Article
Materials Science, Ceramics
Xiao Huang, Jianmeng Su, Zhen Song, Tongping Xiu, Jun Jin, Michael E. Badding, Zhaoyin Wen
Summary: The study found that by using Li6.4Ga0.2La3Zr2O12 powder calcined at 850 degrees Celsius, a cubic LLZO phase can be obtained, and ceramic pellets sintered at 1100 degrees Celsius for 320 minutes using this powder have relative densities higher than 94%, with conductivities higher than 1.2 x 10(-3) S cm(-1) at 25 degrees Celsius.
CERAMICS INTERNATIONAL
(2021)
Article
Chemistry, Multidisciplinary
Huanyu Zhang, Faruk Okur, Claudia Cancellieri, Lars P. H. Jeurgens, Annapaola Parrilli, Dogan Tarik Karabay, Martin Nesvadba, Sunhyun Hwang, Antonia Neels, Maksym V. Kovalenko, Kostiantyn V. Kravchyk
Summary: Li dendrites form in Li7La3Zr2O12 (LLZO) solid electrolytes due to volume changes and voids at the Li metal/LLZO interface. Dense-porous LLZO membranes provide a solution by storing lithium in the pores, avoiding volume changes and void formation. The reported method of sequential tape-casting allows for the production of bilayer membranes with high performance.
Article
Chemistry, Physical
Evgeniya Ilina, Efim Lyalin, Maxim Vlasov, Artem Kabanov, Kirill Okhotnikov, Elena Sherstobitova, Mirijam Zobel
Summary: Solid electrolytes based on Li7La3Zr2O12 (LLZO) with a garnet structure are potential candidate materials for high-energy lithium and lithium-ion power sources. In this study, solid electrolytes of the Li7-xLa3Zr2-xTaxO12 system were synthesized and it was found that Ta doping can enhance the lithium-ion conductivity of the materials. The highest conductivity was observed in the compound Li6.4La3Zr1.4Ta0.6O12, indicating that moderate Ta doping is most suitable for improving Li diffusion in LLZO materials. The combined use of density functional theory (DFT) modeling, structural characterization, and conductivity measurements provides insights into this important class of Li-conducting oxides and suggestions for improving their properties.
ACS APPLIED ENERGY MATERIALS
(2022)
Review
Chemistry, Physical
Jie Biao, Chen Bai, Jiabin Ma, Ming Liu, Feiyu Kang, Yidan Cao, Yan-Bing He
Summary: This article reviews the mechanism and solutions for Li dendrite penetration in Garnet-type Li7La3Zr2O12 (LLZO) solid-state electrolytes, including material design, interfacial adaptability, and charge transfer process. The successful inhibition of Li dendrite penetration through stabilizing LLZO phase, densification techniques, interfacial modifications, and grain boundary manipulations provides guidance for the development of LLZO-based solid-state electrolytes and ultra-stable SSLMBs.
ADVANCED ENERGY MATERIALS
(2023)
Article
Nanoscience & Nanotechnology
Li Yang, Xiyuan Tao, Xiao Huang, Changfei Zou, Lingguang Yi, Xiaoyi Chen, Zihao Zang, Zhigao Luo, Xianyou Wang
Summary: The MCLL method proposed in this study effectively controls the Li2O atmosphere during the sintering process of highly conductive LLZO ceramics, resulting in high conductivity and potential applications.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Nanoscience & Nanotechnology
Kaihui Nie, Siyuan Wu, Junyang Wang, Xiaorui Sun, Zhao Yan, Jiliang Qiu, Qi Yang, Ruijuan Xiao, Xiqian Yu, Hong Li, Liquan Chen, Xuejie Huang
Summary: This study investigated the stability and reaction mechanisms of several commonly used organic solvents with garnets, revealing that solvent acidity determines the reaction strength, and solvents with hydroxyl groups may lead to violent reaction. Ether compounds and saturated aliphatic hydrocarbons exhibit high stability against garnets.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Physical
Minjea Kim, Hyun Gyu Park, Kwangjin Park
Summary: The research identified a method for pre-forming the cubic LLZO phase under HRFTP conditions, which helps improve the ionic conductivity of LLZO. Analysis using SEM and XRD confirmed the effectiveness of optimizing sintering temperature to enhance both bulk and grain boundary ionic conductivities.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Materials Science, Multidisciplinary
Xiao-Zhen Liu, Lei Ding, Yu-Ze Liu, Li-Ping Xiong, Jie Chen, Xiao-Long Luo
Summary: The Ba, Y and Al co-doped Li7La3Zr2O12(LLZO) solid electrolyte prepared by the solid-state reaction method showed improved room-temperature total conductivity after sintering, due to elimination of grain boundary resistances and densification control. By adjusting sintering temperature and time, a cubic garnet phase was obtained, resulting in enhanced total conductivity and improved morphology.
