WO2018095202A1 - Composite lithium battery and preparation method therefor - Google Patents

Composite lithium battery and preparation method therefor Download PDF

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WO2018095202A1
WO2018095202A1 PCT/CN2017/108595 CN2017108595W WO2018095202A1 WO 2018095202 A1 WO2018095202 A1 WO 2018095202A1 CN 2017108595 W CN2017108595 W CN 2017108595W WO 2018095202 A1 WO2018095202 A1 WO 2018095202A1
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lithium
sulfur
battery
batteries
energy density
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PCT/CN2017/108595
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French (fr)
Chinese (zh)
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汤卫平
朱蕾
江小标
吴勇民
贾荻
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上海空间电源研究所
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Publication of WO2018095202A1 publication Critical patent/WO2018095202A1/en

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    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581Chalcogenides or intercalation compounds thereof
    • H01M4/5815Sulfides
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825Oxygenated metallic slats or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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

Abstract

Disclosed are a composite lithium battery and a preparation method therefor. The composite lithium battery comprises a cathode, an anode, an electrolyte, and a diaphragm, wherein the cathode comprises a cathode active substance; the cathode active substance is prepared by compounding elemental sulfur and ferric phosphate or by compounding sulfide and lithium iron phosphate; the anode is a lithium metal anode or a composite anode of metallic lithium and carbon. By utilizing the high specific volume of sulfur and the high safety and long service life of a lithium iron phosphate material, the present invention avoids the defect of low discharge energy density of a conventional lithium iron phosphate ion battery, and resolves the deficiency of low safety and poor circulation properties of the lithium sulfur battery, so as to improve comprehensive properties of energy density, safety and circulation service life of the battery.

Description

一种复合锂电池及其制备方法Composite lithium battery and preparation method thereof 技术领域Technical field
本发明属于锂电池领域,涉及一种复合锂电池及其制备方法。The invention belongs to the field of lithium batteries, and relates to a composite lithium battery and a preparation method thereof.
背景技术Background technique
能源是国民经济发展和人民生活水平提高的重要物质基础,也是直接影响经济发展的一个重要因素。由于石油、天然气、煤炭等不可再生能源的日益匮乏以及利用这些能源所带来的日益严峻的环境污染问题,世界各国都在加紧探索新的能源或新的可持续发展能源利用技术,电池就是其一。同时,为了方便像风能、太阳能、潮汐能、地热能等清洁、安全、可再生能源地使用,需要将其转换为电能,即需要利用高容量的电化学电源进行能量存储。随着电子技术的进步、更低功率的要求以及便携式设备的开发,电化学电池被大量用于民用消费、工业和军事领域。同时,用电设备对电池容量和功率特性要求的增长对化学电源的普及也起到一定的促进作用。Energy is an important material basis for the development of the national economy and the improvement of people's living standards, and is also an important factor that directly affects economic development. Due to the growing scarcity of non-renewable energy sources such as oil, natural gas, coal, and the increasingly severe environmental pollution caused by the use of these energy sources, countries around the world are stepping up exploration of new energy sources or new sustainable energy use technologies. One. At the same time, in order to facilitate the use of clean, safe and renewable energy such as wind energy, solar energy, tidal energy, geothermal energy, etc., it needs to be converted into electric energy, that is, energy storage is required by using a high-capacity electrochemical power source. With advances in electronics, lower power requirements, and the development of portable devices, electrochemical cells are used extensively in consumer, industrial, and military applications. At the same time, the increase in battery capacity and power characteristics required by electrical equipment has also contributed to the popularization of chemical power sources.
在众多储能器件中,锂离子电池可提供最高的能量密度,且具有电压稳定、自放电小、寿命长和无记忆效应等优点,广泛应用于航空航天、便携设备、电动工具等方面。锂离子电池的能量密度可以达到150Wh kg-1,仍然无法满足现代社会对能源持续增长的需求,究其原因,根本的挑战在于电池的正极和负极材料比容量的限制。目前,锂离子电池正极材料主要采用过渡金属氧化物或磷酸盐,负极主要采用石墨,由于这些材料的反应原理是脱嵌反应,正极材料比容量约为150–200mAh g-1,负极石墨的比容量约为370mAhg-1,限制了锂离子电池的容量和能量密度,即使优化技术,其能量密度最大可以提升30%,远远无法满足电动汽车800km的续航能力。同时,能量密度的提升增加了锂离子电池的安全风险。为了保证电池的安全性,能量密度偏低、但安全性高的磷酸铁锂电池成为主要的动力电池。Among many energy storage devices, lithium-ion batteries provide the highest energy density, and have the advantages of voltage stability, small self-discharge, long life and no memory effect. They are widely used in aerospace, portable equipment, power tools and so on. The energy density of lithium-ion batteries can reach 150Wh kg -1 , which still cannot meet the needs of modern society for the continuous growth of energy. The fundamental challenge is the limitation of the specific capacity of the positive and negative materials of the battery. At present, the positive electrode material of lithium ion battery mainly uses transition metal oxide or phosphate, and the negative electrode mainly uses graphite. Since the reaction principle of these materials is deintercalation reaction, the specific capacity of positive electrode material is about 150-200 mAh g -1 , and the ratio of negative electrode graphite The capacity is about 370mAhg -1 , which limits the capacity and energy density of lithium-ion batteries. Even with optimized technology, its energy density can be increased by up to 30%, which is far from meeting the 800km battery life of electric vehicles. At the same time, the increase in energy density increases the safety risk of lithium-ion batteries. In order to ensure the safety of the battery, a lithium iron phosphate battery having a low energy density but high safety has become a main power battery.
为了满足持续发展的电动汽车、智能电网等对能量密度的需求,人们开 In order to meet the demand for energy density in the continuous development of electric vehicles, smart grids, etc.

