Glass and Ceramic electrolytes for lithium and lithium-ion batteries
陶瓷领域的SCI期刊
陶瓷领域的SCI期刊SCI收录期刊——陶瓷学科截至到2009年4月SCI扩展版收录陶瓷学科期刊26种（SCI核心版12种），出版地为美国的陶瓷期刊7种，英国6种，荷兰3种，中国、德国、西班牙、捷克、意大利、日本、南斯拉夫、比利时、印度各1种。
其中由中国科学院上海硅酸盐研究所主办、科学出版社出版、郭景坤院士任主编的中文期刊JOURNAL OF INORGANIC MATERIALS《无机材料学报》是目前唯一进入SCI源期刊陶瓷学科的中文期刊。
2005-2008年SCI共收录至少有一位中国作者（不包括台湾）的陶瓷学科论文4448篇，其中2008年966篇（0.9660 %），2007年717篇（0.7555 %），2006年1228篇（1.4261 %），2005年1537篇（1.9896 %）。
4448篇论文包括学术论文2739篇、会议论文1653篇、评论31篇、新闻13篇、通讯6篇、更正4篇、社论2篇。
2005-2008年中国研究论文主要发表在以下几种SCI收录的陶瓷期刊上：KEY ENGINEERING MATERIALS《关键工程材料》1495篇，JOURNAL OF INORGANIC MATERIALS《无机材料学报》1029篇，JOURNAL OF THE AMERICAN CERAMIC SOCIETY《美国陶瓷学会志》603篇，JOURNAL OF NON-CRYSTALLINE SOLIDS《非晶性固体杂志》357篇，CERAMICS INTERNATIONAL《国际陶瓷》320篇，JOURNAL OF THE EUROPEAN CERAMIC SOCIETY 《欧洲陶瓷学会志》172篇，JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY《溶胶-凝胶科学与技术杂志》161篇，JOURNAL OF ELECTROCERAMICS 《电子陶瓷杂志》52篇，JOURNAL OF THE CERAMIC SOCIETY OF JAPAN《日本陶瓷协会杂志》49篇，JOURNAL OF CERAMIC PROCESSING RESEARCH 《陶瓷工艺研究杂志》37篇，INTERNATIONAL JOURNAL OF APPLIED CERAMIC TECHNOLOGY 《国际应用陶瓷技术杂志》33篇。
钙钛矿型氧化物透明导电薄膜的制备与物理性质研究
ＩＩｌ
中国科学技术人学硕上学位论文
摘要
Ｔｈｅ ｗｈｏｌｅ ｔｈｅｓｉｓ ｃｏｎｓｉｓｔｓ ｏｆ ｆｏｕｒ ｃｈａｐｔｅｒｓ Ｃｈａｐｔｅｒ １：Ｔｈｅ ｇｅｎｅｒａｌ ｉｎｔｒｏｄｕｃｔｉｏｎ ｏｆ ｔｈｅ ｔｒａｄｉｔｉｏｎａｌ ＴＣＯ ｆｉｌｍｓ ｉｓ ｇｉｖｅｎ．Ｆｉｒｓｔ， ｗｅ ｄｉｓｃｕｓｓ ｔｈｅ ｉｍｐｏｒｔａｎｔ ｃｈａｒａｃｔｅｒｉｓｔｉｃ ａｎｄ ｐｈｙｓｉｃａｌ ｍｅｃｈａｎｉｓｍ ｏｆ ｔｈｅ ＴＣＯ ｆｉｌｍｓ，ａｎｄ ｔｈｅｎ ｂｒｉｅｆｌｙ ｒｅｖｉｅｗ ｔｈｅ ｐｈｙｓｉｃａｌ ｐｒｏｐｅｒｔｉｅｓ，ｒｅｓｅａｒｃｈｉｎｇ ａｃｔｕａｌｉｔｙ，ａｎｄ ｔｈｅ ｗｉｄｅｌｙ ａｐｐｌｉｃａｔｉｏｎｓ ｏｆ ｔｒａｄｉｔｉｏｎａｌ ＴＣＯ ｆｉｌｍｓ．Ｉｍｐｏｒｔａｎｔｌｙ，ｗｅ ｂｒｉｎｇ ｆｏｒｗａｒｄ ａ ｎｅｗ ｔｙｐｅ ｏｆ ＴＣＯ ｆｉｌｍｓ ｗｉｔｈ ｔｈｅ ｐｅｒｏｖｓｋｉｔｅ ｓｔｒｕｃｔｕｒｅ：Ｌａ—ｄｏｐｅｄ ＳｒＴｉ０３ ａｎｄ ＳｒＳｎ０３．Ｉｎ ｔｈｅ ｅｎｄ ｏｆ ｃｈａｐｔｅｒ １ ｗｅ ｓｉｍｐｌｙ ｉｎｔｒｏｄｕｃｅ ｓｏｍｅ ｐｒｅｐａｒａｔｉｏｎ ｍｅｔｈｏｄｓ ｏｆ ｔｈｉｎ ｆｉｌｍｓ． Ｃｈａｐｔｅｒ ２：Ｔｈｅ ｆｉｌｍｓ ｐｒｅｐａｒａｔｉｏｎ ｍｅｔｈｏｄ ａｎｄ ｓａｍｐｌｅｓ ｍｅａｓｕｒｅｍｅｎｔ ａｒｅ ｉｎｔｒｏｄｕｃｅｄ．Ｅｓｐｅｃｉａｌｌｙ，ｔｈｅ ｐｕｌｓｅｄ ｌａｓｅｒ ｄｅｐｏｓｉｔｉｏｎ ｍｅｔｈｏｄ ａｎｄ Ｘ—ｒａｙ ｄｉｆｆｒａｃｔｉｏｎ ａｒｅ ｄｅｓｃｒｉｂｅｄ ｉｎ ｄｅｔａｉｌｓ．
本论文中，我们通过对５％Ｌａ掺杂的钛酸锶、锡酸锶氧化物薄膜体系的制备 条件、微观结构、电光学性质的研究，探索了掺杂钙钛矿型氧化物材料体系作为 透明导电薄膜材料的应用潜力，以及制备条件对薄膜性能的影响。
硅烷添加剂在锂离子电池电解液中的应用
第49卷第1期 2021年1月硅 酸 盐 学 报Vol. 49，No. 1 January ，2021JOURNAL OF THE CHINESE CERAMIC SOCIETY DOI ：10.14062/j.issn.0454-5648.20200377硅烷添加剂在锂离子电池电解液中的应用徐 菲1,2，李世友1,2，赵冬妮1,2，杨 莉1,2，王 洁1,2(1. 兰州理工大学石油化工学院，兰州 730050；2. 甘肃省锂离子电池电解液材料工程实验室，兰州 730050)摘 要：硅烷添加剂因具有高热稳定性、低可燃性、无毒性、高电导率和高分解电压等优点，近年来成为了锂离子电池电解液新型添加剂的研究热点。
本文重点介绍了在硅烷电解液添加剂中Si—O 结构、Si—N 结构所发挥的作用以及机理，最后对硅烷添加剂的进一步研究趋势和应用前景进行了展望。
关键词：锂离子电池；电解液；硅烷添加剂；机理中图分类号：TM911.3 文献标志码：A 文章编号：0454–5648(2021)01–0161–06 网络出版时间：2020–12–17Application of Silane Additive in Electrolyte of Lithium Ion BatteryXU Fei 1,2, LI Shiyou 1,2, ZHAO Dongni 1,2, YANG Li 1,2, WANG Jie 1,2(1. College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou 730050, China; 2. Gansu Engineering Laboratory of Electrolyte Material for Lithium-ion Battery, Lanzhou 730050, China)Abstract: Silane additives have attracted recent attention as novel electrolytes for lithium-ion batteries due to their high thermal stability, low flammability, non-toxicity, high conductivity and high decomposition voltage. The role and mechanism of Si—O and Si—N structure in silane electrolyte additives were mainly reviewed. In addition, the further research trends and application prospects of silane additives were also prospected.Keywords: lithium-ion battery; electrolyte; silane additive; mechanism锂离子电池因具有高电压、高容量、长寿命等显著优点，已被广泛应用于消费类电子产品、新能源汽车、航空航天及军事装备等领域[1]。
机械英语文章中英文对照
Ceramics and Glasses陶瓷和玻璃A ceramic is often broadly defined as any inorganic nonmetallic material． By this definition, ceramic materials would also include glasses; however, many materials scientists add the stipulation that “ceramic” must also be crystalline.陶瓷通常被概括地定义为无机的非金属材料。
照此定义，陶瓷材料也应包括玻璃；然而许多材料科学家添加了“陶瓷”必须同时是晶体物组成的约定。
A glass is an inorganic nonmetallic material that does not have a crystalline structure. Such materials are said to be amorphous.玻璃是没有晶体状结构的无机非金属材料。
这种材料被称为非结晶质材料。
Properties of Ceramics and GlassesSome of the useful properties of ceramics and glasses include high melting temperature, low density, high strength, stiffness, hardness, wear resistance, and corrosion resistance.陶瓷和玻璃的特性高熔点、低密度、高强度、高刚度、高硬度、高耐磨性和抗腐蚀性是陶瓷和玻璃的一些有用特性。
Many ceramics are good electrical and thermal insulators. Some ceramics have special properties: some ceramics are magnetic materials; some are piezoelectric materials; and a few special ceramics are superconductors at very low temperatures. Ceramics and glasses have one major drawback: they are brittle.许多陶瓷都是电和热的良绝缘体。
无水电解液 英语