Review
Chemistry, Physical
Hamed Salimkhani, Alp Yurum, Selmiye Alkan Gursel
Summary: Lithium lanthanum zirconates (LLZOs) are a type of solid electrolyte with excellent ionic conductivity and high stability. Research has shown that the properties of LLZOs can be tailored for various applications by using supervalent dopants. Many studies have been published on the structure and site preference of compositional ions in LLZO electrolytes.
Article
Electrochemistry
Xing Xiang, Yanhua Zhang, Huihu Wang, Chenhuinan Wei, Fei Chen, Qiang Shen
Summary: In this study, a film of silver was successfully deposited on the surface of LLZO using magnetron sputtering technique, leading to a decrease in interfacial impedance between Li7La3Zr2O12 and lithium anode. This modification improved the electrochemical performance of the battery, demonstrated by stable voltage output in lithium plating and striping tests.
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Wanzheng Lu, Mingzhe Xue, Cunman Zhang
Summary: SSLB is regarded as a promising candidate for energy storage devices, with LLZO solid-state electrolyte playing a key role, and significant progress has been made in research, although challenges remain to be addressed.
ENERGY STORAGE MATERIALS
(2021)
Article
Materials Science, Ceramics
Li Yang, Xiao Huang, Changfei Zou, Xiyuan Tao, Lei Liu, Kaili Luo, Peng Zeng, Qiushi Dai, Yongfang Li, Lingguang Yi, Zhigao Luo, Xianyou Wang
Summary: The LLZNO-LPO ceramic electrolyte, prepared by rapid sintering method with LPO as sintering aids, has been successfully applied to construct a shuttle-effect free solid-state Li-S battery, showing improved Li+ conductivity and critical current density, as well as good charge-discharge performance and stability.
CERAMICS INTERNATIONAL
(2021)
Article
Materials Science, Ceramics
Libin Zhuang, Xiao Huang, Yang Lu, Jiawen Tang, Yongjian Zhou, Xin Ao, Yan Yang, Bingbing Tian
Summary: Cubic phase garnet-type Li7La3Zr2O12 (LLZO) is a safe solid electrolyte for Li-ion batteries, while Al-doped LLZO (Al-LLZO) has been widely studied for its low cost, but the ionic conductivity is affected by Al3+-Li+ substitution and Li(x)AlOy segregation.
CERAMICS INTERNATIONAL
(2021)
Article
Materials Science, Ceramics
V Gajraj, A. Kumar, S. Indris, H. Ehrenberg, N. Kumar, C. R. Mariappan
Summary: This work focuses on the preparation and characterization of Al-doped garnet-type Li7La3-xAlxZr2O12 electrolytes for solid-state Li-ion batteries. The electrical properties of the materials were evaluated, and the results indicate an increasing trend in ionic conductivity, DC conductivity, hopping rates, and diffusion coefficient with increasing temperature.
CERAMICS INTERNATIONAL
(2022)
Article
Chemistry, Physical
Bin Sun, Panpan Wang, Jing Xu, Qianzheng Jin, Zili Zhang, Hui Wu, Yang Jin
Summary: A new molten Li-I-2 battery design utilizing solid-state garnet electrolyte and eutectic iodate cathode has been developed in this study to address the issues of traditional Li-I-2 batteries. This solid-state battery system demonstrates high safety and excellent electrochemical performance, with a simple structure that allows for easy assembly process and electrode material recycling.
Article
Energy & Fuels
Patrick Posch, Sarah Lunghammer, Alexandra Wilkening, Katharina Hogrefe, H. Martin R. Wilkening
Summary: In this study, nucleus-specific Li-7 and Na-23 nuclear magnetic resonance (NMR) spectroscopy was used to investigate the motion processes in mixed-conducting Li4Na (x) Ti5O12 materials. The results show that the diffusivity of Li+ ions increases significantly in the early stages of chemical sodiation, while there is limited data on the diffusion properties of Na+ ions. In addition, the formation of interfacial solid solutions was observed at very low sodiation levels (x = 0.1), and these regions covered almost the entire crystallite area at x = 0.5, enabling facile long-range ion transport.
