Tetrahedral Occupied V Ions Enabling Reversible Three-Electron Redox of Cr3+ /Cr6+ in Layered Cathode Materials for Potassium-Ion Batteries.

Reversible three-electron redox of Cr3+ /Cr6+ in layered cathode materials for rechargeable batteries is very attractive in layered cathode materials, which leads to high capacity and energy density for rechargeable batteries. However, the poor reversibility and Cr-ion migration make it very challenging. In this work, by introducing V ions into tetrahedral sites of layer-structured NaCrO2 , reversible three-electron redox of Cr3+ /Cr6+ is realized successfully in NaCr0.92 V0.05 O2 (NCV05) cathode for potassium-ion batteries with a cut-off voltage of 4.0 V. V ions can weaken the attraction of Cr to electrons, leading to enhanced valence change of Cr ions. On the other hand, V in tetrahedral sites can facilitate the reversible migration of Cr between octahedral and tetrahedral sites via coulombic repulsion to realize the reversible redox between Cr3+ and Cr6+ during charge and discharge processes. In addition, V ions can inhibit the phase transition from O3 phase to O'3 phase during the charge process by adjusting the crystal lattices. As a result, the NaCr0.92 V0.05 O2 cathode exhibits a high reversible capacity of 130 mAh g-1 with promising cycle stability and rate capability. The strategy opens new opportunity for developing high-capacity cathode materials for potassium-ion batteries.

Stacking Order Induced Anion Redox Regulation for Layer-Structured Na0.75 Li0.2 Mn0.7 Cu0.1 O2 Cathode Materials.

Stacking order plays a key role in defining the electrochemical behavior and structural stability of layer-structured cathode materials. However, the detailed effects of stacking order on anionic redox in layer-structured cathode materials have not been investigated specifically and are still unrevealed. Herein, two layered cathodes with the same chemical formula but different stacking orders: P2-Na0.75 Li0.2 Mn0.7 Cu0.1 O2 (P2-LMC) and P3-Na0.75 Li0.2 Mn0.7 Cu0.1 O2 (P3-LMC) are compared. It is found that P3 stacking order is beneficial to improve the oxygen redox reversibility compared with P2 stacking order. By using synchrotron hard and soft X-ray absorption spectroscopies, three redox couples of Cu2+ /Cu3+ , Mn3.5+ /Mn4+ , and O2- /O- are revealed to contribute charge compensation in P3 structure simultaneously, and two redox couples of Cu2+ /Cu3+ and O2- /O- are more reversible than those in P2-LMC due to the higher electronic densities in Cu 3d and O 2p orbitals in P3-LMC. In situ X-ray diffraction reveals that P3-LMC exhibits higher structural reversibility during charge and discharge than P2-LMC, even at 5C rate. As a result, P3-LMC delivers a high reversible capacity of 190.3 mAh g-1 and capacity retention of 125.7 mAh g-1 over 100 cycles. These findings provide new insight into oxygen-redox-involved layered cathode materials for SIBs.

Reversible Li Plating on Graphite Anodes through Electrolyte Engineering for Fast-Charging Batteries.

The difficulties to identify the rate-limiting step cause the lithium (Li) plating hard to be completely avoided on graphite anodes during fast charging. Therefore, Li plating regulation and morphology control are proposed to address this issue. Specifically, a Li plating-reversible graphite anode is achieved via a localized high-concentration electrolyte (LHCE) to successfully regulate the Li plating with high reversibility over high-rate cycling. The evolution of solid electrolyte interphase (SEI) before and after Li plating is deeply investigated to explore the interaction between the lithiation behavior and electrochemical interface polarization. Under the fact that Li plating contributes 40 % of total lithiation capacity, the stable LiF-rich SEI renders the anode a higher average Coulombic efficiency (99.9 %) throughout 240 cycles and a 99.95 % reversibility of Li plating. Consequently, a self-made 1.2-Ah LiNi0.5 Mn0.3 Co0.2 O2 | graphite pouch cell delivers a competitive retention of 84.4 % even at 7.2 A (6 C) after 150 cycles. This work creates an ingenious bridge between the graphite anode and Li plating, for realizing the high-performance fast-charging batteries.

Transition Metal Vacancy in Layered Cathode Materials for Sodium-Ion Batteries.

