Phosphate Polyanion Materials as High-Voltage Lithium-Ion Battery Cathode: A Review

Abstract

Followed by decades of successful efforts in developing cathode materials for high specific capacity lithium-ion batteries, currently the attention is on developing a high-voltage battery (>5 V vs Li/Li+) with an aim to increase the energy density for their many fold advantages over conventional <4 V batteries. Among the various cathode materials, phosphate polyanion materials (LiMPO4, where M is a single metal or a combination of metals) showed promising candidacy given their high electrochemical potential (4.8–5 V vs Li/Li+), long cycle stability, low cost, and achieved specific capacity (∼165 mAh·g–1) near to its theoretical limit (170 mAh·g–1). In this review, factors affecting the electrochemical potential of the cathode materials are reviewed and discussed. Techniques to improve the electrical and ionic conductivities of phosphate polyanion cathodes, namely, surface coating, particle size reduction, doping, and morphology engineering, are also discussed. A processing–property correlation in phosphate polyanion materials is also undertaken to understand relative merits and drawbacks of diverse processing techniques to deliver a material with targeted functionality. Strategies required for high-voltage phosphate polyanion cathode materials are envisioned, which are expected to deliver lithium-ion battery cathodes with higher working potential and gravimetric specific capacity.

Electrospun Ternary Composite Metal Oxide Fibers as an Anode for Lithium-Ion Batteries

“…Ever since its discovery in the beginning of 1980s, rechargeable lithium-ion battery (LIB) attracted tremendous attention as one of the crucial elements to the decarbonized energy sector for a sustainable society (Mizushima et al, 1980;Goodenough, 2018). Following its commercialization by Sony, efforts are mostly focused on developing cathode materials with improved electrochemical properties, such as nickel-lithium-rich nickel-cobalt-manganese oxide (NCM) and nickel-cobalt-aluminum oxide (NCA) (Song et al, 2020;Wang et al, 2020;Xu et al, 2020) (Tolouei et al, 2019;Zhang et al, 2019;Guanjie Li et al, 2020) as well as high potential spinel LiMn 1.5 Mn 0.5 O 4 and olivine LiMPO 4 (where M = Co, Ni, Mn) (Chemelewski et al, 2013;Liang et al, 2020;Ling et al, 2021a) materials. Recently, demand to deploy LIBs in long-mileage electric vehicles as well as smart energy grid applications urged the enhancement of their energy density.…”

Highly Conducting Li(Fe1−xMnx)0.88V0.08PO4 Cathode Materials Nanocrystallized from the Glassy State (x = 0.25, 0.5, 0.75)

“…This opened a new era for the Li-ion battery market. In 1997, J.B. Goodenough et al [ 3 ] proposed a new class of cathode materials—phospho-olivines—and since then LiMPO (M = Fe, Mn, Co, Ni) materials have been widely studied for their application [ 4 ]. From the whole family of isostructural compounds, only LiFePO was successfully introduced into mass production.…”

“…LiMnPO has a significantly higher potential versus metallic lithium compared to LiFePO (4.13 V and 3.43 V, respectively) and a comparable theoretical gravimetric capacity ca. 170 mAh/g [ 4 ]. However, the synthesis of LiMnPO compounds, which can work in batteries with high loads, is more difficult [ 5 ].…”

“…The low electronic conductivity of LiMPO materials belongs to a group of factors that significantly limit their electrochemical performances [ 4 ]. This issue is usually addressed by surface coating with a highly conducting nanometer thickness layer or by particle size control.…”

Enhancing the cycle stability of Zr-doped LiNi0.83Co0.12Mn0.05O2 by co-precipitation

“…They have been extensively used in small energy storage equipment especially mobile phones and laptops, and are gradually applied in new energy vehicles with the improvement of battery technology [4]. The cathode material, which is the most critical part of LIBs, is the core material that determines the capacity, safety and cost of LIBs [5,6].…”