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Article
Na3Zr2Si2PO12: A Stable Na+-Ion Solid Electrolyte for Solid-State Batteries
Zhizhen Zhang, Sebastian Wenzel, Yizhou Zhu, Joachim Sann, Lin Shen, Jing Yang, Xiayin
Yao, Yong-Sheng Hu, Christopher Wolverton, Hong Li, Liquan Chen, and Jürgen Janek
ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.0c00820 • Publication Date (Web): 24 Jun 2020
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Page 1 of 26 ACS Applied Energy Materials
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Na3Zr2Si2PO12: A Stable Na+-Ion Solid Electrolyte for Solid-State Batteries
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5 Zhizhen Zhang 1,2†*, Sebastian Wenzel 3†, Yizhou Zhu 4†, Joachim Sann 3, Lin Shen, 5
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7 Jing Yang, 5 Xiayin Yao, 5 Yong-Sheng Hu 1*, Christopher Wolverton 4, Hong Li 1,
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9 Liquan Chen 1, Jürgen Janek 3*
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12 1. Key Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy
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14 Materials and Devices, Beijing National Laboratory for Condensed Matter Physics,
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16 Institute of Physics, Chinese Academy of Sciences, School of Physical Sciences,
17 University of Chinese Academy of Sciences, Beijing 100190, China
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19 2. School of Materials, Sun Yat-Sen University, Guangzhou 510006, China
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21 3. Institute of Physical Chemistry & Center for Materials Research, Justus-Liebig-
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University Giessen, Heinrich-Buff-Ring 17, Giessen 35392, Germany
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24 4. Department of Materials Science and Engineering, Northwestern University,
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26 Evanston, IL 60208, USA
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28 5. Ningbo Institute of Materials Technology and Engineering, Chinese Academy of
29 Sciences, Ningbo, 315201, China
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47 † Z. Zhang, S. Wenzel and Y. Zhu contribute equally to this work
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50 Correspondence should be addressed to
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52 Z. Zhang (Email: zhangzhizhen1@126.com);
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Y. S. Hu (Email: yshu@iphy.ac.cn);
55 J. Janek (Email: Juergen.Janek@phys.Chemie.uni-giessen.de);
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ACS Applied Energy Materials Page 2 of 26
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ABSTRACT
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5 Solid electrolytes (SEs) offer great potential as basis for safer rechargeable batteries
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7 with high energy density. Aside from excellent ion conductivity, the stability of SEs
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9 against the highly reactive metal anode is also a prerequisite to achieve good
10 performance in solid-state batteries (SSBs). Yet, most SEs are found to have limited
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12 thermodynamic stability and are unstable against Li/Na metal. With the combination of
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14 AC impedance spectroscopy, first principles calculations and in situ X-ray
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16 photoelectron spectroscopy, we unequivocally reveal that NaSICON-structured
17 Na3Zr2Si2PO12 electrolyte forms a kinetically stable interface against sodium metal.
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19 Prolonged galvanostatic cycling of symmetric Na|Na3Zr2Si2PO12|Na cells shows stable
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21 plating/stripping behavior of sodium metal at a current density of 0.1 mA cm-2 and an
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areal capacity of 0.5 mAh cm-2 at room temperature. Evaluation of Na3Zr2Si2PO12 as
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24 an electrolyte in a solid-state battery further demonstrates its good cycling stability for
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26 over 120 cycles with very limited capacity degradation. This work provides strong
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28 evidence that Na3Zr2Si2PO12 is one of the few electrolytes that simultaneously achieve
29 superionic conductivity and excellent chemical/electrochemical stability, making it a
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31 very promising alternative to liquid electrolytes. Our findings open up a fertile avenue
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33 of exploration for SSBs based on Na3Zr2Si2PO12 and related SEs.
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43 Keywords: NaSICON, SEI, Interface, XPS, Solid-State Batteries
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INTRODUCTION
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5 Solid-state batteries (SSBs) are gaining tremendous interest as they promise high safety,
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7 high energy density, and long cycle life compared to conventional liquid-electrolyte
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9 (LEs) based batteries.1 The use of solid electrolytes (SEs) as alternative to the
10 traditional combustible organic electrolytes offer the potential to improve the safety of
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12 batteries. Another attractive prospect of solid electrolytes is their possible compatibility
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14 with high voltage cathodes and metal anodes, which increase the energy density of
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16 batteries considerably.1 Moreover, the solidification of electrolytes would enable
17 bipolar geometries to improve packing density of cells.2 An ideal solid electrolyte is
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19 expected to possess high ionic conductivity (ideally achieving 10-2 S cm-1 at room
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21 temperature in case of the catholyte, > 10-3 S cm-1 in case of the separator), negligible
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electronic conductivity, a wide electrochemical window (> 5 V), chemical and
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24 electrochemical compatibility with electrode materials, and good thermal stability.3
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26 Recently, remarkably high conductivities (up to 10-2 S cm-1) approaching and even
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28 surpassing those of LEs have been achieved in a wide range of materials, typically in
29 thiophosphates. Examples include Li10GeP2S12 (“LGPS”; σi = 12 mS·cm-1)4 and its
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31 derivatives, 4-5 Li9.54Si1.74P1.44S11.7Cl0.3 (σi = 25 mS·cm-1),6 Li7P3S11 (σi = 17 mS·cm-1),7
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33 Li-argyrodites Li7+x-yPn1-xMxS6-yXy (Pn = P, Sb; M = Si, Ge, Sn; X = Cl, Br, I) (σi =
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3~17 mS·cm-1),8-11 Na11Sn2PnX12 (Pn = P, Sb; X = S, Se; σi = 0.5~3.7 mS·cm-1),12-15
36 Na3PnX4 (Pn = P, Sb, W; X = S, Se; σi = 0.2 ~ 32 mS·cm-1).16-23 Pivotal progress on the
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38 fundamental understanding on fast ion conduction has also been accomplished.24-27
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40 However, simultaneously achieving excellent ionic conductivity and sufficient
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electrochemical stability remains a great challenge. While most thiophosphates display
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43 very high ion conductivities, they typically show significantly narrower thermodynamic
