Li-Rich Layered Oxides: Structure and Doping Strategies to Enable Co-Poor/Co-Free Cathodes for Li-Ion Batteries
Lithium-rich layered oxides (LRLO) are a wide class of innovative active materials used in positive electrodes in lithium-ion (LIB) and lithium–metal secondary batteries (LMB). LRLOs are over-stoichiometric layered oxides rich in lithium and manganese with a general formula Li<sub>1+x</sub&...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-01-01
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| Series: | Crystals |
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| Online Access: | https://www.mdpi.com/2073-4352/13/2/204 |
| _version_ | 1797621585994055680 |
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| author | Laura Silvestri Arcangelo Celeste Mariarosaria Tuccillo Sergio Brutti |
| author_facet | Laura Silvestri Arcangelo Celeste Mariarosaria Tuccillo Sergio Brutti |
| author_sort | Laura Silvestri |
| collection | DOAJ |
| description | Lithium-rich layered oxides (LRLO) are a wide class of innovative active materials used in positive electrodes in lithium-ion (LIB) and lithium–metal secondary batteries (LMB). LRLOs are over-stoichiometric layered oxides rich in lithium and manganese with a general formula Li<sub>1+x</sub>TM<sub>1−x</sub>O<sub>2</sub>, where TM is a blend of transition metals comprising Mn (main constituent), Ni, Co, Fe and others. Due to their very variable composition and extended defectivity, their structural identity is still debated among researchers, being likely an unresolved hybrid between a monoclinic (mC24) and a hexagonal lattice (hR12). Once casted in composite positive electrode films and assembled in LIBs or LMBs, LRLOs can deliver reversible specific capacities above 220–240 mAhg<sup>−1</sup>, and thus they exceed any other available intercalation cathode material for LIBs, with mean working potential above 3.3–3.4 V vs Li for hundreds of cycles in liquid aprotic commercial electrodes. In this review, we critically outline the recent advancements in the fundamental understanding of the physical–chemical properties of LRLO as well as the most exciting innovations in their battery performance. We focus in particular on the elusive structural identity of these phases, on the complexity of the reaction mechanism in batteries, as well as on practical strategies to minimize or remove cobalt from the lattice while preserving its outstanding performance upon cycling. |
| first_indexed | 2024-03-11T08:59:08Z |
| format | Article |
| id | doaj.art-975c37f9a8bf4dc18c85c644eea61491 |
| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-03-11T08:59:08Z |
| publishDate | 2023-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Crystals |
| spelling | doaj.art-975c37f9a8bf4dc18c85c644eea614912023-11-16T19:54:54ZengMDPI AGCrystals2073-43522023-01-0113220410.3390/cryst13020204Li-Rich Layered Oxides: Structure and Doping Strategies to Enable Co-Poor/Co-Free Cathodes for Li-Ion BatteriesLaura Silvestri0Arcangelo Celeste1Mariarosaria Tuccillo2Sergio Brutti3Dipartimento di Tecnologie Energetiche e Fonti Rinnovabili, ENEA C.R. Casaccia, Via Anguillarese 301, 00123 Rome, ItalyDipartimento di Tecnologie Energetiche e Fonti Rinnovabili, ENEA C.R. Casaccia, Via Anguillarese 301, 00123 Rome, ItalyDipartimento di Chimica, Sapienza Università di Roma, P.le Aldo Moro 5, 00185 Rome, ItalyDipartimento di Chimica, Sapienza Università di Roma, P.le Aldo Moro 5, 00185 Rome, ItalyLithium-rich layered oxides (LRLO) are a wide class of innovative active materials used in positive electrodes in lithium-ion (LIB) and lithium–metal secondary batteries (LMB). LRLOs are over-stoichiometric layered oxides rich in lithium and manganese with a general formula Li<sub>1+x</sub>TM<sub>1−x</sub>O<sub>2</sub>, where TM is a blend of transition metals comprising Mn (main constituent), Ni, Co, Fe and others. Due to their very variable composition and extended defectivity, their structural identity is still debated among researchers, being likely an unresolved hybrid between a monoclinic (mC24) and a hexagonal lattice (hR12). Once casted in composite positive electrode films and assembled in LIBs or LMBs, LRLOs can deliver reversible specific capacities above 220–240 mAhg<sup>−1</sup>, and thus they exceed any other available intercalation cathode material for LIBs, with mean working potential above 3.3–3.4 V vs Li for hundreds of cycles in liquid aprotic commercial electrodes. In this review, we critically outline the recent advancements in the fundamental understanding of the physical–chemical properties of LRLO as well as the most exciting innovations in their battery performance. We focus in particular on the elusive structural identity of these phases, on the complexity of the reaction mechanism in batteries, as well as on practical strategies to minimize or remove cobalt from the lattice while preserving its outstanding performance upon cycling.https://www.mdpi.com/2073-4352/13/2/204lithium-rich layered oxidessecondary aprotic batteriespositive electrode materialsLi-ioncathodes |
| spellingShingle | Laura Silvestri Arcangelo Celeste Mariarosaria Tuccillo Sergio Brutti Li-Rich Layered Oxides: Structure and Doping Strategies to Enable Co-Poor/Co-Free Cathodes for Li-Ion Batteries Crystals lithium-rich layered oxides secondary aprotic batteries positive electrode materials Li-ion cathodes |
| title | Li-Rich Layered Oxides: Structure and Doping Strategies to Enable Co-Poor/Co-Free Cathodes for Li-Ion Batteries |
| title_full | Li-Rich Layered Oxides: Structure and Doping Strategies to Enable Co-Poor/Co-Free Cathodes for Li-Ion Batteries |
| title_fullStr | Li-Rich Layered Oxides: Structure and Doping Strategies to Enable Co-Poor/Co-Free Cathodes for Li-Ion Batteries |
| title_full_unstemmed | Li-Rich Layered Oxides: Structure and Doping Strategies to Enable Co-Poor/Co-Free Cathodes for Li-Ion Batteries |
| title_short | Li-Rich Layered Oxides: Structure and Doping Strategies to Enable Co-Poor/Co-Free Cathodes for Li-Ion Batteries |
| title_sort | li rich layered oxides structure and doping strategies to enable co poor co free cathodes for li ion batteries |
| topic | lithium-rich layered oxides secondary aprotic batteries positive electrode materials Li-ion cathodes |
| url | https://www.mdpi.com/2073-4352/13/2/204 |
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