锂离子电池基础科学问题(X)——全固态锂离子电池
高中化学选修4人教版复习：4.2锂离子电池的详细介绍
6.能量密度表示方法有两种，一为体积能量密度(Wh/l)，另一 为重量能量密度(Wh/kg)，用以表示单位体积或单位重量能取出的 能量。电池的能量密度越大，那么在同能量的情况下电池的尺寸/ 质量越小。
Li+变少
Li+的移动方向为从LixC6 Li+
放电时：
负极
Li1-xCoO2
正极
负极 LixC6 - xe- = xLi++ C6
正极 Li1-xCoO2 + xe- + xLi+ = LiCoO2
充电时： 正变阳，负变阴
充电时：
阴极 xLi+ + xe- + C6 = LixC6 阳极 LiCoO2 - xe- = Li1-xCoO2 + xLi+
锂离子电池工作原理图
schematic representation and operation principle of rechargeable
lithium ion battery
解题方法： 根据Li+的移动方向
钴酸锂电池放电
Li+变多
原电池正向正，负向负 电解池阳向阴，阴向阳
Li1-xCoO2 + LixC6 = LiCoO2 + C6 (x<1)。
目前锂离子电池负极材料多以石墨为主，石墨的理 论克容量372mAh/g。正极材料磷酸铁锂理论克容量只有 160mAh/g，而三元材料镍钴锰(NCM)约为200mAh/g。根据木 桶理论，锂离子电池的能量密度下限取决于正极材料，所 以当前能够达到的能量密度水平大约在100~200Wh/kg，这 一数值还是比较低的，在许多场合都成为锂离子电池应用 的瓶颈。这一问题同样出现在电动汽车领域，在体积和重 量都受到严格限制的情况下，电池的能量密度决定了电动 汽车的单次最大行驶里程，于是出现了“里程焦虑症”这 一特有的名词。如果要使得电动汽车的单次行驶里程达到 500公里(与传统燃油车相当)，电池单体的能量密度必须达 到300Wh/kg以上。
锂离子电池固态电解质
锂离子电池固态电解质
锂离子电池的固态电解质是一种工程材料，由于具有高电压、高安全性、高容量、高温和耐冲击性能等优点，因此，越来越多的应用于家用电子、支持电力系统和新能源车辆的电池组件中。
固态电解质通常由二次电池中的三种组分组成，即锂离子电解质、正极和负极，它们与聚合物和有机溶剂相结合，形成一种能够容纳和存储锂离子的特定分子结构。
正极电解质主要是碳纳米管、金属氧化物或聚合物复合物，常用金属氧化物有锂钴酸和锂钛磷酸，它们可以有效地存储锂离子。
负极电解质主要是石墨烯、碳纳米管复合材料或碳量子点，它们可以有效地容纳锂离子电解质，并具有良好的电动势和抗冲击性能，使电池存储能力更强。
固态电解质为锂离子电池提供高安全、高容量和高温稳定性，是一种理想的固态终端产品。
随着新材料开发技术的不断深入，固态电解质也许能为锂离子电池的应用提供更多的可能性。
固态电池中锂离子传输动力学
固态电池中的锂离子传输动力学是一个复杂的过程，主要涉及锂离子在固体电解质中的迁移。
在固态电池中，锂离子通过固体电解质进行传输，不同于传统的液态电池中的传输机制。