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45 stability windows than oxide-based SEs. The direct contact of thiophosphates with a
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47 Li/Na metal anode or cathode materials leads to severe reduction or oxidation, and
48 protecting interlayers are required for stable operation.28 In contrast, oxide electrolytes
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50 often exhibit better electrochemical stability, but are generally less conductive than
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52 their thiophosphate counterparts. Nonetheless, the ion conductivity can be further
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increased to above 1.0 mS·cm-1 through chemical engineering. Successful examples are
55 LLZO (σi = 0.4~1.3 mS·cm-1), 29-30 and NaSICON (Na3+xMyM’2-ySi3-zPzO12; M/M’ =
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57 Zr, Ca, Mg, Zn, La, Sc, Ti, Nb, etc; σi = 0.67~4.0 mS·cm-1).26, 31-34
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3 Another challenge that SSBs face is the significant degradation and poor rate
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5 performance.35-36 The poor cell kinetics is typically ascribed to the sluggish charge-
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7 transfer process across the SE|electrode interface due to high interfacial resistance.1
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Possible origins for the high interfacial resistance are suggested to be the poorly ion-
10 conducting interphases formed by chemical or electrochemical decomposition,37
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12 inferior physical contact at the interfaces,38 and mechanical failure of the contacts with
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14 volume variation during charge/discharge process.39 Interphase formation can occur
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due to several reasons: (1) the reduction (at the negative electrode) or oxidation of SEs
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17 (at the positive electrode) due to the intrinsic thermodynamic instability of the SEs; (2)
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19 reactions between the SE and the cathode materials caused by the chemical instability
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21 between these two layers; (3) by electrochemical reactions of the SE|electrode interface
22 during charge/discharge processes.40 These interphase layers have significant effects on
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24 the interfacial resistance and the overall performance of the solid-state batteries.
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26 In situ X-ray photoelectron spectroscopy (XPS) and first principles calculations
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have been demonstrated to be very powerful approaches to investigate the stability of
29 solid electrolytes toward Li metal.40-46 As the most promising group of Na+-ion
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31 conductors, NaSICON-structured SEs show excellent ion conductivities (up to 4 mS
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33 cm-1 through chemical engineering 26, 31-32 and great potential for utilization in bulk-
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type solid-state batteries.31 Herein, we assess the compatibility of the parent phase,
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36 Na3Zr2Si2PO12 with Na metal using a combination of AC time-resolved impedance, first
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38 principles calculations, and in situ XPS technique. Our studies provide comprehensive
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40 and reliable information about the interphase and interfacial chemical reactions. A
41 kinetically stable interphase is revealed to form between Na3Zr2Si2PO12 and Na metal.
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43 The superior compatibility, together with the excellent ion conductivity (5 mS cm-1 at
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45 80°C), enables excellent cell performance of NVP|SE|Na solid-state battery that
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exhibits stable cycling for over 120 cycles.
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48 METHODS
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50 Experimental Sections
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52 Materials Synthesis: Na3Zr2Si2PO12 solid electrolyte and carbon coated Na3V2(PO4)3
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(NVP, with 5 wt% carbon) cathode material were prepared by sol-gel method and solid-
55 state reaction, respectively. Details on the synthesis and the structure analysis were
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57 provided in our previous works.26, 31, 47 Rietveld refinement of the X-ray diffraction data
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59 suggested the high crystallinity and high purity of the targeted materials. 26, 31, 47
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3 Electrochemical Impedance Spectroscopy Measurement:
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5 The chemical stability of the NaSICON solid electrolyte was studied with symmetric
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7 cells of the type Na|Na3Zr2Si2PO12|Na. To avoid possible reaction with moisture or
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carbon oxide in the air, Na3Zr2Si2PO12 pellets were cleaned with ethanol and transferred
10 to the glove box immediately after the calcination process was finished. The sodium
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12 metal cubes were mechanically surface-cleaned and cut into thin slices, subsequently
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14 roll pressed, and eventually punched into thin films. The chemical stability of
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Na3Zr2Si2PO12 against Na metal was then investigated by attaching Na metal foils
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17 mechanically onto each side of the Na3Zr2Si2PO12 pellet. Afterwards, a flat rod wrapped
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19 with a plastic bag was used to apply sufficient force to the surface of Na metal, in order
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21 to yield a smooth surface of the Na metal and to ensure good contact between the Na
22 metal and the Na3Zr2Si2PO12 pellet. A wave washer was positioned between the spacer
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24 and the cap to maintain the pressure during the measurement. Time-resolved impedance
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26 spectroscopy was performed with the Na|Na3Zr2Si2PO12|Na symmetric cells inside an
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argon filled glove box, within the frequency range of 8 MHz to 100 mHz with a sinus
29 amplitude of 5 mV. The time span between the first contact with sodium metal and the
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31 start of the first measurement was less than 2 minutes. All measurements were carried
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33 out in an argon filled glove box (p(H2O)/p° < 1 ppm, p(O2)/p° < 1 ppm) at room
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temperature. Sodium plating/stripping cycling was conducted with a
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36 Na|Na3Zr2Si2PO12|Na symmetric cell at different current densities from 0.1 to 2.0 mA
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38 cm-2 (with an increase step of 0.1 mA cm-2 below 1.0 mA cm-2 and 0.2 mA cm-2 above
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40 1.0 mA cm-2) at both room temperature and 80°C. A pouch cell design was adopted for
41 these galvanostatic cycling measurements. The areal capacity for the plating step was
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43 set to be 0.5 mAh cm-2.
