Lithium-ion transport in inorganic solid state electrolyte

An overview of ion transport in lithium-ion inorganic solid state electrolytes is presented, aimed at exploring and de signing better electrolyte materials. Ionic conductivity is one of the most important indices of the performance of inorganic solid state electrolytes. The general definition of solid state electrolytes is presented in terms of their role in a working cell （to convey ions while isolate electrons）, and the history of solid electrolyte development is briefly summarized. Ways of using the available theoretical models and experimental methods to characterize lithium-ion transport in solid state elec- trolytes are systematically introduced. Then the various factors that affect ionic conductivity are itemized, including mainly structural disorder, composite materials and interface effects between a solid electrolyte and an electrode. Finally, strategies for future material systems, for synthesis and characterization methods, and for theory and calculation are proposed, aiming to help accelerate the design and development of new solid electrolytes.

Synthesis and electrochemical performance of 5V spinel LiNi_(0.5)Mn_(1.5)O_4 prepared by solid-state reaction

Spinel compound LiNi0.5Mn1.5O4 with high capacity and high rate capability was synthesized by solid-state reaction. At first, MnCl2·4H2O and NiCl2·6H2O were reacted with (NH4)2C2O4·H2O to produce a precursor via a low-temperature solid-state route, then the precursor was reacted with Li2CO3 to synthesize LiNi0.5Mn1.5O4. The effects of calcination temperature and time on the physical properties and electrochemical performance of the products were investigated. Samples were characterized by thermal gravimetric analysis(TGA), scanning electron microscopy(SEM), X-ray diffractometry(XRD), charge-discharge tests and cyclic voltammetry measurements. Scanning electron microscopy(SEM) image shows that as calcination temperature and time increase, the crystallinity of the samples is improved, and their grain sizes are obviously increased. It is found that LiNi0.5Mn1.5O4 calcined at 800 ℃ for 6 h exhibits a typical cubic spinel structure with a space group of Fd3m. Electrochemical tests demonstrate that the sample obtained possesses high capacity and excellent rate capability. When being discharged at a rate as high as 5C after 30 cycles, the as-prepared LiNi0.5Mn1.5O4 powders can still deliver a capacity of 101 mA·h/g, which shows to be a potential cathode material for high power batteries.

Preparation of transparent yttrium aluminum garnet ceramics by relatively low temperature solid-state reaction

A new preparation method for a highly sinterable Y 2O 3 powder was developed, using the mixture of the powder with Al 2O 3 powder, a transparent yttrium aluminum garnet(YAG) ceramic was prepared at relatively low temperature by a solid state reaction method. Yttrium nitrate was used as a mother salt, and aqueous ammonia was used as a precipitant reagent, the fine and dendritic precursor crystalline was prepared by adding 0.5% ammonium sulfate into the precipitation reaction system. The highly pure and low agglomerated Y 2O 3 powders were obtained by calcinating the precursor at 1 100 ℃, the primary particles are spherical and 60 nm in diameter. The mixture of Y 2O 3 and Al 2O 3 powders was calcinated, and the resulting mixture compact pressed in mold could be sintered to transparency under vacuum at 1 700 ℃. The sintered transparent YAG polycrystalline exhibits a homogeneous microstructure and its transmittance reaches 45% in the visible light region and 70% in the near infrared wavelength region.

Electrochemical properties of spinel LiMn_2O_4 and LiAl_(0.1)Mn_(1.9)O_(3.9)F_(0.1) synthesized by solid-state reaction

Two types of spinel cathode powders, LiMn2O4 and LiAl0.1Mn1.9O3.9F0.1, were synthesized by solid-state reaction, X-ray diffraction （XRD） patterns of the prepared samples were identified as the spinel structure with a space group of Fd 3^- m. The cubic lattice parameter was determined from least-squares fitting of the XRD data. The LiAl0.1Mn1.9O3.9F0.1 sample showed a little lower initial capacity, but better cycling performance than the LiMn2O4 sample at both room temperature and an elevated temperature. The Vanderbilt method was used to test the electrochemical conductivity of the LiMn2O4 samples. The electrochemical impedance spectroscopy （EIS） method was employed to investigate the electrochemical properties of these spinel LiMn2O4 samples.

