Neutron diffraction evidence of the 3-dimensional structure of Ba2MnTeO6 and misidentification of the triangular layers within the face-centred cubic lattice Otto H. J. Mustonen, Charlotte E. Pughe, Helen C. Walker, Heather M. Mutch, Gavin B. G. Stenning, Fiona C. Coomer, Edmund J. Cussen Scientific Reports, 2025 Ba 2 MnTeO 6 was first characterised using X-ray diffraction and reported to show a small distortion 1 from the idealised cubic perovskite which displays face-centred cubic arrangement of Mn 2+ . A recent report has asserted that this leads to a layered configuration of Mn 2+ that serves as an example of a triangular lattice, i.e. a 2D structure containing discreet layers 2 . Here we show how neutron scattering gives great confidence in establishing the crystal structure being an undistorted cubic phase and how this can be mis-assigned as a triangular layered structure. This has profound implications for the understanding of the magnetic properties of the system.
Impact of Secondary Phases on the Electrochemical Performance of Li6.4La3Zr1.4Ta0.6O12Garnet Solid Electrolytes through Grain Boundary Engineering Sebastian J. Altus, Innes McClelland, Stephen W. T. Price, Julian S. Dean, Olof Gutowski, Hany El-Shinawi, Samuel G. Booth, Serena A. Cussen, Edmund J. Cussen Chemistry of Materials, 2025 High Resolution Image Download MS PowerPoint Slide Fast-conducting Li 7 La 3 Zr 2 O 12 (LLZO)-type garnet solid-state electrolytes face the considerable challenge of deleterious metallic dendrite formation during operation, with suggestions that this behavior may be linked to electronic conductivity effects. To examine in detail how electronic conductivity effects at the grain boundary can affect the electronic properties of cubic LLZO-type garnets, we report a family of Ta-doped LLZO garnets with a Mn-containing secondary phase, which is spatially selective toward the grain boundaries. The inclusion of this targeted grain boundary phase, whose composition is revealed as La 4 LiMnO 8, alters the ionic and local electronic conductivities of the final composite, resulting in improvements in the observed critical current densities. We find that the critical current density before short-circuiting is highly dependent on this secondary phase, increasing with increasing content up to a maximum of 0.30 mA cm –2 . X-ray absorption spectroscopy and X-ray diffraction computed tomography studies complement these findings, revealing that a darkening of the composite electrolyte post cycling is accompanied by Mn reduction and a reduction in the phase fraction of La 4 LiMnO 8 . Guided by electrochemical characterization and finite element analysis, we highlight the critical role of grain boundaries in bulk garnet degradation pathways and evidence how spatially targeted secondary phases, introduced during initial synthesis, can impact electrochemical performance in LLZO-type garnets.
Structure, Spin Correlations, and Magnetism of the S = 1/2 Square-Lattice Antiferromagnet Sr2CuTe1-xWxO6 (0 ≤ x ≤ 1) Otto H. J. Mustonen, Ellen Fogh, Joseph A. M. Paddison, Lucile Mangin-Thro, Thomas Hansen, Helen Y. Playford, Maria Diaz-Lopez, Peter Babkevich, Sami Vasala, Maarit Karppinen, Edmund J. Cussen, Henrik M. Ro̷nnow, Helen C. Walker Chemistry of Materials, 2024 Quantum spin liquids are highly entangled magnetic states with exotic properties. The S = 1/2 square-lattice Heisenberg model is one of the foundational models in frustrated magnetism with a predicted, but never observed, quantum spin liquid state. Isostructural double perovskites Sr2CuTeO6 and Sr2CuWO6 are physical realizations of this model but have distinctly different types of magnetic order and interactions due to a d10/d0 effect. Long-range magnetic order is suppressed in the solid solution Sr2CuTe1–xWxO6 in a wide region of x = 0.05–0.6, where the ground state has been proposed to be a disorder-induced spin liquid. Here, we present a comprehensive neutron scattering study of this system. We show using polarized neutron scattering that the spin liquid-like x = 0.2 and x = 0.5 samples have distinctly different local spin correlations, which suggests that they have different ground states. Low-temperature neutron diffraction measurements of the magnetically ordered W-rich samples reveal magnetic phase separation, which suggests that the previously ignored interlayer coupling between the square planes plays a role in the suppression of magnetic order at x ≈ 0.6. These results highlight the complex magnetism of Sr2CuTe1–xWxO6 and hint at a new quantum critical point between 0.2 < x < 0.4.
Liquid-Phase Approach to Glass-Microfiber-Reinforced Sulfide Solid Electrolytes for All-Solid-State Batteries Hany El-Shinawi, Ed Darnbrough, Johann Perera, Innes McClelland, David E. J. Armstrong, Edmund J. Cussen, Serena A. Cussen ACS Applied Materials and Interfaces, 2023 Deformable, fast-ion conducting sulfides enable the construction of bulk-type solid-state batteries that can compete with current Li-ion batteries in terms of energy density and scalability. One approach to optimizing the energy density of these cells is to minimize the size of the electrolyte layer by integrating the solid electrolyte in thin membranes. However, additive-free thin membranes, as well as many membranes based on preprepared scaffolds, are difficult to prepare or integrate in solid cells on a large scale. Here, we propose a scalable solution-based approach to produce bulk-type glass-microfiber-reinforced composites that restore the deformability of sulfide electrolytes and can easily be shaped into thin membranes by cold pressing. This approach supports both the ease of preparation and enhancement of the energy density of sulfide-based solid-state batteries.