固态电池中的锂离子传输主要依赖于空位机制，即锂离子在固态电解质中移动时，占据空位或创造新的空位。
在充电过程中，锂离子从负极移动到正极，在正极侧的固态电解质中产生空位。
这些空位随后向负极侧移动，并在负极侧被填充。
固态电池中的锂离子传输动力学还受到其他因素的影响，如固态电解质的晶体结构和缺陷密度。
这些因素可以影响锂离子的迁移路径和速度。
此外，固态电解质的离子电导率也是影响锂离子传输动力学的重要参数。
综上所述，固态电池中的锂离子传输动力学是一个复杂的过程，涉及多种因素和机制。
为了更好地理解这一过程，需要进一步研究固态电解质的物理和化学性质，以及它们与锂离子传输动力学之间的相互作用。
这些研究将有助于改进固态电池的设计和性能，并推动其在实际应用中的进一步发展。
锂离子电池基础科学问题(Ⅷ)——负极材料
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LiPON固态电解质与全固态薄膜锂离子电池制备及特性研究
LiPON固态电解质与全固态薄膜锂离子电池制备及特性探究随着电池技术的不息进步，人们对能源存储设备的要求也越来越高。
传统液态电池电解液存在燃烧和泄漏等安全隐患，同时液态电解质也会造成电池体积较大、能量密度低等问题。
因此，探究人员开始将目光聚焦于全固态电池，其中LiPON固态电解质作为最重要的组成部分之一，具有重要的探究意义。
LiPON （lithium phosphorus oxynitride）是一种典型的固态电解质，它被广泛应用于锂离子电池、全固态薄膜电池等多种能源存储装置中。
LiPON的导电性能优异，能够保证电荷的快速传输，同时能够有效隔离阳极和阴极，提高电池的安全性能。
此外，LiPON还具有较高的化学稳定性和热稳定性，能够在高温环境下保持良好的电化学性能，延长电池的寿命。
制备全固态薄膜锂离子电池的关键是制备优质的LiPON固态电解质。
目前，制备LiPON固态电解质主要有物理气相沉积法、离子束沉积法、溅射法等。
这些方法能够获得具有较高导电性能和较好化学稳定性的LiPON薄膜。
物理气相沉积法是一种常用的制备LiPON薄膜的方法。
该方法通过将固态源材料加热，使其蒸发，然后沉积在衬底上形成薄膜。
离子束沉积法是一种较新的制备技术，该方法利用离子束在材料表面产生化学反应，生成所需的LiPON薄膜。
溅射法是一种常用的制备薄膜的方法，该方法通过将固态材料溅射到衬底上，形成所需的薄膜。
制备过程中的关键参数如沉积温度、沉积速率等也对最终的LiPON薄膜性能有显著影响。
因此，探究人员需要进一步优化制备过程，以获得更高质量的LiPON固态电解质。
除了制备LiPON固态电解质，探究人员还对全固态薄膜锂离子电池的性能进行了探究。
试验结果表明，全固态薄膜锂离子电池具有较高的能量密度、良好的循环性能和较长的使用寿命。
与传统液态电池相比，全固态薄膜锂离子电池具有更低的内阻、更快的充放电速率和更低的自放电率。
然而，全固态薄膜锂离子电池仍面临着一些挑战。
全固态电池表界面化学基础研究
全固态电池表界面化学基础研究一、引言全固态电池是一种新型的电池技术，具有高能量密度、快速充电、长寿命等优点。
