率可达在 50 A/g (30 C)条件下可逆容量为 1730 mAh/g。并且在限制容量 500 mAh/g 的情况下保持容量不衰减地循环 40次以上。 [0021] 6. Thanks to the optimization of the interface between the oxygen electrode and the negative electrode end and the solid electrolyte, the charge and discharge rate of the battery system can reach a reversible capacity of 1730 mAh/g at 50 A/g (30 C). And the capacity is kept for more than 40 times without damping while limiting the capacity of 500 mAh/g.

对附图的简要说明 Brief description of the drawing

附图说明 DRAWINGS

[0022] 图 1为本发明一个实施方式中全固态锂空气电池的结构示意图，图中显示的是该器件各个部件的截面，其中， 1-不锈钢槽， 2-负极金属锂， 3-锂镧锆氧基陶瓷电解质片， 4-氧电极， 5-高温封装材料； 1 is a schematic structural view of an all-solid lithium air battery according to an embodiment of the present invention, and shows a cross section of each component of the device, wherein: 1-stainless steel tank, 2-nano metal lithium, 3-lithium germanium Zirconium oxide ceramic electrolyte sheet, 4-oxygen electrode, 5-high temperature encapsulating material;

[0023] 图 2为本发明实施例 1中锂空气电池体系在不同温度下的首次充放电测试，其中纵坐标为电压，横坐标为比容量； 2 is a first charge and discharge test of a lithium air battery system at different temperatures according to Embodiment 1 of the present invention, wherein The ordinate is the voltage and the abscissa is the specific capacity;

[0024] 图 3为本发明实施例 1中锂空气电池体系的循环性能测试； 3 is a cycle performance test of a lithium air battery system according to Embodiment 1 of the present invention;

[0025] 图 4为本发明实施例 1中锂空气电池体系的倍率性能测试； 4 is a rate performance test of a lithium air battery system according to Embodiment 1 of the present invention;

[0026] 图 5为本发明实施例 5中锂空气电池使用不同多孔氧电极材料的充放电曲线对比图； 5 is a comparison diagram of charge and discharge curves of a lithium-air battery using different porous oxygen electrode materials in Embodiment 5 of the present invention;

[0027] 表 1固态锂-空气电池各部分组成对应实施例及对应模拟电池的电化学性能。 [0027] Table 1 The solid state lithium-air battery components constitute the electrochemical performance of the corresponding examples and corresponding simulated batteries.

本发明的实施方式 Embodiments of the invention

[0028] 以下结合附图和下述实施方式进一步说明本发明，应理解，附图及下述实施方式仅用于说明本发明，而非限制本发明。 The invention will be further described in conjunction with the accompanying drawings and the embodiments of the invention.

[0029] 本发明目的在于针对目前基于非水有机电解质体系锂空气电池存在的上述问题，提出了一种新型固态电解质体系的锂空气电池。 [0029] The object of the present invention is to provide a lithium air battery of a novel solid electrolyte system for the above problems existing in a lithium air battery based on a nonaqueous organic electrolyte system.

[0030] 本发明公幵了一种新型大容量固态电解质体系的锂空气电池。该电池至少包括可提供锂的负极；能在室温至 250°C的温度范围，在空气下直接工作的多孔氧电极；以及对锂稳定、能在室温至 250°C温度范围内工作的固态电解质；以及能在 2 50-500°C的电池封装材料；在室温至 250°C工作的导电极耳或极柱组成。 [0030] The present invention discloses a lithium air battery of a novel large capacity solid electrolyte system. The battery includes at least a negative electrode capable of providing lithium; a porous oxygen electrode capable of operating directly under air at a temperature ranging from room temperature to 250 ° C; and a solid electrolyte stable to lithium and capable of operating at a temperature ranging from room temperature to 250 ° C ; and can be used in battery packaging materials at 2 50-500 ° C; electrode or poles working at room temperature to 250 ° C.

[0031] 本发明涉及的固态锂空气电池由多孔氧电极、负极以及介于两者之间的固态电解质，其中正极为自然空气，也可以是纯氧气或含氧气的混合气。氧电极为多孔碳与锂盐的复合材料，负极为金属锂，固态电解质为一种对金属锂稳定的高致密度薄膜状或薄片状的快锂离子导体材料。 [0031] The present invention relates to a solid-state lithium air battery comprising a porous oxygen electrode, a negative electrode, and a solid electrolyte between them, wherein the positive electrode is natural air or a mixture of pure oxygen or oxygen. The oxygen electrode is a composite material of porous carbon and lithium salt, and the negative electrode is metallic lithium. The solid electrolyte is a high-density film-like or flake-like fast lithium ion conductor material which is stable to metallic lithium.

[0032] 本发明具有以下显著优点：金属锂负极由固态电解质完全保护而与空气完全隔幵，避免了金属锂被空气腐蚀；由于固态电解质具有良好的的热稳定性，该电池具有较宽的使用温度 (从室温至锂熔点 180.5°C以上)；在室温下工作吋 (干燥空气气氛下)，该体系放电吋吸收空气中的氧气和二氧化碳并将其转化为碳酸锂，可作为一次电池使用。随着温度的升高，放电产物碳酸锂可以在充电吋被分解，因此该体系还可作为二次电池使用。 [0032] The present invention has the following significant advantages: The lithium metal negative electrode is completely protected by the solid electrolyte and completely separated from the air, thereby avoiding metal lithium being corroded by air; since the solid electrolyte has good thermal stability, the battery has a wide Use temperature (from room temperature to lithium melting point above 180.5 ° C); Work at room temperature 干燥 (under dry air atmosphere), the system discharges 吋 absorbs oxygen and carbon dioxide in the air and converts it into lithium carbonate, which can be used as a primary battery . As the temperature rises, the discharge product lithium carbonate can be decomposed in the charging crucible, so the system can also be used as a secondary battery.

[0033] 本发明提供了一种固态锂空气电池体系。该体系包括负极、氧电极以及电解质。其中负极为金属锂，采用与锂盐和高温粘结剂复合的多孔碳作为氧电极，正极为直接从空气中获取的并吸附于氧电极表面的氧气和二氧化碳。电解质采用一种对锂稳定的锂镧锆氧基陶瓷电解质片 (快锂离子导体)。 The present invention provides a solid state lithium air battery system. The system includes a negative electrode, an oxygen electrode, and an electrolyte. The negative electrode is metallic lithium, and porous carbon combined with a lithium salt and a high temperature binder is used as an oxygen electrode. Oxygen and carbon dioxide obtained directly from the air and adsorbed on the surface of the oxygen electrode. The electrolyte employs a lithium yttrium zirconium oxide ceramic electrolyte sheet (fast lithium ion conductor) which is stable to lithium.