JOURNAL OF PHYSICS-ENERGY
(2023)
Article
Chemistry, Physical
Subhajit Sarkar, Bowen Chen, Chengtian Zhou, Shahram Nouri Shirazi, Frederieke Langer, Julian Schwenzel, Venkataraman Thangadurai
Summary: A synthetic approach combining AlCl3 Lewis acid and fluoroethylene carbonate is used to create an electrolyte design that forms a mechanically robust and ionically conductive Al-rich interphase. This design overcomes the interface problems between solid electrolytes and Li anodes/cathodes, resulting in a high critical current density and stable cycling performance. The assembled hybrid full cell demonstrates an impressive specific capacity retention, making it a promising direction for the development of safe, long-lasting, and high-energy solid-state lithium-metal batteries.
ADVANCED ENERGY MATERIALS
(2023)
Review
Energy & Fuels
Abinaya Sivakumaran, Alfred Junio Samson, Venkataraman Thangadurai
Summary: All solid-state sodium batteries (ASSSBs) are a promising alternative to lithium-ion batteries due to their increased safety and the widespread availability and low cost of sodium. However, current organic liquid electrolytes used in battery systems have safety concerns due to their low-thermal stability, flammability, and leakage tendency. In contrast, solid electrolytes offer improved safety but suffer from insufficient ionic conductivity and other limitations. Sodium rare-earth silicates, with their high-ionic conduction, may hold the key to building next-generation ASSSBs.
Review
Nanoscience & Nanotechnology
Aroosa Javed, Paulina Palafox Gonzalez, Venkataraman Thangadurai
Summary: In the 21st century, proton exchange membrane fuel cells (PEMFCs) are a promising source of power generation due to their high efficiency and eco-friendly design. However, the critical component of PEMFCs, proton exchange membranes (PEMs), have drawbacks such as high cost and reduction in proton conductivity at high temperatures. Recent research has focused on modifying PEMs through composite materials to improve their stability and proton conductivity. This article discusses the current developments in membranes for PEMFCs, with emphasis on hybrid membranes based on Nafion, PBI, and other nonfluorinated proton conducting membranes.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Maicon Pierre Lourenco, Alain Tchagang, Karthik Shankar, Venkataraman Thangadurai, Dennis R. Salahub
Summary: In this work, a new artificial intelligence method based on active learning is proposed to guide new experiments with as little data as possible, for optimum experimental design. The method is applied to ABO3 perovskites, and several regressor algorithms are employed. The developed method has the potential to be applied in various fields such as inorganic and organic synthesis and materials science.
CANADIAN JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Jonas Spychala, H. Martin R. Wilkening, Alexandra Wilkening
Summary: Li2OHCl is a suitable Li+ ionic conductor composed of abundant elements excluding Li. Its low melting point enables easy synthesis methods. However, the clear picture of Li+ self-diffusion is still challenging to prove, as it is suggested to be coupled to OH- rotational dynamics in Li2OHCl.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Maria Gombotz, Caroline Hiebl, Florian Stainer, H. Martin R. Wilkening
Summary: The development of ceramic proton conductors is of great interest due to their potential use in energy storage systems. Li6La3ZrTaO12 (LLZTO) has been found to exhibit rapid Li+ diffusivity. By treating a single crystal in water or glacial acetic acid, mobile Li+ ions can be exchanged with protons, resulting in a mixed proton-lithium ionic conductor. In this study, the diffusion of H+ protons and Li+ ions in the exchanged LLZTO has been investigated using element-specific H-1 and Li-7 NMR spectroscopy. The results show slower long-range Li-7 diffusion but relatively high H+ diffusivity, albeit slower than Li+ dynamics. By measuring spin-lattice relaxation and self-diffusion coefficient D(H) of H+ dynamics, energy barriers and transport properties have been determined, suggesting the potential of designing fast transport pathways for protons in ceramics.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Materials Science, Multidisciplinary
Patrick Bottke, Katharina Hogrefe, Julia Kohl, Suliman Nakhal, Alexandra Wilkening, Paul Heitjans, Martin Lerch, H. Martin R. Wilkening
Summary: The visualization of atomic or ionic jump processes on a nanometer length scale is important for understanding diffusion pathways in solid electrolytes. This study used high-resolution 6Li nuclear magnetic resonance (NMR) spectroscopy to investigate Li+ exchange processes in Li3VF6. The results confirmed the preferred diffusion pathways and provided further insights into ion dynamics between corner-shared Li-bearing polyhedra.