Claims (1)

  1. 始开发新型电化学体系的电池。基于转换反应且能与更多离子和电子反应的电极材料成为很好的选择。近来,锂–空气和锂硫电池因其能量密度高(分别为3500Wh kg-1和2500Wh kg-1)得到广泛关注,成为新型电化学体系电池的代表。锂–空气电池的负极为锂金属,正极从环境中吸收氧气,在空气电极内部氧化还原。然而,由于锂–空气电池关键组件的技术尚未突破,使得其可充电性能及循环性能面临着巨大挑战。与锂–空气电池相比,正极和负极材料分别为单质硫和金属锂的锂硫电池所面临的挑战则要小一些,被认为更容易实用化。其理论能量密度可达2600Wh kg-1,约为目前商业化电池的5倍,正极和负极材料的理论比容量分别为1672mAh g-1和3860mAh g-1,单质硫的高容量基于单质硫的转化反应,一个硫原子可以与两个锂原子反应生成Li2S。单质硫不仅理论比容量高,而且储量丰富,环境友好,成本低。Started to develop batteries for new electrochemical systems. Electrode materials based on conversion reactions and capable of reacting with more ions and electrons are a good choice. Recently, lithium-air and lithium-sulfur batteries have attracted wide attention due to their high energy density (3500Wh kg -1 and 2500Wh kg -1 , respectively ), and have become representative of new electrochemical system batteries. The negative electrode of the lithium-air battery is lithium metal, and the positive electrode absorbs oxygen from the environment and is redoxed inside the air electrode. However, due to the breakthrough of the technology of the key components of the lithium-air battery, its chargeability and cycle performance are facing enormous challenges. Compared with lithium-air batteries, lithium-sulfur batteries with positive and negative materials, which are elemental sulfur and lithium metal, are less challenging and are considered to be easier to use. Its theoretical energy density can reach 2600Wh kg -1 , which is about 5 times that of current commercial batteries. The theoretical specific capacities of positive and negative materials are 1672mAh g -1 and 3860mAh g -1 respectively . The high capacity of elemental sulfur is based on elemental sulfur. In the conversion reaction, a sulfur atom can react with two lithium atoms to form Li 2 S. Elemental sulfur is not only theoretically high in specific capacity, but also rich in reserves, environmentally friendly, and low in cost.
    尽管锂硫电池在比能量密度有很大的优势,但是较差的循环性能、安全性限制了其实际应用。从锂硫电池循环过程和机理的研究表明硫基正极材料主要存在如下问题:Although lithium-sulfur batteries have a large advantage in specific energy density, poor cycle performance and safety limit their practical applications. The research on the cycle process and mechanism of lithium-sulfur batteries shows that the sulfur-based cathode materials mainly have the following problems:
    (1)单质硫在室温下是电子和离子绝缘体(室温电导率为5×10-30S/cm),需要添加大量导电剂,提高正极的电子电导率和离子电导率;(1) Elemental sulfur is an electron and ionic insulator at room temperature (room temperature conductivity is 5×10-30S/cm), and a large amount of conductive agent needs to be added to improve the electronic conductivity and ionic conductivity of the positive electrode;
