NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries

Grey, Clare P.; Dupré, Nicolas

doi:10.1021/cr020734p

Cited by 623 publications

(649 citation statements)

References 159 publications

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“…ssNMR can be used in situ to study dynamic processes occurring on the NMR timescale. 106,107 To date, in situ NMR is difficult to combine with sample rotation, i.e. Magic Angle Spinning (MAS), which is crucial for chemical (and hyperfine) shift resolution enhancement of paramagnetic materials in ssNMR.…”

Section: Studying Phase Transformations and Electronic Phenomena Occumentioning

confidence: 99%

Review—Manganese-Based P2-Type Transition Metal Oxides as Sodium-Ion Battery Cathode Materials

Clément

Bruce

Grey

2015

J. Electrochem. Soc.

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429

388

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Sodium transition metal oxides (NaMO 2 ) with a P2 structure exhibit good Na + ion conductivity and are promising sodium-ion battery cathode materials. Manganese-based compounds have a high working potential vs. Na + /Na, and high capacity. Yet, the layered nature of these materials means that they are prone to structural rearrangements at high voltage/low Na contents, the phase transformations and Na + ion/vacancy ordering transitions resulting in capacity fade and poor reversibility. This review discusses the latest advances in the field and focuses mainly on recent work on Na y Mn 1-x M x O 2 (x, y ≤ 1, M = Ni, Mg, Li) compounds. We compare the different lithium and sodium transition metal layered oxides (P2, O3, etc.) and describe the structures and mechanisms observed on alkali (de)intercalation. The strategies used to enhance the electrochemical properties and stabilize the structural framework of sodium transition metal oxides are reviewed. We show how X-ray diffraction and 7 Li/ 23 Na solid-state Nuclear Magnetic Resonance can be combined to provide a detailed insight into the structural and electronic processes occurring upon electrochemical cycling of these materials. Why Are We Interested in Na-Ion Battery Cathodes?Together, the increasing demand for energy and the threat from Global Warming make electrical energy storage (EES) a world wide strategic priority. EES is expected to play a key role in the decarbonization of electric power sources. The two billion people worldwide not currently served by a reliable electricity supply are likely to be connected via local grids, for which EES is essential. While Li-ion batteries (LIBs) will play a role, a key challenge is to develop lower cost batteries that deliver safe, reliable storage with high cycle and calendar life. In this regard, Na-ion batteries (NIBs) are potentially important. NIBs operate in a similar fashion to LIBs, offering both advantages and disadvantages. Concerning the former, the ability to use Al instead of Cu as a current collector at the anode could substantially reduce cost. Na is also far more abundant in the Earth's crust than Li, and more widely distributed geographically. Regarding the disadvantages, the standard operating potential of Na metal is 300 mV more positive than Li metal. This generally translates into lower operating potentials for Na-ion systems, although the potential of a full cell depends on the difference in the chemical potentials of Na in the anode and cathode materials. There are considerable opportunities for scientists to develop new combinations of anode, electrolyte and cathode that are optimized for a variety of applications with different criteria such as high energy density, high power, and high operating potential. This has encouraged a rapid growth of interest in research into NIB components. Hard carbons show some promise as anodes, [1][2][3] but more must be done to improve performance. The cathode remains a major challenge and it is to this that we direct the current review. A comparative plot sho...

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Section: Studying Phase Transformations and Electronic Phenomena Occumentioning

confidence: 99%

Review—Manganese-Based P2-Type Transition Metal Oxides as Sodium-Ion Battery Cathode Materials

Clément

Bruce

Grey

2015

J. Electrochem. Soc.

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429

388

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“…Upon further lithiation, at Li 2.0 (i.e., at the end of process A), a broad resonance close to ~25 ppm is observed. In general, such a broad and shifted resonance is due to hyperfine interactions arising due to lithium ions being close to paramagnetic ions, 34 and is therefore indicative of formation of reduced V 4+ species at this stage of the discharge process. This broad feature becomes broader on further discharge, remains until Li 3.4, and then disappears into the baseline.…”

Section: In-situ X-ray Diffractionmentioning

confidence: 99%

Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide

et al. 2015

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ABSTRACTcompound. Eventually reduction to Li 2 S plus elemental V occurs. Despite the complex redox processes involving both the cation and the anion occurring in this material, the system is found to be partially reversible between 0 and 3 V. The unusual redox processes in this system are elucidated using a suite of short range characterization tools including 51 V Nuclear Magnetic Resonance spectroscopy (NMR), S Kedge X-ray Absorption Near Edge Spectroscopy (XANES) and Pair Distribution Function (PDF) Analysis of X-ray data.2

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“…For example, a combined x-ray and neutron diffraction analysis shows that nickel migrates to the lithium layer, and nuclear magnetic resonance spectroscopy can determine the presence of lithium in the transition metal layer, the identities of its neighbors, and also whether it is in octahedral or tetrahedral sites. 29,30 Magnetic susceptibility measurements have shown the presence of nickel ions in the lithium layer and how these interactions change as the lithium content is lowered on charging. 31 Even more challenging will be the characterization of advanced nanomaterials, which are often amorphous or at best poorly crystalline.…”

Section: The Characterization Of Materials and Cells In Electrical Enmentioning

confidence: 99%

Materials Challenges Facing Electrical Energy Storage

2008

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During the past two decades, the demand for the storage of electrical energy has mushroomed both for portable applications and for static applications. As storage and power demands have increased predominantly in the form of batteries, the system has evolved. However, the present electrochemical systems are too costly to penetrate major new markets, still higher performance is required, and environmentally acceptable materials are preferred. These limitations can be overcome only by major advances in new materials whose constituent elements must be available in large quantities in nature; nanomaterials appear to have a key role to play. New cathode materials with higher storage capacity are needed, as well as safer and lower cost anodes and stable electrolyte systems. Flywheels and pumped hydropower also have niche roles to play.

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NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries

Cited by 623 publications

References 159 publications

Review—Manganese-Based P2-Type Transition Metal Oxides as Sodium-Ion Battery Cathode Materials

Review—Manganese-Based P2-Type Transition Metal Oxides as Sodium-Ion Battery Cathode Materials

Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide

Materials Challenges Facing Electrical Energy Storage

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