Electrolyte Engineering toward Rational Electrode–Electrolyte Interfacial Designs for Metal Batteries

This contribution systematically discusses the philic‐phobic interface design, working principles, and regulatory strategies for interfacial issues in metal batteries. It also elaborates on the underlying mechanisms, implementation strategies, and their impacts on battery performance, while emphatically exploring the influence mechanisms of electrode–electrolyte interface design on metal battery performance under extreme environments. Abstract Lithium, zinc, sodium, potassium, and magnesium metal batteries have emerged as the core direction of next‐generation energy storage technologies due to their ultrahigh theoretical capacities. However, the uncontrollable dendrite growth and unstable solid electrolyte interface of metal anodes during cycling lead to battery short‐circuiting, capacity fading, and safety hazards, severely hindering their commercialization process. Further design of excellent electrode‐electrolyte interfaces requires precisely identifying and addressing related scientific challenges from multiple dimensions. Specifically, this review focuses on the evolution of the solid electrolyte interphase with philic‐phobic properties on the surface of metal electrodes and discusses key influencing factors governing its evolution, including electrolyte additives and artificial solid electerolyte interphase. The research progress in solid electrolyte interface with philic‐phobic properties regulation using electrolyte additives and other methods in recent years is systematically summarized. Additionally, the influence mechanisms of electrode–electrolyte interface design on battery performance under extreme environments for lithium metal batteries and novel metal batteries are emphatically discussed. Future research needs to deeply explore the micro‐mechanisms and develop more efficient materials and technologies to further improve battery performance and meet the growing demands of the energy storage field. This contribution systematically discusses the philic-phobic interface design, working principles, and regulatory strategies for interfacial issues in metal batteries. It also elaborates on the underlying mechanisms, implementation strategies, and their impacts on battery performance, while emphatically exploring the influence mechanisms of electrode–electrolyte interface design on metal battery performance under extreme environments. Abstract Lithium, zinc, sodium, potassium, and magnesium metal batteries have emerged as the core direction of next-generation energy storage technologies due to their ultrahigh theoretical capacities. However, the uncontrollable dendrite growth and unstable solid electrolyte interface of metal anodes during cycling lead to battery short-circuiting, capacity fading, and safety hazards, severely hindering their commercialization process. Further design of excellent electrode-electrolyte interfaces requires precisely identifying and addressing related scientific challenges from multiple dimensions. Specifically, this review focuses on the evolution of the solid electrolyte interphase with philic-phobic properties on the surface of metal electrodes and discusses key influencing factors governing its evolution, including electrolyte additives and artificial solid electerolyte interphase. The research progress in solid electrolyte interface with philic-phobic properties regulation using electrolyte additives and other methods in recent years is systematically summarized. Additionally, the influence mechanisms of electrode–electrolyte interface design on battery performance under extreme environments for lithium metal batteries and novel metal batteries are emphatically discussed. Future research needs to deeply explore the micro-mechanisms and develop more efficient materials and technologies to further improve battery performance and meet the growing demands of the energy storage field. Advanced Science, Volume 12, Issue 48, December 29, 2025.