新型固态化锂二次电池及相关材料的制备与性能研究

发布时间：2018-05-30 23:34

  本文选题：锂二次电池 + 薄膜电极　； 参考：《北京理工大学》2014年博士论文

【摘要】：本文重点综述了固态化锂电池及相关电极与电解质材料的研究进展。固态化锂二次电池具有比常规液态锂离子电池更高的比能量，且由于电池中几乎不含有液态电解质，对解决液态锂离子电池在非常规环境下可能产生的漏液、易燃、易爆等安全性问题，具有重要意义。固态化电解质的应用能简化电池结构，使电池的形状尺寸具有更灵活的可设计性。随着便携式电子设备和电动汽车日益增长的对高能量、高功率和高安全性需求的发展，固态化锂二次电池已成为国际研发的热点之一。开发新型薄膜电极和固态化电解质材料，优化电池结构设计是发展高性能固态化锂二次电池的基础。本文从开发制备新型电极和电解质材料入手，结合它们的物化特性，优化设计出新型固态化电池构造，首次制备出高安全性的固态化锂离子电池，继而研制出高比能和高安全性的固态化金属锂电池，实现了从固态化锂离子电池到固态化金属锂二次电池的技术转化；研究新材料，探索新概念，开发新体系，发展新技术，推动固态化锂二次电池的发展，实现规模化生产与应用，从而为进一步发展全固态锂二次电池奠定技术基础。本文围绕开发新型高性能固态化锂二次电池进行了系统的研究工作，主要取得了以下阶段性成果和进展。 (1)采用磁控溅射技术制备出新型三元电极薄膜，，用作固态化锂电池正极。通过射频磁控溅射在高纯氩气或氧-氩混合气中制备了三元正极薄膜，通过控制退火温度和时间，生成了一系列具有不同结晶度和欠锂化学组分的薄膜。预沉积薄膜为无定型态，具有高的化学扩散系数，表现出较好的电化学性能，这种薄膜电极适应于小电流微型电子设备，可应用于薄膜锂电池；高温退火薄膜具有稳定的晶体结构、欠锂化学组成、纳米粒子生长及微米厚度设计，表现出独特且良好的电化学性能，这种薄膜电极具有高的能量密度，适用于高比能锂电池正极材料，可应用到固态化锂电池。 (2)采用磁控溅射技术制备出新型玻璃态磷酸锂包覆磷酸铁锂电极，可作为固态化锂电池正极。以磷酸锂为靶，磷酸铁锂电极为基片，通过射频磁控溅射制备了磷酸锂包覆磷酸铁锂复合电极，通过调节溅射功率和沉积时间，制备了一组具有不同包覆形貌的复合电极。包覆的磷酸锂薄膜是一种良好的锂离子导体，具有玻璃态结构本质，与磷酸铁锂电极形成珊瑚状多孔交联网络结构，促进了电极的离子和电子的传输，提高了界面电荷传质效率，改善了电极的结构稳定性。这类电极具有高的比容量和良好的功率特性，可应用于锂动力电池。 (3)采用反应磁控溅射法制备出Li-Al-Ti-P-O-N薄膜电解质，用于全固态薄膜锂电池。以NASICON结构的Li Al Ti P O化合物为靶材，通过射频磁控溅射法在高纯氮气中制备了新型的Li-Al-Ti-P-O-N薄膜，通过改变沉积温度制得了一系列的薄膜。研究发现氮参杂取代了部分氧原子，降低了反应活化能，形成了更丰富的交联网络结构，促进了锂离子的传导；高温沉积提高了薄膜的结晶度，形成晶态-非晶态混合结构，同样有利于锂离子的传导。这类薄膜电解质具有较高的离子电导率和良好的电化学稳定性，可作为全固态薄膜锂电池用新一代电解质材料，未见文献报道。 (4)采用溶胶-凝胶法合成出新型固态化介孔二氧化硅/离子液体复合电解质，并首次组装成固态化锂离子电池。复合电解质由多孔二氧化硅骨架原位吸附离子液体电解质组成，其中二氧化硅起支撑作用并吸附大量离子液体，离子液体被分散在孔道网络中，具有流体特征，作为锂离子的传导介质。复合电解质表现出接近液态电解质的高离子传导率和良好的电化学稳定性，它们还具有良好的热稳定性、化学稳定性和机械强度，成为一种新型高性能固态化电解质材料。利用复合电解质组装形成的新型固态化锂离子电池能正常工作，表现出良好的电池性能。 (5)采用原位组装技术设计制备出新型固态化金属锂二次电池，完成了从固态化锂离子电池到固态化金属锂二次电池的技术转化，实现了金属锂电极的安全利用。这种固态化锂电池具有全新电池结构设计，表现出良好的电池综合性能，在实际应用中具有诸多优点：相比传统固态化电池体系，表现出更高的比能量和比功率；具有不漏液、耐高温、抗冲击和防止锂枝晶生长等的高安全性；原料丰富，制备简单，成本低廉，具有灵活的可设计性，易实现规模化生产；高效节能，绿色环保。这种新型固态化电池构造，为固态化锂电池技术的发展提供了新的科学思路，并对固态化锂电池的发展应用具有一定的促进作用。
[Abstract]:This paper focuses on the progress in the research of solid state lithium batteries and related electrodes and electrolyte materials. The solid-state lithium two battery has a higher specific energy than the conventional liquid lithium ion battery. And because the liquid electrolyte is hardly contained in the battery, the leakage of liquid lithium ion battery in the unconventional environment can be solved easily, flammable and easy. The application of solid-state electrolytes can simplify the battery structure and make the shape and size of the battery more flexible. With the growing demand for high energy, high power and high security for portable electronic equipment and electric vehicles, the two battery of solid state lithium has become an international research. Developing new type of film electrodes and solid-state electrolyte materials and optimizing the design of battery structure is the basis for the development of high performance solid state lithium two batteries. This paper, starting with the development and preparation of new electrodes and electrolyte materials, combines their physical and chemical properties, optimizes the design of a new solid state battery structure, and makes high safety for the first time. The solid-state lithium ion battery has been developed, and the solid-state lithium battery with high specific energy and high safety has been developed. The technology conversion from solid state lithium ion battery to solid lithium two battery is realized, new materials are studied, new concepts are explored, new system is developed, new technology is developed, and the development of the two battery of solid state lithium is realized. Large-scale production and application have laid a technical foundation for the further development of all solid state lithium two batteries. This paper focuses on the development of a new type of high performance solid-state lithium two battery, and the following achievements and progress have been achieved.
(1) a new three element electrode film was prepared by magnetron sputtering, which was used as the positive pole of the solid state lithium battery. By RF magnetron sputtering, three positive electrode films were prepared in high pure argon or oxygen argon mixture. By controlling annealing temperature and time, a series of thin films with different crystallinity and less lithium chemical components were produced. The film is amorphous, with high chemical diffusion coefficient and good electrochemical performance. This film electrode is adapted to small current micro electronic equipment and can be applied to thin film lithium battery. The thin film has stable crystal structure, less lithium chemical composition, nano particle growth and micrometer thickness design, showing unique and good performance. The thin film electrode has high energy density and is suitable for high specific energy lithium battery cathode material and can be applied to solid state lithium battery.