[0034] 其工作温度为室温到 250°C,优选工作温度为 80-250°C, [0034] the working temperature is from room temperature to 250 ° C, preferably the working temperature is 80-250 ° C,

再优选工作温度为 180-220°C。 Further preferably, the working temperature is from 180 to 220 °C.

[0035] 所述氧气的来源可以是纯氧，也可以是含有氧气的混合气体，也可以是自然存在的空气。 [0035] The source of the oxygen may be pure oxygen, a mixed gas containing oxygen, or a naturally occurring air.

[0036] 所述的固体电解质为致密薄膜状或薄片状材料，该材料为锂镧锆氧、锂镧钛氧 [0036] The solid electrolyte is a dense film or flake material, the material is lithium lanthanum zirconium oxide, lithium niobium titanium oxide

、磷酸钛铝锂、硅磷酸锂等的一种或多种。固体电解质厚度为 100ηιη-500 μιη。 One or more of lithium aluminum aluminum phosphate, lithium silicon phosphate, and the like. The solid electrolyte has a thickness of 100 ηηη - 500 μιη.

[0037] 所述的多孔氧电极至少包括多孔导电载体，催化剂，离子导体材料，锂盐，粘接剂。 [0037] The porous oxygen electrode comprises at least a porous conductive support, a catalyst, an ion conductor material, a lithium salt, and an adhesive.

[0038] 所述的可提供金属锂的负极包括金属锂、锂合金（合金元素包括 Mg， Ca, B, [0038] The negative electrode that can provide lithium metal includes lithium metal, lithium alloy (alloying elements include Mg, Ca, B,

Al, Ga, In, Si, Ge, Sn, Pb, Sb的一种或以上）、含金属锂的复合物的一种或几种。在可提供金属锂的负极中，锂的含量超过 20 wt%。 One or more of Al, Ga, In, Si, Ge, Sn, Pb, Sb, or a metal lithium-containing composite. In the negative electrode which can provide metallic lithium, the content of lithium exceeds 20 wt%.

[0039] 所述的含金属锂的复合物中至少含有 20 \^%的金属锂元素，复合物中还可以包括碳颗粒、碳纳米管、碳纤维、石墨烯、石墨片、多孔金属、多孔碳、惰性氧化物、铜粉。 [0039] The metal lithium-containing composite contains at least 20% metal lithium element, and the composite may further include carbon particles, carbon nanotubes, carbon fibers, graphene, graphite sheets, porous metals, porous carbon. , inert oxide, copper powder.

[0040] 所述的多孔氧电极中的多孔导电载体，包括多孔碳、乙炔黑、石墨、石墨烯、氧化石墨烯、碳纳米管、碳纤维、氮惨杂的碳等一种或多种混合物，导电氧化物质 (如一氧化钌 RuO等)。 [0040] The porous conductive carrier in the porous oxygen electrode comprises one or more mixtures of porous carbon, acetylene black, graphite, graphene, graphene oxide, carbon nanotubes, carbon fiber, nitrogen miscible carbon, and the like. A conductive oxidizing substance (such as ruthenium oxide RuO, etc.).

[0041] 所述的多孔氧电极中的催化剂包括过渡金属氧化物、过渡金属氮化物、 Pt, Pd,[0041] The catalyst in the porous oxygen electrode comprises a transition metal oxide, a transition metal nitride, Pt, Pd,

Au及其合金等。过渡金属氧化物优选为氧化锰、氧化亚锰、氧化铁、氧化镍、氧化钴、氧化钌、氧化铱、氧化钼、氧化铈；过渡金属氮化物包括氮化锰、氮化铁、氮化镍、氮化钛、氮化钴。 Au and its alloys. The transition metal oxide is preferably manganese oxide, manganese oxide, iron oxide, nickel oxide, cobalt oxide, cerium oxide, cerium oxide, molybdenum oxide or cerium oxide; transition metal nitrides include manganese nitride, iron nitride, nickel nitride , titanium nitride, cobalt nitride.

[0042] 所述的离子导体材料为锂镧锆氧、锂镧钛氧、磷酸钛铝锂、硅磷酸锂等的一种或多种。固体电解质粉体颗粒尺寸为 10 ηιη-5μιη。 [0042] The ion conductor material is one or more of lithium lanthanum zirconium oxide, lithium lanthanum titanium oxide, lithium aluminum aluminum phosphate, lithium silicon phosphate, and the like. The solid electrolyte powder has a particle size of 10 ηιη - 5 μιη.

[0043] 所述的锂盐选自 LiN03、 Li2S04、 LiCl、 Li2C03、 LiBOB、 LiC(S02CF3)3、 Li[0043] The lithium salt is selected from the group consisting of LiN03, Li2S04, LiCl, Li2C03, LiBOB, LiC(S02CF3)3, Li

[(FS02)(n-C4F9S02)N]、 LiN(S02CF3)2、 LiFNFSI、 LiCF3S03等的一种或几种 [0044] 所述的粘接剂包括聚偏氟乙烯（PVDF)、聚四氟乙烯 PTFE、聚酰胺酰亚胺、聚酰亚胺 (PI)、海藻酸钠、羧甲基纤维素（CMC)等等的一种或几种。 One or more of [(FS02)(n-C4F9S02)N], LiN(S02CF3)2, LiFNFSI, LiCF3S03, etc. [0044] The adhesive includes polyvinylidene fluoride (PVDF), polytetrafluoroethylene PTFE, polyamideimide, polyimide (PI), sodium alginate, carboxymethyl cellulose (CMC) One or more of the others.

[0045] 所述的能在高温工作的固态锂空气电池，可以在规模储能、电动汽车、通讯基站、轨道交通等领域应用。 [0045] The solid-state lithium air battery capable of operating at high temperature can be applied in the fields of large-scale energy storage, electric vehicles, communication base stations, rail transit, and the like.

[0046] 本发明的反应机理是，以金属锂为负极的全固态锂空气电池为例： [0046] The reaction mechanism of the present invention is an example of an all-solid lithium air battery using lithium metal as a negative electrode:

[0047] 2Li + 0 2 +CO ₂ ~~ >Li ₂CO ₃ (1) 2Li + 0 2 +CO ₂ ~~ >Li ₂ CO ₃ (1)

[0048] 放电产物为沉积在氧电极表面的 Li ₂CO ₃。在金属锂和固态电解质表面的界面上，锂离子和电子解离，锂离子穿过固态电解质到达氧电极表面，氧气在氧电极表面接受一个电子和锂离子结合成锂氧化合物，再和二氧化碳进一步结合成碳酸锂。充电吋碳酸锂分解，反应吋为上述反应的可逆过程。 [0048] The discharge product is Li ₂ CO ₃ deposited on the surface of the oxygen electrode. At the interface between the surface of the metal lithium and the solid electrolyte, lithium ions and electrons dissociate. Lithium ions pass through the solid electrolyte to reach the surface of the oxygen electrode. Oxygen accepts an electron and lithium ion on the surface of the oxygen electrode to form a lithium oxide compound, and further carbon dioxide. Combined into lithium carbonate. The charged lithium carbonate is decomposed, and the reaction enthalpy is a reversible process of the above reaction.