表界面化学是全固态电池研究中的重要领域，涉及到固体电解质特性、界面反应机制、锂离子传输动力学等方面的研究。
本文将就全固态电池表界面化学基础研究进行深入探讨。
二、固体电解质特性固体电解质是全固态电池的重要组成部分，其特性直接影响到电池的电化学性能。
固体电解质需要具备高离子电导率、宽电化学稳定窗口、高机械强度等特点。
目前常用的固体电解质有聚合物电解质和无机固体电解质两大类，其研究主要涉及到材料的组成、晶体结构、离子传输机制等方面。
三、界面反应机制界面反应是全固态电池中一个重要现象，涉及到电极与固体电解质之间的相互作用。
界面反应机制的研究对于理解电池性能衰减的原因以及提高电池寿命具有重要意义。
目前对于界面反应机制的研究主要涉及到微观结构、化学组成、反应动力学等方面的研究。
四、锂离子传输动力学锂离子传输动力学是全固态电池中另一个重要的研究方向。
锂离子在固体电解质中的传输速率直接影响着电池的充放电性能。
锂离子传输动力学的研究主要涉及到离子在固体电解质中的迁移过程、扩散系数、传输通道等方面的研究。
五、界面稳定性及寿命界面稳定性及寿命是全固态电池实用化需要解决的重要问题之一。
全固态电池在充放电过程中，电极与固体电解质之间的界面会发生变化，导致电池性能衰减。
因此，研究界面的稳定性及寿命对于提高全固态电池的寿命具有重要意义。
六、影响因素及调控方法影响全固态电池表界面性能的因素有很多，如材料类型、制备工艺、使用环境等。
了解这些影响因素有助于优化材料的选择和制备工艺，从而提高电池的性能。
同时，针对影响因素提出有效的调控方法也是提高全固态电池性能的关键。
常见的调控方法包括表面处理、掺杂改性、复合电极等。
这些方法可以有效改善固体电解质和电极表面的物理和化学性质，从而提高锂离子的传输效率和界面的稳定性。
七、性能优化及提高为了满足实际应用的需求，全固态电池的性能还需要进一步的优化和提高。
0000全固态锂离子电池用PEO基聚合物电解质的研究进展_赵旭东
全固态锂离子电池用ＰＥＯ基聚合物电解质的研究进展＊赵旭东，朱 文，李镜人，贾迎宾（华中科技大学材料成型与模具技术国家重点实验室，武汉４３００７４）摘要 锂离子电池作为重要的能量储存元件在消费类电子产品、电动汽车和可再生能源存储等领域具有广泛的应用。
传统液态电解质锂离子电池受到能量密度低、安全性差等诸多缺陷的限制，采用固态电解质替代液态电解质制备新型固态锂离子电池目前备受关注。
ＰＥＯ基固态聚合物电解质由于其设计简单、易于制造、使用安全等优点已被认为是替代传统液体电解质的首选。
介绍了当前ＰＥＯ基聚合物电解质的主要研究种类、特点和性能；阐述了锂离子在ＰＥＯ基聚合物电解质中的导电机制；分析了与ＰＥＯ络合的锂盐种类对聚合物电解质的电导率的影响规律；在此基础上提出了几种改善ＰＥＯ基聚合物电解质性能的措施和方法。