无水电解液英语Electrochemical energy storage devices, such as batteries and supercapacitors, have become increasingly important in our modern society. These devices play a crucial role in powering a wide range of electronic devices, from smartphones and laptops to electric vehicles and renewable energy systems. However, the traditional electrolytes used in these devices often rely on water-based solutions, which can limit their performance and safety. The development of water-free electrolytes, or "dry electrolytes," has emerged as a promising solution to address these limitations.One of the primary advantages of dry electrolytes is their enhanced energy density and power density compared to their water-based counterparts. This is because water-free electrolytes can withstand higher voltages without the risk of electrochemical decomposition or gas evolution, which can occur in water-based systems. By operating at higher voltages, dry electrolytes can store more energy per unit volume or mass, leading to more compact and efficient energy storage devices.Moreover, dry electrolytes are less susceptible to freezing or boiling at extreme temperatures, making them suitable for a wider range ofoperating conditions. This is particularly important for applications in harsh environments, such as electric vehicles or renewable energy storage systems, where temperature fluctuations can significantly impact the performance and safety of traditional water-based electrolytes.Another key benefit of dry electrolytes is their improved safety profile. Water-based electrolytes can be flammable and pose a risk of thermal runaway reactions, which can lead to fires or explosions in the event of a malfunction or abuse. In contrast, dry electrolytes, which are typically composed of non-flammable organic solvents or solid-state materials, are generally more stable and less prone to such safety concerns.The development of dry electrolytes has been an active area of research in the field of electrochemical energy storage. Researchers have explored a variety of materials and approaches to create effective water-free electrolytes, including ionic liquids, polymer electrolytes, and solid-state electrolytes.Ionic liquids, which are molten salts with low melting points, have emerged as a promising class of dry electrolytes. These materials exhibit high ionic conductivity, wide electrochemical stability windows, and low flammability, making them attractive for use in advanced energy storage devices. Polymer electrolytes, on the otherhand, offer the advantage of mechanical flexibility and the ability to be easily integrated into various device architectures.Solid-state electrolytes, such as ceramic or glass-ceramic materials, have also garnered significant attention due to their high safety, thermal stability, and the potential for improved energy density. These electrolytes can be used in all-solid-state batteries, which eliminate the need for liquid electrolytes and can lead to more compact and reliable energy storage systems.Despite the promising potential of dry electrolytes, their widespread adoption faces several challenges that need to be addressed. One of the key challenges is the development of scalable and cost-effective manufacturing processes for these materials. Additionally, improving the ionic conductivity and electrochemical performance of dry electrolytes to match or exceed the capabilities of water-based systems is an ongoing research focus.Researchers are also exploring ways to integrate dry electrolytes with advanced electrode materials and device designs to further enhance the overall performance and safety of electrochemical energy storage systems. This includes the development of hybrid approaches that combine the benefits of dry electrolytes with other innovative technologies, such as solid-state batteries or supercapacitors.In conclusion, the development of water-free electrolytes, or "dry electrolytes," represents a significant advancement in the field of electrochemical energy storage. These materials offer the potential for improved energy density, safety, and operational flexibility, making them a crucial component in the ongoing quest for more efficient and reliable energy storage solutions. As research and development in this field continue to progress, we can expect to see increasingly widespread adoption of dry electrolytes in a variety of applications, from consumer electronics to large-scale energy storage systems.。
Control of interface of glass-ceramic electrolyte-liquid electrolyte for aqueous lithium batteries
