37 research outputs found
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Modification of Transition-Metal Redox by Interstitial Water in Hexacyanometalate Electrodes for Sodium-Ion Batteries.
A sodium-ion battery (SIB) solution is attractive for grid-scale electrical energy storage. Low-cost hexacyanometalate is a promising electrode material for SIBs because of its easy synthesis and open framework. Most hexacyanometalate-based SIBs work with aqueous electrolyte, and interstitial water in the material has been found to strongly affect the electrochemical profile, but the mechanism remains elusive. Here we provide a comparative study of the transition-metal redox in hexacyanometalate electrodes with and without interstitial water based on soft X-ray absorption spectroscopy and theoretical calculations. We found distinct transition-metal redox sequences in hydrated and anhydrated NaxMnFe(CN)6·zH2O. The Fe and Mn redox in hydrated electrodes are separated and are at different potentials, leading to two voltage plateaus. On the contrary, mixed Fe and Mn redox in the same potential range is found in the anhydrated system. This work reveals for the first time how transition-metal redox in batteries is strongly affected by interstitial molecules that are seemingly spectators. The results suggest a fundamental mechanism based on three competing factors that determine the transition-metal redox potentials. Because most hexacyanometalate electrodes contain water, this work directly reveals the mechanism of how interstitial molecules could define the electrochemical profile, especially for electrodes based on transition-metal redox with well-defined spin states
Spectroscopic Signature of Oxidized Oxygen States in Peroxides
Recent debates on the oxygen redox behaviors in battery electrodes have
triggered a pressing demand for the reliable detection and understanding of
non-divalent oxygen states beyond conventional absorption spectroscopy. Here,
enabled by high-efficiency mapping of resonant inelastic X-ray scattering
(mRIXS) coupled with first-principles calculations, we report distinct mRIXS
features of the oxygen states in Li2O, Li2CO3, and especially, Li2O2, which are
successfully reproduced and interpreted theoretically. mRIXS signals are
dominated by valence-band decays in Li2O and Li2CO3. However, the oxidized
oxygen in Li2O2 leads to partially unoccupied O-2p states that yield a specific
intra-band excitonic feature in mRIXS. Such a feature displays a specific
emission energy in mRIXS, which disentangles the oxidized oxygen states from
the dominating transition-metal/oxygen hybridization features in absorption
spectroscopy, thus providing critical hints for both detecting and
understanding the oxygen redox reactions in transition-metal oxide based
battery materials.Comment: 25 pages, 4 figures, plus 11 pages of Supplementary Information with
4 figure
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Dissociate lattice oxygen redox reactions from capacity and voltage drops of battery electrodes.
The oxygen redox (OR) activity is conventionally considered detrimental to the stability and kinetics of batteries. However, OR reactions are often confused by irreversible oxygen oxidation. Here, based on high-efficiency mapping of resonant inelastic x-ray scattering of both the transition metal and oxygen, we distinguish the lattice OR in Na0.6[Li0.2Mn0.8]O2 and compare it with Na2/3[Mg1/3Mn2/3]O2. Both systems display strong lattice OR activities but with distinct electrochemical stability. The comparison shows that the substantial capacity drop in Na0.6[Li0.2Mn0.8]O2 stems from non-lattice oxygen oxidations, and its voltage decay from an increasing Mn redox contribution upon cycling, contrasting those in Na2/3[Mg1/3Mn2/3]O2. We conclude that lattice OR is not the ringleader of the stability issue. Instead, irreversible oxygen oxidation and the changing cationic reactions lead to the capacity and voltage fade. We argue that lattice OR and other oxygen activities should/could be studied and treated separately to achieve viable OR-based electrodes
High Reversibility of Lattice Oxygen Redox in Na-ion and Li-ion Batteries Quantified by Direct Bulk Probes of both Anionic and Cationic Redox Reactions
The reversibility and cyclability of anionic redox in battery electrodes hold
the key to its practical employments. Here, through mapping of resonant
inelastic X-ray scattering (mRIXS), we have independently quantified the
evolving redox states of both cations and anions in Na2/3Mg1/3Mn2/3O2. The
bulk-Mn redox emerges from initial discharge and is quantified by
inverse-partial fluorescence yield (iPFY) from Mn-L mRIXS. Bulk and surface Mn
activities likely lead to the voltage fade. O-K super-partial fluorescence
yield (sPFY) analysis of mRIXS shows 79% lattice oxygen-redox reversibility
during initial cycle, with 87% capacity sustained after 100 cycles. In
Li1.17Ni0.21Co0.08Mn0.54O2, lattice-oxygen redox is 76% initial-cycle
reversible but with only 44% capacity retention after 500 cycles. These results
unambiguously show the high reversibility of lattice-oxygen redox in both
Li-ion and Na-ion systems. The contrast between Na2/3Mg1/3Mn2/3O2 and
Li1.17Ni0.21Co0.08Mn0.54O2 systems suggests the importance of distinguishing
lattice-oxygen redox from other oxygen activities for clarifying its intrinsic
properties.Comment: 33 pages, 8 Figures. Plus 14 pages of Supplementary Materials with 12
Figure
Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes
The discovery of facile Li transport in disordered, Li-excess rocksalt materials has opened a vast new chemical space for the development of high energy density, low cost Li-ion cathodes. We develop a strategy for obtaining optimized compositions within this class of materials, exhibiting high capacity and energy density as well as good reversibility, by using a combination of low-valence transition metal redox and a high-valence redox active charge compensator, as well as fluorine substitution for oxygen. Furthermore, we identify a new constraint on high-performance compositions by demonstrating the necessity of excess Li capacity as a means of counteracting high-voltage tetrahedral Li formation, Li-binding by fluorine and the associated irreversibility. Specifically, we demonstrate that 10–12% of Li capacity is lost due to tetrahedral Li formation, and 0.4–0.8 Li per F dopant is made inaccessible at moderate voltages due to Li–F binding. We demonstrate the success of this strategy by realizing a series of high-performance disordered oxyfluoride cathode materials based on Mn²+/⁴+ and V⁴+/⁵+ redox.Vehicle Technologies Program (U.S.) (Contract No. DE-AC02-05CH11231)United States. Department of Energy. Office of Energy Efficiency and Renewable Energy. Advanced Battery Materials Research Program (Subcontract No. 7056411)National Science Foundation (U.S.) (Reward No. OCI-1147503)National Science Foundation (U.S.) (grant number ACI- 105357)National Science Foundation (U.S.) (NSF DMR 172025)United States. Department of Energy (Contract No. DE-AC02-06C H11357)United States. Department of Energy. Office of Science (contract no. DE-AC02-05CH11231
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Elemental-sensitive Detection of the Chemistry in Batteries through Soft X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering.