Investigation of Li-ion transport in Li7P3S11 and solid-state lithium batteries

The high Li-ion conductivity of the Li7P3S11 sulfide-based solid electrolyte makes it a promising candidate for all-solid-state lithium batteries. The Li-ion transport over electrode-electrolyte and electrolyteelectrolyte interfaces, vital for the performance of solid-state batteries, is investigated by impedance spectroscopy and solid-state NMR experiments. An all-solid-state Li-ion battery is assembled with the Li7P3S11 electrolyte, nano-Li2S cathode and Li-In foil anode, showing a relatively large initial discharge capacity of 1139.5 m Ah/g at a current density of 0.064 m A/cm^ 2 retaining 850.0 m Ah/g after 30 cycles. Electrochemical impedance spectroscopy suggests that the decrease in capacity over cycling is due to the increased interfacial resistance between the electrode and the electrolyte. 1D exchange ^7Li NMR quantifies the interfacial Li-ion transport between the uncycled electrode and the electrolyte, resulting in a diffusion coefficient of 1.70(3) ×10^-14cm^2/s at 333 K and an energy barrier of 0.132 e V for the Li-ion transport between Li2S cathode and Li7P3S11 electrolyte. This indicates that the barrier for Li-ion transport over the electrode-electrolyte interface is small. However, the small diffusion coefficient for Li-ion diffusion between the Li2S and the Li7P3S11 suggests that these contact interfaces between electrode and electrolyte are relatively scarce, challenging the performance of these solid-state batteries.

Preparation of Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_2 powders for cathode material in secondary battery by solid-state method

Employing Li2CO3, NiO, Co3O4, and MnCO3 powders as starting materials, Li[Ni1/3Co1/3Mn1/3]O2 was synthesized by solid-state reaction method. Various grinding aids were applied during milling in order to optimize the synthesis process. After successive heat treatments at 650 and 950 ℃, the prepared powders were characterized by X-ray diffraction (XRD) analysis, scanning electron microscopy, and transmission electron microscopy. The powders prepared by adding salt (NaCl) as grinding aid exhibit a clear R3m layer structure. The powders by other grinding aids like heptane show some impurity peaks in the XRD pattern. The former powders show a uniform particle size distribution of less than 1 μm average size while the latter shows a wide distribution ranging from 1 to 10 μm. Energy dispersive X-ray (EDX) analysiss show that the ratio of Ni, Co, and Mn content in the powder is approximately 1/3, 1/3, and 1/3, respecively. The EDX data indicate no incorporation of sodium or chlorine into the powders. Charge-discharge tests gave an initial discharge capacity of 160 mAh·g-1 for the powders with NaCl addition while 70 mAh·g-1 for the powders with heptane.

Preparation and electrochemical characteristics of Co_3(PO_4)_2-coated LiNi_(0.8)Co_(0.2)O_2 by solid-state reaction at room temperature

LiNi0.8Co0.2O2 particles were modified by Co3（PO4）2 coating. The effects of the Co3（PO4）2 coating on the structure and electrochemical properties of the LiNi0.8Co0.2O2 cathode material were investigated. The Co3（PO4）2 coating forms a thin layer on the surface of the LiNi0.8Co0.2O2 material and a solid solution by interacting with the LiNi0.8Co0.2O2 core material during calcination at 700℃ for 4 h. Charge-discharge experiment results show that the Co3（PO4）2 coating improves the cycling stability of the LiNi0.8Co0.2O2 cathode material. The capacity retention of the pristine LiNi0.8Co0.2O2 cathode after 50 cycles is 83.6%, whereas it is 91.7% in the case of the LiNi0.8Co0.2O2 cathode coated with 1 wt.% Co3（PO4）2. Storage tests of the 4.35 V charged electrode at 60℃ after a month show that the Co3（POg）2-coated sample exhibits good storage properties compared with the pristine sample.

