
Citation: |
Marie-Claude Bay, Rabeb Grissa, Konstantin V Egorov, Ryo Asakura, Corsin Battaglia. Low Na- |
All-solid-state batteries with a lithium or sodium metal anode are considered as next-generation batteries as they promise high energy density as well as enhanced operation safety by replacing the flammable liquid electrolyte used in lithium-ion batteries with an ideally non-flammable solid electrolyte [1-3]. While solid electrolytes with lithium- and sodium-ion conductivity comparable to liquid electrolytes have been developed, their integration into all-solid-state cells with stable interfaces enabling long-term cycling and high current densities remains challenging [4-6].
During the past decade, a major research focus has been on achieving stable solid electrolyte/alkali metal anode interfaces [7-11]. High interfacial resistance at the solid electrolyte/alkali metal anode interface leads to the formation and propagation of alkali metal dendrites upon battery charging, limiting the operation current density [12-15]. Some of us demonstrated low interfacial resistance <10 cm2 at the interface between a Na-
However, the integration of ceramic electrolytes with high-energy intercalation cathodes remains challenging. Poor contact at the solid-solid interface results in large interfacial resistance and unsatisfactory electrochemical performance [22]. Sintering of ceramic composites including the electrolyte and the cathode active material may represent an option for zero-strain cathodes, which may avoid fracturing of the ceramic composite during electrochemical dis-/charge cycling. However, obtaining stable interfaces with low interfacial resistance by sintering remains challenging due to the elevated temperatures required to generate intimate contact between the electrolyte and cathode [23, 24]. Alternatively, cathode materials were integrated with ceramic electrolytes by employing liquid [25], gel [26, 27], or soft polymer [28-30] secondary electrolytes, which guarantee sufficient mechanical contact and low interfacial resistance.
In this study, we propose a novel strategy to contact a cathode to a rigid Na-
Spray-dried lithium-stabilized Na-
NaCrO2 was synthesized according to [38]. Cr2O3 (Sigma-Aldrich) and Na2CO3 (Sigma-Aldrich) were mixed for 15 min in a mortar. The powder mixture was pressed into a pellet and heat treated in argon atmosphere for 5 h at 900 C. X-ray analysis as well as scanning electron micrographs of the as-synthesized NaCrO2 powder are shown in figure S2. After passive cool down in argon, the resulting powder was ground in a mortar. The slurry for the cathode preparation consisted in the as-synthesized NaCrO2 active material powder, polyvinylidene difluoride (PVDF) binder (KF1100, Kureha), and conductive carbon additives (Super C65, Imerys) in a 95:2:3 weight ratio using N-methyl-2-pyrrolidone as solvent. The slurry was tape-casted on an aluminum current collector with a mass loading between 3.1 and 6.5 mg cm-2 (see table S7). Discs of 12 mm diameter were punched out from the obtained cathode sheet, followed by drying under vacuum for 12 h at 120 C.
Hydroborate electrolyte precursors Na2B12H12 and Na2B10H10 were purchased from Katchem and prepared according to [34]. An equimolar ratio of the hydroborate precursors Na2B12H12 and Na2B10H10 were dissolved in anhydrous ethanol (>99.5% purity, Sigma-Aldrich) with a concentration of 100 mg ml-1. An amount of 30
Cross sections were prepared using a broad-beam argon-ion miller (Hitachi IM4000 Plus). For the Na-
Electrochemical characterization was performed by a multichannel galvanostat/potentiostat (Biologic VSP) in home-built electrochemical cells allowing the application of pressure to the cell stack under argon atmosphere in a glovebox (MBraun). Electrochemical impedance spectroscopy (EIS) was conducted at frequencies between 0.1 Hz and 1 MHz with a 20 mV sinusoidal amplitude. Galvanostatic charge/discharge measurements were performed at increasing C-rates ranging from C/10 to 1 C (1 C = 120 mA g-1) between 2 V and 3.6 V vs. Na+/Na. Long-term cycling measurements were performed at a rate of 1 C between 2 V and 3.3 V vs. Na+/Na to minimize hydroborate oxidation [33, 39]. Both experiments were conducted after a 12 h rest at room temperature (25 C-30 C) and EIS data were recorded after the end of discharge.
Figure 1(a) illustrates and summarizes the cell assembly protocol described in detail in the previous section and figure 1(b) shows a sketch of the completed cell architecture. The full cell consists of a sodium metal anode, a Na-
The densification step of the hydroborate interlayer is critical to obtain a low resistance at the Na-
The saturation of the interfacial resistance at 25 cm2 at pressure 70 MPa indicates that full compaction and good mechanical and ionic contact are obtained above this threshold pressure. The remaining interfacial resistance of 25 cm2 may originate from pressure-independent contributions.
In figure 2(b), we investigate the impact of the processing solvent on the surface properties of Na-
The impact of the densification pressure on the electrochemical performance of the full cell was further studied by rate performance measurements at increasing C-rates ranging from C/10 to 1 C between 2 V and 3.6 V. A stack pressure of 3.4 MPa was applied using a home-built pressure cell to avoid excessive void formation at the Na-
Based on these results, long-term cycling was performed with a cell assembled at a pressure of 70 MPa at 1 C rate with a cathode areal capacity of 0.4 mAh cm-2. In order to minimize partial hydroborate oxidation during long-term cycling above its oxidative stability limit as determined in another study [39, 43], the upper cut-off voltage was set to 3.3 V. Cycling data shown in figures 3(b) and (c) indicate an initial discharge capacity of 42 mAh g-1. Note that the higher initial capacity compared to the cell in figure 3(a) can be explained by the lower mass loading of 3.1 mg cm-2 compared to 6.5 mg cm-2 facilitating cycling at a faster rate (table S6). The cell features an excellent capacity retention of 88% after 100 cycles with a high Coulombic efficiency >99.9%. EIS performed before cycling and after the 1st and 100th cycle shows that capacity fading is related to an increase in total cell resistance (figure 3(d)). While the contribution at 1 kHz related to the hydroborate/Na-
To analyze the mechanical contact of the Na-
Based on the unique property of hydroborates to fully densify by cold pressing, we developed a novel all-solid-state sodium cell architecture to contact a slurry-casted porous NaCrO2 cathode with a Na-
Towards fast-charging applications, the rate performance must be improved further e.g. by reducing the thickness of the Na-
Marie-Claude Bay acknowledges support from the BRIDGE Proof-of-Concept program under contract number 40B1-0_198678/2. The authors thank Roman Flury for his help with cells preparation and characterization as well as Ulrich Sauter for argon-ion cross-section milling and Lo Duchne for SEM characterization of cathode active materials.
Authors to whom any correspondence should be addressed.
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