CN111193010B - A lithium battery composite material - Google Patents

A lithium battery composite material Download PDF

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CN111193010B
CN111193010B CN202010016034.5A CN202010016034A CN111193010B CN 111193010 B CN111193010 B CN 111193010B CN 202010016034 A CN202010016034 A CN 202010016034A CN 111193010 B CN111193010 B CN 111193010B
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lithium
metal
composite material
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lithium battery
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CN111193010A (en
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陈胜洲
麦鍠旺
谢谦
丘秀莲
杨伟
邹汉波
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Guangzhou University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381Alkaline or alkaline earth metals elements
    • H01M4/382Lithium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42Alloys based on zinc
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The invention provides a lithium battery composite material which comprises a solid electrolyte and a metal mixed melt coating which is used as a cathode and coated on the surface of the solid electrolyte, wherein the metal mixed melt coating is a mixed melt of metal lithium, metal zinc and lithium oxide. According to the lithium battery composite material, the metal lithium, the metal zinc and the lithium oxide form a mixed melt and then are coated on the surface of the solid electrolyte to form a coating, so that the specific surface area difference between the cathode material and the contact surface of the solid electrolyte is reduced, the lithium battery composite material has smaller impedance and conductivity, and the charging and discharging performance is better.

Description

一种锂电池复合材料A lithium battery composite material

技术领域technical field

本发明涉及电池材料领域,具体涉及一种锂电池复合材料。The invention relates to the field of battery materials, in particular to a lithium battery composite material.

背景技术Background technique

锂离子电池被广泛应用于众多电子产品和动力设备源。由于液态有机锂离子电池容易在受到碰撞或刺破时发生剧烈燃烧,而导致人员或财产损失,因此全固态锂离子电池是具有较高安全性的能源存储设备。但是由于熔融金属锂和固态电解质存在巨大的比表面能,使得金属锂不能在固态电解质铺展,导致固态电解质和金属锂存在巨大的离子传输电阻,高达2319Ωcm-2,以及导致熔融金属锂和固态电解质界面接触不良造成离子传输路径不均匀,从而导致局部电流过大,加速了锂枝晶生长,最终导致电池短路。申请号201810210158.X的发明专利中描述了一种无机-有机复合固态电解质,但是目前有机固态电解质电导率比无机固态电解质低一到两个数量级,因此该电解质电导率比无机固态电解质的电导率低,并且该电解质由于有机物的添加导致固态电解质机械强度下降,整体致密度下降,容易被锂枝晶刺破,容易导致电池短路从而导致严重事故。Lithium-ion batteries are widely used in numerous electronic products and power equipment sources. Since liquid organic lithium-ion batteries are prone to violent combustion when they are bumped or punctured, resulting in personal or property damage, all-solid-state lithium-ion batteries are energy storage devices with high safety. However, due to the huge specific surface energy of molten metal lithium and solid electrolyte, metal lithium cannot be spread in solid electrolyte, resulting in huge ion transport resistance of solid electrolyte and metal lithium, up to 2319Ωcm -2 , and leading to molten metal lithium and solid electrolyte. Poor interfacial contact results in uneven ion transport paths, resulting in excessive local current, accelerating lithium dendrite growth, and ultimately leading to short-circuiting of the battery. The invention patent of application number 201810210158.X describes an inorganic-organic composite solid electrolyte, but the current conductivity of organic solid electrolyte is one to two orders of magnitude lower than that of inorganic solid electrolyte, so the conductivity of this electrolyte is higher than that of inorganic solid electrolyte. In addition, due to the addition of organic substances, the electrolyte reduces the mechanical strength of the solid-state electrolyte, the overall density decreases, and is easily punctured by lithium dendrites, which can easily lead to short-circuit of the battery and cause serious accidents.

发明内容SUMMARY OF THE INVENTION

本发明的目的在于克服现有技术存在的不足之处而提供一种锂电池复合材料。The purpose of the present invention is to overcome the shortcomings of the prior art and provide a lithium battery composite material.