Anionic redox has been considered as a promising strategy to break the capacity limitation of cathode materials that solely relies on the intrinsic cationic redox in secondary batteries. Vacancy, as a kind of defect, can be introduced into transition metal layer to trigger oxygen redox, thus enhancing the energy density of layer-structured cathode materials for sodium-ion batteries. Herein, the formation process, recent progress in working mechanisms of triggering oxygen redox, as well as advanced characterization techniques for transition metal (TM) vacancy were overviewed and discussed. Strategies applied to stabilize the vacancy contained structures and harness the reversible oxygen redox were summarized. Furthermore, the challenges and prospects for further understanding TM vacancy were particularly emphasized.

Pilot-Scale Synthesis Sodium Iron Fluorophosphate Cathode with High Tap Density for a Sodium Pouch Cell.

Sodium-ion batteries (SIBs) have attracted wide interest for energy storage because of the sufficient sodium element reserve on the earth; however, the electrochemical performance of SIBs cannot achieve the requirements so far, especially, the limitation of cathode materials. Here, a kilogram-scale route to synthesize Na2 FePO4 F/carbon/multi-walled carbon nanotubes microspheres (NFPF@C@MCNTs) composite with a high tap density of 1.2 g cm-3 is reported. The NFPF@C@MCNTs cathode exhibits a reversible specific capacity of 118.4 mAh g-1 at 0.1 C. Even under 5 C with high mass loading (10 mg cm-2 ), the specific capacity still maintains at 56.4 mAh g-1 with a capacity retention rate of 97% after 700 cycles. In addition, a hard carbon||NFPF@C@MCNTs pouch cell is assembled and tested, which exhibits a volumetric energy density of 325 Wh L-1 and gravimetrical energy density of 210 Wh kg-1 (base on electrode massing), and it provides more than 200 cycles with a capacity retention rate of 92%. Furthermore, the pouch cell can operate in an all-climate environment ranging from -40 to 80 °C. These results demonstrate that the NFPF@C@MCNTs microspheres are a promising candidate cathode for SIBs and facilitate its practical application in sodium cells.

The Raw Mixed Conducting Interphase Affords Effective Prelithiation in Working Batteries.

Contact prelithiation is an important strategy to compensate the initial capacity loss of lithium-ion batteries. However, the dead Li generated from inadequate Li conversion reduces the cycling stability of rechargeable batteries. Herein a mono-solvent dimethyl carbonate (DMC) electrolyte was employed in contact prelithiation for the first time. We discover that the low-organic-content raw electrolyte interphase (REI) induced by this electrolyte on Li source and anode is a mixed ion/electron conductor. Therefore, electron channels can be maintained even when the Li source has been completely wrapped by the DMC-derived REI. As a result, an outstanding Li source utilization of 92.8 % and a negligible dead Li yield can be realized. This strategy renders batteries with a very high initial Coulombic efficiency (90.0 %) and an excellent capacity retention (94.9 %) over 210 cycles, highlighting the significance of REI for effective contact prelithiation.

Anomalous Redox Features Induced by Strong Covalency in Layered NaTi1-y Vy S2 Cathodes for Na-Ion Batteries.

The rising demand for energy density of cathodes means the need to raise the voltage or capacity of cathodes. Transition metal (TM) doping has been employed to enhance the electrochemical properties in multiple aspects. The redox voltage of doped cathodes usually falls in between the voltage of undoped layered cathodes. However, we found anomalous redox features in NaTi1-y Vy S2 . The first discharge platform potential (2.4 V) is significantly higher than that of undoped NaTiS2 and NaVS2 (both around 2.2 V), and the energy density is raised by 15 %. We speculate that the anomalous voltage is mainly attributed to the strong hybridization in the Ti-V-S system. Ti3+ and V3+ undergo charge transfer and form a more stable Ti (t2g 0 eg 0 ) and V (t2g 3 eg 0 ) electronic configuration. Our results indicate that higher voltage of cathode materials could be achieved by strong TM-ligand covalency, and this conclusion provides possible opportunities to explore high voltage materials for future layered cathodes.

A Low-Voltage Layered Na2 TiGeO5 Anode for Lithium-Ion Battery.