Direct Observation of Dynamic Lithium Diffusion Behavior in Nickel-Rich, LiNi0.8Mn0.1Co0.1O2 (NMC811) Cathodes Using Operando Muon Spectroscopy Innes McClelland, Samuel G. Booth, Nirmalesh N. Anthonisamy, Laurence A. Middlemiss, Gabriel E. Pérez, Edmund J. Cussen, Peter J. Baker, Serena A. Cussen Chemistry of Materials, 2023 Ni-rich layered oxide cathode materials such as LiNi0.8Mn0.1Co0.1O2 (NMC811) are widely tipped as the next-generation cathodes for lithium-ion batteries. The NMC class offers high capacities but suffers an irreversible first cycle capacity loss, a result of slow Li+ diffusion kinetics at a low state of charge. Understanding the origin of these kinetic hindrances to Li+ mobility inside the cathode is vital to negate the first cycle capacity loss in future materials design. Here, we report on the development of operando muon spectroscopy (μSR) to probe the Å-length scale Li+ ion diffusion in NMC811 during its first cycle and how this can be compared to electrochemical impedance spectroscopy (EIS) and the galvanostatic intermittent titration technique (GITT). Volume-averaged muon implantation enables measurements that are largely unaffected by interface/surface effects, thus providing a specific characterization of the fundamental bulk properties to complement surface-dominated electrochemical methods. First cycle measurements show that the bulk Li+ mobility is less affected than the surface Li+ mobility at full depth of discharge, indicating that sluggish surface diffusion is the likely cause of first cycle irreversible capacity loss. Additionally, we demonstrate that trends in the nuclear field distribution width of the implanted muons during cycling correlate with those observed in differential capacity, suggesting the sensitivity of this μSR parameter to structural changes during cycling.
Perspectives for next generation lithium-ion battery cathode materials Samuel G. Booth, Alisyn J. Nedoma, Nirmalesh N. Anthonisamy, Peter J. Baker, Rebecca Boston, Hugo Bronstein, Simon J. Clarke, Edmund J. Cussen, Venkateswarlu Daramalla, Michael De Volder, Siân E. Dutton, Viktoria Falkowski, Norman A. Fleck, Harry S. Geddes, Naresh Gollapally, Andrew L. Goodwin, John M. Griffin, Abby R. Haworth, Michael A. Hayward, Stephen Hull, Beverley J. Inkson, Beth J. Johnston, Ziheng Lu, Judith L. MacManus-Driscoll, Xabier Martínez De Irujo Labalde, Innes McClelland, Kirstie McCombie, Beth Murdock, Debasis Nayak, Seungkyu Park, Gabriel E. Pérez, Chris J. Pickard, Louis F. J. Piper, Helen Y. Playford, Simon Price, David O. Scanlon, Joe C. Stallard, Nuria Tapia-Ruiz, Anthony R. West, Laura Wheatcroft, Megan Wilson, Li Zhang, Xuan Zhi, Bonan Zhu, Serena A. Cussen APL Materials, 2021
2021 roadmap for sodium-ion batteries Nuria Tapia-Ruiz, A Robert Armstrong, Hande Alptekin, Marco A Amores, Heather Au, Jerry Barker, Rebecca Boston, William R Brant, Jake M Brittain, Yue Chen, Manish Chhowalla, Yong-Seok Choi, Sara I R Costa, Maria Crespo Ribadeneyra, Serena A Cussen, Edmund J Cussen, William I F David, Aamod V Desai, Stewart A M Dickson, Emmanuel I Eweka, Juan D Forero-Saboya, Clare P Grey, John M Griffin, Peter Gross, Xiao Hua, John T S Irvine, Patrik Johansson, Martin O Jones, Martin Karlsmo, Emma Kendrick, Eunjeong Kim, Oleg V Kolosov, Zhuangnan Li, Stijn F L Mertens, Ronnie Mogensen, Laure Monconduit, Russell E Morris, Andrew J Naylor, Shahin Nikman, Christopher A O’Keefe, Darren M C Ould, R G Palgrave, Philippe Poizot, Alexandre Ponrouch, Stéven Renault, Emily M Reynolds, Ashish Rudola, Ruth Sayers, David O Scanlon, S Sen, Valerie R Seymour, Begoña Silván, Moulay Tahar Sougrati, Lorenzo Stievano, Grant S Stone, Chris I Thomas, Maria-Magdalena Titirici, Jincheng Tong, Thomas J Wood, Dominic S Wright, Reza Younesi Jphys Energy, 2021
2020 roadmap on solid-state batteries Mauro Pasta, David Armstrong, Zachary L. Brown, Junfu Bu, Martin R Castell, Peiyu Chen, Alan Cocks, Serena A Corr, Edmund J Cussen, Ed Darnbrough, Vikram Deshpande, Christopher Doerrer, Matthew S Dyer, Hany El-Shinawi, Norman Fleck, Patrick Grant, Georgina L. Gregory, Chris Grovenor, Laurence J Hardwick, John T S Irvine, Hyeon Jeong Lee, Guanchen Li, Emanuela Liberti, Innes McClelland, Charles Monroe, Peter D Nellist, Paul R Shearing, Elvis Shoko, Weixin Song, Dominic Spencer Jolly, Christopher I Thomas, Stephen J Turrell, Mihkel Vestli, Charlotte K. Williams, Yundong Zhou, Peter G Bruce Jphys Energy, 2020
