Paper
Journal of Materials Chemistry A
of BTMSDB (Fig. 1) as a redox shuttle is the combination of the
superb performance and the ease of tracing the products of its
9 J. Chen, C. Buhrmester and J. R. Dahn, Electrochem. Solid-
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redox potential at 4.1 V vs. Li/Li+, which is suitable for over-
146, 1256–1261.
charge protection of LiFePO4 cathode. We demonstrate that 11 C. Buhrmester, J. Chen, L. Moshurchak, J. Jiang, R. L. Wang
BTMSDB provides overcharge protection to the LiFePO4/MCMB and J. R. Dahn, J. Electrochem. Soc., 2005, 152, A2390–A2399.
coin cells for 81 cycles, without the contaminant discharge 12 L. M. Moshurchak, C. Buhrmester and J. R. Dahn, J.
capacity loss. By the current standards, this is a remarkable Electrochem. Soc., 2005, 152, A1279–A1282.
performance. Still, the direct comparison of BTMSDB and DDB 13 Z. Zhang, L. Zhang, J. A. Schlueter, P. C. Redfern, L. Curtiss
under the same conditions indicates that DDB provides 3X and K. Amine, J. Power Sources, 2010, 195, 4957–4962.
longer overcharge protection than BTMSDB despite the striking 14 L. Zhang, Z. Zhang, P. C. Redfern, L. A. Curtiss and K. Amine,
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of BTMSDB radical cation that eliminates the protective trime- 15 L. M. Moshurchak, W. M. Lamanna, M. Bulinski, R. L. Wang,
thylsilyl groups. Both the radical cation and the products of
decomposition were directly observed. This reaction can
R. R. Garsuch, J. Jiang, D. Magnuson, M. Triemert and
J. R. Dahn, J. Electrochem. Soc., 2009, 156, A309–A312.
become more facile on the surface of the anode, where it is 16 W. Weng, Y. Tao, Z. Zhang, P. C. Redfern, L. A. Curtiss and
facilitated by alkylcarbonate bases generated via the electrolyte K. Amine, J. Electrochem. Soc., 2013, 160, A1711–A1715.
breakdown during SEI formation. Our study suggests that the 17 W. Weng, Z. Zhang, P. C. Redfern, L. A. Curtiss and
improvement strategy for the redox shuttles should be advanced K. Amine, J. Power Sources, 2011, 196, 1530–1536.
in the full awareness of such detrimental side reactions, as their 18 J. Huang, L. Cheng, R. S. Assary, P. Wang, Z. Xue,
occurrence undermines the long term performance of the pro-
tected LIBs. Our study also provides a still rare example of a
A. K. Burrell, L. A. Curtiss and L. Zhang, Adv. Energy
Mater., 2014, DOI: 10.1002/aenm.201401782.
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has been traced to a specic chemical cause. The generality of 20 L. Zhang, J. Huang, K. Youssef, P. C. Redfern, L. A. Curtiss,
this mechanistic insight needs to be further explored.
K. Amine and Z. Zhang, J. Electrochem. Soc., 2014, 161,
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21 I. A. Shkrob, Y. Zhu, T. W. Marin and D. P. Abraham, J. Phys.
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Acknowledgements
This work was supported by the U. S. Department of Energy,
Office of Science, Office of Basic Energy Sciences, Division of
Chemical Sciences, Geosciences and Biosciences under contract
No. DE-AC02-06CH11357; it was also supported as part of the
Joint Center for Energy Storage Research (JCESR), an Energy
Innovation Hub funded by the U.S. Department of Energy,
Office of Science, Basic Energy Sciences.
22 Z. Chen, Y. Ren, A. N. Jansen, C.-k. Lin, W. Weng and
K. Amine, Nat. Commun., 2013, 4, 1513.
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