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45 In situ X-ray Photoemission Spectroscopy: The SE sample (pellet) was thinned in air
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47 and then cut into small pieces. The sample surface was mechanically cleaned before
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49 transferring to the XPS chamber. All transfer and measurements were performed under
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inert argon atmosphere.
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53 The in situ XPS measurements were performed in a PHI 5000 Versaprobe Scanning
54 ESCA Microprobe (Physical Electronics) employing a monochromatized Al Kα X-ray
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56 source (beam diameter 200 μm, X-ray power of 50 W) equipped with an argon ion gun
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58 for depth profiling. The chamber pressure was ~10−7 Pa throughout the experiment.
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Before the in situ XPS measurement was started, a survey spectrum was recorded to
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3 identify the elements. Thereby, the elements sodium (Na), zirconium (Zr), silicon (Si),
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5 phosphorus (P), carbon (C) and oxygen (O) were identified. Details for the
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7 measurement procedure are referred to our previous paper.40 The pass energy and the
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step size were set to 46.95 eV and 0.2 eV, respectively. Sputtering of the sodium was
10 performed using an acceleration voltage of 4 kV and an argon ion current of 4 μA, with
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12 the angle between the sputter gun and sample surface to be 33°. Deposition time was
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14 chosen as 5 min. Beside monochromatized Al radiation, non-monochromatized Mg
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radiation was used in order to separate the O 1s signal from the Na-Auger lines.
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18 Evaluation of the Solid-State Battery Cells: To prepare the NVP composite cathode,
19 the synthesized carbon coated NVP cathode active material and super P were mixed
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21 and ground for 30 min before transferring into a centrifuge tube. Afterwards, the proper
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23 amount of ionic liquid (0.2 M sodium bis(fluorosulfonyl)imide (NaFSI) in N-Methyl-
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N-Propylpiperidinium bis(fluorosulfonyl)imide (PP13FSI)) was added into the tube,
26 which was then mounted to the rubber cup of a vortex mixer. The mass ratio of NVP,
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28 ionic liquid, and super P in the composite cathode was 60: 37: 3, representing a volume
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30 of approx. 43.3 µL ionic liquid per 100 mg Na3V2(PO4)3 active material. A uniform and
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thick slurry was obtained after ~4 hours vigorous vortex mixing. The slurry was then
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33 casted onto one side of the sintered Na3Zr2Si2PO12 pellet (thickness: ~1.2 mm). These
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35 composite electrodes, loaded on the substrate of SE pellet, with an areal NVP loading
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37 of 2.5 mg cm-2 (theoretical areal capacity of 0.293 mAh cm-2) were dried at 80°C before
38 use. The NVP|SE|Na solid-state battery was assembled in Ar filled glovebox by
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40 applying a piece of Na foil (10 mm in diameter) onto the unpainted side of the
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42 Na3Zr2Si2PO12 pellet. Electrochemical tests were conducted by galvanostatic cycling
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the cells between 2.5 and 3.7 V.
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46 First principles calculations: The density functional theory (DFT) calculations in this
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work were performed using the Vienna Ab initio Simulation Package (VASP)48 within
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49 the projector augmented-wave approach49. The generalized gradient approximation
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51 (GGA) functional parameterized by Perdew-Burke-Ernzerhof (PBE) was employed to
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53 describe the exchange-correlation potential.50 We used a cutoff energy of 520 eV for
54 the plane-wave basis set and Γ-centered k-meshes with the density of 2500 k-points per
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56 reciprocal atom in all calculations.
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3 The structure of Na2.8Zr2Si1.8P1.2O12, Na3Zr2Si2PO12, Na3.2Zr2Si2.2P0.8O12 used in the
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5 DFT calculations is based on the structure model established in our previous work.26
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7 Since the structure shows disorder on the cation lattice sites (Si/P and Na/Vacancy), we
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used enumlib to enumerate possible orderings and selected 20 configurations with
10 the lowest electrostatic energy as candidate structures. DFT calculations were
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12 performed for these 20 structures and the one with the lowest energy was selected as
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14 the representative ground state structure.
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The phase stability and electrochemical stability were calculated by constructing the
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17 phase diagram and the grand potential phase diagram based on data from the Open
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19 Quantum Materials Database (OQMD).52-53 All the calculated reaction energies and
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21 voltages neglected the contribution of the PV terms and the entropy terms as in previous
22 studies. 45-46
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25 RESULTS AND DISCUSSION
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27 According to the differences in thermodynamic and kinetic stability, the Me/SE (Me
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29 refers to metallic anode, such as Li, Na) interface is usually classified into three types40:
30 (1) Thermodynamically stable interface; it requires that both phases, metal Me and the
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32 solid electrolyte in contact, are in thermodynamic equilibrium a priori, as in the case
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34 of Li/LiI and Li/Li3N; (2) a reactive and mixed ionic-electronic conducting interphase
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(MCI) with both reasonably high ionic and electronic conductivity; this interphase
37 allows for continuous flux of M+-ions and electrons, leading to the formation of a thick
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39 decomposition layer or even the complete lithiation (sodiation) of solid electrolyte; (3)
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41 a metastable, thermodynamically unstable but kinetically stable (non-growing) solid-
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electrolyte interphase (SEI); the growth of this interphase is kinetically hindered after
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44 formation due to the complete insulating character or fairly-low electronic conductivity
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46 of the products. As required for the SEI formed in liquid electrolytes, this third type of
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48 interphase ideally shows sufficiently high ionic conductivity and negligible electronic
49 conductivity.