为实现上述目的,本发明采取的技术方案为:一种锂电池复合材料,所述锂电池复合材料包括固态电解质和作为阴极的涂覆在所述固态电解质表面的金属混合熔融物涂层,所述金属混合熔融物涂层为金属锂、金属锌和氧化锂的混合熔融物。In order to achieve the above purpose, the technical solution adopted in the present invention is: a lithium battery composite material, the lithium battery composite material includes a solid electrolyte and a metal mixed melt coating that is coated on the surface of the solid electrolyte as a cathode, so the The metal mixed melt coating is a mixed melt of metallic lithium, metallic zinc and lithium oxide.

上述锂电池复合材料通过将金属锂、金属锌和氧化锂形成混合熔融物之后涂覆在固态电解质表面形成涂层,降低了阴极材料与固态电解质接触面之间的比表面积差值,使得包含有锂金属的金属混合熔融物涂层更好地贴合在固体电解质表面,金属锂、金属锌和氧化锂形成的金属混合熔融物涂层中形成了锌锂合金可以形成电子和锂离子传输通道加大负极中的锂的利用率,同时氧化锂可以作为充放电过程中负极膨胀形变的缓冲物,使得上述锂电池复合材料具有更小的阻抗和导电率,充放电性能更好。The above-mentioned lithium battery composite material is coated on the surface of the solid electrolyte by forming a mixed melt of metal lithium, metal zinc and lithium oxide to form a coating, which reduces the specific surface area difference between the contact surface of the cathode material and the solid electrolyte, so that it contains The metal mixed melt coating of lithium metal adheres better to the surface of the solid electrolyte, and the zinc-lithium alloy is formed in the metal mixed melt coating formed by metal lithium, metal zinc and lithium oxide, which can form electron and lithium ion transport channels. The utilization rate of lithium in the negative electrode is large, and lithium oxide can be used as a buffer for the expansion and deformation of the negative electrode during the charging and discharging process, so that the above-mentioned lithium battery composite material has lower impedance and conductivity, and better charging and discharging performance.

优选地,所述金属锂、金属锌和氧化锂的重量比为10:(1~1.20):(1~1.20)。Preferably, the weight ratio of the metallic lithium, metallic zinc and lithium oxide is 10:(1-1.20):(1-1.20).

发明人经过研究发现,作为阴极的涂覆在所述固态电解质表面的金属混合熔融物涂层中当金属锂、金属锌和氧化锂的重量比为10:(1~1.20):(1~1.20)时,上述锂电池复合材料的阻抗更小,充放电性能更好。The inventors have found through research that when the weight ratio of metal lithium, metal zinc and lithium oxide is 10:(1~1.20):(1~1.20) in the metal mixed melt coating coated on the surface of the solid electrolyte as the cathode ), the impedance of the lithium battery composite material is smaller, and the charge and discharge performance is better.

优选地,所述金属锂、金属锌和氧化锂的重量比为10:(1~1.12):(1~1.12)。Preferably, the weight ratio of the metallic lithium, metallic zinc and lithium oxide is 10:(1-1.12):(1-1.12).

发明人经过研究发现,作为阴极的涂覆在所述固态电解质表面的金属混合熔融物涂层中当金属锂、金属锌和氧化锂的重量比为10:(1~1.12):(1~1.12)时,上述锂电池复合材料的阻抗更小,充放电性能更好。The inventors have found through research that when the weight ratio of metal lithium, metal zinc and lithium oxide is 10:(1~1.12):(1~1.12 ), the impedance of the lithium battery composite material is smaller, and the charge and discharge performance is better.

优选地,所述金属锂、金属锌和氧化锂的重量比为10:1:1.11。Preferably, the weight ratio of the metallic lithium, metallic zinc and lithium oxide is 10:1:1.11.

发明人经过研究发现,作为阴极的涂覆在所述固态电解质表面的金属混合熔融物涂层中当金属锂、金属锌和氧化锂的重量比为10:1:1.11时,上述锂电池复合材料的阻抗更小,充放电性能更好。The inventors found through research that when the weight ratio of metal lithium, metal zinc and lithium oxide in the metal mixed melt coating coated on the surface of the solid electrolyte as the cathode is 10:1:1.11, the above lithium battery composite material The impedance is smaller and the charge and discharge performance is better.

优选地,所述固态电解质为锂镧锆氧。Preferably, the solid electrolyte is lithium lanthanum zirconium oxygen.