关键词 固态锂离子电池 ＰＥＯ 聚合物电解质 固态电解质中图分类号：ＴＭ９１１ 文献标识码：ＡＲｅｓｅａｒｃｈ Ｐｒｏｇｒｅｓｓ ｉｎ ＰＥＯ Ｂａｓｅｄ Ｐｏｌｙｍｅｒ Ｅｌｅｃｔｒｏｌｙｔｅｓ ｏｆ ＡｌｌＳｏｌｉｄ Ｓｔａｔｅ Ｌｉｔｈｉｕｍ Ｉｏｎ ＢａｔｔｅｒｙＺＨＡＯ Ｘｕｄｏｎｇ，ＺＨＵ Ｗｅｎ，ＬＩ Ｊｉｎｇｒｅｎ，ＪＩＡ Ｙｉｎｇｂｉｎ（Ｓｔａｔｅ Ｋｅｙ Ｌａｂｏｒａｔｏｒｙ ｏｆ Ｍａｔｅｒｉａｌ Ｐｒｏｃｅｓｓｉｎｇ ａｎｄ Ｄｉｅ ＆Ｍｏｕｌｄ Ｔｅｃｈｎｏｌｏｇｙ，Ｈｕａｚｈｏｎｇ Ｕｎｉｖｅｒｓｉｔｙ ｏｆ Ｓｃｉｅｎｃｅ ａｎｄＴｅｃｈｎｏｌｏｇｙ，Ｗｕｈａｎ ４３００７４）Ａｂｓｔｒａｃｔ Ａｓ ａｎ ｉｍｐｏｒｔａｎｔ ｃｏｍｐｏｎｅｎｔ ｏｆ ｅｎｅｒｇｙ ｓｔｏｒａｇｅ，ｌｉｔｈｉｕｍ－ｉｏｎ ｂａｔｔｅｒｙ ｈａｓ ｂｅｅｎ ｗｉｄｅｌｙ ｕｓｅｄ ｉｎ ｃｏｎｓｕｍｅｒｅｌｅｃｔｒｏｎｉｃｓ ｐｒｏｄｕｃｔｓ，ｅｌｅｃｔｒｉｃ ｖｅｈｉｃｌｅｓ ａｎｄ ｒｅｎｅｗａｂｌｅ ｅｎｅｒｇｙ ｓｔｏｒａｇｅ．Ｂｅｃａｕｓｅ ｔｈｅ ｔｒａｄｉｔｉｏｎａｌ ｌｉｔｈｉｕｍ－ｉｏｎ ｂａｔｔｅｒｙ ｗｈｉｃｈｕｓｅｄ ｌｉｑｕｉｄ ｅｌｅｃｔｒｏｌｙｔｅ ｈａｓ ｌｉｍｉｔａｔｉｏｎｓ ｏｎ ｅｎｅｒｇｙ ｄｅｎｓｉｔｙ ａｎｄ ｓｅｃｕｒｉｔｙ，ｕｓｉｎｇ ｓｏｌｉｄ ｓｔａｔｅ ｅｌｅｃｔｒｏｌｙｔｅ ｉｎｓｔｅａｄ ｏｆ ｌｉｑｕｉｄ ｅｌｅｃ－ｔｒｏｌｙｔｅ ｔｏ ｄｅｖｅｌｏｐ ｎｏｖｅｌ ａｌｌ ｓｏｌｉｄ ｓｔａｔｅ ｌｉｔｈｉｕｍ－ｉｏｎ ｂａｔｔｅｒｙ ｉｓ ｂｅｃｏｍｉｎｇ ｍｏｒｅ ａｎｄ ｍｏｒｅ ａｔｔｒａｃｔｉｖｅ．ＰＥＯ－ｂａｓｅｄ ｓｏｌｉｄ ｐｏｌｙ－ｍｅｒ ｅｌｅｃｔｒｏｌｙｔｅ ｈａｓ ｂｅｅｎ ｃｏｎｓｉｄｅｒｅｄ ａｓ ａ ｐｒｅｆｅｒｒｅｄ ａｌｔｅｒｎａｔｉｖｅ ｔｏ ｔｈｅ ｃｏｎｖｅｎｔｉｏｎａｌ ｌｉｑｕｉｄ ｅｌｅｃｔｒｏｌｙｔｅ ｂｅｃａｕｓｅ ｏｆ ｉｔｓ ａｄｖａｎ－ｔａｇｅｓ ｉｎ ｔｅｒｍｓ ｏｆ ｓｉｍｐｌｉｃｉｔｙ ｏｆ ｄｅｓｉｇｎ，ｅａｓｙ ｐｒｏｄｕｃｔｉｏｎ ａｎｄ ｏｐｅｒａｔｉｏｎａｌ ｓａｆｅｔｙ．Ｔｈｅ ｃｕｒｒｅｎｔ ｒｅｓｅａｒｃｈ ａｂｏｕｔ ｍａｊｏｒ ｔｙｐｅｓ，ｃｈａｒａｃｔｅｒｉｓｔｉｃｓ ａｎｄ ｐｅｒｆｏｒｍａｎｃｅｓ ｏｆ ＰＥＯ－ｂａｓｅｄ ｐｏｌｙｍｅｒ ｅｌｅｃｔｒｏｌｙｔｅｓ ａｒｅ ｐｒｅｓｅｎｔｅｄ．Ｔｈｅ ｃｏｎｄｕｃｔｉｏｎ ｍｅｃｈａｎｉｓｍ ｏｆ ｌｉ－ｔｈｉｕｍ ｉｏｎ ｉｎ ＰＥＯ－ｂａｓｅｄ ｐｏｌｙｍｅｒ ｅｌｅｃｔｒｏｌｙｔｅｓ ｉｓ ｄｅｓｃｒｉｂｅｄ，ａｎｄ ｔｈｅ ｅｆｆｅｃｔｓ ｏｆ ｔｈｅ ｋｉｎｄｓ ｏｆ ｌｉｔｈｉｕｍ ｓａｌｔｓ ｈａｖｉｎｇ ｔｈｅ ｃｏｍｐ－ｌｅｘａｔｉｏｎ ｗｉｔｈ ＰＥＯ ｏｎ ｔｈｅ ｃｏｎｄｕｃｔｉｖｉｔｙ ｏｆ ｒｅｓｕｌｔａｎｔ ｐｏｌｙｍｅｒ ｅｌｅｃｔｒｏｌｙｔｅｓ ａｒｅ ａｎａｌｙｓｅｄ．Ｂａｓｅｄ ｏｎ ｔｈｅｓｅ，ｓｅｖｅｒａｌ ｍｅａｓｕｒｅｓａｎｄ ｍｅｔｈｏｄｓ ｆｏｒ ｉｍｐｒｏｖｉｎｇ ｐｅｒｆｏｒｍａｎｃｅ ｏｆ ＰＥＯ－ｂａｓｅｄ ｐｏｌｙｍｅｒ ｅｌｅｃｔｒｏｌｙｔｅｓ ａｒｅ ｐｒｏｐｏｓｅｄ．