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Professor Clare Grey FRS

Room M21


Materials Chemistry: Structure and Function


We use a wide range of techniques, including solid state NMR and diffraction, to investigate local structure and the role that this plays in controlling the physical properties of technologically important, but disordered materials.


Rechargeable Batteries


New batteries are required for transport applications and for storage and load-leveling on the electrical grid. These batteries should be capable of being charged and discharged faster, and should store much more power, than the batteries currently available. This requires the development of new electrode chemistries and an understanding of how these systems function. To this end, we study a variety of different rechargeable batteries including lithium and sodium ion batteries (LIBs and NIBs).  We probe the mechanisms for lithium insertion and extraction by, for example, using 6Li/7Li NMR and investigate the effect of local structure and electronic properties on LIB battery performance. Two types of electrode materials are investigated, those that operate via intercalation reactions, where the structure remains largely intact upon Li insertion, and those that react via conversion reactions where the structures transform completely upon reaction with Li. In the latter reactions, our studies focus on identifying the nano-sized (or amorphous) phases that form on Li reaction, how they are formed and how to improve the reversibilities of these reactions. Studies of intercalation compounds include the effect of cation doping and ordering on the mechanisms by which these materials react.


 



In-situ NMR Studies of Battery and Supercapacitor Function


We have developed NMR methodology to monitor structural changes that occur during the operation of a battery/supercapacitor. These in-situ NMR studies allow us to, for example, capture metastable phases, follow reactions between the electrolyte and the electrode materials and to investigate the effect of rapid charging and cycling of the battery.  For supercapacitors, we can, for example, monitor ions entering or leaving the pores of the highly porous materials that form the electrodes of these devices. 


 


Solid-State Electrolytes for Fuel Cell Membranes


We use NMR to study investigate mechanisms for ionic conduction. By identifying individual crystallographic or interstitial sites in often highly disordered materials, we can determine which sites are responsible for ionic conduction, where the vacancies or interstitial ions are located, and obtain a much deeper understanding of how these materials function as ionic conductors. Current studies focus on perovskite materials, which can act as both oxygen and proton (when hydrated) conductors.


 


Select Recent Publications


"Cycling Li-O-2 batteries via LiOH formation and decomposition", T. Liu, M. Leskes, W.J. Yu, A.J. Moore, L.N. Zhou, P.M. Bayley, G. Kim, C.P. Grey, Science, 350, 530-533 (2015). DOI: 10.1126/science.aac7730


“Capturing metastable structures during high rate cycling of LiFePO4 nanoparticle electrodes”, H. Liu, F. C. Strobridge, O. J. Borkiewicz, K. M. Wiaderek, K. W. Chapman, P. J. Chupas, Clare P. Grey, Science, 344, no 6191 (2014) DOI: 10.1126/science.1252817.  The paper can be downloaded, free of charge, via the following links.  


“On the Cause of the Excess Capacities in Metal Oxide/Fluoride Battery Electrodes” , Y.-Y. Hu, Z. Liu, K. –W. Nam, O. J. Borkiewicz, X. Hua, J. Cheng, M. Dunstan, X. Yu, L.-S. Du, K. W. Chapman, P. J. Chupas, X. Yang, Clare P. Grey, Nature Materials 12, 1130 – 1136 (2013).


“Proton trapping in yttrium-doped barium zirconate”, Y. Yamazaki, F. Blanc, Y. Okuyama, L. Buannic, J.C. Lucio-Vega, C.P. Grey, and S.M. Haile, Nature Materials, 12, 647 – 651 (2013). 


“Density functional theory-based bond pathway decompositions of hyperfine shifts: Equipping solid-state NMR to characterize atomic environments in paramagnetic materials”, D.S. Middlemiss, A.J. Ilott, R.J. Clément, F.C. Strobridge, and C.P. Grey, Chem. Mat., 25, 1723-1734 (2013).


7Li MRI of Li batteries reveals location of microstructural lithium”, S. Chandrashekar, S.M. Trease, H.J. Chang, L.S. Du, C.P. Grey and A. Jerschow, Nature Materials, 11, 311-315, (2012).