优选地,所述锂电池复合材料的制备方法包括以下步骤:Preferably, the preparation method of the lithium battery composite material comprises the following steps:

(1)将固态电解质表面抛光后用有机溶剂冲洗后干燥;(1) After polishing the surface of the solid electrolyte, rinse it with an organic solvent and then dry it;

(2)将金属锂加热至180~250℃得到金属锂熔融物A;(2) heating lithium metal to 180-250° C. to obtain molten lithium metal A;

(3)将金属锌和氧化锂加入到金属锂熔融物A中于180~250℃下搅拌得到金属混合熔融物B;(3) adding metallic zinc and lithium oxide to metallic lithium melt A and stirring at 180-250° C. to obtain metallic mixed melt B;

(4)将步骤(3)得到的金属混合熔融物B涂覆在固态电解质表面形成金属混合熔融物涂层,得到所述锂电池复合材料。(4) Coating the metal mixed melt B obtained in step (3) on the surface of the solid electrolyte to form a metal mixed melt coating to obtain the lithium battery composite material.

优选地,所述步骤(2)中,将金属锂加热至200℃得到金属锂熔融物A。Preferably, in the step (2), the metal lithium is heated to 200° C. to obtain the metal lithium melt A.

本发明还提供一种锂电池,所述锂电池包括如上述任一所述的锂电池复合材料。The present invention also provides a lithium battery, the lithium battery comprising the lithium battery composite material described above.

上述的锂电池应用上述任一所述的锂电池复合材料具有更好的充放电性能。The above-mentioned lithium battery application of any one of the above-mentioned lithium battery composite materials has better charge-discharge performance.

本发明的有益效果在于:本发明提供了一种锂电池复合材料,本发明的锂电池复合材料通过将金属锂、金属锌和氧化锂形成混合熔融物之后涂覆在固态电解质表面形成涂层,降低了阴极材料与固态电解质接触面之间的比表面积差值,使得包含有锂金属的金属混合熔融物涂层更好地贴合在固体电解质表面,金属锂、金属锌和氧化锂形成的金属混合熔融物涂层中形成了锌锂合金可以形成电子和锂离子传输通道加大负极中的锂的利用率,同时氧化锂可以作为充放电过程中负极膨胀形变的缓冲物,使得本发明的锂电池复合材料具有更小的阻抗和导电率,充放电性能更好。The beneficial effects of the present invention are as follows: the present invention provides a lithium battery composite material. The lithium battery composite material of the present invention forms a coating on the surface of a solid electrolyte by forming a mixed molten metal lithium, metal zinc and lithium oxide, and then coating it on the surface of the solid electrolyte. The specific surface area difference between the contact surface of the cathode material and the solid electrolyte is reduced, so that the metal mixed melt coating containing lithium metal can better adhere to the surface of the solid electrolyte. The metal formed by metal lithium, metal zinc and lithium oxide The zinc-lithium alloy formed in the mixed melt coating can form electron and lithium ion transport channels to increase the utilization rate of lithium in the negative electrode, and at the same time, lithium oxide can be used as a buffer for the expansion and deformation of the negative electrode during charging and discharging, so that the lithium The battery composite material has smaller impedance and conductivity, and better charge-discharge performance.

附图说明Description of drawings

图1为本发明实施例和对比例的锂电池复合材料的扫描电子显微镜(SEM)图。FIG. 1 is a scanning electron microscope (SEM) image of the lithium battery composite materials of the examples and comparative examples of the present invention.

图2为本发明实施例和对比例的锂电池复合材料的表征性能图。FIG. 2 is a graph showing the characterization performance of the lithium battery composite materials according to the embodiment of the present invention and the comparative example.

图3为本发明实施例和对比例的锂电池复合材料的交流阻抗谱图。FIG. 3 is an AC impedance spectrum diagram of the lithium battery composite material of the embodiment and the comparative example of the present invention.

图4为本发明实施例和对比例的锂电池复合材料的充放电性能曲线图。FIG. 4 is a graph showing the charge-discharge performance of the lithium battery composite materials according to the embodiment of the present invention and the comparative example.

具体实施方式Detailed ways

为更好的说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明。In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below with reference to specific embodiments.