Ｋｅｙ ｗｏｒｄｓ ｓｏｌｉｄ ｓｔａｔｅ ｌｉｔｈｉｕｍ ｉｏｎ ｂａｔｔｅｒｙ，ＰＥＯ，ｐｏｌｙｍｅｒ ｅｌｅｃｔｒｏｌｙｔｅｓ，ｓｏｌｉｄ ｅｌｅｔｒｏｌｙｔｅｓ ＊国家自然科学基金（２１１７３０９０）；深圳市战略性新兴产业发展专项资金（ＪＣＹＪ２０１２０６１８１００５５７１１９） 赵旭东：男，１９９２年生，硕士生，主要从事固体电解质研究 Ｅ－ｍａｉｌ：ｍｉｃａｌｕｎ＠ｇｍａｉｌ．ｃｏｍ 朱文：通讯作者，男，１９７１年生，教授，博士生导师，从事新能源研究 Ｔｅｌ：０２７－８７５５８４７６ Ｅ－ｍａｉｌ：ｗｅｎｎａｒ＠ｈｕｓｔ．ｅｄｕ．ｃｎ 当前锂离子电池对人们日常生活以及国民经济所产生的影响巨大，其应用涵盖商业化电子产品（如手机、电脑等）、汽车动力装置以及可再生能源发电站的能量存储（如风能和太阳能）等。
全固态锂电池的电极制备与组装方法
含 4 个阶段：概念开发和产品规划阶段(调研)、详
不论其化学组分如何，晶粒电导率高低，宏观尺寸
细设计阶段(实验室)、小规模生产阶段(小试)、增
下的电解质块体或片材需要将氧化物粉体颗粒烧结
量生产阶段(中试)，全固态锂电池也不例外。而实
成陶瓷坯才能够达到室温电导率超过 10−4 S/cm 数
验室中的基础研发是为首要阶段，正是对以上问题
锂离子电池已难以同时提升安全性及能量密度，一
方法进行了较为详尽的综述，希望对广大科研人员
定程度上制约了上述领域的发展。归功于固体电解
具有一定的借鉴意义。
质高的化学及电化学稳定性、高热稳定性和高机械
强度，全固态锂电池有望实现高能量正极与金属锂
1
负极的匹配使用，兼顾高能量密度与高安全性，已
成为新型电化学储能器件的热点研究方向。
solid-state lithium batteries are quite different from those of existing liquid lithium batteries.
Here we summarize the typical assembly approaches of prototype all-solid-state batteries
位对电极脱、嵌锂时的体积变化在可接受范围，最
紧密接触的正极层。丝网印刷的目的是为了得到较
终使得该全固态锂电池具有媲美液态电池的倍率
薄的正极层，而共烧结过程可以去除黏结剂中的有
corresponding performance characteristics of several typical all-solid-state lithium batteries
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第３卷第４期 ２０１４年７月 储能科学与技术
Ｅｎｅｒｇｙ Ｓｔｏｒａｇｅ Ｓｃｉｅｎｃｅ ａｎｄ Ｔｅｃｈｎｏｌｏｇｙ Ｖ０１．３ Ｎｏ．４
Ｊｕ１．２Ｏｌ４
锂离子电池基础科学问题（Ｘ）——全固态锂离子电池 张舒，王少飞，凌仕刚，高健，吴娇杨，肖睿娟，李 泓，陈立泉 （中国科学院物理研究所，北京１００１９０）