[0049] 该发明具有以下显著优点： [0049] The invention has the following significant advantages:

[0050] 该电池体系的氧电极直接面对空气、正极可稳定从空气中获取，不需要配备专门的高效过滤膜对空气进行过滤。 [0050] The oxygen electrode of the battery system directly faces the air, and the positive electrode can be stably obtained from the air, and does not need to be equipped with a special high-efficiency filter membrane to filter the air.

[0051] 氧电极端界面得到优化：该电池的氧电极由活性物质、锂盐、导电添加剂和高温粘结剂复合混合后干燥制备而成。氧电极的制备过程相比于之前关于全固态电池的制备方法 (一般是将固态电解质粉与活性物质混合后再在高温下进行烧结) ，更加简单，节能环保。 [0051] The oxygen electrode end interface is optimized: the oxygen electrode of the battery is prepared by compounding and mixing the active material, the lithium salt, the conductive additive and the high temperature binder. The preparation process of the oxygen electrode is simpler, energy-saving and environmentally friendly than the previous preparation method of the all-solid-state battery (generally, the solid electrolyte powder is mixed with the active material and then sintered at a high temperature).

[0052] 负极端界面得到优化：该电池在最佳工作温度 180-220摄氏度下工作吋，负极金属锂为熔融态，即优化了金属锂和锂镧锆氧基陶瓷电解质片之间的界面问题，又解决了金属锂在有机电解质中存在的锂枝晶问题。 [0052] The interface of the negative electrode end is optimized: the battery is operated at an optimum working temperature of 180-220 degrees Celsius, and the lithium metal of the negative electrode is in a molten state, that is, the interface problem between the metallic lithium and the lithium lanthanum zirconium ceramic electrolyte sheet is optimized. The lithium dendrite problem of metallic lithium in the organic electrolyte is also solved.

[0053] 该电池体系在室温的干燥空气中放电吋可以吸收空气中二氧化碳 (C02)作为氧电极反应活性物质，将其转化为碳酸锂，可作为一次电池使用。其充放电曲线见图 2中的黑色曲线。因此该电池体系除了可以作为未来的一种重要储能器件，还可以作为未来解决温室效应 (减少大气中的二氧化碳含量)的潜在方案。 [0053] The battery system is discharged in a dry air at room temperature, and can absorb carbon dioxide (C02) in the air as an oxygen electrode reactive material, and convert it into lithium carbonate, which can be used as a primary battery. Its charge and discharge curve is shown in the black curve in Figure 2. Therefore, in addition to being an important energy storage device in the future, the battery system can also be used as a potential solution to solve the greenhouse effect (reducing the carbon dioxide content in the atmosphere) in the future.

[0054] 能量密度高：电池体系具有超过目前商业化钴酸锂电池将近 5-10倍的比容量。 [0054] High energy density: The battery system has a specific capacity of nearly 5-10 times that of currently commercial lithium cobalt oxide batteries.

室温下的放电比容量高达 650 mAh/g; 在 100摄氏度下，比容量高达 1250 mAh/g ，并且此吋的电池充电效率高达 100 %; 在 200摄氏度下，容量高达 1400 mAh/g ，对应的能量密度为 4000Wh/kg能量效率高：该体系的放电最终产物主要为碳酸锂，该电池在充电吋碳酸锂可以大部分解，并且充放电之间的过电压差约为 0.4 V，对应的能量效率约为 87.6%。 The specific discharge capacity at room temperature is up to 650 mAh/g; at 100 degrees Celsius, the specific capacity is up to 1250 mAh/g, and the battery charging efficiency of this crucible is as high as 100%; at 200 degrees Celsius, the capacity is up to 1400 mAh/g, corresponding The energy density is 4000Wh/kg, and the energy efficiency is high: the final product of the discharge of the system is mainly carbonated. Lithium, the battery can be largely solved in charging lithium niobate, and the overvoltage difference between charge and discharge is about 0.4 V, and the corresponding energy efficiency is about 87.6%.

[0055] 得益于氧电极和负极端与固态电解质界面的优化，该电池体系充放电倍率可达在 50 A/g (30 C)条件下可逆容量为 1730 mAh/g。并且在限制容量 500 mAh/g的情况下保持容量不衰减地循环 40次以上。 [0055] Thanks to the optimization of the interface between the oxygen electrode and the negative electrode end and the solid electrolyte, the charge and discharge rate of the battery system can reach a reversible capacity of 1730 mAh/g at 50 A/g (30 C). And, while limiting the capacity of 500 mAh/g, the capacity is kept for more than 40 times without attenuation.

[0056] 下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。 [0056] The embodiments are further exemplified below to explain the present invention in detail. It is to be understood that the following examples are only intended to illustrate the invention and are not to be construed as limiting the scope of the invention, and that some non-essential improvements and modifications made by those skilled in the art in light of the The scope of protection. The following specific process parameters and the like are also only one example of a suitable range, and those skilled in the art can make a suitable range selection by the description herein, and are not limited to the specific numerical values exemplified below.

[0057] 实施例 1 Embodiment 1

[0058] 一种新型高能量密度高功率密度的固态锂空气电池体系，装置的结构与图 1相同，采用的固态电解质层 4、氧电极 5、负极 2及具体如下： [0058] A novel high energy density high power density solid state lithium air battery system, the structure of the device is the same as that of FIG. 1, using the solid electrolyte layer 4, the oxygen electrode 5, the negative electrode 2 and the specifics are as follows:

[0059] 固态电解质层：使用高致密度的陶瓷电解质片作为既可以传输锂离子又可以保护金属锂的电解质层，所述的固体电解质为致密薄膜状或薄片状材料，该材料为锂镧锆氧、锂镧钛氧、磷酸钛铝锂、硅磷酸锂等的一种或多种。固体电解质厚度为 100nm-500 μηι。 [0059] Solid electrolyte layer: A high-density ceramic electrolyte sheet is used as an electrolyte layer capable of transporting both lithium ions and metal lithium, and the solid electrolyte is a dense film-like or flake-like material, and the material is lithium lanthanum zirconium. One or more of oxygen, lithium lanthanum titanium oxide, lithium aluminum aluminum phosphate, lithium silicon phosphate, and the like. The thickness of the solid electrolyte is from 100 nm to 500 μη.