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51 As expected, most Li-SEs, e. g., LixPOyNz (LiPON), Li3xLa2/3-xTiO3 (LLTO), Ti4+ or
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53 Ge4+ containing Li1+xM2-xAlx(PO4)3 (NaSICON, M = Ti4+/Ge4+), Li10GeP2S12 (LGPS),
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Li7P3S11, are thermodynamically unstable against Li metal.45-46 The highly conducting
56 thiophosphates are generally not stable when in contact with Li metal.45 The reduction
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58 products of thiophosphates and Li are revealed to be Li3P and Li2S, and for electrolyte
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60 materials containing Ge, Cl, and I as constituents, Li-Ge alloy, LiCl and LiI are the
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3 other main reaction products, respectively. Amongst oxides, garnet-type SEs, in
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5 particular, Li7La3Zr2O12 (LLZO) and its derivatives, exhibit the best resistance to
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7 reduction by Li.45 In the case of sodium SEs, very limited work has been reported so
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far. The stability of Na-β”-Al2O3 against Na metal was proven by Janek’s group in a
10 combined XPS and impedance study, while the instability of Na3PS4 was also
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12 evidenced in the same work. 54
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14 In a real battery, it is not very likely that a thermodynamically stable interface will
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form between Li/Na metal and a solid electrolyte because of the high reactivity of Li/Na
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17 metal. While a thermodynamically stable interface is desirable, the most possible
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19 interface in a real system will either be a mixed conducting interphase that would
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21 continue growing into the bulk of the SE layer, or a stable non-growing SEI that would
22 only conduct ions but is electronically insulating otherwise. Generally, an MCI type
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24 interphase would cause a destruction of the SE layer, and result in rapid deterioration
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26 and eventual self-discharge of the battery, whereas, a SEI type may not be harmful to
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the long-term battery performance if the additional resistance originating from the
29 interphase is not too large. Some electrolytes, for example, LiPON, as well as
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31 thiophosphates such as Li3PS4, and Li7P2S8I (which appears to be better described as
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33 Li4PS4I),55 are practically observed to be compatible with Li metal. This is due to
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kinetic factors: the interphase passivates the SEs and mitigates continued reactions. As
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36 a result, the decomposition of the SEs advances only very slowly into the bulk and the
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38 SE materials are stabilized by the interphase layer. In light of these considerations, a
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40 stable SEI interface with low resistance is preferred in a solid-state battery.
41 In this work, we utilize time-resolved impedance, DFT calculations, with a
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43 combination of an in situ XPS technique, to uncover the thermodynamic and kinetic
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45 stability of NaSICON structured Na3Zr2Si2PO12. The Na3Zr2Si2PO12 pellets we used
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throughout this work exhibit a total ionic conductivity of ~0.67 mS cm-1 at room
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48 temperature (25°C) and ~5 mS cm-1 at 80°C, respectively.31 The characterization of its
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50 properties - chemical/electrochemical stability against Na metal and compatibility in
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52 full cell - from both experimental and theoretical perspective, are demonstrated below.
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54 Time-Resolved Impedance and Galvanostatic Cycling Measurements of
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56 Symmetric Na/Na3Zr2Si2PO12/Na Cell
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58 Time-resolved impedance spectroscopy has been revealed to be a reliable technique to
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explore the compatibility of solid electrolyte with Li/Na metal.42, 44 Here the interphase
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48 Figure 1. (a) Nyquist plots showing the evolution of the Na|Na3Zr2Si2PO12|Na symmetric cell
49 impedance after contacting Na3Zr2Si2PO12 directly with two Na metal electrodes. An increasing
50 impedance with time at the first 15 minutes suggests a fast reaction of Na3Zr2Si2PO12 electrolyte
51 when in contact with Na metal. The constant resistance after 15 minutes implies a stable
52 interphase has been formed at the Na3Zr2Si2PO12|Na interface. Selected frequencies of the
53 spectra are labelled. The inset shows the fitting results of two impedance data together with the
54 equivalent circuit used for the fitting; (b) The fitted overall areal specific resistance (ASR) of
55 the cell (RTotal), the Na3Zr2Si2PO12 solid electrolyte (RSE), and solid electrolyte interface (RSEI)
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formed between Na3Zr2Si2PO12 and Na metal as a function of reaction time. Galvanostatic
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cycling profiles of the Na|Na3Zr2Si2PO12|Na symmetric cell at different current densities of 0.1,
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0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 0.9, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0 mA cm-2 to a fixed areal capacity of 0.5
60 mAh cm-2 at (c) room temperature; (d) 80°C; (e) Prolonged cycles (800 h) of the symmetrical
cell at a current density of 0.1 mA cm-2 to an areal capacity of 0.5 mAh cm-2 at room temperature.9/25
formation between Na3Zr2Si2PO12 and two Na metal foils was monitored by time-
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3 resolved impedance spectroscopy. Impedance spectra collected during a time span of
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5 30 days are shown in Figure 1a. The equivalent circuit and the fit model for two
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7 representative spectra, after 5 minutes and 1 day of contact, are shown in the inset. For
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the fresh cell, only one semicircle is seen in the spectrum, which is mainly attributed to
10 the resistance of the Na3Zr2Si2PO12 solid electrolyte (RSE). A minor contribution from
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12 the newly formed interphase is probably also included, but cannot be separated from
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14 the RSE at this early stage of the reaction. As the contact time advances, a second
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semicircle emerges and increases within the first 15 minutes, reflecting the progressive
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17 growth of the interphase. This is distinct from the evolution of the areal specific
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19 resistance (ASR) of the SEI interphase, RSEI, as a function of contact time, as shown in
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21 Figure 1b. The increase in RSEI within the first 10 minutes can be explicitly observed,
22 suggesting that a rapid initial reaction/deterioration happens at the Na3Zr2Si2PO12|Na
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24 interface. Further increase in RSEI is seen upon the increase in contact time, but the
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26 deterioration slows down. After 15 minutes, RSEI and the ASR of the total resistance,
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RTotal, remain unchanged, indicating that no further SEI formation extends into the bulk
29 of the SE. The ASR of the SEI (for one electrode) of ~64.5 Ω cm2 is fairly small, lower
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31 than the total ASR of the bulk electrolyte of 105 Ω cm2 (for a Na3Zr2Si2PO12 pellet with
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33 ~1 mm thickness). This is quite different from what happens at the interface of LGPS
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or Na3PS4 with the corresponding alkali metal, in which a continuous increase in the
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36 ASR of the interphase is evident from the time-resolved impedance spectra. Our results
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38 suggest that Na3Zr2Si2PO12 forms a kinetically stable SEI-type interphase at room
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40 temperature when in contact with Na metal, namely, the reaction between the two can
41 be effectively hindered by the interphase layer. Whether the growth kinetics is better
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43 described by an interface-controlled linear rate or a square root t law caused by
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45 diffusion control cannot be decided unequivocally. As the resulting SEI is relatively
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thin and only a few nm thick, and as its growth is quite fast until further growth stops,
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48 we tend to believe that the growth kinetics is linear rather than parabolic. At this point
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50 we would like to note that an in-depth study of the SEI growth kinetics, the SEI
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52 composition and structure is far beyond the current study, and rather will be part of
53 future work.