Solid-Contact Ion-Selective Electrodes Based on Graphite Paste for Potentiometric Nitrate and Ammonium Determinations

Robust and easy-to-handle solid-contact ion-selective electrodes (SC-ISEs) based on graphite paste have been developed for the potentiometric detection of NO-3 and NH+4 in environmental samples. Polypyrrole (PPy) has been used as intermediate layer and solid contact between the electron-conducting graphite paste substrate and the ion-conducting polyvinylchloride (PVC)-containing membrane with the immobilized ionophore. For the nitrate- and ammonium-selective electrodes, tridodecylmethylammonium nitrate (TDMA-NO3) and nonactin have been used as ion-complexing compounds, respectively. Both ISEs show nearly Nernstian response in the linear range from 10-5 mol/L to 10-1 mol/L with average slopes of >58 mV/decade. The ISEs possess short response times (<20 s).

Structure, conductivity, and ion emission properties of RbAg4I5 solid electrolyte film prepared by pulsed laser deposition

We fabricated a silver ion emitter based on the solid state electrolyte film of RbAg4 I5 prepared by pulsed laser deposition. The RbAg4 I5 target for PLD process was mechano-chemically synthesized by high-energy ball milling in Ar atmosphere using β-AgI and RbI as raw materials. The ion-conducting properties of RbAg4 I5 were studied by alternating current(AC) impedance spectroscopy and the ionic conductivity at room temperature was estimated 0.21 S/m. The structure, morphology, and elemental composition of the RbAg4 I5 film were investigated. The Ag+ ion-conducting property of the prepared superioni-conductor film was exploited for ion–beam generation. The temperature and accelerating voltage dependences of the ion current were studied. Few nA current was obtained at the temperature of 196?C and the accelerating voltage of 10 kV.

Synthesis and characterization of Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3-coated LiMn_2O_4 by wet chemical route

Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 was prepared by wet chemical route. The phase,surface morphology,and electrochemical properties of the prepared powders were characterized by X-ray diffraction,scanning electron micrograph,and galvanostatic charge-discharge experiments. Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 has similar X-ray diffraction patterns as LiMn2O4. The corner and border of Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 particles are not as clear as the uncoated one. The two powders show similar values of l...

Influence of Incident Velocity on the Penetration for C20 Clusters Moving through Oxides

A theoretical model is established to simulate the penetration process of C20 clusters in oxides （Al2O3, SiO2） at different incident velocities. The induced spatial potential by the incident clusters is described by the dielectric response formalism, in which the Mermin-type dielectric function is adopted to provide a realistic evaluation of the electronic properties of the oxides. The charge distribution of individual ions is derived by using the Brandt-Kitagawa effective charge model, also under the consideration of the asymmetric influence from the wake potential. The stopping power of the clusters and the Coulomb explosion processes are derived by solving the motion equation of the individual ions, when taking into account the multiple scattering effect simulated by using the Monte Carlo method. It is found that the dynamical interaction potential between ions leads to a spatial asymmetry to the cluster structure and the charge distribution for high velocity clusters, and will not be in effect as the incident velocities decrease.

Characteristics of Ions Emitted from Laser-Induced Silver Plasma

In this work, study of laser-induced ions is presented. The plasma was produced by focusing a Nd：YAG laser, with a wavelength of 1064 nm, a pulsed width of 9-14 ns, a power of 1.1 MW and energy of 10 mJ, on silver target in vacuum （10-3 Torr= 1.3332 Pa）. The characteristics of ion streams were investigated by CR-39 detectors located at angles of 0°, 30°, 60° and 90° with respect to normal of the target. The distance between the silver target and each detector was 11 cm. The energy of silver ions was found ranging from 1.5 eV to 1.06E4 eV. There was a high concentration of ions with low energy as compared to those with high energy, showing the energy distribution amongst the ions. The flux of ions was maximum in the axial direction which was decreasing with the angle increase with respect to normal of the target, and finally became minimum in the radial direction. Hence the silver ions have shown anisotropic behaviour.