    (2)单质硫在放电过程中会形成易溶的多硫化物,溶于电解液造成活性物质的流失,致使其循环性能变差,多硫离子扩散到负极直接与负极发生自放电反应,形成“飞梭效应”,致使电池充放电效率变差。(2) Elemental sulfur will form a soluble polysulfide during discharge, which will cause the loss of active material in the electrolyte, resulting in poor cycle performance. The polysulfide ions diffuse to the negative electrode and directly react with the negative electrode to form a self-discharge reaction. The "shuttle effect" causes the battery to be inefficient in charging and discharging.
    (3)电池放电不溶性终产物Li2S2和Li2S在正极表面沉积,造成正极表面钝化,严重影响电池的电化学反应。(3) Battery discharge insoluble end products Li 2 S 2 and Li 2 S are deposited on the surface of the positive electrode, causing passivation of the surface of the positive electrode, which seriously affects the electrochemical reaction of the battery.
    针对这些问题,研发人员对锂硫电池进行改性,得到了一定程度解决。但纵观目前的改性技术都是围绕合成含硫复合正极,通过正极复合材料的微观结构改良,以期获达到克服、改善电化学性能的目的。但是由于无法完全避免活性物质的损失,从根本上各服缺点。这是锂硫电池虽经过了数十年的研究开发,但仍然没有达到产业化的根本原因。In response to these problems, the R&D personnel have modified the lithium-sulfur battery to a certain extent. However, the current modification technology is based on the synthesis of sulfur-containing composite positive electrode, through the improvement of the microstructure of the positive electrode composite material, in order to achieve the purpose of overcoming and improving the electrochemical performance. However, since the loss of the active substance cannot be completely avoided, the disadvantages are fundamentally overcome. Although lithium-sulfur batteries have been researched and developed for decades, they still have not reached the root cause of industrialization.
    发明的公开Disclosure of invention
    本发明的目的是克服现有锂电池中活性物质容易损失的缺陷,提供一种缓解锂硫电池安全性低、循环性能差的弊端,提升电池在比能量密度、安全 The object of the present invention is to overcome the defects that the active material in the existing lithium battery is easy to be lost, and to provide a relief of the low safety and poor cycle performance of the lithium-sulfur battery, and improve the specific energy density and safety of the battery.
PCT/CN2017/108595 2016-11-25 2017-10-31 Composite lithium battery and preparation method therefor WO2018095202A1 (en)

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CN106410194A (en) * 2016-11-25 2017-02-15 上海空间电源研究所 Composite lithium battery and preparation method thereof
CN107342412B (en) * 2017-07-07 2019-12-17 江西省科学院应用化学研究所 Preparation method of nano microsphere phosphotungstate/sulfur positive electrode material
CN109167034A (en) * 2018-08-21 2019-01-08 南开大学 Using ternary material as lithium-sulfur battery composite cathode material of carrier and preparation method thereof
CN108987725A (en) * 2018-08-21 2018-12-11 南开大学 A kind of anode composite material of lithium sulfur battery and preparation method thereof
CN109148854A (en) * 2018-08-21 2019-01-04 南开大学 The lithium sulfur battery anode material and preparation method of carbon doping phosphoric acid ferrimanganic lithium sulfur loaded

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