摘要：商用锂离子电池由于采用含有易燃有机溶剂的液体电解质，存在着安全隐患。发展全固态锂离子电池 是提升电池安全性的可行技术途径之一。目前全固态锂离子电池的应用还需要解决一些科学与技术问题，包括： 开发能在宽温度范围使用，兼顾高电导率与电化学稳定性的固体电解质材料；减小电解质相与电极相界面间离 子输运电阻的技术；适合全固态电池使用的正负极材料；相关材料与电池的设计与规模化制造技术。本文从固 体电解质材料的研究开发进展，高通量计算用于固体电解质材料的筛选以及电极材料与固体电解质界面问题等 方面进行了小结。 关键词：储能；全固态锂离子电池；固体电解质；高通量计算；界面 ｄｏｉ：１０．３９６９／ｊ．ｉｓｓｎ．２０９５－４２３９．２０１４．０４．０１２ 中图分类号：Ｏ ６４６．２１ 文献标志码：Ａ 文章编号：２０９５．４２３９（２０１４）０４．３７６．１９
Ｆｕｎｄａｍｅｎｔａｌ ｓｃｉｅｎｔｉｆｉｃ ａｓｐｅｃｔｓ ｏｆ ｌｉｔｈｉｕｍ ｉｏｎ ｂａｔｔｅｒｉｅｓ ＡＪＩ１．ｓｏｆｉｄ．ｓｔａｔｅ ｆｉｔｈｉｕｍ－ｉｏｎ ｂａｔｔｅｒｉｅｓ
ＺＨＡＮＧ Ｓｈｕ，ＷＡＮＧ Ｓｈａｏｆｅｉ，ＬＩＮＧ Ｓｈｉｇａｎｇ，ＧＡＯＪｉａｎ，ＷＵＪｉａｏｙａｎｇ， ＸＩＡＯ Ｒｕｉｊｕａｎ，ＬＩＨｏｎｇ，ＣＨＥＮＬｉｑｕａｎ （Ｉｎｓｔｉｔｕｔｅ ｏｆＰｈｙｓｉｃｓ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ ｏｆ Ｓｃｉｅｎｃｅｓ，Ｂｅｉｊｉｎｇ １００１９０，Ｃｈｉｎａ）
Ａｂｓｔｒａｃｔ：Ｃｏｍｍｅｒｃｉａｌ ｌｉｔｈｉｕｍ ｉｏｎ ｂａｔｔｅｒｉｅｓ ｕｓｉｎｇ ｆｌａｍｍａｂｌｅ ｎｏｎａｑｕｅｏｕｓ ｅｌｅｃｔｒｏｌｙｔｅｓ ｈａｖｅ ｔｈａｔ ｈｉｄｄｅｎ ｓａｆｅｔｙ ｐｒｏｂｌｅｍｓ．Ａ１１一ｓｏｌｉｄ－ｓｔａｔｅ ｌｉｔｈｉｕｍ ｉｏｎ ｂａｔｔｅｒｉｅｓ ｉＳ ｏｎｅ ｏｆ ｔｈｅ ｐｏｓｓｉｂｌｅ ｔｅｃｈｎｏｌｏｇｉｃ ａｐｐｒｏａｃｈｅｓ ｔｏ ａｄｄｒｅｓｓ ｔｈｉｓ ｐｒｏｂｌｅｍ．Ｆｏｒ ｐｒａｃｔｉｃａｌ ａｐｐｌｉｃａｔｉｏｎｓ ｓｏｍｅ ｓｃｉｅｎｔｉｆｉｃ ａｎｄ ｔｅｃｈｎｏｌｏｇｉｃａｌ ｂａｒｒｉｅｒｓ ｎｅｅｄ ｔｏ ｂｅ ｏｖｅｒｃｏｍｅ，ｉｎｃｌｕｄｉｎｇ ｅｘｐｌｏｒｉｎｇ ｓｏｌｉｄ ｅｌｅｃｔｒｏｌｙｔｅ ｍａｔｅｒｉａｌ ｗｉｔｈ ｈｉｇｈ ｃｏｎｄｕｃｔｉｖｉｔｙ ａｎｄ ｅｌｅｃｔｒｏｃｈｅｍｉｃａｌ ｓｔａｂｉｌｉｔｙ；ｄｅｃｒｅａｓｉｎｇ ｉｎｔｅｒｆａｃｅ ｉｏｎｉｃ ｔｒａｎｓｐｏｒｔ ｒｅｓｉｓｔａｎｃｅ ｂｅｔｗｅｅｎ ｓｏｌｉｄ ｅｌｅｃｔｒｏｌｙｔｅ ａｎｄ ｅｌｅｃｔｒｏｄｅ ｐｈａｓｅ； ｓｕｉｔａｂｌｅ ａｎｏｄｅ ａｎｄ ｃａｔｈｏｄｅ ｍａｔｅｒｉａｌｓ ｆｏｒ ａｌｌ—ｓｏｌｉｄ ｂａｔｔｅｒｉｅｓ；ｐｒｏｄｕｃｔｉｏｎ ｔｅｃｈｎｏｌｏｇｉｅｓ ｆｏｒ ｍａｔｅｒｉａｌｓ：ｄｅｓｉｇｎ ａｎｄ ｍａｎｕｆａｃｔｕｒｉｎｇ ｏｆ ｂａｔｔｅｒｉｅｓ．