Article
Electrochemistry
Xuebao Li, Chao Zhao, Jingjing He, Yong Li, Ying Wang, Luzhi Liu, Jiemeng Huang, Chenchen Li, Ding Wang, Jianguo Duan, Yingjie Zhang
Summary: Nickel-rich layered oxides are promising cathode materials for lithium-ion batteries, but their practical application is hindered by voltage attenuation during charging and discharging. This study developed a strategy to address this issue by removing lithium residues and forming a boron-containing lithium compound coating, leading to improved cycle stability and electrochemical performance.
ELECTROCHIMICA ACTA
(2022)
Article
Chemistry, Physical
Ryan Brow, Anthony Donakowski, Alex Mesnier, Drew J. Pereira, K. Xerxes Steirer, Shriram Santhanagopalan, Arumugam Manthiram
Summary: Nickel-rich cathode materials, despite being a promising choice for electric vehicles, face challenges related to long-term cycle life retention and air stability. This study investigates the use of surface treatments, specifically the coating of LiNi0.9Mn0.05Al0.05O2 cathode materials with lithium phosphate, to improve their performance. The results show that low concentration phosphoric acid coating leads to delayed voltage decay and enhanced discharge capacity during high-voltage cycling.
ACS APPLIED ENERGY MATERIALS
(2022)
Article
Engineering, Environmental
Hang Dong, Miao Xie, Mingzhi Cai, Hao Liu, Zhuang Zhang, Bin Ye, Pei Zhao, Wujie Dong, Fuqiang Huang
Summary: In this study, a facile fluorine glaze modification method is proposed to improve the performance of nickel-rich layered cathode, preventing grain cracking and surface collapse, and promoting lithium-ion transport.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Yongkang Han, Yingchuan Zhang, Yike Lei, Dongdong Xiao, Jie Ni, Weiguang Lin, Pingwen Ming, Cunman Zhang, Qiangfeng Xiao
Summary: To address the issues of Ni-rich NCM, Al (CF3SO3)(3) was proposed as a solid electrolyte additive to regulate the CEI in single-crystalline NCM811. The facile oxidation of CF3SO3- and subsequent reactions with reactive species from NCM811 and electrolyte lead to the formation of a robust sandwich CEI film containing sulfur and aluminum species. This CEI film not only prevents electrolyte decomposition but also alleviates the formation of inactive rock-salt phase on NCM811 surface, resulting in a high-capacity retention of 91.5% after 200 cycles under 0.5 C.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Engineering, Multidisciplinary
You Jin Kim, Ga-Yoon Kim, Hyun-Soo Kim, Suji Kim, Boran Kim, Yoo Jung Choi, Jaekook Kim, Jinsoo Kim, Won-Hee Ryu
Summary: The introduction of black ZrO2-x spheres improves the electrical conductivity and stability of Ni-rich cathodes. It effectively suppresses gas evolution and enhances the capacity and surface protection of the cathode.
COMPOSITES PART B-ENGINEERING
(2022)
Article
Electrochemistry
Lukman Noerochim, Suwarno Suwarno, Nurul Hayati Idris, Hermawan K. Dipojono
Summary: The exponential growth in production of electric vehicles has led to an increased demand for low-cost, high-performance lithium-ion batteries. However, concerns over the availability of cobalt, a high-cost and rare material used in high-nickel cathodes, may impact the price due to supply constraints. Developing cobalt-free high-nickel cathode materials, such as LiNi1-x-yMnxAlyO2, is necessary to address the reliance on cobalt and its high cost.
Article
Chemistry, Physical
Tianpeng Jiao, Gaopan Liu, Lin Huang, Yue Zou, Xiaozhen Zhang, Jianming Zheng, Yong Yang
Summary: By introducing the BVSM electrolyte additive, the cycling stability and rate capability of the NCM90 cathode have been successfully improved, leading to the formation of a more reliable CEI film that reduces interfacial side reactions and enhances electrode kinetics.
JOURNAL OF POWER SOURCES
(2022)
Article
Chemistry, Physical
Jing Liu, Shan Gao, Zheng Si, Baozhao Shi, Huimin Li, Jinli Zhang, Wei Li
Summary: The addition of a lanthanum oxyfluoride (LaOF) coating layer on the cathode material improves the electrochemical performance and cycling stability of lithium-ion batteries.
APPLIED SURFACE SCIENCE
(2022)
Article
Chemistry, Physical
Tianpeng Jiao, Gaopan Liu, Yue Zou, Xuerui Yang, Xiaozhen Zhang, Ang Fu, Jianming Zheng, Yong Yang
Summary: The research reveals that a stable CEI layer formed on the LiNi0.9Co0.05Mn0.05O2 cathode material through the addition of TMSFS multifunctional additive can significantly improve the cycling performance and electrochemical performance of lithium-ion batteries.