Titanium-based anode materials have achieved much progress with the wide studies in lithium-ion batteries. However, these known materials usually possess high discharge voltage platforms and limited energy densities. Herein, a titanium-based oxide of Na2 TiGeO5 with layered structure, two-dimensional lamellar frame and exposed highly active (001) facet, exhibiting good electrochemical performance in terms of high capacity (410 mAh g-1 with a current density of 50 mA g-1 ), excellent rate capability and cycling stability with no obvious capacity attenuation after 4000 cycles, is reported. The appropriate discharge voltage plateau at around 0.2 V endows the Na2 TiGeO5 anode material high security compared with graphite and high energy density compared with spinel Li4 Ti5 O12 . Combining the electrochemical tests and the density functional theory calculations, the Li+ storage mechanism of Na2 TiGeO5 is elucidated and the conversion reaction process is revealed. More importantly, this study provides a way to develop low-voltage and high-capacity titanium-based anode materials for efficient energy storage.

Anionic Redox Regulated via Metal-Ligand Combinations in Layered Sulfides.

The increasing demand for energy storage is calling for improvements in cathode performance. In traditional layered cathodes, the higher energy of the metal 3d over the O 2p orbital results in one-band cationic redox; capacity solely from cations cannot meet the needs for higher energy density. Emerging anionic redox chemistry is promising to access higher capacity. In recent studies, the low-lying O nonbonding 2p orbital was designed to activate one-band oxygen redox, but they are still accompanied by reversibility problems like oxygen loss, irreversible cation migration, and voltage decay. Herein, by regulating the metal-ligand energy level, both extra capacities provided by anionic redox and highly reversible anionic redox process are realized in NaCr1- y Vy S2 system. The simultaneous cationic and anionic redox of Cr/V and S is observed by in situ X-ray absorption near edge structure (XANES). Under high d-p hybridization, the strong covalent interaction stabilizes the holes on the anions, prevents irreversible dimerization and cation migration, and restrains voltage hysteresis and voltage decay. The work provides a fundamental understanding of highly reversible anionic redox in layered compounds, and demonstrates the feasibility of anionic redox chemistry based on hybridized bands with d-p covalence.

Stabilizing Transition Metal Vacancy Induced Oxygen Redox by Co2+ /Co3+ Redox and Sodium-Site Doping for Layered Cathode Materials.

Anionic redox is an effective way to boost the energy density of layer-structured metal-oxide cathodes for rechargeable batteries. However, inherent rigid nature of the TMO6 (TM: transition metals) subunits in the layered materials makes it hardly tolerate the inner strains induced by lattice glide, especially at high voltage. Herein, P2-Na0.8 Mg0.13 [Mn0.6 Co0.2 Mg0.07 □0.13 ]O2 (□: TM vacancy) is designed that contains vacancies in TM sites, and Mg ions in both TM and sodium sites. Vacancies make the rigid TMO6 octahedron become more asymmetric and flexible. Low valence Co2+ /Co3+ redox couple stabilizes the electronic structure, especially at the charged state. Mg2+ in sodium sites can tune the interlayer spacing against O-O electrostatic repulsion. Time-resolved in situ X-ray diffraction confirms that irreversible structure evolution is effectively suppressed during deep desodiation benefiting from the specific configuration. X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations demonstrate that, deriving from the intrinsic vacancies, multiple local configurations of "□-O-□", "Na-O-□", "Mg-O-□" are superior in facilitating the oxygen redox for charge compensation than previously reported "Na-O-Mg". The resulted material delivers promising cycle stability and rate capability, with a long voltage plateau at 4.2 V contributed by oxygen, and can be well maintained even at high rates. The strategy will inspire new ideas in designing highly stable cathode materials with reversible anionic redox for sodium-ion batteries.

Boosting Reversibility of Mn-Based Tunnel-Structured Cathode Materials for Sodium-Ion Batteries by Magnesium Substitution.

