A reflection on lithium-ion battery cathode chemistry

Lithium-ion batteries have aided the portable electronics revolution for nearly three decades. They are now enabling vehicle electrification and beginning to enter the utility industry. The emergence and dominance of lithium-ion batteries are due to their higher energy density compared to other rechargeable battery systems, enabled by the design and development of high-energy density electrode materials. Basic science research, involving solid-state chemistry and physics, has been at the center of this endeavor, particularly during the 1970s and 1980s. With the award of the 2019 Nobel Prize in Chemistry to the development of lithium-ion batteries, it is enlightening to look back at the evolution of the cathode chemistry that made the modern lithium-ion technology feasible. This review article provides a reflection on how fundamental studies have facilitated the discovery, optimization, and rational design of three major categories of oxide cathodes for lithium-ion batteries, and a personal perspective on the future of this important area. The 2019 Nobel Prize in Chemistry has been awarded to a trio of pioneers of the modern lithium-ion battery. Here, Professor Arumugam Manthiram looks back at the evolution of cathode chemistry, discussing the three major categories of oxide cathode materials with an emphasis on the fundamental solid-state chemistry that has enabled these advances.

[1]  Daniel H. Doughty,et al.  A General Discussion of Li Ion Battery Safety , 2012 .

[2]  Michael M. Thackeray,et al.  Structural Considerations of Layered and Spinel Lithiated Oxides for Lithium Ion Batteries , 1995 .

[3]  A. Manthiram,et al.  Current Status and Future Prospects of Metal–Sulfur Batteries , 2019, Advanced materials.

[4]  Jean-Marie Tarascon,et al.  Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries , 2018 .

[5]  Michael M. Thackeray,et al.  Improved capacity retention in rechargeable 4 V lithium/lithium- manganese oxide (spinel) cells , 1994 .

[6]  K. S. Nanjundaswamy,et al.  Phospho‐olivines as Positive‐Electrode Materials for Rechargeable Lithium Batteries , 1997 .

[7]  A. Manthiram,et al.  Chemical synthesis and properties of Li1−δ−xNi1+δO2 and Li[Ni2]O4 , 1992 .

[8]  M. Whittingham,et al.  Electrical Energy Storage and Intercalation Chemistry , 1976, Science.

[9]  J. Dahn,et al.  Synthesis and Electrochemistry of LiNi x Mn2 − x O 4 , 1997 .

[10]  L. Nazar,et al.  Nanostructured Composites: A High Capacity, Fast Rate Li3V2(PO4)3/Carbon Cathode for Rechargeable Lithium Batteries , 2002 .

[11]  V. Koch Status of the secondary lithium electrode , 1981 .

[12]  K. Brandt,et al.  Historical development of secondary lithium batteries , 1994 .

[13]  A. Manthiram,et al.  Soft Chemistry Synthesis and Characterization of Layered Li1-xNi1-yCoyO2-δ (0 ≤ x ≤ 1 and 0 ≤ y ≤ 1) , 2001 .

[14]  metallic oxides , 2020, Catalysis from A to Z.

[15]  A. Manthiram,et al.  Synthesis and Electrochemical Properties of LiCo2 O 4 Spinel Cathodes , 2002 .

[16]  J. C. Hunter Preparation of a new crystal form of manganese dioxide: λ-MnO2 , 1981 .

[17]  B. Dunn,et al.  Electrical Energy Storage for the Grid: A Battery of Choices , 2011, Science.

[18]  A. Manthiram,et al.  Comparison of the chemical stability of the high energy density cathodes of lithium-ion batteries , 2001 .

[19]  A. Manthiram,et al.  Comparison of Metal Ion Dissolutions from Lithium Ion Battery Cathodes , 2006 .

[20]  John B Goodenough,et al.  The Li-ion rechargeable battery: a perspective. , 2013, Journal of the American Chemical Society.

[21]  Huilin Pan,et al.  Carbon coated Na3V2(PO4)3 as novel electrode material for sodium ion batteries , 2012 .

[22]  John B. Goodenough,et al.  Lithium insertion into Fe2(MO4)3 frameworks: Comparison of M = W with M = Mo , 1987 .

[23]  A. H. Thompson Electron-Electron Scattering in TiS2 , 1975 .

[24]  A. Manthiram,et al.  Lattice doping regulated interfacial reactions in cathode for enhanced cycling stability , 2019, Nature Communications.

[25]  M. Thackeray,et al.  Insertion/extraction reactions of lithium with LiV2O4 , 1985 .

[26]  J. Goodenough,et al.  Synthesis and structural characterization of the normal spinel Li[Ni2]O4 , 1985 .

[27]  John B. Goodenough,et al.  LixCoO2 (0, 1980 .