Control of interface of glass-ceramic electrolyte/liquid electrolyte for aqueous lithium batteriesTonghuan Yang a ,Xingjiang Liu a ,b ,*,Lin Sang b ,Fei Ding ba School of Chemical Engineering and Technology,Tianjin University,Tianjin 300072,China bNational Key Lab of Power Source,Tianjin Institute of Power Source,Tianjin 300384,Chinah i g h l i g h t sThe water-stable lithium electrodes (WSLE)were prepared with LAGP and LATP glass-ceramic plates. A modi fied layer was deposited at glass-ceramic/organic electrolyte interface by magnetron sputtering. The discharge performance of WSLE was improved 70e 80%by the modi fied layer.a r t i c l e i n f oArticle history:Received 29November 2012Received in revised form 15March 2013Accepted 13April 2013Available online 20April 2013Keywords:Lithium-air batteryWater-stable lithium electrode Glass-ceramic electrolyte Interfacial modi ficationa b s t r a c tThe discharge performance of the water-stable lithium electrode (WSLE)is improved by introducing the surface modi fication of the glass-ceramic plate (LAGP and LATP).The water-stable lithium electrodes are prepared with the NASICON-type glass-ceramic plates as protection layer,and using organic electrolyte as interlayer.The glass-ceramic plates with ionic conductivity of 4Â10À4À5.7Â10À4S cm À1are water-stable and 300e 500m m thick.The modi fied layer is deposited onto the glass-ceramic plates by RF magnetron sputtering from a Li 4Ti 5O 12target.The modi fied layer is analyzed by XRD,SEM-EDX,Raman and XPS.The Li-air test-cells are assembled with an SCE as reference electrode in aqueous solution.In the Li-air test-cells,the AC impedance and constant polarization potential measurements are carried out to identify the improvement of modi fication.The impedance of interface between the glass-ceramic plate and organic electrolyte decreases about 20e 50%.Consequently,the discharge current is promoted about 70e 80%.Then,by introducing interfacial modi fication of glass-ceramic plate,the power performance of WSLE is remarkably promoted.Ó2013Elsevier B.V.All rights reserved.1.IntroductionThe lithium-air and lithium-water battery has attracted many researchers ’attention,as the extremely high speci fic energy stor-age system in principle.Although the energy potentiality is high comparing with other electrochemical systems,the practical implementation still has to face several issues regarding both the electrodes and electrolytes.One of the issues,which have to be solved,is that the discharge product Li 2O 2is insoluble in organic electrolyte and clogs the porous air-electrode gradually.Visco et al.and Imanishi et al.proposed a water-stable lithium anode protected by Li 3M 2(PO 4)solid electrolyte,which conquered this issue [1e 4].The Li 3M 2(PO 4)with NASICON-type structure is akind of water-stable lithium-ion super conductor.And since the Li 3M 2(PO 4)has reduction reaction with lithium metal in con-tact,a lithium-ion conductive interlayer was employed between Li 3M 2(PO 4)and the Li-metal.At first solid-state lithium-ion con-ductors have been proposed as protective interlayer,such as LiPON etc.However,the solid-state interlayer has low ionic conductivity and can ’t adapt to the surface-morphological changes of Li-metal electrode during discharge.Subsequently,the polymer electrolyte and organic electrolyte was proposed as the interlayer for better lithium-ion conductivity and surface-morphological adaptability [5e 10].In our previous work,it is found that the interface imped-ance between the solid electrolyte plate and the organic electrolyte is dominant during discharge in WSLE,which is controlling the current density [11].Then,the interface impedance between the solid electrolyte and organic electrolyte became important.For improving the performance of water-stable lithium anode pro-tected by solid electrolyte plate,the interface impedance must be reduced.*Corresponding author.National Key Lab of Power Source,Tianjin Institute of Power Source,Tianjin 300384,China.Tel.:þ86(0)2223383783;fax:þ86(0)2223959300.E-mail addresses:xjliu@ ,klpsc@ (X.Liu).Contents lists available at SciVerse ScienceDirectJournal of Power Sourcesjournal h omepage:www.elsevier.co m/lo cate/jp owsour0378-7753/$e see front matter Ó2013Elsevier B.V.All rights reserved./10.1016/j.jpowsour.2013.04.071Journal of Power Sources 244(2013)43e 49In this work,the water-stable electrolyte plates were prepared by a Li2O e Al2O3e TiO2e P2O5(LATP)or Li2O e Al2O3e TiO2e P2O5 (LAGP)system glass-ceramic,which primarily consisted of Li1þx Ti2-x Al x(PO4)3(x¼0.3)or Li1þx Ge2-x Al x(PO4)3(x¼0.5)respectively.Andthe thickness was about300e500m m.The surface of the glass-ceramic plates was modified to promote the electrochemical per-formance of the interface between glass-ceramic plate and organic electrolyte.2.Experimental2.1.Glass-ceramic plate preparationThe LATP glass-ceramic[14Li2O9Al2O338TiO239P2O5(mol%)] exhibits high lithium-ion conductivity and has been prepared into thin plates in reports[12e14].The14Li2O9Al2O338TiO239P2O5 glass-ceramic was synthesized by reagent grade chemicals, including Li2CO3,Al2O3,TiO2,and NH4H2PO4.The synthesis process is same with the report by Thokchom et al.