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Department of Chemistry

 

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

Fluorine-free water-in-ionomer electrolytes for sustainable lithium-ion batteries
X He, B Yan, X Zhang, Z Liu, D Bresser, J Wang, R Wang, X Cao, Y Su, H Jia, CP Grey, H Frielinghaus, DG Truhlar, M Winter, J Li, E Paillard
– Nature Communications
(2018)
9,
5320
The Role of Ionic Liquid Breakdown in the Electrochemical Metallization of VO
MA Hope, KJ Griffith, B Cui, F Gao, SE Dutton, SSP Parkin, CP Grey
– Journal of the American Chemical Society
(2018)
140,
16685
Three-dimensional localization of nanoscale battery reactions using soft X-ray tomography.
Y-S Yu, M Farmand, C Kim, Y Liu, CP Grey, FC Strobridge, T Tyliszczak, R Celestre, P Denes, J Joseph, H Krishnan, FRNC Maia, ALD Kilcoyne, S Marchesini, TPC Leite, T Warwick, H Padmore, J Cabana, DA Shapiro
– Nature Communications
(2018)
9,
921
Importance of Incorporating Explicit 3D-Resolved Electrode Mesostructures in Li-O 2 Battery Models
A Torayev, PCMM Magusin, CP Grey, C Merlet, AA Franco
– ACS Applied Energy Materials
(2018)
1,
6433
Correction: Synthesis of Ca(PF6)2, formed via nitrosonium oxidation of calcium
EN Keyzer, PD Matthews, Z Liu, AD Bond, CP Grey, DS Wright
– Chemical communications (Cambridge, England)
(2018)
54,
12271
Interface Instability in LiFePO 4 -Li 3+ x P 1- x Si x O 4 All-Solid-State Batteries
MF Groh, MJ Sullivan, MW Gaultois, O Pecher, KJ Griffith, CP Grey
– Chemistry of Materials
(2018)
30,
5886
The use of strontium ferrite in chemical looping systems
E Marek, W Hu, M Gaultois, CP Grey, SA Scott
– Applied Energy
(2018)
223,
369
Electrochemical Performance of Nanosized Disordered LiVOPO 4
Y Shi, H Zhou, ID Seymour, S Britto, J Rana, LW Wangoh, Y Huang, Q Yin, PJ Reeves, M Zuba, Y Chung, F Omenya, NA Chernova, G Zhou, LFJ Piper, CP Grey, MS Whittingham
– ACS Omega
(2018)
3,
7310
Niobium Tungsten Oxides for High-rate Lithium-ion Charge Storage
KJ Griffith, KM Wiaderek, G Cibin, LE Marbella, CP Grey
– Nature
(2018)
559,
556
Study of Defect Chemistry in the System La2–xSrxNiO4+δ by 17O Solid-State NMR Spectroscopy and Ni K-Edge XANES
DM Halat, MT Dunstan, MW Gaultois, S Britto, CP Grey
– Chemistry of Materials
(2018)
30,
4556
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Research Group

Research Interest Groups

Telephone number

01223 336509

Email address

cpg27@cam.ac.uk