Electrochemical irreversibility and sluggish mobility of Na+ in the cathode materials result in poor cycle stability and rate capability for sodium-ion batteries. Herein, a new strategy of introducing Mg ions into the hinging sites of Mn-based tunnel-structured cathode material is designed. Highly reversible electrochemical reaction and phase transition in this cathode are realized. The resulted Na0.44Mn0.95Mg0.05O2 with Mg2+ in the hinging Mn-O5 square pyramidal exhibits promising cycle stability and rate capability. At a current density of 2 C, 67% of the initial discharge capacity is retained after 800 cycles (70% at 20 C), much improved than the undoped Na0.44MnO2. The improvement is attribute to the enhanced Na+ diffusion kinetics and the lowered desodiation energy after Mg doping. Highly reversible charge compensation and structure evolution are proved by synchrotron-based X-ray techniques. Differential charge density and atom population analysis of the average electron number of Mn indicate that Na0.44Mn0.95Mg0.05O2 is more electron-abundant in Mn 3d orbits near the Fermi level than that in Na0.44MnO2, leading to higher redox participation of Mn ions.

Whole-Voltage-Range Oxygen Redox in P2-Layered Cathode Materials for Sodium-Ion Batteries.

Oxygen-redox of layer-structured metal-oxide cathodes has drawn great attention as an effective approach to break through the bottleneck of their capacity limit. However, reversible oxygen-redox can only be obtained in the high-voltage region (usually over 3.5 V) in current metal-oxide cathodes. Here, we realize reversible oxygen-redox in a wide voltage range of 1.5-4.5 V in a P2-layered Na0.7 Mg0.2 [Fe0.2 Mn0.6 □0.2 ]O2 cathode material, where intrinsic vacancies are located in transition-metal (TM) sites and Mg-ions are located in Na sites. Mg-ions in the Na layer serve as "pillars" to stabilize the layered structure during electrochemical cycling, especially in the high-voltage region. Intrinsic vacancies in the TM layer create the local configurations of "□-O-□", "Na-O-□" and "Mg-O-□" to trigger oxygen-redox in the whole voltage range of charge-discharge. Time-resolved techniques demonstrate that the P2 phase is well maintained in a wide potential window range of 1.5-4.5 V even at 10 C. It is revealed that charge compensation from Mn- and O-ions contributes to the whole voltage range of 1.5-4.5 V, while the redox of Fe-ions only contributes to the high-voltage region of 3.0-4.5 V. The orphaned electrons in the nonbonding 2p orbitals of O that point toward TM-vacancy sites are responsible for reversible oxygen-redox, and Mg-ions in Na sites suppress oxygen release effectively.

Freestanding Double-Layer MoO3/CNT@S Membrane: A Promising Flexible Cathode for Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have been regarded as a promising candidate of secondary batteries to satisfy the enormous demand for electric vehicles and energy storage applications. However, Li-S batteries still suffer from severe capacity fading due to the shuttle effect of lithium polysulfides. Here, we develop a freestanding double-layer MoO3/carbon nanotube@S (FMC@S) membrane by hydrothermal and suction filtration strategy, without polymer binder and current collector substrate. FMC@S contains a polysulfide blocking layer and an active material layer. Except for S content, the two layers have the same components and are integrated together, so there is no distinct interface between the two layers, which can facilitate ion and electron transport. As a result, the FMC@S cathode delivers promising capacity retention and rate capability. The hierarchical integrated design provides a new strategy to develop high-performance flexible cathodes for Li-S batteries.

Improving the Electrochemical Performance and Structural Stability of the LiNi0.8Co0.15Al0.05O2 Cathode Material at High-Voltage Charging through Ti Substitution.

LiNi0.8Co0.15Al0.05O2 (NCA) has been proven to be a good cathode material for lithium-ion batteries (LIBs), especially in electric vehicle applications. However, further elevating energy density of NCA is very challenging. Increasing the charging voltage of NCA is an effective method, but its structural instability remains a problem. In this work, we revealed that titanium substitution could improve cycle stability of NCA under high cutoff voltage significantly. Titanium ions with a relatively larger ion radius could modify the oxygen lattice and change the local coordination environment of NCA, leading to decreased cation migration, better kinetic and thermodynamic properties, and improved structural stability. As a result, the Ti-substituted NCA cathode exhibits impressive reversible capacity (198 mA h g-1 at 0.1C) with considerable cycle stability under a cutoff voltage up to 4.7 V. It is also revealed that Ti could suppress oxygen release in the high-voltage region, benefitting cycle and thermal stabilities. This work provides valuable insight into the design of high-voltage layered cathode materials for high-energy-density LIBs.