[0060] 氧电极：将炭黑、锂盐、锂镧锆氧粉 (10 ηιη-5μιη)和粘结剂以重量百分比 4:4:1:1 称取，以 Ν甲基吡咯烷酮为分散剂，将其搅拌混合均匀，通过用刮刀涂覆的方法把浆料涂覆到陶瓷电解质片上，固体电解质厚度为 100nm-50(Vm。然后将涂覆于电解质片上的氧电极置于 120°C保温 1小吋，将溶剂挥发掉的同吋使粘结剂固化。 [0060] Oxygen electrode: carbon black, lithium salt, lithium lanthanum zirconium oxide powder (10 ηιη-5 μιη) and a binder are weighed in a weight ratio of 4:4:1:1, with Νmethylpyrrolidone as a dispersing agent. The mixture was stirred and uniformly mixed, and the slurry was applied onto the ceramic electrolyte sheet by a doctor blade coating method, and the thickness of the solid electrolyte was 100 nm to 50 (Vm. Then, the oxygen electrode coated on the electrolyte sheet was placed at 120 ° C for 1 time. Small 吋, the same solvent that volatilizes the solvent to cure the binder.

[0061] 负极：将涂覆氧电极后的陶瓷电解质置于 Ar气氛手套箱中，然后将负极金属锂压附在陶瓷电解质片的另一边。然后使用高温封装材料将陶瓷电解质贴有锂片的一端密封在不锈钢壳体的槽上，装配成图 1中描述的电池。然后将该电池在室温 (25°C)、 60°C、 100°C和 200°C下进行测试。 Negative Electrode: The ceramic electrolyte coated with the oxygen electrode was placed in an Ar atmosphere glove box, and then the negative electrode metal lithium was pressure-bonded to the other side of the ceramic electrolyte sheet. Then, one end of the ceramic electrolyte with the lithium sheet attached thereto was sealed on the groove of the stainless steel casing using a high-temperature packaging material, and assembled into the battery described in Fig. 1. The battery was then tested at room temperature (25 ° C), 60 ° C, 100 ° C and 200 ° C.

[0062] 正极：所述的空气正极可以是纯氧，也可以是含有氧气的混合气体，也可以是自然存在的空气。 [0063] 图 2为本发明固态电解质体系的锂空气电池典型的充放电测试曲线图，结果列于表 i。其中纵坐标为电压单位；横坐标为比容量。 [0062] Positive electrode: The air positive electrode may be pure oxygen, a mixed gas containing oxygen, or a naturally occurring air. 2 is a typical charge and discharge test curve of a lithium air battery of the solid electrolyte system of the present invention, and the results are shown in Table i. Where the ordinate is the voltage unit; the abscissa is the specific capacity.

[0064] 本实施例循环性能测试见图 3，具体数据列于表 1中。 [0064] The loop performance test of this embodiment is shown in FIG. 3, and the specific data is listed in Table 1.

[0065] 本实施例倍率性能测试见图 4，具体数据列于表 1中。 [0065] The rate performance test of this embodiment is shown in FIG. 4, and the specific data is listed in Table 1.

[0066] 实施例 2 Example 2

[0067] 一种新型高能量密度高功率密度的固态锂空气电池体系，装置的结构与实施例 [0067] A novel high energy density high power density solid state lithium air battery system, structure and embodiment of the device

1相同，采用的固态电解质层 4、氧电极 5、负极 2及具体如下： 1 is the same, the solid electrolyte layer 4, the oxygen electrode 5, and the negative electrode 2 are used as follows:

[0068] 固态电解质层同实施例 1。 The solid electrolyte layer was the same as in Example 1.

[0069] 氧电极制备步骤同实例 1。 [0069] The oxygen electrode preparation step was the same as in Example 1.

[0070] 负极：使用可提供金属锂的金属锂合金化合物作为负极，包括金属锂、锂合金 [0070] A negative electrode: a metal lithium alloy compound capable of providing metallic lithium is used as a negative electrode, including metallic lithium, lithium alloy

(合金元素包括 Mg， Ca, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb的一种或以上）、含金属锂的复合物的一种或几种。在可提供金属锂的负极中，锂的含量超过 20 wt%。与将涂覆氧电极后的陶瓷电解质置于 Ar气氛手套箱中，然后将负极锂合金压附在陶瓷电解质片的另一边。然后使用高温封装材料将陶瓷电解质贴有锂片的一端密封在不锈钢壳体的槽上，装配成图 1中描述的电池。然后将该电池在室温 (25 °C)、 60°C、 100°C和 200°C下进行测试。 (The alloying element includes one or more of Mg, Ca, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb), and one or more of the metal lithium-containing composite. In the negative electrode which can provide metallic lithium, the content of lithium exceeds 20 wt%. The ceramic electrolyte after coating the oxygen electrode was placed in an Ar atmosphere glove box, and then the negative electrode lithium alloy was pressed against the other side of the ceramic electrolyte sheet. Then, one end of the ceramic electrolyte with the lithium sheet attached thereto was sealed on the groove of the stainless steel casing using a high-temperature packaging material, and assembled into the battery described in Fig. 1. The battery was then tested at room temperature (25 ° C), 60 ° C, 100 ° C and 200 ° C.

[0071] 正极同实例 1所述气体。 [0071] The positive electrode was the same as the gas of Example 1.

[0072] 本实施例充放电测试数据列于表 1中。 [0072] The charge and discharge test data of this embodiment are listed in Table 1.

[0073] 实施例 3 Example 3

[0074] 一种新型高能量密度高功率密度的固态锂空气电池体系，装置的结构与实施例 [0074] A novel high energy density high power density solid state lithium air battery system, structure and embodiment of the device

[0075] 固态电解质层同实施例 1。 [0075] The solid electrolyte layer was the same as in Example 1.

[0076] 氧电极制备步骤同实例 1。 [0076] The oxygen electrode preparation step was the same as in Example 1.

[0077] 负极：使用可提供金属锂的含金属锂的复合物，其中锂含量至少大于 20 wt%。 Negative Electrode: A metal lithium-containing composite which can provide metallic lithium, wherein the lithium content is at least greater than 20% by weight.