[13,14].The LATP glass-ceramic plates were refined shape and polished to a300e500m m thick plate.The LAGP glass-ceramic[0.8Li2O0.25Al2O3 1.5GeO2 1.5P2O5 (mol%)]has the same structure with LATP and was made into thin electrolyte plates[15e17].In this work,the LAGP plates were synthesized by Li2CO3,Al2O3,GeO2,and NH4H2PO4.The four raw materials were weighted and mixed by the stoichiometry of 0.8Li2O0.25Al2O31.5GeO21.5P2O5.To begin with,the mixed raw materials were heated slowly to723K and kept for1.5h to release gaseous production.Subsequently,the mixture was heated up to 1723K and melted for2h.And then the molten mixture was poured in a heated plate mold and pressed by another one.The glass plate,which was casted by the molten mixture,was annealed at823K for2h and cooled in furnace.After being annealed,the glass plate crystallized at1223K for12h and became a dense opaque white specimen.This specimen was refined shape and polished to a300e500m m thick plate[11].2.2.Glass-ceramic plate surface modificationA thinfilm of lithium titanium oxide(LTO)was deposited onto glass-ceramic plate surface by RF magnetron sputtering in argon (Ar:50%)/oxygen(O2:50%)plasmas.The sputtering targets were prepared by compressing Li4Ti5O12powder(99.9%)into a100mm diameter pellet and were sintered at1023K for6h in air.The vacuum chamber was evacuated to a base pressure10À3Pa.The Ar/ O2mixture gas pressure was maintained at1Pa.The deposition rate was15 A minÀ1at300W RF power.2.3.CharacterizationsIn all physical and electrochemical measurements,a big glass-ceramic plate was cut into10e20pieces of small ones(about 1cm2each)in order to exclude the effect of different batches of the glass-ceramic plate.Half of them were tested after surface modi-fication;others were tested in same way for comparison.The surface morphology of the glass-ceramics with and without modification was characterized by a Hitachi S-4800field emission scanning electron microscopy(SEM-EDX).The X-ray diffraction (XRD)patterns of LAGP,LATP and modified layer were recorded by a Rigaku TTRAXⅢdiffractometer employing a Cu e K a source.Raman spectra of samples were recorded on a Jobin-Yvon T64000double monochromator equipped with a spatialfilter.The modified layer samples,prepared for Raman testing,were deposited on nickel plate to avoid the influence of glass-ceramic plate substrate.2.4.Electrochemical measurementsThe ionic conductivity of glass-ceramic plate was measured by AC impedance.A0.5m m thick Ag coating was evaporated onto both sides of the glass-ceramic plate.The Ag coated platefixed by two stainless blocking electrodes in a cell.At the room temperature (298K),the impedance measurements were carried out on the cell using a Solartron instrument(model1470Eþ1455A)in0.1to106 frequency range.The electrochemical impedance spectra were fitted using Zview software.A test-cell was designed for electrochemical measurements,as shown in Fig.1.The test-cell was separated into a Li electrode area and an air-electrode area by0.25cm2glass-ceramic plate with a thickness of300e500m m.The Li electrode area contained a Li-metal electrode in organic electrolyte(EC:DEC:EMC¼1:1:1, 1M LiPF6);the air-electrode area contained an air-electrode(Super-P carbon loaded Ni foam)and a reference electrode(an SCE con-nected by salt bridge)in water solution(0.5M LiOH and0.5M KCl).3.Results and discussionFig.2(LAGP)shows an XRD patterns of the LAGP plate which consists of Li1þx Al x Ge2-x(PO4)3(x¼0.5)and AlPO4crystals[15e17]. The Li1þx Al x Ge2-x(PO4)3(x¼0.5)phase is dominant in LAGP glass-ceramic,and other peaks indicate the presence of an AlPO4phase. Fig.2(LATP)provides an XRD patterns of the LATP plate,which consists of Li1þx Ti2-x Al x(PO4)3(x¼0.3)and AlPO4phases,the peaks corresponding to them are observed in XRD patterns[13,14].The Li1þx Ti2-x Al x(PO4)3(x¼0.3)phase is dominant in LATP glass-ceramics.The peak around36 indicates the presence of an AlPO4 phase.Fig.3shows the morphology of the LAGP surface(a,b)and LATP surface(c,d).The LAGP and LATP surface is close-grained and has visible traces of polishing.Few chips of LAGP/LATP glass-ceramic attach on surface,which were produced by polishing.Figs.4and 5is the impedance spectrum of LAGP and LATP plate by blocking electrode test.The ionic conductivity of LAGP and LATP plate can be calculated and can reach5.7Â10À4S cmÀ1and4Â10À4S cmÀ1, respectively.