JOURNAL OF POWER SOURCES
(2021)
Article
Chemistry, Physical
Luozeng Zhou, Siyi Qian, Cheng Yang, Tingting Han, Yuanzhe Song, Yuzhuo Jiang, Huahui Zhang, Jianqin Zhang, Linsen Li, Jie Liu, Tao Qian
Summary: This study reports on the effective synergistic effect of a BTFC and SN electrolyte in suppressing TM nickel ion dissolution in a nickel-rich lithium metal battery by building a reliable and protective electrode/electrolyte interface. The electrolyte manipulation strategy successfully improves the battery's cycling stability and capacity retention.
ACS APPLIED ENERGY MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Yu-Jie Guo, Chao-Hui Zhang, Sen Xin, Ji-Lei Shi, Wen-Peng Wang, Min Fan, Yu-Xin Chang, Wei-Huan He, Enhui Wang, Yu-Gang Zou, Xin'an Yang, Fanqi Meng, Yu-Ying Zhang, Zhou-Quan Lei, Ya-Xia Yin, Yu-Guo Guo
Summary: Chemical modification of electrode materials by heteroatom dopants is crucial for improving storage performance in rechargeable batteries. This study investigates the competitive doping chemistry of boron and aluminum in nickel-rich cathode materials. The atomic radii difference between B and Al leads to different spatial configurations of bonding with lattice oxygen. The findings provide insights into stabilizing the structural evolution and surface chemistry of the cathode.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Lihan Zhang, Shuwei Wang, Liang Zhu, Lunhua He, Shun He, Xianying Qin, Chenglong Zhao, Feiyu Kang, Baohua Li
Summary: This research presents a sustainable synthesis route to improve the cycling stability, rate capability, and humidity tolerance of high-energy nickel-rich layered oxide cathodes through uniform surface/interface-coating. The formation of highly dense and resistive structures effectively protects the cathode particles from degradation and side reactions with electrolytes.
Article
Chemistry, Physical
Yujing Bi, Yaobin Xu, Ran Yi, Dianying Liu, Peng Zuo, Jiangtao Hu, Qiuyan Li, Jing Wu, Chongmin Wang, Sha Tan, Enyuan Hu, Jingnan Li, Rebecca O'Toole, Liu Luo, Xiaoguang Hao, Subramanian Venkatachalam, Job Rijssenbeek, Jie Xiao
Summary: A new nanoscale phase separation process has been discovered to promote the growth and segregation of single crystal LiNi0.8Mn0.1Co0.1O2 (NMC811). This process occurs directly during high-temperature calcination without significant agglomeration. The conversion of transition metal hydroxide precursors into transition metal oxide intermediates before reacting them with lithium salt is the key factor.
ENERGY STORAGE MATERIALS
(2023)
Review
Chemistry, Physical
Lili Lin, Lihan Zhang, Shuwei Wang, Feiyu Kang, Baohua Li
Summary: Polycrystalline nickel-rich layered transition metal oxides (NRLOs) are potential cathodes for commercial lithium-ion batteries, especially in the electric vehicle market. However, they suffer from structural degradation and severe electrochemical performance deterioration. This review focuses on the structure-activity relationship of NRLOs and discusses recent progress in different microstructures, synthesis strategies, and future perspectives on micro- and nano-structure modifications.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Physical
Jianxiong Lin, Hui Guo, Kun Sun, Liang Fang
Summary: In this study, a simple dry-coating method was used to modify the nickel (Ni)-rich layered oxide cathode in lithium batteries with a dual conductive compound of dot-like Nb12WO33 and film-like lithium boron oxide (Li-B-O). The coating improved the initial efficiency and cycle stability by segregating the cathode from the electrolyte, while the Nb12WO33 provided a fast Li-ion transition channel, enhancing the rate performance of the Ni-rich oxide layer. The modified cathode exhibited significantly improved electrochemical performance.
