An All-Solid State Nasicon Sodium Battery Operating at 200°C
Authors: Lalère Fabien , Leriche Jean-Bernard , Courty Matthieu , Boulineau Sylvain , Viallet Virginie , Masquelier Christian , Seznec Vincent 
Published: February 2020

Na-ion batteries have attracted recent interest and start now to be counted as viable alternatives vs. Li-ion technologies for specific applications. Indeed, recent works on phosphate-based Na-containing positive electrodes such as Na3V2(PO4)3
1 and Na3V2(PO4)2F3
2 have demonstrated excellent performances and can be considered as a new step on the way of sodium-ion technology development. However, like for the Li-ion technology, safety issues related to the use of flammable liquid electrolytes remain, especially due to the high reactivity of sodium with moisture and oxygen. All-solid state batteries, which use non-flammable solid electrolytes instead of organic liquid ones, have been proposed as strong candidates for alternative energy storage devices 3-5.

Following a recent approach developed for Li-ion all-solid state batteries6,7, we were able to assemble a monolithic all-solid state Na-ion battery using NASICON-type electrodes and electrolyte in a single 10’ step using the spark plasma sintering technique at 900°C (see Fig. 1). Na3V2(PO4)3 was used as both positive (V4+/V3+) and negative (V3+/V2+) electrodes while Na3Zr2Si2PO12 was used as the solid electrolyte. Both compositions present order-disorder phase transitions and present decent ionic conductivities of 1.5 x10-3 S cm-1 and 1.9 x10-4 S cm-1 at 200°C for Na3Zr2Si2PO12 and Na3V2(PO4)3, respectively.

Fig. 1: (top) Photo of the battery and (down) SEM backscattered electrons of the cross-section of the battery.

Thanks to a new experimental set-up, we report for the first time the electrochemical characteristics of an all-solid state Na-ion battery at temperatures as high as 200°C8. The potential limitations were selected so that the optimal capacity of Na3V2(PO4)3 could be attained at both negative and positive electrodes, given that it can be either reduced (Na3V2(PO4)3 → Na4V2(PO4)3 at 1.6 V vs. Na+/Na) or oxidized (Na3V2(PO4)3 → NaV2(PO4)3 at 3.4 V vs. Na+/Na), hence providing a theoretical voltage of 1.8 V for the symmetrical charged cell. The full battery supplies 85% of the theoretical capacity attained at C/10 with satisfactory capacity retention and low polarization, for an overall energy density of 1.87 x10-3 W h cm-2 and a capacity of 1.04 mA h cm-2(see Fig. 2).

Fig. 2: (top) Galvanostatic cycling at current rate of C/2 or C/10 with potential limitation of 2.2 V for the 3rd, 6th and 26thcycles and (down) capacity retention over cycling at 200°C.

References

1. K. Saravanan, C. W. Mason, A. Rudola, K. H. Wong and P. Balaya, Adv. Energy Mater.,
3, 444 (2013)

2. A. Ponrouch, R. Dedryvere, D. Monti, A. E. Demet, J.-M. Ateba Mba, L. Croguennec, C. Masquelier, P. Johansson and M. R. Palacin, Energy Envir. Sci.,
6, 2361 (2013)

3. T. Ohtomo, A. Hayashi, M. Tatsumisago, Y. Tsuchida, S. Hama and K. Kawamoto, J. Power Sources,
233, 231 (2013)

4. M. Nagao, Y. Imade, H. Narisawa, T. Kobayashi, R. Watanabe, T. Yokoi, T. Tatsumi and R. Kanno, J. Power Sources,
222, 237 (2013)

5. S. Boulineau, J.-M. Tarascon, J.-B. Leriche and V. Viallet, Solid State Ionics,
242, 45 (2013)

6. A. Aboulaich, R. Bouchet, G. Delaizir, V. Seznec, L. Tortet, M. Morcrette, P. Rozier, J. M. Tarascon, V. Viallet and M. Dollé, Adv. Energy Mater.,
1, 179 (2011)

7. G. Delaizir, V. Viallet, A. Aboulaich, R. Bouchet, L. Tortet, V. Seznec, M. Morcrette, J.-M. Tarascon, P. Rozier and M. Dollé, Adv. Funct. Mater.,
22, 2140 (2012)

8. F. Lalère, J. B. Leriche, M. Courty, S. Boulineau, V. Viallet, C. Masquelier and V. Seznec, J. Power Sources,
247, 975 (2014)