[The formula:ε¼d/(S$R);d:thickness of electrolyte plate;S:area of electrolyte plate;R:resistance of electrolyte plate].Fig.6shows the small angle XRD patterns obtained from modified layer on LATP.The XRD pattern suggests that the LTO modified layer is amorphous,because it is prepared by RF magnetron sputtering.Fig.7shows the surface morphology of the LTO modified layer on SiO2plate(a)and LAGP plate(b,c,d).The surface of SiO2is Fig.1.A schematic representation of the3electrode Li-air test-cell.T.Yang et al./Journal of Power Sources244(2013)43e49 44smoother than LAGP and LATP plate.It ’s better for the analysis of the LTO modi fied layer ’s morphology without the in fluence of morphology of the LAGP and LATP surface.As shown in Fig.7(a),the modi fied layer,which is deposited onto the surface of SiO 2sub-strate,is continuous and uniform.Fig.7(b)is a SEM cross-section of a modi fied layer on the LAGP substrate.The cross-section shows a modi fied layer is deposited onto the surface of the LAGP substrate.The thickness of the modi fied layer is about 400nm.Fig.7(c,d)shows the SEM top view images of the modi fied layer on the LAGP surface.The modi fied layer is composed of many small grains and rougher than the LAGP surface.The modi fied layer would change the electrochemical characteristic of the interface between the organic electrolyte and LAGP plate,which covered on both hills and valleys of the whole LAGP surface.According to the observation of SEM images,the LAGP surface is completely covered by the modi-fied layer which is prepared by RF magnetron sputtering from aLi 4Ti 5O 12target.And the modi fied layer is a continuous,close-grained and uniform deposition layer,which closely growing on the LAGP surface.Fig.8shows an EDX mapping of the modi fied layer on the LAGP for Ti element and Ge element.Existence of the Ti element of modi fied layer is observed and uniformly distributed.And exis-tence of the Ge element of the LAGP substrate can also be observed,because the analysis depth of EDX is 1e 2m m which is more than the 400nm thickness of the modi fied layer.As Fig.9(b)shows,a Raman spectrum of the Li 4Ti 5O 12target has six characteristic bands which appear at 165,239,344,430,674,and 754cm À1.The bands at 239cm À1can be assigned to the bending vibrations of O e Ti e O bonds;the bands at 674and 754cm À1are attributed to vibrations of Ti e O bonds in TiO 6octa-hedra,the bands at 344and 430cm À1are attributed to the stretching vibrations of the Li e O bonds in LiO 4and LiO 6polyhedra,respectively [18].The weak feature at 165cm À1is attributed to bending vibrations of O e Li e O bonds and 274cm À1assigned to F2g modes [18e 21].In Fig.9(a),the evolution of the Raman spectrum is caused by the structural changes that occurred in the LTO modi fied layer upon the RF magnetron sputtering.The Raman spectrum of the modi fied layer still has the bands at 674and 754cm À1,which can be attributed to vibrations of Ti e O bonds in TiO 6octahedra.The band at 430cm À1disappears due to the absent of LiO 6polyhedra by the RF magnetron sputtering.And the Raman spectrum shows the bands at 200and 360cm À1and the absence of the bands at 239and 344cm À1.As Julien et al.report,the Li 7Ti 5O 12displays a tetragonal structure with 141/amd (D 194h)space group,which induces three typical Raman bands located at 200,360and 465cm À1[21].When x >1.4of Li 4þx Ti 5O 12,the Raman spectrum displays the bands at 200and 360cm À1and the bands at 239and 344cm À1disappear.The lack of band at 465cm À1could be attributed to the weak Raman-activity of it [21].The band at 1096cm À1can be assigned to the vibration of CO 32Àwhich is formed at surface in reaction be-tween super fluous lithium and CO 2.Then,the modi fied layer should consist of Li 4þx Ti 5O 12(1.4<x <3).Fig.3.SEM images of the LAGP plate (a,b)and the LATP plate(c,d).Fig.2.XRD patterns of the LAGP and the LATP.T.Yang et al./Journal of Power Sources 244(2013)43e 4945To obtain direct information about Ti valence of the modi fied layer,a modi fied layer is deposited onto nickel plate and studied by XPS,and the corresponding Ti 2p spectra are shown in Fig.10.In Fig.10,the XPS spectrum of the modi fied layer has two peaks at 458.8and 464.6eV.The two peaks of Ti 2p binding energies is mixed-valence of Ti (þⅣ)and Ti (þⅢ).The binding energies at 458.8and 464.8eV indicate the existence of Ti (þⅣ)[22,23].The peaks locate at 462.8and 456.8eV belongs to Ti (þⅢ),which demonstrate the existence of Ti (þⅢ)[22e 25].According to the analysis of each peak,the Ti (þⅢ)occupy about 36e 50%.This suggests that the x of Li 4þx Ti 5O 12should be 1.8e 2.5,because the x of Li 4þx Ti 5O 12is equal to the number of Ti 3þin each five Ti-atoms.Thus,the modi fied layer includes Ti 3þand Ti 4þ,and the x of Li 4þx Ti 5O 12is 1.8e 2.5,which agrees with the analysis result of Raman spectra,but more accurate.According to the analysis of EDX mapping,XRD patterns,Raman spectra and XPS spectra,the modi fied layer is amorphous and composed of Li 4þx Ti 5O 12(1.8<x <2.5).The water-stable lithium metal electrode consists of lithium metal,organic