JOURNAL OF ALLOYS AND COMPOUNDS
(2023)
Article
Chemistry, Inorganic & Nuclear
Darren M. Driscoll, Richard C. Shiery, Mahalingam Balasubramanian, John L. Fulton, David C. Cantu
Summary: Temperature affects the structures of lanthanide complexes, but the dynamic disorder of Ln(3+) ions in liquid water makes temperature-induced changes not clearly manifest. The first coordination sphere of the Lu3+ ion at 25 and 90 degrees C shows very similar structures.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
James R. Neilson, Allyson M. Fry-Petit, Natalia Drichko, Matthew B. Stone, Anna Llobet, Mahalingam Balasubramanian, Matthew R. Suchomel, Tyrel M. McQueen
Summary: Here, we provide spectroscopic evidence of spontaneous formation of metal-metal bonds above T similar to 50 K in the layered metal KNi2Se2. These bonds form zig-zag chains that lower the local symmetry from tetragonal to monoclinic. Energy-resolved pair distribution function measurements exclude a pure phonon origin of our observations, and instead imply the existence of extra, slowly fluctuating, Ni-Ni bonds above T=50 K. Density functional theory calculations support this lower symmetry configuration as an instability of tetragonal KNi2Se2. We thus demonstrate that the phenomena of emphansis is not limited to local electric dipole formation, but can also be driven by the formation of metal-metal bonds.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2022)
Article
Chemistry, Physical
Noel J. Leon, Xiaowei Xie, Mengxi Yang, Darren M. Driscoll, Justin G. Connell, Sanghyeon Kim, Trevor Seguin, John T. Vaughey, Mahalingam Balasubramanian, Kristin A. Persson, Chen Liao
Summary: This study reports a non-aqueous electrolyte capable of plating and stripping calcium at room temperature, and demonstrates stable plating and stripping of high-voltage cathode materials. X-ray experiments were used to investigate the solvation structure around calcium and possible decomposition pathways of the TPFA anion.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Physical
Soumen Ghosh, Harsh Agarwal, Mirza Galib, Ba Tran, Mahalingam Balasubramanian, Nirala Singh, John L. Fulton, Niranjan Govind
Summary: The solvation structure of transition metal ions is crucial for various fields such as geochemistry, biochemistry, energy storage, and environmental chemistry. This study investigates the solvation structure of hydrated first-row transition metal ions with different d orbital occupancy. The X-ray absorption pre-edge and near-edge spectra are used to analyze the coordination environment and lowest-energy ligand field d-d transitions. Time-dependent DFT and restricted active space second-order perturbation theory are employed for accurate calculations.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Nanoscience & Nanotechnology
Marm Dixit, Nitin Muralidharan, Anand Parejiya, Charl Jafta, Zhijia Du, Sabine M. Neumayer, Rachid Essehli, Ruhul Amin, Mahalingam Balasubramanian, Ilias Belharouak
Summary: This study reports the interfacial properties of thiophosphate and argyrodite solid electrolytes, and showcases the differences in surface morphology and adhesion using atomic force microscopy. The physical, chemical, and structural characterizations of the materials highlight the differences in surface morphology, chemical makeup, and distribution of inorganic phases between the two types of solid electrolytes.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Inorganic & Nuclear
Darren M. Driscoll, Richard C. Shiery, Nicolas D'Annunzio, Daria Boglaienko, Mahalingam Balasubramanian, Tatiana G. Levitskaia, Carolyn I. . Pearce, Niranjan Govind, David C. Cantu, John L. Fulton
Summary: The aqueous hydration structure of the Bi3+ ion is influenced by the water stabilization of a lone-pair electronic state involving the mixed 6s and 6p orbitals. The first-solvent water shell exhibits anomalous features in the EXAFS spectra, indicating its highly asymmetric nature. The distinct multimodal distribution of water molecules in the first shell, separated by about 0.2 angstrom, is stabilized by multiple waters localized near the lone-pair anti-bonding site.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Jian Zheng, Laura Loebbert, Saumil Chheda, Navneet Khetrapal, Julian Schmid, Carlo Alberto Gaggioli, Benjamin Yeh, Ricardo Bermejo-Deval, Radha Kishan Motkuri, Mahalingam Balasubramanian, John L. Fulton, Oliver Y. Gutierrez, J. Ilja Siepmann, Matthew Neurock, Laura Gagliardi, Johannes A. Lercher
Summary: Homotopic sites are ideal for mechanistic studies and optimal control of catalytic transformations. Nickel cations in different environments show different selectivity in the reaction of 1-butene, and the reaction mechanism follows the Cossee-Arlman mechanism.
JOURNAL OF CATALYSIS
(2022)
Article
Multidisciplinary Sciences
Quanquan Pang, Jiashen Meng, Saransh Gupta, Xufeng Hong, Chun Yuen Kwok, Ji Zhao, Yingxia Jin, Like Xu, Ozlem Karahan, Ziqi Wang, Spencer Toll, Liqiang Mai, Linda F. Nazar, Mahalingam Balasubramanian, Badri Narayanan, Donald R. Sadoway
Summary: We have developed a bidirectional, rapidly charging aluminium-chalcogen battery using a molten-salt electrolyte and a positive elemental-chalcogen electrode. This battery offers high charging rates, stability during cycling, low cost, recyclability, and fire resistance.
