Knowledge of structure-performance relationship is a fundamental issue in the field of material design and engineering. Functional-directed fine tune of the crystal structure has always been inspiring but rarely implemented in energy storage materials. Here we develop an approach to improve the performance of LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811), a typical Ni-rich layered cathode material, through building monoclinic surfaces onto hexagonal primary grains, simply accomplished by oxidizing the flake-like primary precursors with KMnO₄. In this way, the local octahedral ligand field has been engineered by inducing Jahn-Teller distortion of low spin Ni³⁺ state, resulting in a three-dimensional monoclinic functional network spreading over a secondary particle. Such an elaborate monoclinic architecture stabilizes the hexagonal structure of primary grains from phase transitions, and also offers an interconnected highway for both ionic and electronic transportations. Accordingly, an enhanced cycling stability and an outstanding rate capability have been achieved in our designed NCM811 material. Our approach starts a prospective way of designing Ni-rich cathode material with local electronic and structural engineering, which could be expanded to widespread battery researches.

结构-性能关系的知识是材料设计和工程领域的一个基本问题。晶体结构的功能导向微调一直是鼓舞人心的，但很少在储能材料中实施。在这里，我们开发了一种方法来提高 LiNi _0.8 Co _0.1 Mn _0.1 O ₂ (NCM811) 的性能，这是一种典型的富镍层状正极材料，通过在六角形初级晶粒上构建单斜晶面，简单地通过氧化片状初级前体来完成与 KMnO ₄。通过这种方式，通过诱导低自旋 Ni ^{3+的 Jahn-Teller 畸变来设计局部八面体配体场}状态，导致在次级粒子上扩展的三维单斜函数网络。这种精细的单斜结构稳定了相变中初级晶粒的六边形结构，并且还为离子和电子传输提供了一条相互连接的高速公路。因此，我们设计的 NCM811 材料实现了增强的循环稳定性和出色的倍率性能。我们的方法开创了一种利用局部电子和结构工程设计富镍正极材料的前瞻性方法，该方法可以扩展到广泛的电池研究。