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55 The chemical stability of Na3Zr2Si2PO12 against Na metal is also examined by
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57 plating/stripping the Na|Na3Zr2Si2PO12|Na symmetric cell at different current densities
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from 0.1 to 2.0 mA cm-2 (with an increment of 0.1 mA cm-2 below 1 mA cm-2 and 0.2
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3 mA cm-2 above 1 mA cm-2) with a plating capacity of 0.5 mAh cm-2, both at room
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5 temperature (RT) and 80°C (Figure 1c, 1d). When galvanostatically cycled at room
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7 temperature, the symmetric cells show an ohmic current-voltage behavior up to 0.2 mA
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cm-2, after which the cells experience a dramatic drop of the cell voltage output,
10 indicative of a short-circuit of the cells due to the dendrite formation. This represents a
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12 critical current density (CCD) of 0.2 mA cm-2 for Na3Zr2Si2PO12 at room temperature,
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14 higher than that of garnet LLZO (0.1 mA cm-2).56 Note that the CCD of ceramic pellets
15
can potentially be enhanced via doping, as already demonstrated by Ga doping in LLZO
16
17 in a previous work.56 At a moderate temperature of 80°C, significantly lower voltage
18
19 polarizations (2.2 mV at 0.3 mA cm-2, 5.8 mV at 0.5 mA cm-2, 12.1 mV at 1.0 mA cm-
20 2,
21 26.2 mV at 2.0 mA cm-2) were observed than at room temperature (Figure 1d).
22 Strikingly, no short-circuit of the cells was observed up to 2 mA cm-2 at a plating
23
24 capacity of 0.5 mAh cm-2, indicating excellent sodium ion transfer capability across the
25
26 Na|Na3Zr2Si2PO12 interface. The prolonged galvanostatic cycling at current density of
27
28
0.1 mA cm-2 for more than 800 h over repeated cycles (cycling still in progress) at room
29 temperature demonstrates no observable increase in the polarization, which further
30
31 verifies the kinetic stability of Na3Zr2Si2PO12 pellets against Na metal.
32
33 Phase stability and electrochemical stability of NaSICON
34
35 7 Na3Zr2Si2PO12 + 72 Na → 12 Na4SiO4 + 7 Na3P + 12 Na2ZrO3 + 2 ZrSi; (1) at 0 V
36
37
38
39 We evaluated the phase stability of Na3Zr2Si2PO12 by constructing the pseudo-
40
quaternary phase diagram based on the OQMD database.52-53 The representative ground
41
42 state of Na3Zr2Si2PO12 is on the energy convex hull, indicating that it is a stable phase
43
44 (Figure 2a).
45
46 The electrochemical stability of Na3Zr2Si2PO12 is evaluated by constructing the
47 grand potential phase diagram. Our calculations (Figure 2b) predict that Na3Zr2Si2PO12
48
49 has a thermodynamic stability window from 1.11 V to 3.41 V (referenced to Na+/Na).
50
51 We also identified the phase equilibria and decomposition reaction energies of
52
53
Na3Zr2Si2PO12 against Na metal at low voltages. It is revealed that the reduction of
54 Na3Zr2Si2PO12 starts at 1.11 V, and thus, it is thermodynamically unstable against Na
55
56 metal. The reduction of Na3Zr2Si2PO12 at 0 V (in equilibrium with Na metal), forms
57
58 Na4SiO4, Na2ZrO3, Na3P, and ZrSi (Eq.1) with a small reaction energy (-0.27 eV/atom).
59
In comparison, the calculated decomposition energies of LGPS, Li7P3S11, LiPON in
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1
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3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Figure 2. (a) Pseudo-quaternary phase diagram of Na2O-ZrO2-SiO2-P2O5 system; The
21 ground state of Na3Zr2Si2PO12 falls on the energy convex hull, suggesting that it is a
22 stable phase; (b) The voltage profile of Na3Zr2Si2PO12 and the phase equilibria of all
23 the reaction stages. The calculated electrochemical stability window of Na3Zr2Si2PO12
24 is between 1.11 V and 3.41 V (referenced to Na+/Na). NZPO and NZSO represent for