复合物中可以包括碳颗粒、碳纳米管、碳纤维、石墨烯、石墨片、多孔金属、多孔碳、惰性氧化物、铜粉。将涂覆氧电极后的陶瓷电解质置于 Ar气氛手套箱中，负极为含金属锂的复合物，（其中锂含量大于 20%)，将其压附在陶瓷电解质片的另一边。然后使用高温封装材料将陶瓷电解质贴有锂片的一端密封在不锈钢壳体的槽上，装配成图 1中描述的电池。然后将该电池在室温 (25°C)、 60°C、 1The composite may include carbon particles, carbon nanotubes, carbon fibers, graphene, graphite flakes, porous metal, porous carbon, inert oxide, copper powder. The ceramic electrolyte coated with the oxygen electrode was placed in an Ar atmosphere glove box, and the negative electrode was a metal lithium-containing composite (in which the lithium content was more than 20%), which was pressed against the other side of the ceramic electrolyte sheet. Then use a high-temperature packaging material to seal the end of the ceramic electrolyte with the lithium sheet in the stainless The tank of the steel casing is assembled into the battery described in Fig. 1. Then the battery is at room temperature (25 ° C), 60 ° C, 1

00°C和 200°C下进行测试。 The test was carried out at 00 ° C and 200 ° C.

[0078] 正极同实例 1所述气体。 [0078] The positive electrode was the same as the gas of Example 1.

[0079] 本实施例充放电测试数据列于表 1中。 [0079] The charge and discharge test data of this embodiment is listed in Table 1.

[0080] 实施例 4 Example 4

[0081] 一种新型高能量密度高功率密度的固态锂空气电池体系，装置的结构与实施例 [0081] A novel high energy density high power density solid state lithium air battery system, structure and embodiment of the device

[0082] 固态电解质层同实施例 1。 The solid electrolyte layer was the same as in Example 1.

[0083] 氧电极：使用可以构建氧电极内部导电网络的材料作为多孔导电载体，包括多孔碳，乙炔黑、石墨、石墨烯、氧化石墨烯、碳纳米管、碳纤维、氮惨杂的碳等一种或多种混合物，导电氧化物。将多孔导电载体、锂盐、锂镧锆氧粉 (10 ηιη-5μιη)和粘结剂以重量百分比 4:4:1:1称取，以 Ν甲基吡咯烷酮为分散剂，将其搅拌混合均匀，通过用刮刀涂覆的方法把浆料涂覆到陶瓷电解质片上，固体电解质厚度为 100nm-50(Vm。然后将涂覆于电解质片上的氧电极置于 120°C保温 1小吋，将溶剂挥发掉的同吋使粘结剂固化。 [0083] Oxygen electrode: A material capable of constructing an internal conductive network of an oxygen electrode is used as a porous conductive support, including porous carbon, acetylene black, graphite, graphene, graphene oxide, carbon nanotube, carbon fiber, nitrogen, and the like. One or more mixtures, conductive oxides. The porous conductive support, lithium salt, lithium lanthanum zirconium oxide powder (10 ηιη-5 μιη) and binder are weighed in a weight ratio of 4:4:1:1, and Νmethylpyrrolidone is used as a dispersing agent, and the mixture is stirred and mixed uniformly. The slurry is applied to the ceramic electrolyte sheet by a doctor blade coating method, and the thickness of the solid electrolyte is 100 nm to 50 (Vm. Then, the oxygen electrode coated on the electrolyte sheet is placed at 120 ° C for 1 hour, and the solvent is used. The volatilized co-cure cures the binder.

[0084] 负极制备方法同实例 2。 The preparation method of the negative electrode was the same as in Example 2.

[0085] 正极同实例 1所述气体。 The positive electrode was the same as the gas of Example 1.

[0086] 本实施例充放电测试数据列于表 1中。 [0086] The charge and discharge test data of this embodiment are listed in Table 1.

[0087] 实施例 5 Example 5

[0088] 一种新型高能量密度高功率密度的固态锂空气电池体系，装置的结构与实施例 [0088] A novel high energy density high power density solid state lithium air battery system, structure and embodiment of the device

[0089] 固态电解质层同实施例 1。 [0089] The solid electrolyte layer was the same as in Example 1.

[0090] 氧电极：添加催化剂到复合多孔氧电极中。其中催化剂材料包括过渡金属氧化物、过渡金属氮化物、 Pt, Pd, Au及其合金等。过渡金属氧化物优选为氧化锰、氧化亚锰、氧化铁、氧化镍、氧化钴、氧化钌、氧化铱、氧化钼、氧化铈；过渡金属氮化物包括氮化锰、氮化铁、氮化镍、氮化钛、氮化钴。将催化剂材料、多孔导电载体材料、锂盐、锂镧锆氧粉 (lO nm-5 [0090] Oxygen electrode: A catalyst is added to the composite porous oxygen electrode. The catalyst material includes transition metal oxides, transition metal nitrides, Pt, Pd, Au and alloys thereof. The transition metal oxide is preferably manganese oxide, manganese oxide, iron oxide, nickel oxide, cobalt oxide, cerium oxide, cerium oxide, molybdenum oxide or cerium oxide; transition metal nitrides include manganese nitride, iron nitride, nickel nitride , titanium nitride, cobalt nitride. Catalyst material, porous conductive support material, lithium salt, lithium lanthanum zirconium oxide powder (lO nm-5

μηι)和粘结剂以重量百分比 4:2:2:1:1称取，以 Ν甲基吡咯烷酮为分散剂，将其搅拌混合均匀，通过用刮刀涂覆的方法把浆料涂覆到陶瓷电解质片上，固体电解质厚度为 100nm-50(Vm。然后将涂覆于电解质片上的氧电极置于 120°C保温 1小吋Ηηι) and binder are weighed in 4:2:2:1:1 by weight, and Νmethylpyrrolidone is used as a dispersing agent. The mixture is uniformly mixed, and the slurry is applied to the ceramic electrolyte sheet by a doctor blade coating method, and the thickness of the solid electrolyte is 100 nm to 50 (Vm. Then, the oxygen electrode coated on the electrolyte sheet is placed at 120 ° C for 1 hour.

，将溶剂挥发掉的同吋使粘结剂固化。 The same solvent that volatilizes the solvent cures the binder.

[0091] 负极制备方法同实例 2。 [0091] The negative electrode preparation method was the same as in Example 2.

[0092] 正极同实例 1所述气体。 [0092] The positive electrode was the same as the gas of Example 1.

[0093] 本实施例充放电测试曲线见图 5，具体数据列于表 1中。 [0093] The charging and discharging test curve of this embodiment is shown in FIG. 5, and the specific data is listed in Table 1.

[0094] 实施例 6 Example 6

[0095] 一种新型高能量密度高功率密度的固态锂空气电池体系，装置的结构与实施例 [0095] A novel high energy density high power density solid state lithium air battery system, structure and embodiment of the device

[0096] 固态电解质层同实施例 1。 [0096] The solid electrolyte layer was the same as in Example 1.