electrolyte,and glass-ceramics electrolyte plate,in which the organic electrolyte is employed as an interlayer to reduce the contact resistance between the glass-ceramic plate and lithium electrode,and to protect the reduction of LATP by lithium metal [2].Fig.11shows impedance spectra of three-electrode test-cell with the LAGP and the modi fied LAGP plate.The impedance spectra of test-cell with the LAGP display a small semicircle at high frequency and a large semicircle at low frequency which may be a pressed semicircle or two overlapped semicircles.The impedance spectrum of test-cell with the modi fied LAGP shows a small semicircle at high frequency,a half semicircle at middle frequency and a large semi-circle at low frequency.The modi fied layer between the LAGP plate and the organic electrolyte has made an impedance decrease of test-cell,which should be corresponding to the half semicircle at middle frequency.And the large semicircle of the LAGP test-cell should be two overlapped semicircle.The equivalent circuit,proposed for fitting,is similar with re-ports,which include Re,Rg,Rint and Rsei with respective constant phase element (CPE1,CPE2and CPE3),and W (represent a Warburg resistance)[5e 7].Re represents the bulk resistance of the LAGP plate,organic electrolyte and wires,which is corresponding to the intercept of the small semicircle with the real axis.Rg is the grain boundary resistance in LAGP plate,which is corresponding to the small semicircle.The large circle includes two overlapped semi-circles,which represent the interfacial resistance of the LAGP plate at middle frequency range (Rint),and the interfacial resistance of the lithium electrode at low frequency range (Rsei).While dis-charging,the SEI impedance (Rsei)decreased with polarization potential,but the organic electrolyte/LAGP impedance (Rint)changed a little and became the major impedance [11].The impedance of electrolyte/LAGP interface controlled the discharge current density [11].Then,the improvement of modi fication can be estimated by the contrast of Rint,which is corresponding to the middle frequency semicircle.The simulated impedance spectra of the equivalent circuit fit with the impedance spectra well,and the parameter of the equivalent circuit is listed in Table 1.In Table 1,Re,Rg and Rsei of the test-cell with the LAGP plate are roughly equal to the one with the modi fied LAGP plate.However,the Rint with modi fied LAGP is decreased 40%e 50%(about 220U ).Accordingly,the discharge current of the test-cell with the modi fiedFig.5.Impedance spectra of theLATP.Fig.6.XRD patterns of the LTO modi fiedlayer.Fig.4.Impedance spectra of the LAGP.T.Yang et al./Journal of Power Sources 244(2013)43e 4946LAGP plate should increase.Then,some tests about discharge cur-rent have been carried out.Fig.12shows two constant potential polarization curves of the WSLE with and without interface modi fication.At À2.9V vs.SCE (about 0.4V vs.Li/Li þ),the current of the WSLE with interface modi fication is about 100%more than the one without.At the samepolarization potential,the current curves of the WSLE with and without interface modi fication could represent the power perfor-mance when discharging.Then,the power performance of the WSLE can be remarkably promoted by introducing the modi fied layer,which is deposited by RF magnetron sputtering from the Li 4Ti 5O 12target.The 50%decrease of Rint resulted in the 100%in-crease of discharge current,which is also an evidence of our pre-vious results that the organic electrolyte/LAGP impedance controlled the current density when discharging [11].At the interface of solid-state electrolyte or organic electrolyte,the ionic conduction phenomena have been explained by two different theories respectively.At the interface of solid-state electrolyte,the phenomena are characterized by the term “nanoionics ”to describe about ionic conduction [26].At the interface,two kinds of solid-stateionicFig.7.SEM images of the modi fied layer:(a)on SiO 2;(b)a cross-section of the modi fied layer on the LAGP plate (c,d)on the LAGPplate.Fig.8.EDX mapping images of the modi fied layer on the LAGPplate.Fig.9.Raman spectra of the LTO raw material and the LTO modi fied layer.T.Yang et al./Journal of Power Sources 244(2013)43e 4947conductor correspond to two different phenomena of ionic conduction.One is the contact of the electron-insulating ionic conductors.And one example is that two kinds of F Àion conductor (BaF 2and CaF 2)were brought into contact with each other [27].The com-positions and structures of solid electrolytes have been well tailored to achieve high ionic conductivities.However,the com-positions deviate from the optima at the space-charge layer.And therefore,the