The success story of the triphylite-type LiFePO₄ immediately boosted the development of numerous classes of polyanion-based electrode materials for metal-ion batteries. A number of advantages including thermal and structural stability, polyanionic inductive effect, and variety of crystal types and chemical compositions render these materials attractive for grid and large-scale applications ensuring high safety standards, environmental friendliness and cost benefits. In this review, we focus on a specific family of polyanion-based electrode materials adopting the KTiOPO₄-type structure that captured particular attention recently due to the unique 3D-framework. This framework features thermal, structural and long-term electrochemical cycling stability, fast ionic transport, possibility to accommodate two alkali ions per transition metal cation enabling multi-electron transitions, and unprecedented high electrode potentials for a specific redox couple among all known polyanion materials. The recent advances and overview of KTiOPO₄-type and related positive and negative electrode materials for metal-ion batteries are presented with a special emphasis on the interrelations between crystal structure peculiarities and electrochemical properties.

三铁型LiFePO ₄的成功故事立即推动了用于金属离子电池的多种类型的基于聚阴离子的电极材料的开发。包括热和结构稳定性，聚阴离子感应效应以及各种晶体类型和化学组成在内的诸多优势使这些材料对网格和大规模应用具有吸引力，从而确保了高安全标准，环境友好性和成本优势。在这篇综述中，我们重点介绍采用KTiOPO ₄的特定聚阴离子基电极材料系列类型的结构由于独特的3D框架而在最近引起了特别的关注。该框架具有热，结构和长期电化学循环稳定性，快速的离子迁移，每个过渡金属阳离子可容纳两个碱离子的可能性，从而实现了多电子跃迁，并且在所有已知的聚阴离子材料中，特定的氧化还原对具有前所未有的高电极电势。介绍了用于金属离子电池的KTiOPO ₄型及相关的正负电极材料的最新进展和概况，特别强调了晶体结构特性与电化学性能之间的关系。