ＴｈｉＳ Ｐａｐｅｒ ｓｕｍｍａｒｉｚｅｓ ｂｒｉｅｆｌｙ ｔｈｅ ｓｔａｔｕｓ ｏｆ ｓｏｌｉｄ ｅｌｅｃｔｒｏｌｙｔｅ ｍａｔｅｒｉａｌｓ， ｅｆｆｏｒｔｓ ｏｆ ｈｉｇｈ—ｔｈｒｏｕｇｈｐｕｔ ｃａｌｃｕｌａｔｉｏｎ ｏｎ ｓｏｌｉｄ ｅｌｅｃｔｒｏｌｙｔｅ ｍａｔｅｒｉａｌｓ ａｎｄ ｔｈｅ ｉｎｔｅｒｆａｃｅ ｉｓｓｕｅｓ ｂｅｔｗｅｅｎ ｅｌｅｃｔｒｏｄｅ ｍａｔｅｒｉａｌ ａｎｄ ｓｏｌｉｄ ｅｌｅｃｔｒｏｌｙｔｅ． Ｋｅｙ ｗｏｒｄｓ：ｅｎｅｒｇｙ ｓｔｏｒａｇｅ；ａｌｌ・－ｓｏｌｉｄ—－ｓｔａｔｅ ｌｉｔｈｉｕｍ－－ｉｏｎ ｂａｔｔｅｒｙ；ｓｏｌｉｄ ｅｌｅｃｔｒｏｌｙｔｅ；ｈｉｇｈ－－ｔｈｒｏｕｇｈｐｕｔ ｃａｌｃｕｌａｔｉｏｎ：ｉｎｔｅｒｆａｃｅ
近年来随着电动汽车的发展以及电网储能及小型 储能需求的发展，开发能够在宽的温度范围使用，具 有高安全性、高能量密度及功率密度的电池十分必要。 收稿日期：２０１４。０６—０１；修改稿日期：２０１４—０６ ０５。 基金项目：北京市科委项目（Ｚ１３１ １ １０００３４００００），国家重点基础研究 发展计划（９７３）（２０１２ＣＢ９３２９００）及国家自然科学基金杰出青年基金 （５１３２５２０６）项目。 第一作者：张舒（１９９Ｏ一），女，博士研究生，研究方向为无机固态电 解质及全固态电池，Ｅ．ｍａｉｌ：ｃｕｔｅｓｈｕ＠１６３．ｃｏｒｎ；通讯联系人：李泓，研 究员，研究方向为固体离子学与锂电池材料，Ｅ．ｍａｉｌ：ｈｌｉ＠ｉｐｈｙ ａｃ．ｃｎ。 在各种商业化可充放电化学储能装置中，锂离 子电池拥有最高的能量密度。现有的商用锂离子电 池主要包含两种类型：一种是采用液态电解质的锂 离子电池；另外一种是采用凝胶电解质的锂离子电 池。液态电解质的锂盐溶于有机溶液中，并包含多 种功能添加剂。锂盐为ＬｉＰＦ６、ＬｉＦＳＩ等；有机溶剂 为环状碳酸酯（ＥＣ、ＰＣ）、链状碳酸酯（ＤＥＣ、ＤＭＣ、 ＥＤＣ）、羧酸酯类（ＭＦ、ＭＡ、ＥＡ、ＭＰ等）。凝胶 电解质是在多孔的聚合物基体中吸附电解液形成的 第４期 张舒等：锂离子电池基础科学问题（ｘ）——全固态锂离子电池 ３７７ 电解质。与液体电解液相同，凝胶电解质中的电解 液起到离子传导及在负极表面形成稳定的固体电解 质膜（ＳＥＩ）的作用。 液态电解质与凝胶电解质拥有较高的室温离 子电导率，电解液能够有效地浸润电极颗粒，并 能够在正负极活性材料的表面形成稳定的固体电 解质膜，因此现有商用锂离子电池在室温附近具 有低的电池内阻及较好的循环稳定性。但有机液 体电解质在低温下发生液固转化，离子电导率显 著下降，导致温度降低时（一２０℃以下）电池内 阻显著增大，无法满足低温应用要求。当电池外 部温度升高或大电流充放电或短路导致电池内部 温度升高时，电解液与电极之间的化学反应速度 加剧，进一步产生热量，可以导致热失控。这一 过程产生气体，最终导致电池密封失效，可燃的 气体与有机溶剂在高温下遇到氧气起火燃烧爆 炸。凝胶型电解质中电解液的含量相对较少，安 全性能有所提高，但无法从根本上解决安全性问 题。此外，液体电解液在低电位会被还原，在负 极表面形成固体电解质膜；在高电位会发生氧化 分解，造成电池充放电库仑效率降低。另外，目 前，商用锂离子电池电解液体系中一般采用ＬｉＰＦ６ 作为电解质盐，ＬｉＰＦ６热稳定性差，与水反应生成 ＨＦ，进攻正负极表面，造成电池性能恶化。