Synthesis and Characterization of LiCo_xMn_(2-x)O_4 Cathode Materials

LiCoxMn2.04 cathode materials for lithium ion batteries were synthesized by mechanical activation-solid state reaction at 750 ℃ for 24 h in air atmosphere, and their crystal structure, morphology, element composition and electrochemical performance were characterized with XRD, SEM, ICP-AES and charge-discharge test. The experimental results show that all samples have a single spinel structure, well formed crystal shape and uniformly particle size distribution. The lattice parameters of LiCo Mn2-xO4 decrease and the average oxidation states of manganese ions increase with an increase in Co content. Compared with pure LiMn2O4, the LiCo Mn2xO4 （x=0.03-0.12） samples show a lower special capacity, but their cycling life are improved. The capacity loss of LiCo009Mn191O4 and LiCo0.1Mn1.88O4 is only 1.85% and 0.95%, respectively, after the 20th cycle. The improvement of the cycle performance is attributed to the substitution of Co at the Mn sites in the spinel structure, which suppresses the Jahn-Teller distortion and improves the structural stability.

共掺La^(3+)和过量Sr^(2+)对荧光粉Sr_(1.96)Eu_(0.04)SiO_4发光性质的影响

采用高温固相法制备了荧光粉Sr_(1.96-x)Eu_(0.04)SiO_(4)∶xLa^(3+)(x=0、0.01、0.02、0.03、0.04、0.05)和Sr_(1.94+y)Eu_(0.04)La_(0.02)SiO_(4)∶ySr^(2+)(y=0、0.05、0.10、0.20、0.30).使用X射线粉末衍射仪、荧光分光光度计表征了荧光粉的物质结构和发光性质.结果表明:荧光粉的XRD均与Sr_(2)SiO_(4)标准卡片PDF 39-1256对应,没有杂质相产生.荧光粉Sr_(1.96)Eu_(0.04)SiO_(4)中掺入La^(3+)能增强其发光强度,且发射峰的位置不变.当La^(3+)掺杂量为2%(摩尔分数)时,荧光粉Sr_(1.94)Eu_(0.04)La_(0.02)SiO_(4)的发光强度最强.在Sr_(1.94)Eu_(0.04)La_(0.02)SiO_(4)中掺入一系列过量浓度Sr^(2+),能增强其发光强度,且不改变发射峰的位置和形状.当Sr^(2+)过量10%时,荧光粉的发光强度最强.荧光粉的宽带发射光谱可以拟合为2个独立的发射峰,对应Eu^(2+)的4f~65d~1→4f~7跃迁,2个发射峰的强度随着通气量的增大有规律变化,使得荧光粉的发光颜色从绿光区过渡到黄光区.

Current Situation and Developing Trend of Optical Thin Films for DPSSL

A series of optical thin films for LD pumped all- solid- state laser are discussed. Because of the difference between the pumped wavelength and the output wavelength, various kinds of pumping ways, resonator structures and laser crystals, there are so many new kinds of optical thin films, including novel edge filters ,high reflection and an- tireflection coatings. The key problems in designing and coating are analyzed, and the researches carried out world- wide in this field are also given.

基于固态电解质膜的软包电池制备与初步表征

固态电池安全性高、可适应高比能正负极,是蓄电池发展的方向,但存在固相界面阻抗大、界面结构稳定性差等问题。为了快速评估固态电池技术在实用型蓄电池中的作用,本文采用流延法制备了在50℃下离子电导率为6.16×10^(-4)S/cm的固态电解质膜。以高镍三元为正极、石墨为负极,制备了质量为1.1214 g、容量为53.44 mAh的微型软包电池和容量为7252.8 mAh的大容量软包电池。微型软包电池实现了5 C高倍率的放电和150次循环,大容量软包电池在放电深度(DOD)为13.78%时,实现了439次循环充放电。以上结果说明固态电解质膜满足在锂离子电池中使用的要求,然而这些电池的界面构筑仍有不足之处。基于本文结果,通过对固态电解质膜材料、电池化成制度等进行改进,有望促进高性能电池的研发。