[0097] 氧电极：使用可以在复合氧电极中构建锂离子传输网络的快锂离子导体作为离子导体材料，包括锂镧锆氧、锂镧钛氧、磷酸钛铝锂、硅磷酸锂等的一种或多种。固体电解质粉体颗粒尺寸为 10 ηιη-5μιη。将催化剂、炭黑、锂盐、锂离子导体材料和粘结剂以重量百分比 4:2:2:1:1称取，以 Ν甲基吡咯烷酮为分散剂，将其搅拌混合均匀，通过用刮刀涂覆的方法把浆料涂覆到陶瓷电解质片上，固体电解质厚度为 100nm-50(Vm。然后将涂覆于电解质片上的氧电极置于 120°C保温 1小吋，将溶剂挥发掉的同吋使粘结剂固化。 Oxygen electrode: A fast lithium ion conductor capable of constructing a lithium ion transport network in a composite oxygen electrode is used as an ion conductor material, including lithium lanthanum zirconium oxide, lithium lanthanum titanium oxide, lithium aluminum aluminum phosphate, lithium silicon phosphate, and the like. Kind or more. The solid electrolyte powder has a particle size of 10 ηιη - 5 μιη. The catalyst, carbon black, lithium salt, lithium ion conductor material and binder are weighed in a weight percentage of 4:2:2:1:1, and Νmethylpyrrolidone is used as a dispersing agent, which is stirred and mixed uniformly, by using a doctor blade The coating method applies the slurry to the ceramic electrolyte sheet, and the thickness of the solid electrolyte is 100 nm to 50 (Vm. Then, the oxygen electrode coated on the electrolyte sheet is placed at 120 ° C for 1 hour, and the solvent is volatilized.吋 Curing the adhesive.

[0098] 负极制备方法同实例 2。 [0098] The negative electrode preparation method is the same as in Example 2.

[0099] 正极同实例 1所述气体。 [0099] The positive electrode was the same as the gas of Example 1.

[0100] 本实施例充放电测试数据列于表 1中。 [0100] The charge and discharge test data of this embodiment are listed in Table 1.

[0101] 实施例 7 Example 7

[0102] 一种新型高能量密度高功率密度的固态锂空气电池体系，装置的结构与实施例 [0102] A novel high energy density high power density solid state lithium air battery system, structure and embodiment of the device

[0103] 固态电解质层同实施例 1。 The solid electrolyte layer was the same as in Example 1.

[0104] 氧电极：使用可以优化复合氧电极中锂离子在界面上传输的锂盐添加到复合氧电极中，所述的锂盐选自 LiN0 ₃、 Li ₂S0 ₄、 LiCl、 Li ₂C0 ₃、 LiBOB、 LiC(SO ₂ CF ₃) ₃、 Li[(FS0 ₂)(n-C ₄F ₉S0 ₂)N]、 LiN(SO ₂CF3) ₂、 LiFNFSI、 LiCF ₃S0 ₃等的一种或几种。将炭黑、锂盐 (LiX)、固体电解质粉和粘结剂以重量百分比 4:4:1:1 称取，以 N甲基吡咯烷酮为分散剂，将其搅拌混合均匀，通过用刮刀涂覆的方法把浆料涂覆到锂镧锆氧基陶瓷电解质片上，固体电解质厚度为 100nm-50(Vm。然后将涂覆于电解质片上的氧电极置于 120°C保温 1小吋，将溶剂挥发掉的同吋使粘结剂固化。 Oxygen electrode: is added to the composite oxygen electrode using a lithium salt which can optimize the transport of lithium ions at the interface in the composite oxygen electrode, the lithium salt being selected from the group consisting of LiN0 ₃ , Li ₂ S0 ₄ , LiCl, Li ₂ C0 ₃ One or more of LiBOB, LiC(SO ₂ CF ₃ ) ₃ , Li[(FS0 ₂ )(nC ₄ F ₉ S0 ₂ )N], LiN(SO ₂ CF3) ₂ , LiFNFSI, LiCF ₃ S0 _{3 ,} etc. . Carbon black, lithium salt (LiX), solid electrolyte powder and binder in a weight ratio of 4:4:1:1 Weighing, using N-methylpyrrolidone as a dispersing agent, stirring and mixing uniformly, the slurry was applied onto a lithium lanthanum zirconium oxide ceramic electrolyte sheet by a doctor blade coating method, and the thickness of the solid electrolyte was 100 nm to 50 (Vm). Then, the oxygen electrode coated on the electrolyte sheet was placed at 120 ° C for 1 hour, and the solvent was volatilized to cure the binder.

[0105] 负极制备方法同实例 2。 [0105] The negative electrode preparation method was the same as in Example 2.

[0106] 正极同实例 1所述气体。 [0106] The positive electrode was the same as the gas of Example 1.

[0107] 本实施例充放电测试数据列于表 1中。 [0107] The charge and discharge test data of this embodiment are listed in Table 1.

[0108] 实施例 8 Example 8

[0109] 一种新型高能量密度高功率密度的固态锂空气电池体系，装置的结构与实施例 [0109] A novel high energy density high power density solid state lithium air battery system, structure and embodiment of the device

[0110] 固态电解质层同实施例 1。 The solid electrolyte layer was the same as in Example 1.

[0111] 氧电极：使用可将复合电极组成材料粘附到陶瓷电解质片上的粘结剂添加到复合氧电极中，所述的粘接剂包括聚四氟乙烯 PTFE、聚偏氟乙烯（PVDF)、聚酰胺酰亚胺、聚酰亚胺 (PI)、海藻酸钠、羧甲基纤维素（CMC)等等的一种或几种。将炭黑、锂盐 Li[(FSO ₂)(n-C ₄F ₉SO ₂)N]、锂镧锆氧粉 (10 nm-5 μηι)和粘结剂以重量百分比 4:4:1:1称取，以 Ν甲基吡咯烷酮为分散剂，将其搅拌混合均匀，通过用刮刀涂覆的方法把浆料涂覆到锂镧锆氧基陶瓷电解质片上，固体电解质厚度为 1 00nm-50(Vm。然后将涂覆于电解质片上的氧电极置于 120°C保温 1小吋，将溶剂挥发掉的同吋使粘结剂固化。 Oxygen electrode: is added to the composite oxygen electrode using a binder that can adhere the composite electrode constituent material to the ceramic electrolyte sheet, and the binder includes polytetrafluoroethylene PTFE, polyvinylidene fluoride (PVDF). One or more of polyamideimide, polyimide (PI), sodium alginate, carboxymethylcellulose (CMC), and the like. Carbon black, lithium salt Li[(FSO ₂ )(nC ₄ F ₉ SO ₂ )N], lithium lanthanum zirconium oxide powder (10 nm-5 μηι) and binder are weighed in a weight ratio of 4:4:1:1 Taking Νmethylpyrrolidone as a dispersing agent, stirring and mixing uniformly, the slurry is applied onto a lithium lanthanum zirconium oxide ceramic electrolyte sheet by a doctor blade coating method, and the solid electrolyte has a thickness of 100 nm to 50 (Vm). Then, the oxygen electrode coated on the electrolyte sheet was placed at 120 ° C for 1 hour, and the solvent was volatilized to cure the binder.