(2) a new type of glass state lithium phosphate lithium phosphate lithium electrode was prepared by magnetron sputtering, which can be used as the positive pole of the solid state lithium battery. The lithium phosphate lithium phosphate composite electrode coated with lithium phosphate was used as the target and the lithium phosphate electrode was used to prepare a lithium phosphate coated lithium phosphate composite electrode by RF magnetron sputtering, and a set of devices was prepared through the sputtering power and deposition time. The coated lithium phosphate film is a good lithium ion conductor, which has the glass structure nature, and forms a coral like porous cross-linking network structure with the lithium iron phosphate electrode, which promotes the transmission of the ion and electron of the electrode, improves the mass transfer efficiency of the interface electric charge and improves the structure stability of the electrode. These electrodes have high specific capacity and good power characteristics and can be applied to lithium power batteries.
(3) Li-Al-Ti-P-O-N thin film electrolyte was prepared by reactive magnetron sputtering. It was used in all solid state thin film lithium batteries. A new type of Li-Al-Ti-P-O-N film was prepared by RF magnetron sputtering in high purity nitrogen by RF magnetron sputtering. A series of thin films were prepared by RF magnetron sputtering, and a series of thin films were prepared by RF magnetron sputtering. The study found that a series of thin films were prepared by RF magnetron sputtering. The Li-Al-Ti-P-O-N thin film was prepared by RF magnetron sputtering, and a series of thin films were prepared by changing the deposition temperature. The nitrogen compounds replaced some oxygen atoms, which reduced the activation energy of the reaction, formed a more rich cross linking network structure and promoted the conduction of lithium ion. High temperature deposition increased the crystallinity of the film, formed a crystalline amorphous mixed structure, and was also beneficial to the conduction of lithium ion. This kind of film electrolyte has high ionic conductivity and good conductivity. The electrochemical stability can be used as a new generation of electrolyte materials for all solid state thin film lithium batteries.
(4) a new solid-state mesoporous silica / ionic liquid composite electrolyte was synthesized by sol-gel method and assembled into a solid state lithium ion battery for the first time. The composite electrolyte is composed of a porous silica framework in situ adsorption ionic liquid electrolyte, in which silica plays a supporting role and adsorbs a large number of ionic liquids. Dispersed in the channel network, it has the characteristics of fluid, as the conduction medium of lithium ion. The composite electrolyte shows high ionic conductivity and good electrochemical stability near the liquid electrolyte. They also have good thermal stability, chemical stability and mechanical strength, which are a new type of high performance solid electrolyte materials. The new solid state lithium ion batteries assembled by composite electrolytes can work normally and show good battery performance.
(5) the new solid-state lithium metal two battery was prepared by in situ assembly technology, and the technology conversion from solid-state lithium ion battery to solid-state lithium metal two battery was completed, and the safe utilization of metal lithium electrode was realized. The solid lithium battery has a new battery structure design, showing good battery comprehensive performance. In practical application, it has many advantages: compared with the traditional solid state battery system, it shows higher specific energy and specific power; it has no leakage, high temperature resistance, impact resistance and preventing the growth of lithium dendrite; it is rich in raw materials, simple in preparation, low in cost, flexible in design, easy to achieve large-scale production, efficient and energy-saving, The new solid state battery structure provides a new scientific idea for the development of solid state lithium battery technology, and has a certain promotion effect on the development and application of solid state lithium battery.
【学位授予单位】：北京理工大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TM912

【参考文献】

中国期刊全文数据库 前1条

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