本文選題：鋰二次電池 + 薄膜電極　； 參考：《北京理工大學(xué)》2014年博士論文

【摘要】：本文重點(diǎn)綜述了固態(tài)化鋰電池及相關(guān)電極與電解質(zhì)材料的研究進(jìn)展。固態(tài)化鋰二次電池具有比常規(guī)液態(tài)鋰離子電池更高的比能量，且由于電池中幾乎不含有液態(tài)電解質(zhì)，對(duì)解決液態(tài)鋰離子電池在非常規(guī)環(huán)境下可能產(chǎn)生的漏液、易燃、易爆等安全性問題，具有重要意義。固態(tài)化電解質(zhì)的應(yīng)用能簡(jiǎn)化電池結(jié)構(gòu)，使電池的形狀尺寸具有更靈活的可設(shè)計(jì)性。隨著便攜式電子設(shè)備和電動(dòng)汽車日益增長(zhǎng)的對(duì)高能量、高功率和高安全性需求的發(fā)展，固態(tài)化鋰二次電池已成為國(guó)際研發(fā)的熱點(diǎn)之一。開發(fā)新型薄膜電極和固態(tài)化電解質(zhì)材料，優(yōu)化電池結(jié)構(gòu)設(shè)計(jì)是發(fā)展高性能固態(tài)化鋰二次電池的基礎(chǔ)。本文從開發(fā)制備新型電極和電解質(zhì)材料入手，結(jié)合它們的物化特性，優(yōu)化設(shè)計(jì)出新型固態(tài)化電池構(gòu)造，首次制備出高安全性的固態(tài)化鋰離子電池，繼而研制出高比能和高安全性的固態(tài)化金屬鋰電池，實(shí)現(xiàn)了從固態(tài)化鋰離子電池到固態(tài)化金屬鋰二次電池的技術(shù)轉(zhuǎn)化；研究新材料，探索新概念，開發(fā)新體系，發(fā)展新技術(shù)，推動(dòng)固態(tài)化鋰二次電池的發(fā)展，實(shí)現(xiàn)規(guī)模化生產(chǎn)與應(yīng)用，從而為進(jìn)一步發(fā)展全固態(tài)鋰二次電池奠定技術(shù)基礎(chǔ)。本文圍繞開發(fā)新型高性能固態(tài)化鋰二次電池進(jìn)行了系統(tǒng)的研究工作，主要取得了以下階段性成果和進(jìn)展。 (1)采用磁控濺射技術(shù)制備出新型三元電極薄膜，，用作固態(tài)化鋰電池正極。通過射頻磁控濺射在高純氬氣或氧-氬混合氣中制備了三元正極薄膜，通過控制退火溫度和時(shí)間，生成了一系列具有不同結(jié)晶度和欠鋰化學(xué)組分的薄膜。預(yù)沉積薄膜為無(wú)定型態(tài)，具有高的化學(xué)擴(kuò)散系數(shù)，表現(xiàn)出較好的電化學(xué)性能，這種薄膜電極適應(yīng)于小電流微型電子設(shè)備，可應(yīng)用于薄膜鋰電池；高溫退火薄膜具有穩(wěn)定的晶體結(jié)構(gòu)、欠鋰化學(xué)組成、納米粒子生長(zhǎng)及微米厚度設(shè)計(jì)，表現(xiàn)出獨(dú)特且良好的電化學(xué)性能，這種薄膜電極具有高的能量密度，適用于高比能鋰電池正極材料，可應(yīng)用到固態(tài)化鋰電池。 (2)采用磁控濺射技術(shù)制備出新型玻璃態(tài)磷酸鋰包覆磷酸鐵鋰電極，可作為固態(tài)化鋰電池正極。以磷酸鋰為靶，磷酸鐵鋰電極為基片，通過射頻磁控濺射制備了磷酸鋰包覆磷酸鐵鋰復(fù)合電極，通過調(diào)節(jié)濺射功率和沉積時(shí)間，制備了一組具有不同包覆形貌的復(fù)合電極。包覆的磷酸鋰薄膜是一種良好的鋰離子導(dǎo)體，具有玻璃態(tài)結(jié)構(gòu)本質(zhì)，與磷酸鐵鋰電極形成珊瑚狀多孔交聯(lián)網(wǎng)絡(luò)結(jié)構(gòu)，促進(jìn)了電極的離子和電子的傳輸，提高了界面電荷傳質(zhì)效率，改善了電極的結(jié)構(gòu)穩(wěn)定性。