实施例1Example 1

作为本发明实施例的一种锂电池复合材料,所述锂电池复合材料包括固态电解质和作为阴极的涂覆在所述固态电解质表面的金属混合熔融物涂层,所述金属混合熔融物涂层为金属锂、金属锌和氧化锂的混合熔融物,所述金属锂、金属锌和氧化锂的重量比为10:1:1,所述固态电解质为锂镧锆氧(LLZTO)。As a lithium battery composite material according to an embodiment of the present invention, the lithium battery composite material includes a solid electrolyte and a metal mixed melt coating as a cathode coated on the surface of the solid electrolyte, the metal mixed melt coating It is a mixed melt of metal lithium, metal zinc and lithium oxide, the weight ratio of the metal lithium, metal zinc and lithium oxide is 10:1:1, and the solid electrolyte is lithium lanthanum zirconium oxide (LLZTO).

本实施例的锂电池复合材料的制备方法包括以下步骤:The preparation method of the lithium battery composite material of the present embodiment includes the following steps:

(1)将直径1cm且厚度1mm的锂镧锆氧固态电解质用2000目的砂纸表面抛光后用乙醇冲洗后干燥;(1) The lithium lanthanum zirconium oxide solid electrolyte with a diameter of 1 cm and a thickness of 1 mm is polished with 2000 mesh sandpaper, rinsed with ethanol and dried;

(2)将0.183g的金属锂加热至200℃得到金属锂熔融物A;(2) heating 0.183 g of lithium metal to 200° C. to obtain molten lithium metal A;

(3)将0.0183g金属锌和0.0183g氧化锂加入到金属锂熔融物A中于200℃下搅拌至白色粉末完全消失后除去表面杂质得到金属混合熔融物B;(3) adding 0.0183g metal zinc and 0.0183g lithium oxide to the metal lithium melt A, stirring at 200° C. until the white powder completely disappears and removing surface impurities to obtain a metal mixed melt B;

(4)将步骤(3)得到的金属混合熔融物B涂覆在固态电解质表面形成金属混合熔融物涂层,冷却后得到所述锂电池复合材料。(4) The metal mixed melt B obtained in step (3) is coated on the surface of the solid electrolyte to form a metal mixed melt coating, and the lithium battery composite material is obtained after cooling.

实施例2Example 2

作为本发明实施例的一种锂电池复合材料,本实施例与实施例1的唯一区别为:所述金属锂、金属锌和氧化锂的重量比为10:1.11:1。As a lithium battery composite material of the embodiment of the present invention, the only difference between this embodiment and Embodiment 1 is that the weight ratio of the metal lithium, metal zinc and lithium oxide is 10:1.11:1.

实施例3Example 3

作为本发明实施例的一种锂电池复合材料,本实施例与实施例1的唯一区别为:所述金属锂、金属锌和氧化锂的重量比为10:1:1.11。As a lithium battery composite material of an embodiment of the present invention, the only difference between this embodiment and Embodiment 1 is that the weight ratio of the metal lithium, metal zinc and lithium oxide is 10:1:1.11.

对比例1Comparative Example 1

作为本发明对比例的一种锂电池复合材料,所述锂电池复合材料包括固态电解质和作为阴极的涂覆在所述固态电解质表面的金属混合熔融物涂层,所述金属混合熔融物涂层为金属锂和氧化锌的混合熔融物,所述金属锂和氧化锌的重量比为10:1,所述固态电解质为锂镧锆氧(LLZTO)。As a lithium battery composite material as a comparative example of the present invention, the lithium battery composite material includes a solid electrolyte and a metal mixed melt coating as a cathode coated on the surface of the solid electrolyte, the metal mixed melt coating It is a mixed melt of metal lithium and zinc oxide, the weight ratio of the metal lithium and zinc oxide is 10:1, and the solid electrolyte is lithium lanthanum zirconium oxide (LLZTO).

本对比例的锂电池复合材料的制备方法包括以下步骤:The preparation method of the lithium battery composite material of this comparative example comprises the following steps:

(1)将直径1cm且厚度1mm的锂镧锆氧固态电解质用2000目的砂纸表面抛光后用乙醇冲洗后干燥;(1) The lithium lanthanum zirconium oxide solid electrolyte with a diameter of 1 cm and a thickness of 1 mm is polished with 2000 mesh sandpaper, rinsed with ethanol and dried;

(2)将0.183g的金属锂加热至200℃得到金属锂熔融物A;(2) heating 0.183 g of lithium metal to 200° C. to obtain molten lithium metal A;

(3)将0.0183g氧化锌加入到金属锂熔融物A中于200℃下搅拌至白色粉末完全消失后除去表面杂质得到金属混合熔融物B;(3) adding 0.0183g of zinc oxide to the molten lithium metal A and stirring at 200° C. until the white powder completely disappears and then removing surface impurities to obtain a mixed molten metal B;

(4)将步骤(3)得到的金属混合熔融物B涂覆在固态电解质表面形成金属混合熔融物涂层,冷却后得到所述锂电池复合材料。(4) The metal mixed melt B obtained in step (3) is coated on the surface of the solid electrolyte to form a metal mixed melt coating, and the lithium battery composite material is obtained after cooling.