"In situ NMR Observation of the Formation of Metallic Lithium Microstructures in Lithium Batteries", R. Bhattacharyya, B. Key, H. Chen, A.S. Best, A.F. Hollenkamp, and C.P. Grey, Nature Materials, 9, 504-510 (2010)


"A study of the lithium conversion mechanism of iron fluoride in a Li ion battery, by using solid state NMR, XRD and PDF analysis studies", N. Yamakawa, M. Jiang, B. Key and C. P. Grey, J. Am. Chem. Soc., 131, 10525-10536 (2009)


"Real-time NMR Investigations of Structural Changes in Silicon Electrodes for Lithium-ion Batteries", B. Key, R. Bhattacharyya, M. Morcrette, V. Seznéc, J.-M. Tarascon and C. P. Grey, J. Am. Chem. Soc., 131, 9239-9249 (2009)


 

Publications

Nanoscale Detection of Intermediate Solid Solutions in Equilibrated LixFePO4 Microcrystals.
BM May, Y-S Yu, MV Holt, FC Strobridge, U Boesenberg, CP Grey, J Cabana
– Nano Lett
(2017)
Identifying the Structural Basis for the Increased Stability of the Solid Electrolyte Interphase Formed on Silicon with the Additive Fluoroethylene Carbonate
Y Jin, N-JH Kneusels, PCMM Magusin, G Kim, E Castillo-Martinez, LE Marbella, RN Kerber, DJ Howe, S Paul, T Liu, CP Grey
– JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2017)
139,
14992
Identifying the Structural Basis for the Increased Stability of the Solid Electrolyte Interphase Formed on Silicon with the Additive Fluoroethylene Carbonate
Y Jin, N-JH Kneusels, PCMM Magusin, G Kim, E Castillo-Martínez, LE Marbella, RN Kerber, DJ Howe, S Paul, T Liu, CP Grey
– Journal of the American Chemical Society
(2017)
139,
14992
Distinguishing faceted oxide nanocrystals with 17O solid-state NMR spectroscopy.
Y Li, X-P Wu, N Jiang, M Lin, L Shen, H Sun, Y Wang, M Wang, X Ke, Z Yu, F Gao, L Dong, X Guo, W Hou, W Ding, X-Q Gong, CP Grey, L Peng
– Nat Commun
(2017)
8,
581
Ion Dynamics and CO<inf>2</inf>Absorption Properties of Nb-, Ta-, and Y-Doped Li<inf>2</inf>ZrO<inf>3</inf>Studied by Solid-State NMR, Thermogravimetry, and First-Principles Calculations
MT Dunstan, H Laeverenz Schlogelhofer, JM Griffin, MS Dyer, MW Gaultois, CY Lau, SA Scott, CP Grey
– Journal of Physical Chemistry C
(2017)
121,
21877
Lithiation Thermodynamics and Kinetics of the TiO
X Hua, Z Liu, MG Fischer, O Borkiewicz, PJ Chupas, KW Chapman, U Steiner, PG Bruce, CP Grey
– Journal of the American Chemical Society
(2017)
139,
13330
Infrared-active optical phonons in LiFePO4 single crystals
TN Stanislavchuk, DS Middlemiss, JS Syzdek, Y Janssen, R Basistyy, AA Sirenko, PG Khalifah, CP Grey, R Kostecki
– Journal of Applied Physics
(2017)
122,
045107
Unraveling the Complex Delithiation and Lithiation Mechanisms of the High Capacity Cathode Material V 6 O 13
W Meng, R Pigliapochi, PM Bayley, O Pecher, MW Gaultois, ID Seymour, HP Liang, W Xu, KM Wiaderek, KW Chapman, CP Grey
– Chemistry of Materials
(2017)
29,
5513
Structural simplicity as a restraint on the structure of amorphous silicon
MJ Cliffe, AP Bartók, RN Kerber, CP Grey, G Csányi, AL Goodwin
– Physical Review B - Condensed Matter and Materials Physics
(2017)
95,
224108
Effects of Antisite Defects on Li Diffusion in LiFePO 4 Revealed by Li Isotope Exchange
H Liu, MJ Choe, RA Enrique, B Orvañanos, L Zhou, T Liu, K Thornton, CP Grey
– Journal of Physical Chemistry C
(2017)
121,
12025
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Research Group

Research Interest Groups

Telephone number

01223 336509

Email address

cpg27@cam.ac.uk