conductivity should be lower than that of bulk,increasing the interfacial resistance [28].For reducing the interfa-cial resistance,the Li 4Ti 5O 12or LiNbO 3layer is introduced as the buffer layer.Because the interposition of buffer layer can suppress the development of space-charge layer,the interfacial resistance is obviously reduced [28,29].The other one is the contact of the mixed conductors,which are materials with a signi ficant fraction of ionic as well as electronic.For instance,a space-charge layer in the LiCoO 2should vanish when in contact with a mixed conductor,because the electronic con-duction resolves the concentration gradient of the Li þions [28].Similar nanoionic phenomena should take place at the LAGP side of interface between the LAGP and the organic electrolyte,developing a space-charge layer.When the LAGP is in contact with the organic electrolyte,the large difference between their chemical potentials can make Li þions accumulate at LAGP interface,further developing the space-charge layer and resulting in a very large interfacial resistance.The interposition of buffer layer is a strategy which has been reported to suppress the space-charge layer [28,29].The buffer layer introduces two interfaces:LAGP/LTO and LTO/organic electrolyte.The space-charge layers at both interfaces will be less developed,because the former consists of solid-state oxides with similar chemical potentials,and the latter consists of mixed conductor materials.And the electronic conductivity of Li 4þx Ti 5O 12(x ¼1.8e 2.5)is enhanced via the generation of mixed-valence titanium [Ti (Ⅲ)/Ti (Ⅳ)].Then,the energy barrier of Li-ion transfer between the LAGP and organic electrolyte is divided into two smaller energy barriers,which are the energy barriers of LAGP/LTO interface and LTO/organic electrolyte interface.The actual process may be more complex,which needed further study.And the Li 4þx Ti 5O 12(1.8<x <2.5)should be a zero strain compound,which has the similar characteristic of Li 4Ti 5O 12[30].In that case,even if the formation of space-charge layer made lithium-ion unhomogeneously distribute,there still has no strain to break the modi fied layer.Fig.13shows the impedance spectra of the three-electrode test-cell with the LATP and the modi fied LATP plate.The impedance spectrum of test-cell with the LATP and the modi fied LATP displays a small semicircle at high frequency,a half semicircle at middle frequency,and a large semicircle at low frequency which is corre-sponding to the SEI impedance.Same to LAGP plate,the equivalent circuit include Re,Rg,Rint and Rsei with respective constant phase elements (CPE1,CPE2and CPE3),and W (represents a Warburg resistance).Re is corresponding to the intercept of the small semicircle with the real axis,and Rg is corresponding to the small semicircle.Rint is corresponding to the half semicircle,and RseiisFig.10.XPS patterns of Ti 2p of the modi fied layer.Table 1The parameter of the equivalent circuit of test-cell with LAGP and modi fied LAGP.Re (U )Rg (U )Rint (U )Rsei (U )LAGP27258557770Modi fied LAGP28234338771Fig.11.Impedance spectra of the WSLE with the LAGP and the modi fied LAGP in the three-electrodetest-cell.Fig.12.Constant potential polarization curves of the WSLE with the LAGP and the modi fied LAGP at À2.9V vs.SCE at 298K.T.Yang et al./Journal of Power Sources 244(2013)43e 4948corresponding to the large semicircle at the low frequency.The fitting lines of impedance spectra are also showed in Fig.13,and the analysis results of impedance are listed in Table 2.In Table 2,Rint with LATP is more than LAGP,which should be attributed to the low Li-ion conductivity of LATP and could also be different from actual area.Rint with modi fied LATP decreased about 240U which is 20e 30%of Rint without modi fication.Fig.14shows two constant potential polarization curves of the WSLE protected by the LATP with and without interface modi fica-tion.At À2.9V vs.SCE (about 0.4V vs.Li/Li þ),the current of the WSLE with interface modi fication is about 80%more than the one without.Then,the power performance of WSLE can be remarkably promoted by the modi fied layer,which is similar as the modi fica-tion of LAGP plate Fig.12.4.ConclusionBy using the modi fication of the interface between the glass-ceramic (LAGP/LATP)plate and the organic electrolyte,the discharge performance of the WSLE can be remarkably promoted in aqueous solution.The modi fied layer decreased the interfacial impedance between the glass-ceramic plate and organic electrolyte.The modi fied layer Li 4þx Ti 5O 12(1.8<x <2.5)can offer more lithium-ions and vacancy sites and has electronic conduction.And,it introduced two in-terfaces,such as glass-ceramic plate/LTO and LTO/organic electro-lyte,at which the space-charge layer was less developed.Because the Li 4þx Ti 5O 12(1.8<x < 2.5)the modi fied layer is a mixed conductor and covered the whole LAGP plate,which buffered the direct contact between the glass-ceramic plate and organic elec-trolyte.Then,the energy barrier of Li-ion transfer between the LAGP and organic electrolyte become two relative small energy barriers.References[1]S.J.Visco, E.Nimon, B.Katz,L.C.D.Jonghe,M.Y.Chu,Abstract 0389,TheElectrochemical Society Meeting Abstracts vol.2006e 2,Cancun,Mexico,2006.Oct.29e Nov.3.