对比例2Comparative Example 2

作为本发明对比例的一种锂电池复合材料,所述锂电池复合材料包括固态电解质和作为阴极的涂覆在所述固态电解质表面的金属混合熔融物涂层,所述金属混合熔融物涂层为金属锂和金属锌的混合熔融物,所述金属锂和金属锌的重量比为10:1.11,所述固态电解质为锂镧锆氧(LLZTO)。As a lithium battery composite material as a comparative example of the present invention, the lithium battery composite material includes a solid electrolyte and a metal mixed melt coating as a cathode coated on the surface of the solid electrolyte, the metal mixed melt coating It is a mixed melt of metal lithium and metal zinc, the weight ratio of the metal lithium and metal zinc is 10:1.11, and the solid electrolyte is lithium lanthanum zirconium oxide (LLZTO).

本对比例的锂电池复合材料的制备方法包括以下步骤:The preparation method of the lithium battery composite material of this comparative example comprises the following steps:

(1)将直径1cm且厚度1mm的锂镧锆氧固态电解质用2000目的砂纸表面抛光后用乙醇冲洗后干燥;(1) The lithium lanthanum zirconium oxide solid electrolyte with a diameter of 1 cm and a thickness of 1 mm is polished with 2000 mesh sandpaper, rinsed with ethanol and dried;

(2)将0.183g的金属锂加热至200℃得到金属锂熔融物A;(2) heating 0.183 g of lithium metal to 200° C. to obtain molten lithium metal A;

(3)将0.0203g金属锌加入到金属锂熔融物A中于200℃下搅拌至白色粉末完全消失后除去表面杂质得到金属混合熔融物B;(3) adding 0.0203 g of metallic zinc into the molten lithium metal A, stirring at 200° C. until the white powder completely disappears, and removing surface impurities to obtain a mixed molten metal B;

(4)将步骤(3)得到的金属混合熔融物B涂覆在固态电解质表面形成金属混合熔融物涂层,冷却后得到所述锂电池复合材料。(4) The metal mixed melt B obtained in step (3) is coated on the surface of the solid electrolyte to form a metal mixed melt coating, and the lithium battery composite material is obtained after cooling.

对比例3Comparative Example 3

作为本发明对比例的一种锂电池复合材料,所述锂电池复合材料包括固态电解质和作为阴极的涂覆在所述固态电解质表面的金属熔融物涂层,所述金属熔融物涂层为金属锂熔融物,所述固态电解质为锂镧锆氧(LLZTO)。As a lithium battery composite material as a comparative example of the present invention, the lithium battery composite material includes a solid electrolyte and a metal melt coating as a cathode, which is coated on the surface of the solid electrolyte, and the metal melt coating is a metal Lithium melt, and the solid electrolyte is lithium lanthanum zirconium oxide (LLZTO).

本对比例的锂电池复合材料的制备方法包括以下步骤:The preparation method of the lithium battery composite material of this comparative example comprises the following steps:

(1)将直径1cm且厚度1mm的锂镧锆氧固态电解质用2000目的砂纸表面抛光后用乙醇冲洗后干燥;(1) The lithium lanthanum zirconium oxide solid electrolyte with a diameter of 1 cm and a thickness of 1 mm is polished with 2000 mesh sandpaper, rinsed with ethanol and dried;

(2)将0.183g的金属锂加热至200℃得到金属锂熔融物A;(2) heating 0.183 g of lithium metal to 200° C. to obtain molten lithium metal A;

(3)将步骤(2)得到的金属混合熔融物A涂覆在固态电解质表面形成金属熔融物涂层,冷却后得到所述锂电池复合材料。(3) Coating the metal mixed melt A obtained in step (2) on the surface of the solid electrolyte to form a metal melt coating, and cooling to obtain the lithium battery composite material.