25 NaZr2(PO4)3, Na2ZrSi2O7, respectively.
26
27 thermodynamic equilibrium with Li are -1.25 eV/atom, -1.67 eV/atom and -0.66
28
29 eV/atom, respectively.45 The much smaller decomposition energy of Na3Zr2Si2PO12 in
30
31 equilibrium with Na metal (-0.27 eV/atom) implies a much smaller thermodynamic
32
driving force and slower kinetics of the reduction reaction compared to thiophosphates
33
34 and LiPON, as the reaction energy is included in the parabolic rate constant of
35
36 diffusion-controlled SEI growth. 57
37
38 Moreover, the major reduction products, Na4SiO4, Na2ZrO3, and Na3P, are
39 electronic insulators, whilst the minor component, ZrSi, is probably intrinsically
40
41 electronic conductive, yet, only constitutes a low volume fraction of 2% in the
42
43 decomposition products, which is well below the percolation threshold. Na3P might
44
show some electronic conductivity, however, its volume fraction would also be too low
45
46 to achieve electronic percolation.54 These features of the reaction products can
47
48 potentially ensure the electronically isolating nature of the SEI layer as a multi-phase
49
50 composite. With the combination of the time-resolved impedance plot, we suggest that
51 the co-existence of these phases does not lead to a MCI-type interphase, but rather an
52
53 SEI-type interphase, which can provide sufficient passivation for the bulk solid
54
55 electrolyte and prevent further decomposition. This is further discussed in the next
56
57
section. We also note that a similar case has been previously reported, 45 where LiPON
58 is predicted to show a thermodynamically favorable reduction against Li metal with a
59
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1
2
3 moderate reaction energy of -0.66 eV/atom. Fortuitously, the reduction products, Li3N,
4
5 Li2O and Li3P, are electronically insulating. As a result, LiPON has been verified to be
6
7 compatible with the Li metal anode,58-59 due to the formation of an electronically
8
9
insulating SEI interlayer.45 For Na3Zr2Si2PO12, the low reaction energy with sodium,
10 the electronic insulating nature of the reduction products, with a combination of the
11
12 time-resolved impedance spectrum, suggest that the reduction of Na3Zr2Si2PO12 with
13
14 Na metal has only a small thermodynamic driving force, and limited reduction is likely
15
to lead to the formation of an SEI-type interphase. This type of SEI interphase is desired,
16
17 as it can effectively protect the bulk solid electrolyte from continuous decomposition
18
19 and maintain a reasonably low interfacial resistance. We note that the decomposition
20
21 energy and ASR of the interphase are not necessarily related. The reaction energy only
22 describes the thermodynamic driving force for the decomposition/reduction at the
23
24 sodium/solid electrolyte interface, whereas the ASR is mainly controlled by the kinetic
25
26 properties of the formed interphase products. A stronger driving force may lead to a
27
28
thicker interlayer, but the transport properties of the interlayer are determined by the
29 kinetic properties of the products in the interphase. So, even a thin interlayer may show
30
31 a high ASR, once the product phases in the interlayer are poorly conducting.
32
33 The oxidation reactions of Na3Zr2Si2PO12 start at 3.41 V and the calculated
34
equilibrium potential of O2 gas release starts from this voltage. The final oxidation
35
36 products are O2, SiO2, Zr2P2O9, ZrSiO4 at the equilibrium oxidation potential of 4.30 V
37
38 (Figure 2b). Notably, the decomposition energies at 4.51 V and 5.0 V are as minor as
39
40 -0.15 and -0.23 eV/atom, respectively. Given that the O2 release typically has sluggish
41 kinetics,60 at least 1 V overpotential appears reasonable during the oxidation of
42
43 Na3Zr2Si2PO12. Furthermore, the formed decomposition products are all electronically
44
45 insulating phases. This suggests that Na3Zr2Si2PO12 is very likely kinetically stable to
46
potentials above 5 V, due to the electronic insulating nature of the decomposition
47
48 products and the sluggish kinetics of the nucleation and the release of O2. It is therefore
49
50 probable that an over-potential beyond the calculated thermodynamic equilibrium
51
52 potential exists in the oxidation process of Na3Zr2Si2PO12, yielding a high practical
53 oxidation potential of > 5 V as observed in the CV experiments. 61 The electrochemical
54
55 stability windows of other two NaSICON compositions, Na2.8Zr2Si1.8P1.2O12 and
56
57 Na3.2Zr2Si2.2P0.8O12, were also studied, being 1.39-3.41 V and 1.11-3.11 V, respectively
58
59
(Figure S1). The phase equilibria under different voltages are listed in Table S1 in the
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1
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3 Supporting Information. The predicted decomposition products against Na metal are
4
5 the same with those of Na3Zr2Si2PO12, with a decomposition energy of -0.37 eV/atom
6
7 for Na2.8Zr2Si1.8P1.2O12 and -0.18 eV/atom for Na3.2Zr2Si2.2P0.8O12.
8
9 Monitoring the interphase formation by in situ X-ray Photoelectron Spectroscopy
10
11 (XPS)
12
13 To obtain more insight into the reduction of Na3Zr2Si2PO12 when it is brought in contact
14
15 with sodium metal, in situ XPS measurements were conducted to collect interphase
16
information. Figure 3 and 4 exhibits the Zr3d, Na1s, Si2p, P2p and O1s spectra for the
17
18 pristine Na3Zr2Si2PO12 samples and after sodium deposition. The pristine sodium signal
19
20 in Figure 3a shows only one signal at binding energy of 1071.4 eV, which is assigned
21
22 to Na+, in well agreement to the binding energy of Na+ in the case of Na-β”-Al2O3, 54
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54 Figure 3. XPS detail spectra for the pristine Na3Zr2Si2PO12 sample and after sodium
55 deposition. Peak fit model for the Zr 3d and Na 1s signals for the pristine and the reacted
56 sample are shown in (a), (b) and (c), (d), respectively. After sodium metal deposition,
57
an extra but minor signal at higher binding energy appears on the Na1s line, but remains
58
59 unchanged upon further deposition, indicating that the reaction stops very shortly after
60 the first two deposition steps; Zirconium is reduced to sub-oxide species, Zr(4-x)+.