[2]S.J.Visco,E.Nimon,B.Katz,L.C.D.Jonghe,M.Y.Chu,Abstract 53,The 12thInternational Meeting on Lithium Batteries Abstracts,Nara,Japan,2004.[3]T.Zhang,N.Imanishi,S.Hasegawa,A.Hirano,J.Xie,Y.Takeda,O.Yamamoto,N.Sammes,J.Electrochem.Soc.155(2008)A965.[4]S.Hasegawa,N.Imanishi,T.Zhang,J.Xie,A.Hirano,Y.Takeda,O.Yamamoto,J.Power Sources 189(2009)371.[5]T.Zhang,N.Imanishi,S.Hasegawa,A.Hirano,J.Xie,Y.Takeda,O.Yamamoto,N.Sammes,Electrochem.Solid-State Lett.12(2009)A132.[6]T.Zhang,N.Imanishi,Y.Shimonishi,A.Hirano,J.Xie,Y.Takeda,O.Yamamoto,N.Sammes,J.Electrochem.Soc.157(2010)A214.[7]T.Zhang,N.Imanishi,A.Hirano,Y.Takeda,O.Yamanoto,Electrochem.Solid-State Lett.14(2011)A45.[8]Y.Wang,H.Zhou,J.Power Sources 195(2010)358.[9]P.He,Y.Wang,H.Zhou,mun.12(2010)1686.[10]P.He,Y.Wang,H.Zhou,J.Power Sources 196(2011)5611.[11]T.Yang,L.Sang,F.Ding,J.Zhang,X.Liu,Electrochim.Acta.81(2012)179.[12]J.Fu,Solid State Ionics 96(1997)195.[13]J.S.Thokchom,B.Kumar,Solid State Ionics 177(2006)727.[14]J.S.Thokchom,B.Kumar,J.Electrochem.Soc.154(2007)A331.[15]G.Y.Aleshin, D.A.Semenenko, A.I.Belova,T.K.Zakharchenko, D.M.Itkis,E.A.Goodilin,Y.D.Tretyakov,Solid State Ionics 184(2011)62.[16]K.He,Y.H.Wang,C.K.Zu,Y.H.Liu,H.F.Zhao,B.Han,J.Chen,Chin.J.Inorg.Chem.27(2011)2484.[17]J.Kumar,B.Kumar,J.Power Sources 194(2009)1113.[18]P.P.Posini,R.Mancini,L.Petrucci,V.Contini,P.Villano,Solid State Ionics 144(2001)185.[19] C.Julien,136-137,Solid State Ionics (2000)887.[20]T.Yi,L.Jiang,J.Liu,M.Ye,H.Fang,A.Zhou,J.Shu,Ionics 17(2011)799e 802.[21] C.M.Julien,M.Massot,K.Zaghid,J Power Sources 136(2004)72e 79.[22]P.W.Seo,S.S.Kim,S.C.Hong,Korean J.Chem.Eng.27(2010)1220.[23]J.Y.Luo,L.J.Chen,Y.J.Zhao,P.He,Y.Y.Xia,J.Power Sources 194(2009)1075.[24] C.Trapalis,V.Kozhukharov,B.Samuneva,J.Mater.Sci.28(1993)1276.[25]R.Cai,S.Jiang,X.Yu,B.Zhao,H.Wang,Z.Shao,J.Mater.Chem.22(2012)8013.[26]J.Maier,Nat.Mater.4(2005)805.[27]N.Sata,K.Eberman,K.Eberl,J.Maier,Nature 408(2000)946.[28]N.Ohta,K.Takada,L.Zhang,R.Ma,M.Osada,T.Sasaki,Adv.Mater.18(2006)2226.[29]Y.Seino,T.Ota,K.Takada,J Power Sources 196(2011)6488.[30]T.Ohzuku,A.Ueda,N.Yamamoto,J.Electrochem.Soc.142(1995)1431.Table 2The parameter of the equivalent circuit of test-cell with LATP and modi fied LATP.Re (U )Rg (U )Rint (U )Rsei (U )LATP421949791160Modi fied LATP382057321128Fig.13.Impedance spectra of the WSLE with the LATP and the modi fied LATP in the three-electrodetest-cell.Fig.14.Constant potential polarization curves of the WSLE with the LATP and the modi fied LATP at À2.9V vs.SCE at 298K.T.Yang et al./Journal of Power Sources 244(2013)43e 4949。
《固态电化学》导学案
《固态电化学》导学案固态电化学是研究固体中的电荷传输和化学反应的学科。
它的研究对象主要是固体材料中的离子传输、电极反应以及相关的物理化学现象。
本导学案将引导读者了解固态电化学的基本概念、原理和应用。
希望通过学习本文，读者能够深入理解固态电化学的知识并应用于实际问题的解决中。
一、引言固态电化学作为电化学的一个重要分支，研究的基本问题是相对电位和电流密度与各种参数之间的关系。
这一学科的研究对象是固体电解质、固体电极以及固体电池等。
固态电化学在新能源、储能技术、传感器、电分解等领域有着广泛的应用前景。
二、固态电解质1. 固态电解质的定义固态电解质是指在固体状态下具有离子传导能力的材料。
它通常由具有空位的晶格和可移动的离子组成。
固态电解质可以用于电解池、电池及传感器等电化学器件中。
2. 固态电解质的分类固态电解质可以根据离子导电类型的不同分为阴离子导电体和阳离子导电体。
在阴离子导电体中，阴离子是主要的电导贡献者；而在阳离子导电体中，阳离子起到了主要的电导功能。
3. 常见的固态电解质材料常见的固态电解质材料包括氧化物、硫化物、磷酸盐、聚合物等。
例如，氧化物固态电解质氧化锆（ZrO2）在高温下能够导电，并被广泛应用于固态氧化物燃料电池中。
三、固态电极1. 固态电极的定义固态电极是指由固体材料组成的电极，与液态电极相对应。
与液态电极相比，固态电极具有更好的化学稳定性和较小的极化现象，适用于高温、高压和腐蚀性介质等特殊环境中。
2. 常见的固态电极材料常见的固态电极材料包括金属、半导体、导电聚合物等。
例如，金属铂（Pt）常用于固态电池的催化层，提高电池电化学反应速率。
四、固态电池1. 固态电池的定义固态电池是指使用固态电解质和固态电极作为关键组件的电池。
相较于传统液态电池，固态电池具有更高的安全性、更长的使用寿命和更高的工作温度范围。
2. 固态电池的应用固态电池广泛应用于新能源领域，如固态锂离子电池、固态燃料电池等。
材料专业英语-特殊玻璃概要
当微粒半径在20-30微米范围内的这种玻璃 微球通过肝动脉注射到肝脏瘤时，继玻璃 中的Y-89通过中子轰击被激活成β射线源Y90之后，(其半衰期为64.1小时)，它们进入 肝脏瘤的毛细血管床，释放出近射程的、 高离子束β射线巨大的局部放射剂量至肿瘤， 对周围器官并无放射。
The radioactive Y-90 is hardly released from the glass because of its high chemical durability. Radioactivity of the glass decays to a negligible level in 21 days because of short half-time of Y90.
since it heats the cancer locally by magnetic hysteresis loss under an alternately magnetic field, and cancer cells are destroyed above 43 ℃ .
因为它可以在交流磁场作用下，通过磁滞 损耗局部加热癌症，癌症细胞在高于43℃ 时就可以被破坏。
1.
For example, Bioglass in the system Na20-CaO-Si02-P205 is extensively used as periodontal implants, artificial middle ear bones etc. in U.S.A., because of its high bioactivity. 例如在美国，利用其高的生物活性，Na20CaO-Si02-P205系列的生物玻璃广泛的用于 牙周移植，人工中耳骨等。