[28]  Jeremy Barker,et al.  The electrochemical insertion properties of sodium vanadium fluorophosphate, Na3V2(PO4)2F3 , 2006 .

[29]  A. Manthiram,et al.  The Influence of Oxygen Variation on the Crystal Structure and Phase Composition of the Superconductor YBa2Cu3O7_x , 1987 .

[30]  Arumugam Manthiram,et al.  A perspective on the high-voltage LiMn1.5Ni0.5O4 spinel cathode for lithium-ion batteries , 2014 .

[31]  John B. Goodenough,et al.  LixCoO2 (0, 1981 .

[32]  M. Armand,et al.  Building better batteries , 2008, Nature.

[33]  M Cais,et al.  Intercalation Complexes of Lewis Bases and Layered Sulfides: A Large Class of New Superconductors , 1971, Science.

[34]  J. Goodenough,et al.  Structural characterization of delithiated LiVO2 , 1984 .

[35]  A. Manthiram,et al.  A Comprehensive Analysis of the Interphasial and Structural Evolution over Long‐Term Cycling of Ultrahigh‐Nickel Cathodes in Lithium‐Ion Batteries , 2019, Advanced Energy Materials.

[36]  A. Manthiram,et al.  Low-Temperature Synthesis, Structural Characterization, and Electrochemistry of Ni-Rich Spinel-like LiNi2–yMnyO4 (0.4 ≤ y ≤ 1) , 2015 .

[37]  Michael Holzapfel,et al.  Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2. , 2006, Journal of the American Chemical Society.

[38]  John B. Goodenough,et al.  Lithium insertion into manganese spinels , 1983 .

[39]  M. Nishizawa,et al.  Irreversible conductivity change of Li1–xCoO2 on electrochemical lithium insertion/extraction, desirable for battery applications , 1998 .

[40]  A. Manthiram,et al.  Phase Relationships and Structural and Chemical Stabilities of Charged Li1 − x CoO2 − δ and Li1 − x Ni0.85Co0.15 O 2 − δ Cathodes , 2003 .

[41]  Christian Masquelier,et al.  Polyanionic (phosphates, silicates, sulfates) frameworks as electrode materials for rechargeable Li (or Na) batteries. , 2013, Chemical reviews.

[42]  A. Manthiram,et al.  Lithium-Sulfur Batteries: Attaining the Critical Metrics , 2020, Joule.

[43]  L. Nazar,et al.  A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries. , 2009, Nature materials.

[44]  Jun Lu,et al.  Mn(II) deposition on anodes and its effects on capacity fade in spinel lithium manganate–carbon systems , 2013, Nature Communications.

[45]  Evan M. Erickson,et al.  High-nickel layered oxide cathodes for lithium-based automotive batteries , 2020 .

[46]  F. Salzano,et al.  Thermodynamic Properties of the Potassium–Graphite Lamellar Compounds from Solid‐State emf Measurements , 1968 .

[47]  Arumugam Manthiram,et al.  An Outlook on Lithium Ion Battery Technology , 2017, ACS central science.

[48]  C. Delmas,et al.  Optimization of the Composition of the Li1 − z Ni1 + z O 2 Electrode Materials: Structural, Magnetic, and Electrochemical Studies , 1996 .

[49]  A. Dolocan,et al.  Modified High-Nickel Cathodes with Stable Surface Chemistry Against Ambient Air for Lithium-Ion Batteries. , 2018, Angewandte Chemie.

[50]  Wangda Li,et al.  Mn versus Al in Layered Oxide Cathodes in Lithium‐Ion Batteries: A Comprehensive Evaluation on Long‐Term Cyclability , 2018 .

[51]  J. Dahn,et al.  Synthesis and Electrochemistry of LiNixMn2-xO4. , 1997 .

[52]  Peter G. Bruce,et al.  Synthesis of layered LiMnO2 as an electrode for rechargeable lithium batteries , 1996, Nature.

[53]  J. Goodenough,et al.  Structural characterization of the lithiated iron oxides LixFe3O4 and LixFe2O3 (0 , 1982 .

[54]  Feixiang Wu,et al.  Li-ion battery materials: present and future , 2015 .

[55]  Christopher S. Johnson,et al.  Electrochemical and Structural Properties of xLi2M‘O3·(1−x)LiMn0.5Ni0.5O2 Electrodes for Lithium Batteries (M‘ = Ti, Mn, Zr; 0 ≤ x ⩽ 0.3) , 2004 .

[56]  E. Davies Intercalation chemistry , 1983 .

[57]  Jean-Marie Tarascon,et al.  Li-O2 and Li-S batteries with high energy storage. , 2011, Nature materials.

[58]  John B. Goodenough,et al.  Lithium insertion into Fe2(SO4)3 frameworks , 1989 .

[59]  Wangda Li,et al.  Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries , 2017, Nature Communications.