WO2018095202A1 - 一种复合锂电池及其制备方法 - Google Patents
一种复合锂电池及其制备方法 Download PDFInfo
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the invention belongs to the field of lithium batteries, and relates to a composite lithium battery and a preparation method thereof.
- 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.
- the positive electrode material of lithium ion battery mainly uses transition metal oxide or phosphate
- the negative electrode mainly uses graphite.
- 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.
- its energy density can be increased by up to 30%, which is far from meeting the 800km battery life of electric vehicles.
- the increase in energy density increases the safety risk of lithium-ion batteries.
- a lithium iron phosphate battery having a low energy density but high safety has become a main power battery.
Abstract
本发明公开了一种复合锂电池及其制备方法,该复合锂电池包括正极、负极、电解质和隔膜,其中,该正极包含正极活性物质,该正极活性物质由单质硫与磷酸铁复合或硫化物与磷酸铁锂复合制备而成,该负极选择锂金属负极或金属锂与碳的复合负极。本发明利用硫的高比容量和磷酸铁锂材料的高安全性、长寿命,既可以提高传统磷酸铁锂离子电池放电能量密度低的缺陷,也可以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、安全性、循环寿命上的综合性能。
Description
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。
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。
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。
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
Claims (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。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:(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;(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。(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。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。发明的公开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
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CN107342412B (zh) * | 2017-07-07 | 2019-12-17 | 江西省科学院应用化学研究所 | 一种纳米微球磷钨酸盐/硫正极材料的制备方法 |
CN109167034B (zh) * | 2018-08-21 | 2021-07-23 | 南开大学 | 以三元材料为载体的锂硫电池复合正极材料及其制备方法 |
CN108987725A (zh) * | 2018-08-21 | 2018-12-11 | 南开大学 | 一种锂硫电池正极复合材料及其制备方法 |
CN109148854A (zh) * | 2018-08-21 | 2019-01-04 | 南开大学 | 碳掺杂磷酸铁锰锂负载硫的锂硫电池正极材料及制备方法 |
CN116207370A (zh) * | 2023-05-06 | 2023-06-02 | 江苏天合储能有限公司 | 一种高性能sei膜及其制备方法 |
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CN103579590A (zh) * | 2013-05-09 | 2014-02-12 | 中国地质大学(武汉) | 一种锂电池的包覆正极材料的制备方法 |
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