Ionic and electronic transport in electrodes is crucial for electrochemical energy storage technology. To optimize the transport pathway of ions and electrons, electrode materials are minimized to nanometer-sized dimensions, leading to problems of volumetric performance, stability, cost, and pollution. Here we find that a bulk hexagonal molybdenum oxide with unconventional ion channels can store large amounts of protons at a high rate even if its particle size is tens of micrometers. The diffusion-free proton transport kinetics based on hydrogen bonding topochemistry is demonstrated in hexagonal molybdenum oxide whose proton conductivity is several orders of magnitude higher than traditional orthorhombic molybdenum oxide. In situ X-ray diffraction and theoretical calculation reveal that the structural self-optimization in the first discharge effectively promotes the reversible intercalation/de-intercalation of subsequent protons. The open crystal structure, suitable proton channels, and negligible volume strain enable rapid and stable proton transport and storage, resulting in extremely high volumetric capacitance (~1750 F cm^–3), excellent rate performance, and ultralong cycle life (>10,000 cycles). The discovery of unconventional materials and mechanisms that enable proton storage of micrometer-sized particles in seconds boosts the development of fast-charging energy storage systems and high-power practical applications.

电极中的离子和电子传输对于电化学储能技术至关重要。为了优化离子和电子的传输路径，电极材料被最小化到纳米尺寸，从而导致体积性能、稳定性、成本和污染等问题。在这里，我们发现具有非常规离子通道的块状六方氧化钼即使其粒径为数十微米，也可以高速存储大量质子。基于氢键拓扑化学的无扩散质子传输动力学在六方氧化钼中得到证明，其质子电导率比传统的斜方氧化钼高几个数量级。原位X射线衍射和理论计算表明，第一次放电中的结构自优化有效促进了后续质子的可逆嵌入/脱嵌。开放的晶体结构、合适的质子通道和可忽略的体积应变可实现快速稳定的质子传输和存储，从而产生极高的体积电容（~1750 F cm ^–3 ）、优异的倍率性能和超长的循环寿命（>10,000次循环） 。能够在几秒钟内存储微米级粒子质子的非常规材料和机制的发现促进了快速充电储能系统和高功率实际应用的发展。