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1
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3 and is very close to that of 1071.8 eV in Na2O when the chemical shift is considered. 62
4
5 After sodium metal deposition, an additional signal for sodium metal and the
6
corresponding metal plasmons 62 are observed in Figure 3a. The fraction of sodium
7
8
9
metal further increases during deposition, which indicates that the reaction process is
10 finished shortly after the first two deposition steps (approximately 1.4 nm Na metal)
11
12 and that the interphase is not growing. It is visible that after sodium deposition, an extra
13
14 but minor signal at lower binding energy of ~180 eV appears in the Zr 3d line (Figure
15
3b), which remains unchanged during further deposition. These indicate that zirconium
16
17 is reduced to sub-oxide species, containing Zr(4-x)+. This is consistent with our DFT
18
19 calculations showing that minor reduction of Zr may happen and zirconium probably
20
21 exists in the form of ZrSi when Na3Zr2Si2PO12 is in contact with Na metal. The
22 assignment of the reduced zirconium species is, however, difficult, as the reference data
23
24 for such binding states are lacking. Nevertheless, the advance of the reduction process
25
26 into the bulk Na3Zr2Si2PO12 is hindered, as suggested by the unchanged intensities in
27
28
both sodium and zirconium signals during further sodium deposition.
29 Before sodium deposition, the Si2p signal at the binding energy of 101.8 eV
30
31 features only one oxidation state, +4 (Figure 4a), in agreement with the binding energy
32
33 reported for Si2p in ZrSiO4. 63 Upon sodium deposition, the formation of a new line at
34
lower binding energy (100.6 eV) is indicative of minor reduction to a lower state,
35
36 Six+(Figure 4b). A very close binding energy of 100.4 eV for Si2p in Si2O and 101.4
37
38 eV in SiO was reported in a previous paper.64 These suggest that silicon was very likely
39
40 reduced to an oxidation state between +2 and +1 after sodium deposition. We also note
41 that the oxidation state of -2 in the form of ZrSi is absent in the Si 2p signal, although
42
43 our DFT calculations suggest it is the thermodynamically stable phase when
44
45 Na3Zr2Si2PO12 is in contact with sodium. One possible reason is that ZrSi may form
46
during the sodium deposition process, but vanishes very rapidly by reaction with the
47
48 unavoidable trace amount of oxygen and moisture inside the XP spectrometer and is
49
50 eventually oxidized again to Six+. We also note that upon sodium deposition the
51
52 intensity of Si 2p signal is declining since the material is buried underneath sodium
53 metal. Along with this, the P 2p line is almost unaffected by sodium metal deposition,
54
55 except that the intensity is also dampened (Figure 4c). This probably arises from the
56
57 minor reduction of phosphorus to Na3P. Similar to the case of Li3P, P in Na3P shows a
58
59
valence state of -3. However, this minor amount of Na3P probably reacts with the
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22
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28
29
30
31
32 Figure 4. (a), (b) The Si 2p and (c) P 2p signals for the pristine Na3Zr2Si2PO12 sample
33 and after sodium deposition are shown in and c, respectively. Si experienced a minor
34 reduction from a valence state of +4 to a lower state during the sodium deposition
35 process. Only a decrease in the intensity of the P 2p signals is seen; (d) The O 1s signals
36 before and after sodium metal deposition are displayed. The data were obtained with
37
38
Mg Kα radiation. No changes are seen from the O1s signals, suggesting that the anion
39 lattice is not affected.
40
41 residual oxygen and moisture, due to its high reactivity. A similar observation has been
42 reported to Li3P.44 This explains the absence of the reduced phosphorus species Na3P,
43
44 but only decreased intensity of the P 2p line. Aside from this, the decline in the signal
45
46 after sodium deposition may also be due to the fact that the solid electrolyte was buried
47
48
underneath the formed reaction layer and the sputtered metallic sodium. In order to gain
49 insight whether the oxygen signal is affected by sodium deposition, Mg Kα radiation
50
51 was used. The results are shown in Figure 4d for the pristine (black) and reacted (red)
52
53 sample. Notably, no changes for the O 1s signal can be detected, besides that
54
aforementioned signal damping, implicating that the anion lattice is not affected by the
55
56 reduction of zirconium and silicon.
57
58
59
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1
2
3 Evaluation in solid-state batteries
4
5
6 In order to assess the potential use of NaSICON as electrolyte in solid-state batteries, a
7 bulk-type solid-state cell using Na3V2(PO4)3 as cathode and Na metal as the anode was
8
9 fabricated. The NaSICON solid electrolyte is sandwiched between the Na anode and
10
11 the Na3V2(PO4)3 composite cathode layer. Vortex mixing is used to make the slurry of
12
the composite cathode, which enables uniform mixing of the active materials, super P,
13
14 solid electrolyte powder, and ionic liquid. (Details for the preparation of the composite
15
16 cathode is provided in the Methods part). This can be seen from the impedance
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
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39
40
41
42
43
44
45
46
47
48
49
Figure 5. (a) Charge/discharge curves of a NVP|SE|Na solid-state cell at 0.1C, 0.2C, 0.5C and
50 80°C, a polarization of 66 mV, 99 mV and 220 mV are observed at 0.1C, 0.2C and 0.5C,
51 respectively; (b) The rate performance of NVP|SE|Na solid-state cell at 0.1C, 0.2C, 0.5C, 1C
52 and 80°C; (c) The cycling performance of NVP|SE|Na cell at 0.1C and 80°C; (d) The
53 electrochemical impedance spectra of NVP|SE|Na solid-state cell at 80°C before cycling and
54 after 100 cycles (The inset shows the equivalent circuit used for the fitting, where R1 represents
55
56
the resistance of the solid electrolyte, R2 and CPE1 are the the resistor and constant phase
57 element used for the fit of the solid electrolyte interphases formed at the NVP|SE and SE|Na
58 interface).
59
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1
2
3 spectrum of the cell below. The cells were operated at 80°C. Figure 5a shows the
4
5 charge/discharge curves for the NVP|SE|Na cell in the voltage range 2.5-3.7 V at
6
7 different rates (0.1C, 0.2C and 0.5C). Minor polarization of the NVP|SE|Na cell was
8
9
observed at these current densities (66 mV at 0.1C; 99 mV at 0.2C; 220 mV at 0.5C).