效果例1Effect example 1

对实施例1~实施例3、对比例1~对比例3制备得到的锂电池复合材料进行扫描电镜、X-射线衍射分析、充放电性能测试。Scanning electron microscopy, X-ray diffraction analysis, and charge-discharge performance tests were performed on the lithium battery composite materials prepared in Examples 1 to 3 and Comparative Examples 1 to 3.

如图1所示,图1(a)为对比例1的锂电池复合材料的扫描电子显微镜(SEM)图,图1(b)为对比例2的锂电池复合材料的扫描电子显微镜(SEM)图,图1(c)为对比例3的锂电池复合材料的扫描电子显微镜(SEM)图,图1(d)为实施例1的锂电池复合材料的扫描电子显微镜(SEM)图,图1(e)为实施例2的锂电池复合材料的扫描电子显微镜(SEM)图,图1(f)为实施例3的锂电池复合材料的扫描电子显微镜(SEM)图。由图1可知,实施例1~3的锂电池复合材料的粗糙度优于对比例1~3的锂电池复合材料,说明将氧化锂、锌和锂结合起来形成金属混合熔融物涂层平铺在固态电解质表面能够使得锂电池复合材料的电流密度下降,缓解锂枝晶的形成。As shown in FIG. 1 , FIG. 1( a ) is a scanning electron microscope (SEM) image of the lithium battery composite material of Comparative Example 1, and FIG. 1( b ) is a scanning electron microscope (SEM) image of the lithium battery composite material of Comparative Example 2 Fig. 1(c) is a scanning electron microscope (SEM) image of the lithium battery composite material of Comparative Example 3, Fig. 1(d) is a scanning electron microscope (SEM) image of the lithium battery composite material of Example 1, Fig. 1 (e) is a scanning electron microscope (SEM) image of the lithium battery composite material of Example 2, and FIG. 1(f) is a scanning electron microscope (SEM) image of the lithium battery composite material of Example 3. It can be seen from Figure 1 that the roughness of the lithium battery composite materials of Examples 1 to 3 is better than that of the lithium battery composite materials of Comparative Examples 1 to 3, indicating that lithium oxide, zinc and lithium are combined to form a metal mixed melt coating tile. On the surface of the solid electrolyte, the current density of the lithium battery composite material can be reduced and the formation of lithium dendrites can be alleviated.

如图2所示,图2(a)为对比例3的实物图,有图2(a)可知对比例3的金属锂熔融物不能在固态电解质片表面铺展,图2(b)为实施例3的实物图,图2(c)为实施例3的锂电池复合材料的SEM图,图2(d)为实施例3的锂电池复合材料的红外线衍射XRD图。图2(b)显示实施例3的锂电池复合材料中含有锂锌合金、氧化锂和金属锂,由图2(c)、2(d)说明由金属锂、金属锌和氧化锂形成的金属混合熔融物涂层(Li-ZnO)可以平铺在固态电解质(LLZTO)表面并紧紧贴合在固态电解质上面。从图2(d)中可以看出实施例3的锂电池复合材料中金属混合熔融物涂层与固态电解质的接触界面没有空隙。As shown in Fig. 2, Fig. 2(a) is a physical image of Comparative Example 3, and Fig. 2(a) shows that the molten lithium metal of Comparative Example 3 cannot spread on the surface of the solid electrolyte sheet, and Fig. 2(b) is an example 3, FIG. 2(c) is the SEM image of the lithium battery composite material of Example 3, and FIG. 2(d) is the infrared diffraction XRD pattern of the lithium battery composite material of Example 3. Figure 2(b) shows that the lithium battery composite material of Example 3 contains lithium-zinc alloy, lithium oxide and metal lithium, and Figures 2(c) and 2(d) illustrate the metal formed by metal lithium, metal zinc and lithium oxide The mixed melt coating (Li-ZnO) can be spread on the surface of the solid electrolyte (LLZTO) and tightly adhered to the solid electrolyte. It can be seen from FIG. 2(d) that the contact interface between the metal mixed melt coating and the solid electrolyte in the lithium battery composite material of Example 3 has no voids.