[0112] 负极制备方法同实例 2。 [0112] The negative electrode preparation method was the same as in Example 2.

[0113] 正极同实例 1所述气体。 [0113] The positive electrode was the same as the gas of Example 1.

[0114] 本实施例充放电测试数据列于表 1中。 [0114] The charge and discharge test data of this embodiment are listed in Table 1.

[0115] 本发明具有以下显著的优点： [0115] The present invention has the following significant advantages:

[0116] (1)高能量密度 (1) High energy density

[0117] 从图 2可以看出，就活性物质本身的能量密度而言，固态锂空气电池体系远远高于传统锂离子电池的氧电极材料。此外，因为该电池吸收空气中的二氧化碳作为氧电极，因此该电池在解决能源危机的同吋，可能是未来解决温室效应的一个有效途径。 [0118] (2)高功率密度 [0117] As can be seen from FIG. 2, the solid lithium air battery system is much higher than the oxygen electrode material of the conventional lithium ion battery in terms of the energy density of the active material itself. In addition, because the battery absorbs carbon dioxide from the air as an oxygen electrode, the battery's ability to solve the energy crisis may be an effective way to solve the greenhouse effect in the future. (2) High power density

[0119] 传统的固态电池由于受到锂离子传输限制，尤其在温度较低吋离子电导也较低的情况下，导致传统固态电池的动力学性能很差。由于采用高达 180-250°C的测试温度，固态电解质中的锂离子电导率接近 1 S/cm -i,比液态电池中的锂离子在液态溶剂中的电导率还高。另外 200摄氏度的温度下负极金属锂已处于熔融态，因此金属锂和固态电解质的界面得到大大改善。并且氧电极端因为采用锂盐 (例如 LiN0 ₃、 Li ₂S0 ₄、 LiCl、 Li ₂C0 ₃、 LiBOB、 LiC(SO ₂CF ₃) ₃、 Li[(FSO ₂)(n-C ₄F 9S0 ₂)N]、 LiN(S0 ₂CF3) ₂、 LiFNFSI、 LiCF ₃SO ₃ [0119] Conventional solid state batteries are subject to lithium ion transport limitations, especially at lower temperatures and lower ion conductance, resulting in poorer dynamic performance of conventional solid state batteries. Due to the test temperature of up to 180-250 ° C, the lithium ion conductivity in the solid electrolyte is close to 1 S / cm -i, which is higher than the lithium ion in the liquid battery in the liquid solvent. At another temperature of 200 degrees Celsius, the lithium metal of the negative electrode is already in a molten state, so the interface between the metallic lithium and the solid electrolyte is greatly improved. And the oxygen electrode end uses a lithium salt (for example, LiN0 ₃ , Li ₂ S0 ₄ , LiCl, Li ₂ C0 ₃ , LiBOB, LiC(SO ₂ CF ₃ ) ₃ , Li[(FSO ₂ )(nC ₄ F 9S0 ₂ )N ], LiN(S0 ₂ CF3) ₂ , LiFNFSI, LiCF ₃ SO ₃

等的一种或几种作为辅助电解质)，锂离子在氧电极端的界面传输困难也在一定程度上被克服。以上三点使得电池动力学特性大大增强，电池在大倍率充放电性能良好。如图 2所呈现的，电池可以在室温到 250°C的温度范围内工作。 One or more of the other ones act as auxiliary electrolytes, and the difficulty in transporting lithium ions at the interface of the oxygen electrode is also overcome to some extent. The above three points make the battery dynamics greatly enhanced, and the battery has good charge and discharge performance at a large rate. As shown in Figure 2, the battery can operate from room temperature to 250 °C.

[0120] (3)高安全性 (3) High security

[0121] 由于此种体系实现了锂负极的完全密封，即使在高于金属锂熔点锂融化了的情况下也不会有锂漏出，再加上氧化物固态电解质本身具有高热稳定性和高抗腐蚀性，大大地提高了体系工作过程中的安全性能。 [0121] Since such a system realizes complete sealing of the lithium negative electrode, even if lithium is melted higher than the melting point of lithium metal, there is no lithium leakage, and the oxide solid electrolyte itself has high thermal stability and high resistance. Corrosive, greatly improving the safety performance of the system during its work.

[0122] (4)较宽的使用温度范围 (4) Wide operating temperature range

[0123] 由于该电池在室温下可以作为一次电池，在 100-200°C的吋候可以作为二次电池，并且随着温度的升高，电池的能量效率也提高，使得该电池体系具有较好的高低温性能。 [0123] Since the battery can be used as a primary battery at room temperature, it can be used as a secondary battery at 100-200 ° C, and as the temperature increases, the energy efficiency of the battery also increases, making the battery system more Good high and low temperature performance.

Claims

权利要求书 Claim

[权利要求 1] 一种锂空气电池，其特征在于，所述锂空气电池包括负极、多孔氧电极、以及夹在负极和多孔氧电极之间的固态电解质层，其中，负极材质包括锂、锂合金和 /或含金属锂的复合物，多孔氧电极采用多孔导电载体、催化剂、离子导体材料、锂盐和 /或粘接剂均匀混合后干燥得到，固态电解质层的材质包括锂镧锆氧基陶瓷、锂镧钛氧基陶瓷、磷酸钛铝锂基陶瓷和 /或硅磷酸锂基陶瓷。 [Claim 1] A lithium air battery, comprising: a negative electrode, a porous oxygen electrode, and a solid electrolyte layer sandwiched between the negative electrode and the porous oxygen electrode, wherein the negative electrode material comprises lithium, lithium The alloy and/or the metal lithium-containing composite, the porous oxygen electrode is uniformly mixed and dried by using a porous conductive carrier, a catalyst, an ion conductor material, a lithium salt and/or a binder, and the material of the solid electrolyte layer comprises lithium lanthanum zirconium. Ceramic, lithium niobium titanyl ceramic, lithium aluminum aluminum phosphate ceramic and/or lithium silicon phosphate ceramic.