這類電極具有高的比容量和良好的功率特性，可應(yīng)用于鋰動(dòng)力電池。 (3)采用反應(yīng)磁控濺射法制備出Li-Al-Ti-P-O-N薄膜電解質(zhì)，用于全固態(tài)薄膜鋰電池。以NASICON結(jié)構(gòu)的Li Al Ti P O化合物為靶材，通過射頻磁控濺射法在高純氮?dú)庵兄苽淞诵滦偷腖i-Al-Ti-P-O-N薄膜，通過改變沉積溫度制得了一系列的薄膜。研究發(fā)現(xiàn)氮參雜取代了部分氧原子，降低了反應(yīng)活化能，形成了更豐富的交聯(lián)網(wǎng)絡(luò)結(jié)構(gòu)，促進(jìn)了鋰離子的傳導(dǎo)；高溫沉積提高了薄膜的結(jié)晶度，形成晶態(tài)-非晶態(tài)混合結(jié)構(gòu)，同樣有利于鋰離子的傳導(dǎo)。這類薄膜電解質(zhì)具有較高的離子電導(dǎo)率和良好的電化學(xué)穩(wěn)定性，可作為全固態(tài)薄膜鋰電池用新一代電解質(zhì)材料，未見文獻(xiàn)報(bào)道。 (4)采用溶膠-凝膠法合成出新型固態(tài)化介孔二氧化硅/離子液體復(fù)合電解質(zhì)，并首次組裝成固態(tài)化鋰離子電池。復(fù)合電解質(zhì)由多孔二氧化硅骨架原位吸附離子液體電解質(zhì)組成，其中二氧化硅起支撐作用并吸附大量離子液體，離子液體被分散在孔道網(wǎng)絡(luò)中，具有流體特征，作為鋰離子的傳導(dǎo)介質(zhì)。復(fù)合電解質(zhì)表現(xiàn)出接近液態(tài)電解質(zhì)的高離子傳導(dǎo)率和良好的電化學(xué)穩(wěn)定性，它們還具有良好的熱穩(wěn)定性、化學(xué)穩(wěn)定性和機(jī)械強(qiáng)度，成為一種新型高性能固態(tài)化電解質(zhì)材料。利用復(fù)合電解質(zhì)組裝形成的新型固態(tài)化鋰離子電池能正常工作，表現(xiàn)出良好的電池性能。 (5)采用原位組裝技術(shù)設(shè)計(jì)制備出新型固態(tài)化金屬鋰二次電池，完成了從固態(tài)化鋰離子電池到固態(tài)化金屬鋰二次電池的技術(shù)轉(zhuǎn)化，實(shí)現(xiàn)了金屬鋰電極的安全利用。這種固態(tài)化鋰電池具有全新電池結(jié)構(gòu)設(shè)計(jì)，表現(xiàn)出良好的電池綜合性能，在實(shí)際應(yīng)用中具有諸多優(yōu)點(diǎn)：相比傳統(tǒng)固態(tài)化電池體系，表現(xiàn)出更高的比能量和比功率；具有不漏液、耐高溫、抗沖擊和防止鋰枝晶生長(zhǎng)等的高安全性；原料豐富，制備簡(jiǎn)單，成本低廉，具有靈活的可設(shè)計(jì)性，易實(shí)現(xiàn)規(guī)�；a(chǎn)；高效節(jié)能，綠色環(huán)保。這種新型固態(tài)化電池構(gòu)造，為固態(tài)化鋰電池技術(shù)的發(fā)展提供了新的科學(xué)思路，并對(duì)固態(tài)化鋰電池的發(fā)展應(yīng)用具有一定的促進(jìn)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.
【學(xué)位授予單位】：北京理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類號(hào)】：TM912

【參考文獻(xiàn)】

中國(guó)期刊全文數(shù)據(jù)庫(kù) 前1條

1 胡傳躍,李新海,孫銘良,王志興,鄧凌峰;聚合物鋰離子電池的研究進(jìn)展[J];電池工業(yè);2001年02期

本文編號(hào)：1957332