Enhancing room-temperature ionic conductivity of Na2B12H12 via BN incorporation for all-solid-state sodium metal batteries

doi:10.1016/j.metadv.2026.02.033

Abstract

Abstract:

Because of their exceptional safety and thermal stability, all-solid-state sodium batteries are viable next-generation energy storage technologies, while borohydride-based solid electrolytes have garnered considerable interest for their favorable electrochemical stability. Nevertheless, the poor room-temperature ionic conductivity of Na₂B₁₂H₁₂ continues to be a significant obstacle that restricts its usefulness. To address this issue, this work proposes a simple mechanochemical compositing strategy. By introducing boron nitride (BN) as a multifunctional interfacial modifier, the ionic conduction performance is significantly enhanced. The Na₂B₁₂H₁₂/BN composite electrolyte is prepared via high-energy ball milling. Structural characterizations reveal that the incorporation of BN induces a mechanochemistry-driven phase and structural transformation in Na₂B₁₂H₁₂ and creates abundant heterointerfaces. Electrochemical measurements show that the optimized composite electrolyte achieves a high room-temperature ionic conductivity of 2.2 × 10⁻⁴ S cm⁻¹, almost an order of magnitude higher than that of ball-milled pristine Na₂B₁₂H₁₂, with a reduced activation energy of 0.31 eV. Furthermore, the electrolyte exhibits excellent stability against a Na-Sn alloy, enabling symmetric cells to cycle stably for over 800 h. An all-solid-state sodium battery assembled with Na₃V₂(PO₄)₃ as the cathode and a Na-Sn alloy as the anode demonstrates outstanding cycling stability (80% capacity retention after 100 cycles at 0.5 C) and rate capability. This work offers new insights for the creation of sophisticated all-solid-state sodium batteries by rationalizing the design of high-performance borohydride-based solid electrolytes through interfacial engineering using inert nanomaterials.

Key words: All-solid-state sodium battery, Solid electrolyte, Na₂B₁₂H₁₂, Boron nitride, Ionic conductivity

Yiying He, Xu Zhang, Congcong Liu, Yang Yang, Xianhong Rui. Enhancing room-temperature ionic conductivity of Na₂B₁₂H₁₂ via BN incorporation for all-solid-state sodium metal batteries[J]. Metals Advances, 2026, 44: 1-11.

Figures/Tables 10

Fig. 1. (a) XRD pattern, (b) FTIR spectrum, (c) 11B NMR spectrum, and (d) 1H NMR spectrum of the as-synthesized Na2B12H12.

Fig. 2. (a) EIS spectra of Na2B12H12-x wt% BN composite electrolytes and pre-ball-milled Na2B12H12 powder was physically mixed with 20 wt% BN. EIS spectra of ball-milled (b) Na2B12H12-20 wt% BN and (c) pristine Na2B12H12 at different temperatures (30-80 °C). (d) Arrhenius plots derived from the temperature-dependent ionic conductivity of ball-milled Na2B12H12-20 wt% BN and pristine Na2B12H12.

Fig. 3. Electronic conductivity of the ball-milled (a) Na2B12H12-20 wt% BN and (b) Na2B12H12 determined by DC polarization. Electrochemical oxidation stability of the ball-milled (c) Na2B12H12-20 wt% BN and (d) Na2B12H12 evaluated by LSV.

Fig. 4. (a-c) SEM images of Na2B12H12 after ball-milling. (d-f) EDX images of Na2B12H12 after ball-milling.

Fig. 5. (a-c) SEM images of Na2B12H12-20 wt% BN after ball-milling. (d-f) EDX images of Na2B12H12-20 wt% BN after ball-milling.

Fig. 6. (a) XRD patterns, (b) enlarged view of XRD patterns, (c) 11B NMR spectrum, and (d) 1H NMR spectrum of the ball-milled pristine Na2B12H12 and Na2B12H12-20 wt% BN electrolytes.

Fig. 7. (a) Crystalline Na2B12H12 with ordered [B12H12]2− anion framework. (b) Na2B12H12 with local anion orientational disorder. (c) Na+ migration pathway within locally disordered Na2B12H12. (d) Energy profile along the diffusion coordinate for Na+ migration.

Fig. 8. CCD measurement for (a) Na3Sn|Na2B12H12|Na3Sn and (b) Na3Sn|Na2B12H12-20 wt% BN|Na3Sn symmetric cells. (c) Galvanostatic charge-discharge (GCD) profiles of symmetric cells based on Na2B12H12 and Na2B12H12-20 wt% BN electrolytes (inset: enlarged voltage-time profiles).

Fig. 9. (a) Charge-discharge profiles, (b) cycling performance and Coulombic efficiency of the Na3V2(PO4)3|Na2B12H12-20 wt% BN|Na3Sn full cell at 0.5 C. (c) Charge-discharge profiles, (d) cycling performance and Coulombic efficiency of the Na3V2(PO4)3|Na2B12H12|Na3Sn full cell at 0.5 C. (e) Charge-discharge profiles and (f) rate capability of the Na3V2(PO4)3|Na2B12H12-20 wt% BN|Na3Sn full cell at different C-rates from 0.1 C to 1 C.

Fig. 10. (a) Cycling performance and Coulombic efficiency of the Na3V2(PO4)3|Na2B12H12-20 wt% BN|Na3Sn full cell at 0.5 C and 60 °C. (b) Cycling performance and Coulombic efficiency of the Na3V2(PO4)3|Na2B12H12-20 wt% BN|Na3Sn full cell at 0.1 C and −10 °C.

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Enhancing room-temperature ionic conductivity of Na₂B₁₂H₁₂ via BN incorporation for all-solid-state sodium metal batteries

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