如图3所示,图3(a)为对比例1的锂电池复合材料的交流阻抗图,图3(b)为对比例2的锂电池复合材料的交流阻抗图,图3(c)为对比例3的锂电池复合材料的交流阻抗图,图3(d)为实施例1的锂电池复合材料的交流阻抗图,图3(e)为实施例2的锂电池复合材料的交流阻抗图,图3(f)为实施例3的锂电池复合材料的交流阻抗图。对比例1的锂电池复合材料的界面离子转移阻抗为125Ωcm-2,对比例2的锂电池复合材料的界面离子转移阻抗为250Ωcm-2,对比例3的锂电池复合材料的界面离子转移阻抗为2319Ωcm-2,实施例1的锂电池复合材料的界面离子转移阻抗为80Ωcm-2,实施例2的锂电池复合材料的界面离子转移阻抗为85Ωcm-2,实施例3的锂电池复合材料的界面离子转移阻抗为35Ωcm-2,实施例1~实施例3的锂电池复合材料的界面离子转移阻抗远小于对比例1~3的锂电池复合材料的界面离子转移阻抗,说明将氧化锂、锌和锂结合起来形成金属混合熔融物涂层平铺在固态电解质表面能够使得锂电池复合材料的交流阻抗降低。而且对比例实施例1~实施例3发现实施例3的交流阻抗相对更低,说明金属锂、金属锌和氧化锂的重量比为10:1:1.11锂电池复合材料的界面离子转移阻抗更低。As shown in Figure 3, Figure 3(a) is the AC impedance diagram of the lithium battery composite material of Comparative Example 1, Figure 3(b) is the AC impedance diagram of the lithium battery composite material of Comparative Example 2, and Figure 3(c) is The AC impedance diagram of the lithium battery composite material of Comparative Example 3, FIG. 3(d) is the AC impedance diagram of the lithium battery composite material of Example 1, and FIG. 3(e) is the AC impedance diagram of the lithium battery composite material of Example 2 , Figure 3(f) is the AC impedance diagram of the lithium battery composite material of Example 3. The interface ion transfer impedance of the lithium battery composite material of Comparative Example 1 is 125Ωcm -2 , the interface ion transfer impedance of the lithium battery composite material of Comparative Example 2 is 250Ωcm -2 , and the interface ion transfer impedance of the lithium battery composite material of Comparative Example 3 is 2319Ωcm -2 , the interface ion transfer impedance of the lithium battery composite material of Example 1 is 80Ωcm -2 , the interface ion transfer impedance of the lithium battery composite material of Example 2 is 85Ωcm -2 , and the interface of the lithium battery composite material of Example 3 The ion transfer impedance is 35Ωcm -2 , and the interface ion transfer impedance of the lithium battery composite materials of Examples 1 to 3 is much smaller than that of the lithium battery composite materials of Comparative Examples 1 to 3, indicating that lithium oxide, zinc and The combination of lithium to form a metal mixed melt coating spread on the surface of the solid electrolyte can reduce the AC impedance of the lithium battery composite. In addition, the comparative examples from Examples 1 to 3 found that the AC impedance of Example 3 is relatively lower, indicating that the weight ratio of metal lithium, metal zinc and lithium oxide is 10:1:1.11 The interface ion transfer resistance of the lithium battery composite material is lower .