原位合成Si/(SiO+Ag)复合负极材料及其电化学性能

将微米Si和纳米Ag_(2)O进行机械球磨,通过原位固相反应合成了Si基复合材料[Si/(SiO+Ag)],以沥青为碳源采用高温煅烧法制备了碳包覆Si基复合材料[Si/(SiO+Ag)-C]。采用XRD、XPS、SEM、TEM对复合材料进行了表征,测试了其电化学性能。结果表明,微米Si和纳米Ag_(2)O在球磨破碎过程中原位形成Si O和Ag颗粒,并附着在基体Si上,两种复合材料都展现出良好的倍率性能,在低电流密度(0.12 A/g)下Si/(SiO+Ag)和Si/(SiO+Ag)-C循环5次后分别表现出1422和1039 mA·h/g的可逆比容量,而在高电流密度(2.40 A/g)下仍能获得672和393 mA·h/g的可逆比容量;当电流密度再次恢复到0.12 A/g时,可逆比容量可恢复到1329和961m A·h/g,Si/(SiO+Ag)-C表现出更好的循环稳定性,经80次循环后可逆比容量仍稳定在943 m A·h/g,其突出的倍率性能归因于微米Si的颗粒细化以及球磨过程中原位反应形成纳米Ag颗粒导电特性,而循环稳定性的提高与原位形成Si O和包覆碳构成的双相缓冲结构有关。

新型储能技术进展与挑战I:电化学储能技术

新型储能技术日益成为中国建设新型能源体系和新型电力系统的关键技术,已成为中国经济发展的新动能,将在促进可再生能源消纳、实现能源体系转型、提高能源利用效率、减少环境污染等方面发挥重要作用,相关技术研究也在快速发展。开展了该领域的系列评价性综述工作,分为电化学储能技术、物理储能与储热技术、储能集成与规划3个部分,对各类新型储能技术的应用领域、最新研究进展及局限性等问题进行了全面系统的对比分析,并进一步探讨了储能集成、安全、规划调度等储能系统相关领域面临的挑战及发展趋势。第1部分为电化学储能技术,重点对锂离子电池、钠离子电池、液流电池、固态电池和水系电池的技术与工程的相关成果进行了综合分析与讨论。电化学储能技术具有灵活配置的特点,可以满足不同功率和能量的应用需求,锂离子电池技术的成熟度最高,在储能市场占有主体地位,未来进一步发展集中于系统集成和安全技术方面,以推进更大规模的商业化应用。其他一些尚处于基础研究阶段的电池技术也展现出了巨大的发展潜力,比如:固态电池具有更高的安全性,钠离子电池具有优越的低温性能,液流电池具有较长的循环寿命等。

全固态硫化物锂电池中NCM正极及其界面研究

采用硫化物电解质的全固态锂电池被视作解决传统液态锂电池安全问题与能量密度提升的最有效方案。正极材料作为锂电池的主要组成部分之一,很大程度上决定着全固态锂电池的基本性能。镍钴锰酸锂(NCM)三元体系正极材料因具备能量密度较高和成本较低的优点,以及与硫化物电解质的可兼容性而受到广泛关注。然而,NCM三元材料存在安全性低、循环稳定性差等缺点,与硫化物电解质接触界面仍存在许多问题亟待解决。因此,分析和研究NCM三元正极材料的结构组成和界面优化,对于提高全固态锂电池稳定性和安全性具有重要的意义。聚焦于当前主流三元正极材料以及与硫化物固态电解质界面问题的匹配性研究,阐述了NCM三元正极材料在全固态锂电池应用中所面临的挑战、解决策略和发展机遇,并对NCM三元正极的进一步发展和应用提出展望。

固态电解质离子传输机制研究进展

全固态锂金属电池具有较高的安全性和稳定性,是替代传统锂离子电池成为下一代储能装置的理想选择。然而,固态电解质相较于液体电解液而言,其较低的离子电导率仍然是阻碍全固态锂金属电池得到快速发展的一个关键。综述了不同类型固态电解质离子传输机理,总结了提高固态电解质电导率的改进策略和最新研究进展,归纳了改善固态电解质离子传输性能的技术路线,并对未来新型固态电解质的设计与发展作了展望。