10 The cell delivers a capacity of 106.9 mAh/g upon the first cycle charge at 0.1C, which
11
12 corresponds to 91.4% to the theoretical specific capacity (117 mAh/g) of Na3V2(PO4)3.
13
14 The discharge capacity of the first cycle is 103.9 mAh/g, representing a very high initial
15
coulombic efficiency of 97.2%. An increase in both the discharge capacity (~106
16
17 mAh/g) and the Coulombic efficiency (~99.7%) was observed from the second cycle
18
19 (Figure 5b). Upon further increase of the current density to 0.2C and 0.5C, a high
20
21 discharge capacity of 104.5 mAh/g and 103.2 mAh/g was retained, respectively,
22 although the cell can only deliver a reversible capacity of 50 mAh/g at high rate of 1C.
23
24 The cycling performance of NaSICON solid electrolyte was also evaluated using the
25
26 same cell configuration within the same voltage range and the same temperature at the
27
28
current density of 0.1C. As shown in Figure 5c, the cell shows excellent cycling
29 performance at 0.1C, with negligible capacity fade over 120 cycles, and maintains a
30
31 capacity of ~97.6 mAh/g after long term cycling with high coulombic efficiencies.
32
33 To further evidence the excellent electrochemical performance of the solid-state
34
35 battery, the compatibility of the NaSICON solid electrolyte with Na metal and NVP
36
37 cathode was studied by electrochemical impedance spectroscopy. Only one semicircle
38 is found in the Nyquist plot (Figure 5d). The intercept of the semicircle with the x axis
39
40 at high frequency marks the resistance of the SE. The semicircle is attributed to the
41
42 solid electrolyte interphases formed between SE and Na metal and SE and NVP cathode.
43
44
The ASR of the interphases before cycling is only ~15.7 Ω cm2 at 80°C, suggesting
45 good interfacial compatibility of NaSICON solid electrolyte with Na metal at the anode
46
47 side and NVP at the cathode side with the assistance of ionic liquid. After 100 cycles,
48
49 a slight increase in the resistance of the interphases is observed, however, the total
50
internal resistance of the cell remains low. We note that many solid-state cells with an
51
52 unstable interface between SE and electrodes show significant degradation after a few
53
54 cycles, even if the electrodes were coated with an oxide barrier layer.3, 27 The excellent
55
56 cycling performance of the NVP|SE|Na solid-state cell in this work is attributed to the
57 superior electrochemical stability and good compatibility of the NaSICON electrolyte
58
59 with electrodes, as well as the good electrolyte/electrodes interfacial contact
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1
2
3 contributed from excellent ionic and electronic conducting network formed with the
4
5 incorporation of the ionic liquid. Our work points to the significant importance of the
6
7 exploration of stable solid electrolytes in the utilization of solid-state batteries.
8
9 CONCLUSIONS
10
11 We provide direct evidence for the kinetic stability of NaSICON structured
12
13 electrolyte with sodium metal using a combination of time-resolved impedance
14
15 spectroscopy, DFT calculations, and in situ XPS. Minor reduction of zirconium, and
16
17 silicon were observed and the reaction appears to be self-limiting. From the time-
18 revolved impedance, we conclude that the reaction between Na3Zr2Si2PO12 and Na
19
20 metal stops already after 15 minutes at room temperature, indicating that a kinetically
21
22 stable interphase (SEI) has formed. Galvanostatic cycling measurement of symmetric
23
Na|Na3Zr2Si2PO12|Na cells demonstrates stable sodium plating/stripping behavior and
24
25 confirms the kinetical stability of Na3Zr2Si2PO12 against sodium metal. This excellent
26
27 chemical and electrochemical stability, as well as compatibility of Na3Zr2Si2PO12
28
29 further enables solid-state NVP|Na3Zr2Si2PO12|Na batteries with high capacity retention
30 over 120 cycles. Our findings reported in this work will hopefully inspire more work in
31
32 Na3Zr2Si2PO12 and related SEs, and stimulate further endeavors in the field of SSBs.
33
34 ASSOCIATED CONTENT
35
36
Supporting Information Available:
37 Additional details on the calculated voltage profiles, the phase equilibria and the
38
39 electrochemical stability window of Na2.8Zr2Si1.8P1.2O12, Na3Zr2Si2PO12,
40
41 Na3.2Zr2Si2.2P0.8O12.
42
43 Conflicts of Interest
44
45 The authors declare no conflict of interest.
46
47
48 ACKNOWLEDGMENTS
49
50 This work was supported by the National Key Technologies R&D Program, China
51
52 (2016YFB0901500) and the National Natural Science Foundation of China (51725206,
53 51421002, 51622207, 11747009, 11874254, 51802187). J.J acknowledges financial
54
55 support by BMBF (Federal Ministry of Education and Research) with the project
56
57 “NASEBER” (03XPO187C). Y.Z and C.W acknowledge support from the Center for
58
59
Electrochemical Energy Science (CEES), an Energy Frontier Research Center funded
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1
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3 by the U.S. Department of Energy under Award No. DE-AC02-06CH11357 (first
4
5 principles calculations). Computational resources were provided by the National
6
7 Energy Research Scientific Computing Center (U.S. Department of Energy Contract
8
9
DEAC02-05CH11231) and the Extreme Science and Engineering Discovery
10 Environment (National Science Foundation Contract ACI-1548562).
11
12
13
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SEI
e- Na+ e- e-
Na
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Battery26 of 26
105
Specific Capacity (mAh g-1)

Interphase 160 Charge
Charge
Coloumbic Efficiency (%)

Discharge
Discharge
100
120
1 Na+
NaSICON
2 80 95
3 σSEI ˂ σSE
Rinterphase
40 90
4 ACS Paragon Plus Environment
5 0
0 30 60 90
85
120
6 Cycle Number (n)
Time

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Specific Capacity (mAh g-1)

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