Aqueous sodium ion batteries are attractive for large-scale energy storage due to their low cost, intrinsic safety and environmental friendliness [1,2]. A key challenge in designing aqueous batteries is creating electrode pairs that operate within the stable potential window of water, with anode material selection being particularly challenging. Furthermore, good materials for sodium ion cycling are limited [2,3]. TiP2O7 presents a promising anode material due to its lower intercalation/deintercalation potentials, allowing for more optimized use of an aqueous electrolyte’s stability window [1-3]. TiP2O7 is typically reported to exclusively cycle lithium ions, showing no capacity in sodium aqueous electrolytes in cyclic voltammetry tests [3]. One report demonstrated that a low temperature polymorph of TiP2O7 exhibits reversible cycling of sodium ions in an organic electrolyte [4]. In this work, the reversible insertion of sodium ions in TiP2O7 as the anode material in an aqueous battery is demonstrated. Several polymorphs of TiP2O7 are synthesized using a high temperature solid-state route and a low temperature sol gel route. In addition to physical characterization, the materials are electrochemically characterized in an aqueous 1M Na2SO4 electrolyte against Na0.44MnO2 cathode material. While no capacity for sodium ion cycling is reflected in cyclic voltammetry tests of these TiP2O7, all polymorphs exhibited reversible cycling of sodium ions in constant current galvanostatic cycling with potential limitation. To our knowledge, this is the first report of solid-state synthesized TiP2O7 reversibly cycling sodium ions. Specific capacity is found to be positively correlated with both crystallite size and lattice parameter. A full cell rate study with three electrode data in aqueous Na2SO4 electrolyte is presented. Acknowledgments This work is supported by Carnegie Mellon University and Aquion Energy Inc.

Combining high energy mechanical alloying with intimate carbon coating has proven effective in improving electrochemical performance of polyanion-based materials (1, 2). Ball milling with intimate carbon helps to prepare a homogenous mixture of precursors and reduce particle size during following thermal treatment (3, 4). In addition, this combination can decrease the thermal treatment time needed (5). In this study, we demonstrated TiP2O7/graphite prepared by high energy mechanical alloying combined with intimate carbon coating has superior cycling performance in aqueous lithium-ion electrolyte. The TiP2O7/graphite composite material was prepared by an intensive mechanical mixing solid state synthesis method at 700°C. Physical properties were characterized via powder X-ray diffraction, Rietveld refinement, SEM, BET and TGA. Electrochemical performance was evaluated in both a three electrode test setup and two electrode coin cells via cyclic voltammetry and galvanostatic cycling tests. The TiP2O7/Graphite composite demonstrates excellent cycling performance in 1M Li2SO4 when matched with LiMn2O4 as a positive electrode: when cycled at C/2 for 150 cycles, the capacity retention is over 91% with coulombic efficiencies exceeding 99%. The initial discharge capacity obtained at a C/10 rate is 91mAh/g which was about 75% of theoretical capacity 121mAh/g. Reference: 1. W. Wu, A. Mohamed and J. F. Whitacre, Journal of The Electrochemical Society, 160, A497 (2013). 2. W. Wu, J. Yan, A. Wise, A. Rutt and J. F. Whitacre, Journal of The Electrochemical Society, 161, A561 (2014). 3. J.-K. Kim, G. Cheruvally, J.-W. Choi, J.-U. Kim, J.-H. Ahn, G.-B. Cho, K.-W. Kim and H.-J. Ahn, Journal of Power Sources, 166, 211 (2007). 4. J.-K. Kim, J.-W. Choi, G. Cheruvally, J.-U. Kim, J.-H. Ahn, G.-B. Cho, K.-W. Kim and H.-J. Ahn, Materials Letters, 61, 3822 (2007). 5. L.-X. Yuan, Z.-H. Wang, W.-X. Zhang, X.-L. Hu, J.-T. Chen, Y.-H. Huang and J. B. Goodenough, Energy & Environmental Science, 4, 269 (2011). Figure 1

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