MATERIALS RESEARCH BULLETIN
(2023)
Article
Chemistry, Multidisciplinary
Hirotoshi Yamada, Tomoko Ito, Tatsuya Nakamura, Raman Bekarevich, Kazutaka Mitsuishi, Sanoop Palakkathodi Kammampata, Venkataraman Thangadurai
Summary: All-solid-state lithium batteries (ASSLBs) with garnet-type solid electrolytes are prepared using quick liquid phase sintering (Q-LPS) method. Through optimizing materials, processes, and architectures, the battery performance is significantly improved. The initial discharge capacity of the cell with LiCoO2 loading of 8.1 mg reaches 1 mAh cm(-2) and 130 mAh g(-1) at 25 degrees C. The Q-LPS method is suitable for large-scale manufacturing of ASSLBs.
Article
Chemistry, Physical
Alexander Komar, Dirk Wilmer, Martin R. Wilkening, Ilie Hanzu
Summary: The determination of stray capacitance in impedance measuring cells is crucial for studying solid ion conductors. We present a general method that accurately determines stray capacitance and can be applied to various impedance cells or sample holders for temperature conductivity measurements. Experimental calibration on a 2032-type coin cell sample holder demonstrates the reliability of our method for impedance measurements of air sensitive materials. Our method serves as an example of good practice in the field of solid electrolytes, solid state batteries, and dielectric materials investigations.
SOLID STATE IONICS
(2023)
Article
Chemistry, Multidisciplinary
Jian-Fang Wu, Zheyi Zou, Bowei Pu, Lukas Ladenstein, Shen Lin, Wenjing Xie, Shen Li, Bing He, Yameng Fan, Wei Kong Pang, H. Martin R. Wilkening, Xin Guo, Chaohe Xu, Tao Zhang, Siqi Shi, Jilei Liu
Summary: The softness of sulfur sublattice and rotational PS4 tetrahedra in thiophosphates lead to liquid-like ionic conduction, while the existence of such conduction in rigid oxides remains unclear. This study discovers 1D liquid-like Li-ion conduction in LiTa2PO8 and its derivatives, enabled by doping strategies, with low activation energy and short mean residence time of Li ions on interstitial sites. The findings provide principles for the future design of improved solid electrolytes without modifications to achieve stable ionic transport.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Physical
Abinaya Sivakumaran, Alfred Junio Samson, Afshana Afroj Bristi, Vishnu Surendran, Shantel Butler, Samuel Reid, Venkataraman Thangadurai
Summary: We report novel composite sodium silicate electrolytes with high ionic conductivity for solid-state sodium-ion batteries (SIBs). These electrolytes offer a viable alternative to lithium-ion batteries (LIBs) with their low cost, abundance of sodium, and high safety.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Electrochemistry
Prathap Iyapazham Vaigunda Suba, Muhammad Shoaib, Oanh Hoang Nguyen, Kunal Karan, Stephen R. Larter, Venkataraman Thangadurai
Summary: Flexible, scalable, and low-cost energy storage solutions are crucial for the widespread adoption of renewable energy and addressing climate change. This paper presents an innovative battery design approach using Bi/BiOCl and V4+/V5+ reaction-based redox couples in a gel-based architecture, offering a promising solution for grid-scale energy storage.
BATTERIES & SUPERCAPS
(2023)
Article
Chemistry, Physical
Mosayeb Naseri, Shirin Amirian, Mehrdad Faraji, Mohammad Abdur Rashid, Maicon Pierre Lourenco, Venkataraman Thangadurai, D. R. Salahub
Summary: Inspired by the successful transfer of freestanding ultrathin films of SrTiO3 and BiFeO3, this study assessed the structural stability and investigated the electronic, optical, and thermoelectric properties of a group of two-dimensional perovskite-type materials called perovskenes. The findings revealed that these materials are wide bandgap semiconductors with potential application in UV shielding. Moreover, they exhibit better electrical and thermal conductivity at high temperatures, enabling efficient power generation in thermoelectric devices.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Article
Electrochemistry
Oanh Hoang Nguyen, Prathap Iyapazham Vaigunda Suba, Muhammad Shoaib, Venkataraman Thangadurai
Summary: In this study, the solubility and electrochemical characteristics of vanadium electrolyte solutions in vanadium redox flow batteries were investigated. The addition of HCl and MSA as additives improved the ionic conductivity, electrochemical performance, and charge transfer resistance. UV/Vis and Raman spectroscopy were used to propose a reaction mechanism responsible for the improved conductivity and kinetics.
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2023)