Energy storage has become more and more a limiting factor of today's sustainable energy applications, including electric vehicles and green electric grid based on volatile solar and wind sources. The pressing demand of developing high-performance electrochemical energy storage solutions, i.e., batteries, relies on both fundamental understanding and practical developments from both the academy and industry. The formidable challenge of developing successful battery technology stems from the different requirements for different energy-storage applications. Energy density, power, stability, safety, and cost parameters all have to be balanced in batteries to meet the requirements of different applications. Therefore, multiple battery technologies based on different materials and mechanisms need to be developed and optimized. Incisive tools that could directly probe the chemical reactions in various battery materials are becoming critical to advance the field beyond its conventional trial-and-error approach. Here, we present detailed protocols for soft X-ray absorption spectroscopy (sXAS), soft X-ray emission spectroscopy (sXES), and resonant inelastic X-ray scattering (RIXS) experiments, which are inherently elemental-sensitive probes of the transition-metal 3d and anion 2p states in battery compounds. We provide the details on the experimental techniques and demonstrations revealing the key chemical states in battery materials through these soft X-ray spectroscopy techniques
Recommended from our members
Elemental-sensitive Detection of the Chemistry in Batteries through Soft X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering.
Energy storage has become more and more a limiting factor of today's sustainable energy applications, including electric vehicles and green electric grid based on volatile solar and wind sources. The pressing demand of developing high-performance electrochemical energy storage solutions, i.e., batteries, relies on both fundamental understanding and practical developments from both the academy and industry. The formidable challenge of developing successful battery technology stems from the different requirements for different energy-storage applications. Energy density, power, stability, safety, and cost parameters all have to be balanced in batteries to meet the requirements of different applications. Therefore, multiple battery technologies based on different materials and mechanisms need to be developed and optimized. Incisive tools that could directly probe the chemical reactions in various battery materials are becoming critical to advance the field beyond its conventional trial-and-error approach. Here, we present detailed protocols for soft X-ray absorption spectroscopy (sXAS), soft X-ray emission spectroscopy (sXES), and resonant inelastic X-ray scattering (RIXS) experiments, which are inherently elemental-sensitive probes of the transition-metal 3d and anion 2p states in battery compounds. We provide the details on the experimental techniques and demonstrations revealing the key chemical states in battery materials through these soft X-ray spectroscopy techniques
Exploring the Charge Compensation Mechanism of P2-Type Na0.6Mg0.3Mn0.7O2 Cathode Materials for Advanced Sodium-Ion Batteries
P2-type sodium layered transition metal oxides have been intensively investigated as promising cathode materials for sodium-ion batteries (SIBs) by virtue of their high specific capacity and high operating voltage. However, they suffer from problems of voltage decay, capacity fading, and structural deterioration, which hinder their practical application. Therefore, a mechanistic understanding of the cationic/anionic redox activity and capacity fading is indispensable for the further improvement of electrochemical performance. Here, a prototype cathode material of P2-type Na0.6Mg0.3Mn0.7O2 is comprehensively investigated, which presents both cationic and anionic redox behaviors during the cycling process. By a combination of soft X-ray absorption spectroscopy and electroanalytical methods, we unambiguously reveal that only oxygen redox reaction is involved in the initial charge process, then both oxygen and manganese participate in the charge compensation in the following discharge process. In addition, a gradient distribution of Mn valence state from surface to bulk is disclosed, which could be mainly related to the irreversible oxygen activity during the charge process. Furthermore, we find that the average oxidation state of Mn is reduced upon extended cycles, leading to the noticeable capacity fading. Our results provide deeper insights into the intrinsic cationic/anionic redox mechanism of P2-type materials, which is vital for the rational design and optimization of advanced cathode materials for SIBs