如图4所示,图4(a)为对比例1的锂电池复合材料组装成对电极的充放电性能图,图4(b)为对比例2的锂电池复合材料组装成对电极的充放电性能图,图4(c)为对比例3的锂电池复合材料组装成对电极的充放电性能图,图4(d)为实施例1的锂电池复合材料组装成对电极的充放电性能图,图4(e)为实施例2的锂电池复合材料组装成对电极的充放电性能图,图4(f)为实施例3的锂电池复合材料组装成对电极的充放电性能图。由图4可知,在0.1mA cm-2的电流密度下,对比例3的锂电池复合材料组装成对电极出现短路情况,说明对比例3的锂电池复合材料组装的电极不能抑制锂枝晶的生成,对比例1、对比例3和实施例1~3的电压都维持在0.02V左右,当电流密度上升到0.2mA cm-2时,当电流密度上升到0.2mAcm-2时,对比例1和对比例2电压瞬间达到0.12V,说明对比例1和对比例2锂电池复合材料的界面还具有很大的离子传输电阻,并与交流阻抗谱的结果相对应,然后电压逐渐变小,说明锂枝晶开始并逐渐向锂枝晶内部生成,使离子传输距离变小,表观上电压变小。实施例2的锂电池复合材料的电压从0.04V逐渐下降,并出现波动说明实施例2的锂电池复合材料组装成的对电极逐渐出现短路现象,实施例1电压出现锯齿状波动,说明锂枝晶生长使电极短路了。实施例3电压相对稳定,说明实施例3的锂电池复合材料抑制锂枝晶效果最好。As shown in Figure 4, Figure 4(a) is the charge-discharge performance diagram of the lithium battery composite material assembled into the counter electrode of Comparative Example 1, and Figure 4(b) is the charge and discharge performance of the lithium battery composite material assembled into the counter electrode of Comparative Example 2. Discharge performance diagram, Figure 4(c) is the charge and discharge performance diagram of the lithium battery composite material of Comparative Example 3 assembled into a counter electrode, and Figure 4(d) is the charge and discharge performance of the lithium battery composite material of Example 1 assembled into a counter electrode Figure 4(e) is a charge-discharge performance diagram of the lithium battery composite material of Example 2 assembled into a counter electrode, and Figure 4(f) is a charge-discharge performance diagram of the lithium battery composite material of Example 3 assembled into a counter electrode. It can be seen from Fig. 4 that at a current density of 0.1 mA cm -2 , the lithium battery composite material of Comparative Example 3 was assembled into a short circuit situation, indicating that the electrode assembled by the lithium battery composite material of Comparative Example 3 could not inhibit the formation of lithium dendrites. The voltage of Comparative Example 1, Comparative Example 3 and Examples 1 to 3 are all maintained at about 0.02V. When the current density rises to 0.2mAcm- 2 , when the current density rises to 0.2mAcm -2 , Comparative Example 1 Compared with Comparative Example 2, the voltage instantly reached 0.12V, indicating that the interface of the lithium battery composite material in Comparative Example 1 and Comparative Example 2 also has a large ion transfer resistance, which corresponds to the result of the AC impedance spectrum, and then the voltage gradually decreases, indicating that Li dendrites start and gradually grow into the interior of Li dendrites, which reduces the ion transmission distance and the apparent voltage. The voltage of the lithium battery composite material of Example 2 gradually decreased from 0.04V, and there was fluctuation Crystal growth short-circuits the electrodes. The voltage of Example 3 is relatively stable, indicating that the lithium battery composite material of Example 3 has the best effect of inhibiting lithium dendrites.

最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the protection scope of the present invention. Although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that, The technical solutions of the present invention may be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention.

Claims (7)

1. A lithium battery composite material, which is characterized by comprising a solid electrolyte and a metal mixed melt coating as a negative electrode, wherein the metal mixed melt coating is a mixed melt of metal lithium, metal zinc and lithium oxide; the weight ratio of the metal lithium to the metal zinc to the lithium oxide is 10: (1-1.20): (1-1.20).
2. The lithium battery composite material as claimed in claim 1, wherein the weight ratio of the metallic lithium, the metallic zinc and the lithium oxide is 10: (1-1.12): (1-1.12).
3. The lithium battery composite material as claimed in claim 1, wherein the weight ratio of the metallic lithium, the metallic zinc and the lithium oxide is 10: 1: 1.11.
4. the lithium battery composite of claim 1, wherein the solid state electrolyte is lithium lanthanum zirconium oxygen.
5. The lithium battery composite material as claimed in claim 1, wherein the preparation method of the lithium battery composite material comprises the steps of:
(1) polishing the surface of the solid electrolyte, washing with an organic solvent, and drying;
(2) heating the metal lithium to 180-250 ℃ to obtain a metal lithium melt A;
(3) adding metal zinc and lithium oxide into the metal lithium melt A, and stirring at 180-250 ℃ to obtain a metal mixed melt B;
(4) and (4) coating the metal mixed melt B obtained in the step (3) on the surface of a solid electrolyte to form a metal mixed melt coating, so as to obtain the lithium battery composite material.
6. The lithium battery composite material as claimed in claim 5, wherein in the step (2), the metallic lithium is heated to 200 ℃ to obtain the metallic lithium melt A.
7. A lithium battery, characterized in that it comprises a lithium battery composite as claimed in any one of claims 1 to 6.
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