目前 常用有机电解液体系电化学窗口一般小于４．５ Ｖ， 限制了高电压正极材料的使用，影响了高能量密 度锂离子电池的发展。 电动汽车期望电池寿命达到１５年，大规模工业 储能需要储能器件服役寿命能满足２５－３０年的使用 要求，从而显著降低系统的全寿命周期成本。含有 液态有机溶剂的锂离子电池，由于液体电解质与电 极材料、封装材料缓慢地相互作用和反应，长期服 役时溶剂容易干涸、挥发、泄露，电极材料容易被 腐蚀，影响电池寿命。电池的循环寿命与材料中的 杂质含量密切相关。杂质的存在，可以催化液体电 解质在电极表面发生副反应，导致表面膜不断生长， 活性物质不可逆消耗、电解液逐渐耗尽、电池内阻 不断增大。目前，为了应对动力电池、储能电池对 循环性、一致性的要求，高水平的材料制造企业尽 可能做到电池材料杂质含量低于１０ ｐｇ／ｇ。多数企业 生产的电池材料杂质含量在１００￣２００ Ｐｇ／ｇ。杂质含 量的减少，可以显著延长电池的循环寿命，但同时 带来的问题是在所有的制造环节必须考虑防止杂质 的引入，导致制造成本显著提高，电池的可靠性无 法从根本上保障。如果采用固体电解质，则可以避 开液体电解液带来的副反应、泄露、腐蚀问题，从 而有望显著延长服役寿命、降低电池整体制造成本、 降低电池制造技术门槛，有利于大规模推广 使用。 近年来，大容量锂离子电池在电动汽车、飞机 辅助电源方面出现了严重的安全事故，这些问题的 起因与锂离子电池中采用可燃的有机溶剂有关。虽 然通过添加阻燃剂、采用耐高温陶瓷隔膜、正负极 材料表面修饰、优化电池结构设计、优化ＢＭＳ、 在电芯外表面涂覆相变阻燃材料、改善冷却系统等 措施，能在相当程度上提高现有锂离子电池的安全 性，但这些措施无法从根本上保证大容量电池系统 的安全性，特别是在电池极端使用条件下、在局部 电池单元出现安全性问题时。而采用完全不燃的无 机固体电解质，则能从根本上保证锂离子电池的安 全性。
１全固态锂离子电池概述
为了克服现有商业液态锂离子电池所面临的问 题，科研人员正在大力发展基于固体电解质的锂离 子电池，它具有显著的优点：①相对于液体电解质， 固体电解质不挥发，一般不可燃，因此采用固体电 解质的固态电池会具有优异的安全性；②由于固体 电解质能在宽的温度范围内保持稳定，因此全固态 电池能够在宽的温度范围内工作，特别是高温下； ⑧一些固体电解质对水分不敏感，能够在空气中长 时间保持良好的化学稳定性，因此固态电池的制造 全流程不一定需要惰性气氛的保护，会在一定程度 上降低电池的制造成本；④有些固体电解质材料具 有很宽的电化学窗口，这使得高电压电极材料有望 应用，从而提高电池能量密度；⑤相对于多孔的凝 胶电解质及浸润液体电解液的多孔隔膜，固体电解 质致密，并具有较高的强度及硬度，能够有效地阻 止锂枝晶的刺穿，因此提高了电池的安全性，同时 也使得金属Ｌｉ作为负极的使用成为可能。综上所 述，从基本的特性分析考虑，如果寻找到合适的材 料体系，采用固体电解质的全固态锂电池，可以具 有优异的安全特性、循环特性、高的能量密度和低 的成本。 固体电解质包括聚合物固体电解质、无机固体 电解质以及复合电解质。不含液态有机溶剂的全固