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Cobalt-free layered lithium-rich nickel manganese oxides, Li[LixNiyMn1−x−y]O2 (LLNMO), are promising positive electrode materials for lithium rechargeable batteries because of their high energy density and low materials cost. However, substantial voltage decay is inevitable upon electrochemical cycling, which makes this class of materials less practical. It has been proposed that undesirable voltage decay is linked to irreversible structural rearrangement involving irreversible oxygen loss and cation migration. Herein, the authors demonstrate that the voltage decay of the electrode is correlated to Mn4+/Mn3+ redox activation and subsequent cation disordering, which can be remarkably suppressed via simple compositional tuning to induce the formation of Ni3+ in the pristine material. By implementing our new strategy, the Mn4+/Mn3+ reduction is subdued by an alternative redox reaction involving the use of pristine Ni3+ as a redox buffer, which has been designed to be widened from Ni3+/Ni4+ to Ni2+/Ni4+, without compensation for the capacity in principle. Negligible change in the voltage profile of modified LLNMO is observed upon extended cycling, and manganese migration into the lithium layer is significantly suppressed. Based on these findings, we propose a general strategy to suppress the voltage decay of Mn-containing lithium-rich oxides to achieve long-lasting high energy density from this class of materials.

Lithium-ion batteries based on intercalation compounds have dominated the advanced portable energy storage market. The positive electrode materials in these batteries belong to a material group of lithium-conducting crystals that contain redox-active transition metal and lithium. Materials without lithium-conducting paths or lithium-free compounds could be rarely used as positive electrodes due to the incapability of reversible lithium intercalation or the necessity of using metallic lithium as negative electrodes. These constraints have significantly limited the choice of materials and retarded the development of new positive electrodes in lithium-ion batteries. Here, we demonstrate that lithium-free transition metal monoxides that do not contain lithium-conducting paths in their crystal structure can be converted into high-capacity positive electrodes in the electrochemical cell by initially decorating the monoxide surface with nanosized lithium fluoride. This unusual electrochemical behaviour is attributed to a surface conversion reaction mechanism in contrast with the classic lithium intercalation reaction. Our findings will offer a potential new path in the design of positive electrode materials in lithium-ion batteries.

Microstructural engineering is becoming notably important in the realization of cobalt-free, high-nickel layered oxide cathodes for lithium-ion batteries since it is one of the most effective ways to improve the overall performance by enhancing the mechanical and electrochemical properties of cathodes. In this regard, various dopants have been investigated to improve the structural and interfacial stabilities of cathodes with doping. Yet, there is a lack of a systematic understanding of the effects of dopants on microstructural engineering and cell performances. Herein, we show controlling the primary particle size by adopting dopants with different oxidation states and solubilities in the host structure as an effective way for tuning the cathode microstructure and performance. The reduction in the primary particle size of cobalt-free high-nickel layered oxide cathode materials, e.g., LiNi 0.95 Mn 0.05 O 2 (NM955), with high-valent dopants, such as Mo 6+ and W 6+ , gives a more homogeneous distribution of Li during cycling with suppressed microcracking, cell resistance, and transition-metal dissolution compared to lower-valent dopants, such as Sn 4+ and Zr 4+ . Accordingly, this approach offers promising electrochemical performance with cobalt-free high-nickel layered oxide cathodes.

Nickel-rich layered oxides are envisaged as key near-future cathode materials for high-energy lithium-ion batteries. However, their practical application has been hindered by their inferior cycle stability, which originates from chemo-mechanical failures. Here we probe the solid-state synthesis of LiNi 0.6 Co 0.2 Mn 0.2 O 2 in real time to better understand the structural and/or morphological changes during phase evolution. Multi-length-scale observations-using aberration-corrected transmission electron microscopy, in situ heating transmission electron microscopy and in situ X-ray diffraction-reveal that the overall synthesis is governed by the kinetic competition between the intrinsic thermal decomposition of the precursor at the core and the topotactic lithiation near the interface, which results in spatially heterogeneous intermediates. The thermal decomposition leads to the formation of intergranular voids and intragranular nanopores that are detrimental to cycling stability. Furthermore, we demonstrate that promoting topotactic lithiation during synthesis can mitigate the generation of defective structures and effectively suppress the chemo-mechanical failures., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