Review
Chemistry, Physical
Marm Dixit, Chad Beamer, Ruhul Amin, James Shipley, Richard Eklund, Nitin Muralidharan, Lisa Lindqvist, Anton Fritz, Rachid Essehli, Mahalingam Balasubramanian, Ilias Belharouak
Summary: Scalable processing and integration of solid-state battery (SSB) components is crucial for practical deployment of these systems. Isostatic pressing (ISP) is highlighted as a versatile processing platform for large-scale production of solid electrolyte materials. Its development has facilitated SSB research and provided key perspectives and challenges.
ACS ENERGY LETTERS
(2022)
Article
Chemistry, Physical
Jianping Huang, Bin Ouyang, Yaqian Zhang, Liang Yin, Deok-Hwang Kwon, Zijian Cai, Zhengyan Lun, Guobo Zeng, Mahalingam Balasubramanian, Gerbrand Ceder
Summary: Lithium-rich cathodes have high energy densities, but voltage hysteresis limits their practical implementation. This study shows that voltage hysteresis is related to collective migration of metal ions, and introducing partial disorder can create high-capacity reversible cathodes.
Article
Chemistry, Physical
Liliang Huang, Peichen Zhong, Yang Ha, Zijian Cai, Young-Woon Byeon, Tzu-Yang Huang, Yingzhi Sun, Fengyu Xie, Han-Ming Hau, Haegyeom Kim, Mahalingam Balasubramanian, Bryan D. McCloskey, Wanli Yang, Gerbrand Ceder
Summary: This study introduces a strategy of partial Li deficiency engineering to optimize the electrochemical performance of Li-excess disordered rocksalts cathodes. The introduction of cation vacancies during synthesis improves the discharge capacity and rate performance, but more aggressive vacancy doping impairs performance.
ADVANCED ENERGY MATERIALS
(2022)
Review
Electrochemistry
Arturo Gutierrez, Deepti Tewari, Jiajun Chen, Venkat Srinivasan, Mahalingam Balasubramanian, Jason R. Croy
Summary: Broadening the portfolio of cathode active materials for Li-ion battery applications is of great importance in response to concerns over supply chains, sustainability, and security. Manganese-based cathodes, especially those utilizing complex local structures and/or over-lithiated compositions, are particularly interesting. This article discusses the challenges associated with the development of these cathodes and provides considerations for future development at both the atomic-scale and electrode level.
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Mengya Li, Marm Dixit, Rachid Essehli, Charl J. J. Jafta, Ruhul Amin, Mahalingam Balasubramanian, Ilias Belharouak
Summary: Seawater batteries (SWBs) have attracted significant interest in the field of electrochemical energy storage due to their low cost, abundance, and potential for long-duration energy storage. However, their practical application is hindered by poor electrochemical performance related to inadequate interfaces of the solid electrolyte (SE), as well as structural and chemical instabilities and slow ionic transport properties. This study focuses on improving the performance of a surrogate SWB by introducing tailored dopants into the Na3Zr2Si2PO12 (NZSP) solid electrolyte membrane and observing the resulting changes in surface chemistry, local structure, ionic conductivity, and critical current density. The doped NZSP exhibits a more densely packed pellet with a uniformly distributed porous structure, demonstrating enhanced cycling stability and reversible capacities based on different sodium storage mechanisms.
Article
Chemistry, Physical
Jianping Huang, Peichen Zhong, Yang Ha, Zhengyan Lun, Yaosen Tian, Mahalingam Balasubramanian, Wanli Yang, Gerbrand Ceder
Summary: Substituting the labile oxygen with a vacancy in cation-disordered Li-rich rocksalt materials is an effective strategy to inhibit oxygen oxidation, leading to improved capacity and voltage retention in lithium-ion batteries.
Article
Chemistry, Multidisciplinary
Nirala Singh, Cailin A. Buchanan, Dylan Herrera, Mahalingam Balasubramanian, Bryan R. Goldsmith
Summary: In this study, the structures and charge transfer (CT) mechanism of Ce3+ and Ce4+ ions in sulfuric acid were determined through experimental and computational methods. It was found that Ce3+ is coordinated by nine water molecules, while Ce4+ forms complexes with water and bisulfate ions. The kinetics of the Ce3+/Ce4+ redox couple were found to be independent of the electrode, indicating outer-sphere electron-transfer behavior. A two-step mechanism was proposed, in which Ce4+ exchanges bisulfate ions with water in a chemical step, followed by a rate-determining electron transfer step.