[权利要求 2] 根据权利要求 1所述的锂空气电池，其特征在于，锂合金中，锂的含量至少 20 wt<¾，锂合金还含有 Mg、 Ca、 [Claim 2] The lithium air battery according to claim 1, wherein the lithium alloy has a lithium content of at least 20 wt < 3⁄4, and the lithium alloy further contains Mg, Ca,

B、 Al、 Ga、 In、 Si、 Ge、 Sn、 Pb、 Sb中的至少一种； At least one of B, Al, Ga, In, Si, Ge, Sn, Pb, Sb;

含金属锂的复合物含有至少 20 wt%的金属锂，还包含碳颗粒、碳纳米管、碳纤维、石墨烯、石墨片、多孔金属、多孔碳、惰性氧化物和 / 或铜粉； The lithium metal-containing composite contains at least 20 wt% of metallic lithium, and further comprises carbon particles, carbon nanotubes, carbon fibers, graphene, graphite flakes, porous metal, porous carbon, inert oxide and/or copper powder;

所述锂空气电池的氧气源包括纯氧、含有氧气的混合气体、自然存在的空气。 The oxygen source of the lithium air battery includes pure oxygen, a mixed gas containing oxygen, and naturally occurring air.

[权利要求 3] 根据权利要求 1或 2所述的锂空气电池，其特征在于，多孔氧电极中，催化剂包括过渡金属氧化物、过渡金属氮化物、 Pt、 Pd和 /或 Au，过渡金属氧化物优选氧化锰、氧化亚锰、氧化铁、氧化镍、氧化钴、氧化钌、氧化铱、氧化钼和 /或氧化铈，过渡金属氮化物优选氮化锰、氮化铁、氮化镍、氮化钛和 /或氮化钴。 [Claim 3] The lithium air battery according to claim 1 or 2, wherein in the porous oxygen electrode, the catalyst comprises a transition metal oxide, a transition metal nitride, Pt, Pd, and/or Au, and transition metal oxide The material is preferably manganese oxide, manganese oxide, iron oxide, nickel oxide, cobalt oxide, cerium oxide, cerium oxide, molybdenum oxide and/or cerium oxide. The transition metal nitride is preferably manganese nitride, iron nitride, nickel nitride or nitrogen. Titanium and/or cobalt nitride.

[权利要求 4] 根据权利要求 1-3中任一所述的锂空气电池，其特征在于，多孔氧电极中，离子导体材料为锂镧锆氧基陶瓷粉体、锂镧钛氧基陶瓷粉体、磷酸钛铝锂基陶瓷粉体和 /或硅磷酸锂基陶瓷粉体，粉体粒径为 10 ϋΐη-5μηι。 [Claim 4] The lithium air battery according to any one of claims 1 to 3, wherein, in the porous oxygen electrode, the ion conductor material is lithium lanthanum zirconium oxide ceramic powder, lithium lanthanum titanyl oxide ceramic powder The body, the lithium aluminum lithium phosphate ceramic powder and/or the lithium silicon phosphate ceramic powder have a powder particle size of 10 ϋΐ η - 5 μηι.

[权利要求 5] 根据权利要求 1-4中任一所述的锂空气电池，其特征在于，多孔氧电极中，锂盐选自 LiN0 ₃、 Li ₂S0 ₄、 LiCl、 Li ₂C0 ₃、 LiBOB、 LiC(SO ₂ CF ₃) ₃、 Li[(FS0 ₂)(n-C ₄F ₉S0 ₂)N]、 LiN(SO ₂CF3) ₂、 LiFNFSI、 LiCF 380 ₃中的至少一种。 [Claim 5] The lithium air battery according to any one of claims 1 to 4, wherein, in the porous oxygen electrode, the lithium salt is selected from the group consisting of LiN0 ₃ , Li ₂ S0 ₄ , LiCl, Li ₂ C0 ₃ , LiBOB At least one of LiC(SO ₂ CF ₃ ) ₃ , Li[(FS0 ₂ )(nC ₄ F ₉ S0 ₂ )N], LiN(SO ₂ CF 3 ) ₂ , LiFNFSI, LiCF 380 ₃ .

[权利要求 6] 根据权利要求 1-5中任一所述的锂空气电池，其特征在于，多孔氧电极中，粘接剂包括聚偏氟乙烯、聚四氟乙烯、聚酰胺酰亚胺、聚酰亚胺、海藻酸钠、羧甲基纤维素中的至少一种。 [Claim 6] The lithium air battery according to any one of claims 1 to 5, wherein, in the porous oxygen electrode, the binder comprises polyvinylidene fluoride, polytetrafluoroethylene, polyamideimide, At least one of polyimide, sodium alginate, and carboxymethylcellulose.

[权利要求 7] 根据权利要求 1-6中任一所述的锂空气电池，其特征在于，多孔氧电极中，孔导电载体包括多孔碳、乙炔黑、石墨、石墨烯、氧化石墨烯、碳纳米管、碳纤维、氮惨杂的碳中的至少一种、和 /或导电氧化物 [Claim 7] The lithium air battery according to any one of claims 1 to 6, wherein in the porous oxygen electrode, the porous conductive carrier comprises porous carbon, acetylene black, graphite, graphene, graphene oxide, carbon At least one of nanotubes, carbon fibers, nitrogen-doped carbon, and/or conductive oxides

[权利要求 8] 根据权利要求 1-7中任一所述的锂空气电池，其特征在于，固态电解质层的 100ηηι-500μιη。 [Claim 8] The lithium air battery according to any one of claims 1 to 7, characterized in that the solid electrolyte layer is 100 ηι - 500 μηη.

[权利要求 9] 根据权利要求 1-8中任一所述的锂空气电池，其特征在于，所述锂空气电池还包括封装负极、多孔氧电极、固态电解质层的电池封装材料，以及能够在工作温度使用的导电极耳、极柱。 [Claim 9] The lithium air battery according to any one of claims 1 to 8, wherein the lithium air battery further comprises a battery encapsulating material encapsulating a negative electrode, a porous oxygen electrode, a solid electrolyte layer, and The electrode tip and pole used for the working temperature.

[权利要求 10] 根据权利要求 1-9中任一所述的锂空气电池，其特征在于，所述锂空气电池的工作温度为室温到 250°C，优选工作温度为 80-250°C，更优选工作温度为 180-220°C。 [Claim 10] The lithium air battery according to any one of claims 1 to 9, wherein the lithium air battery has an operating temperature of from room temperature to 250 ° C, preferably an operating temperature of 80 to 250 ° C, More preferably, the working temperature is 180-220 °C.