Trend AnalysisEngineering

All-Solid-State Batteries: The Interface Engineering Challenge

All-solid-state batteries (ASSBs) replace the flammable liquid electrolyte of lithium-ion batteries with a solid electrolyte, promising inherent safety (no thermal runaway), higher energy density (lit...

By Sean K.S. Shin
This blog summarizes research trends based on published paper abstracts. Specific numbers or findings may contain inaccuracies. For scholarly rigor, always consult the original papers cited in each post.

The Question

All-solid-state batteries (ASSBs) replace the flammable liquid electrolyte of lithium-ion batteries with a solid electrolyte, promising inherent safety (no thermal runaway), higher energy density (lithium metal anode enabled), and wider operating temperature range. Toyota, Samsung SDI, and QuantumScape project commercialisation by 2027โ€“2030. Yet the fundamental engineering challenge is not the solid electrolyte itself but the interfaces: solid-solid contacts between electrolyte and electrodes create void spaces, chemical reactions, and mechanical stresses that degrade performance. Can interface engineering deliver the cycle life and power density needed for electric vehicles?

Landscape

D. Li et al. (2024) addressed the practical fabrication of sulfide solid electrolyte films. Sulfide electrolytes (Liโ‚†PSโ‚…Cl, Liโ‚ƒPSโ‚„) offer high ionic conductivities among solid electrolytes, but conventional pellet-pressing produces thick layers that reduce energy density. Li et al. developed thin (~40 ยตm), mechanically robust sulfide films achieving ionic conductivity of 1.1 mS/cm while being flexible enough to tolerate electrode volume changes during cycling.

Lin et al. (2025) investigated a safety concern unique to ASSBs: interface thermal runaway between reactive lithium metal and LAGP, a NASICON-type oxide solid electrolyte. While ASSBs eliminate liquid electrolyte flammability, the lithium-SSE interface can itself become thermally unstable. Their study characterised the thermal stability of this interface and proposed strategies to improve interface safety.

Saqib et al. (2024) and Feng et al. (2024) both studied the cathode/sulfide electrolyte interface โ€” arguably the most problematic contact in ASSBs. When NCM811 (nickel-rich cathode) contacts sulfide electrolytes at high voltage, the sulfide decomposes, forming resistive interphases that increase impedance over cycling. The interplay between electronic conductivity (provided by carbon additives) and ionic conductivity (provided by solid electrolyte) must be carefully balanced.

Wu et al. (2025) demonstrated LiDFP (lithium difluorophosphate) additive engineering to stabilise the cathode/sulfide interface, forming a protective cathode electrolyte interphase (CEI) that prevents sulfide decomposition while maintaining ion transport.

Key Claims & Evidence

<
ClaimEvidenceVerdict
Thin sulfide electrolyte films achieve both conductivity and flexibility~40 ยตm films with 1.1 mS/cm conductivity and mechanical robustness (D. Li et al. 2024)Demonstrated; scalable manufacturing unclear
Interface thermal runaway is a real safety concern in ASSBsThermal instability at Li/LAGP oxide interface characterised (Lin et al. 2025)Confirmed; challenges the "inherently safe" narrative
Cathode/sulfide interface degrades at high voltageNCM811/sulfide forms resistive interphases during cycling (Feng et al. 2024; Saqib et al. 2024)Well-established; the dominant capacity fade mechanism
Additive engineering can stabilise cathode interfaceLiDFP forms protective CEI layer (Wu et al. 2025)Demonstrated; long-term stability (>1000 cycles) not yet shown

Open Questions

  • Dendrite penetration: Lithium metal dendrites can penetrate grain boundaries in solid electrolytes, causing short circuits. Can pressure, temperature, and current density management prevent this?
  • Manufacturing cost: Sulfide electrolytes require inert-atmosphere processing (argon gloveboxes). Can dry room or ambient-tolerant processing reduce manufacturing cost?
  • Scalability: Can ASSB cell assembly achieve the throughput (millions of cells per month) and yield needed for automotive volumes?
  • Cold performance: Solid electrolyte conductivity drops at low temperatures. Can ASSBs match liquid Li-ion performance below -20ยฐC?
  • Referenced Papers

    • [1] Li, D. et al. (2024). High Ionic Conductive Sulfide Solid Electrolyte Films for ASSBs. Adv. Funct. Mater., 34, 2315555. DOI: 10.1002/adfm.202315555
    • [2] Lin, Z. et al. (2025). Interface Thermal Runaway Regulation in All-Solid-State Li Metal Battery. Adv. Funct. Mater. DOI: 10.1002/adfm.202424110
    • [3] Saqib, K.S. et al. (2024). Carbon/Sulfide Electrolyte Interface in Ni-Rich Cathode Composites. ACS Appl. Mater. Interfaces. DOI: 10.1021/acsami.4c08670
    • [4] Wu, Z. et al. (2025). LiDFP Additive Engineering for Stable Sulfide-Based ASSB Interface. Energy & Environmental Materials. DOI: 10.1002/eem2.12871
    • [5] Feng, Y. et al. (2024). Ni-Rich Cathodes/Sulfide Electrolyte Interface in Solid-State Battery. ACS Appl. Mater. Interfaces. DOI: 10.1021/acsami.4c05609

    References (5)

    Li, D., Liu, H., Wang, C., Yan, C., Zhang, Q., Nan, C., et al. (2024). High Ionic Conductive, Mechanical Robust Sulfide Solid Electrolyte Films and Interface Design for Allโ€Solidโ€State Lithium Metal Batteries. Advanced Functional Materials, 34(27).
    Lin, Z., Yao, Q., Yang, S., Song, H., Yu, Z., Li, Z., et al. (2025). Highly Safe Allโ€Solidโ€State Lithium Metal Battery Enabled by Interface Thermal Runaway Regulation Between Lithium Metal and Solidโ€State Electrolyte. Advanced Functional Materials, 35(29).
    Saqib, K. S., Embleton, T. J., Choi, J. H., Won, S., Ali, J., Ko, K., et al. (2024). Understanding the Carbon Additive/Sulfide Solid Electrolyte Interface in Nickel-Rich Cathode Composites and Prioritizing the Corresponding Interplay between the Electrical and Ionic Conductive Networks to Enhance All-Solid-State-Battery Rate Capability. ACS Applied Materials & Interfaces, 16(36), 47551-47562.
    Wu, Z., Du, L., Yang, T., Zhang, H., Zhang, W., Xia, Y., et al. (2025). Lithium Difluorophosphate Additive Engineering Enabling Stable Cathodic Interface for Highโ€Performance Sulfideโ€Based Allโ€Solidโ€State Lithium Battery. ENERGY & ENVIRONMENTAL MATERIALS, 8(4).
    Feng, Y., Wang, Z., Deng, D., Yan, G., Guo, H., Li, X., et al. (2024). Ni-Rich Layered Oxide Cathodes/Sulfide Electrolyte Interface in Solid-State Lithium Battery. ACS Applied Materials & Interfaces, 16(29), 37363-37378.

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