Currently, LiFePO₄ is one of the most successfully commercialized cathode materials in the rechargeable lithium-ion battery (LIB) system, owing to its excellent safety performance and remarkable electrochemical properties and is expected to have a broader market in the near future. Although it is widely recognized that the crystalline structure of a cathode material largely dictates its electrochemical properties (e.g. capacity, cycle life and rate capabilities), this intrinsic connection in LiFePO₄ has not been systematically reviewed. Different from the previous reviews, which mainly focus on the improvement of electrochemical performance by all kinds of techniques, in this review, the relationship between its electrochemical performance and bulk/surface structure is reviewed and discussed. First, it is revealed that the intra-particle Li⁺ transfer is influenced by several properties of the bulk, including crystalline structures, antisite defects and electronic structures. Next, it is demonstrated that the surface/interfacial structures of LiFePO₄, which can be reconstructed artificially or spontaneously, also have great impacts on the performances. Lastly, the intrinsic connection between the structure and performance is preliminarily established, showing brand-new perspectives on the strategy for further improvement and contributing to a comprehensive understanding of LiFePO₄.

中文翻译：

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LiFePO4正极材料的结构和性能：从块状到表面。

当前，由于其优异的安全性能和卓越的电化学性能，LiFePO ₄是可再充电锂离子电池（LIB）系统中最成功的商业化阴极材料之一，并有望在不久的将来拥有更广阔的市场。尽管众所周知阴极材料的晶体结构在很大程度上决定了其电化学性能（例如容量，循环寿命和倍率性能），但LiFePO _4中的这种固有联系尚未得到系统的审查。与以前的综述不同，以前的综述主要着重于通过各种技术来改善电化学性能，在本综​​述中，对电化学性能与体积/表面结构之间的关系进行了回顾和讨论。首先，揭示了颗粒内Li ^+的转移受本体的几种性质影响，包括晶体结构，反位缺陷和电子结构。接下来，证明了LiFePO ₄的表面/界面结构可以人工或自发重建的图像，对性能也有很大的影响。最后，初步建立了结构与性能之间的内在联系，显示出对进一步改进策略的全新观点，并有助于对LiFePO ₄的全面理解。