The rampant generation of lithium hydroxide and carbonate impurities, commonly known as residual lithium, is a practical obstacle to the mass-scale synthesis and handling of high-nickel (>90 %) layered oxides and their use as high-energy-density cathodes for lithium-ion batteries. Herein, we suggest a simple in situ method to control the residual lithium chemistry of a high-nickel lithium layered oxide, Li(Ni 0.91 Co 0.06 Mn 0.03 )O 2 (NCM9163), with minimal side effects. Based on thermodynamic considerations of the preferred reactions, we systematically designed a synthesis process that preemptively converts residual Li 2 O (the origin of LiOH and Li 2 CO 3 ) into a more stable compound by injecting reactive SO 2 gas. The preformed lithium sulfate thin film significantly suppresses the generation of LiOH and Li 2 CO 3 during both synthesis and storage, thereby mitigating slurry gelation and gas evolution and improving the cycle stability., (© 2020 Wiley-VCH GmbH.)

Since the discovery of LiNiO 2 several decades ago, a new era of electric vehicles demanding high-energy-density lithium-ion batteries (LIBs) has recently rebooted the interest in this cathode material to eliminate the dependence on expensive and scarcely available cobalt. However, LiNiO 2 has been plagued by cycle instability, thermal instability, and air instability. We present here an exploration of the mutual interaction of magnesium and copper in stabilizing the cobalt-free LiNiO 2 cathode. Although Mg doping is beneficial for the robustness of the bulk structure of LiNiO 2 , surface characterization results of Mg-doped LiNiO 2 implies the need for further surface protection. To that end, we have incorporated Cu in addition to Mg in that Cu stabilizes the surface of Mg-doped LiNiO 2 by forming a protective stable surface layer without harming the bulk. Notable variations of the surface residual lithium composition (Li Li2CO3 /Li LiOH ) along with the incorporation of stabilizers are also discussed. The harmony between Mg and Cu with as little as 0.5 atom % Mg and 0.3 atom % Cu significantly enhances the specific energy and cycle life of LiNiO 2 . This study demonstrates how the co-incorporation of optimal dopants can help stabilize both the bulk and surface and provides new insights toward developing cobalt-free layered oxide cathodes for high-energy-density LIBs.

The electrochemical properties and performances of lithium-ion batteries are primarily governed by their constituent electrode materials, whose intrinsic thermodynamic and kinetic properties are understood as the determining factor. As a part of complementing the intrinsic material properties, the strategy of nanosizing has been widely applied to electrodes to improve battery performance. It has been revealed that this not only improves the kinetics of the electrode materials but is also capable of regulating their thermodynamic properties, taking advantage of nanoscale phenomena regarding the changes in redox potential, solid-state solubility of the intercalation compounds, and reaction paths. In addition, the nanosizing of materials has recently enabled the discovery of new energy storage mechanisms, through which unexplored classes of electrodes could be introduced. Herein, we review the nanoscale phenomena discovered or exploited in lithium-ion battery chemistry thus far and discuss their potential implications, providing opportunities to further unveil uncharted electrode materials and chemistries. Finally, we discuss the limitations of the nanoscale phenomena presently employed in battery applications and suggest strategies to overcome these limitations.

Despite the high energy density of lithium-rich layered-oxide electrodes, their real-world implementation in batteries is hindered by the substantial voltage decay on cycling. This voltage decay is widely accepted to mainly originate from progressive structural rearrangements involving irreversible transition-metal migration. As prevention of this spontaneous cation migration has proven difficult, a paradigm shift toward management of its reversibility is needed. Herein, we demonstrate that the reversibility of the cation migration of lithium-rich nickel manganese oxides can be remarkably improved by altering the oxygen stacking sequences in the layered structure and thereby dramatically reducing the voltage decay. The preeminent intra-cycle reversibility of the cation migration is experimentally visualized, and first-principles calculations reveal that an O2-type structure restricts the movements of transition metals within the Li layer, which effectively streamlines the returning migration path of the transition metals. Furthermore, we propose that the enhanced reversibility mitigates the asymmetry of the anionic redox in conventional lithium-rich electrodes, promoting the high-potential anionic reduction, thereby reducing the subsequent voltage hysteresis. Our findings demonstrate that regulating the reversibility of the cation migration is a practical strategy to reduce voltage decay and hysteresis in lithium-rich layered materials.

Co-intercalation reactions make graphite as promising anodes for sodium ion batteries, however, the high redox potentials significantly lower the energy density. Herein, we investigate the factors that influence the co-intercalation potential of graphite and find that the tuning of the voltage as large as 0.38 V is achievable by adjusting the relative stability of ternary graphite intercalation compounds and the solvent activity in electrolytes. The feasibility of graphite anode in sodium ion batteries is confirmed in conjunction with Na 1.5 VPO 4.8 F 0.7 cathodes by using the optimal electrolyte. The sodium ion battery delivers an improved voltage of 3.1 V, a high power density of 3863 W kg -1 both electrodes , negligible temperature dependency of energy/power densities and an extremely low capacity fading rate of 0.007% per cycle over 1000 cycles, which are among the best thus far reported for sodium ion full cells, making it a competitive choice in large-scale energy storage systems.

The thermodynamic instability of the LiCoO 2 layered structure at >0.5Li extraction has been considered an obstacle for the reversible utilization of its near theoretical capacity at high cutoff voltage (>4.6 V vs Li/Li + ) in lithium-ion batteries. Many previous studies have focused on resolving this issue by surface modification of LiCoO 2 , which has proven to be effective in suppressing phase transformation. To determine the extent to which surface protection of LiCoO 2 is effective despite its thermodynamic instability and presumably incomplete reversibility involving the O1 phase, here we verify the intrinsic reversibility of bulk LiCoO 2 with extended lithium extraction by ruling out the effect of a surface. Specifically, first, we show that, contrary to conventional belief, electrochemical cycling of LiCoO 2 at a cutoff voltage of 4.8 V (vs Li/Li + ) results in better cycle stability and lower polarizations than those at 4.6 V. We demonstrate, using an exhaustive suite of characterization tools, that the rapid cycle degradation under high-voltage cycling is mostly caused by the formation of a surface resistive layer; however, these damaged surfaces are leached out faster than they are accumulated above a certain potential, which results in superior cyclability compared with that achieved for less oxidative 4.6-V cycling. This beneficial leaching out of the resistive surface layer serves as a "subtractive" surface modification and plays a role in enhancing the cycle stability and is distinguished from conventional "additive" surface modification such as coating. This approach allows us to decouple factors of the bulk and surface degradations that contribute to the capacity fade and leads to the finding that, in the absence of a resistive surface, the capacity retention of a LiCoO 2 electrode with 4.8-V cutoff cycling can be intrinsically high, indicating that the instability of the crystalline Li x CoO 2 ( x < 0.5) has a limited effect on the cycle stability. Our findings also explain why the strategy of coating foreign materials on the surface of LiCoO 2 can improve the high-voltage cycling to some extent despite the expected thermodynamic instability of the highly charged phase.

All-solid-state batteries are considered as one of the attractive alternatives to conventional lithium-ion batteries, due to their intrinsic safe properties benefiting from the use of non-flammable solid electrolytes in ASSBs. However, one of the issues in employing the solid-state electrolyte is the sluggish ion transport kinetics arising from the chemical and physical instability of the interfaces among solid components including electrode material, electrolyte and additive agents. In this work, we investigate the stability of the interface between carbon conductive agents and Li 10 GeP 2 S 12 in a composite cathode and its effect on the electrochemical performance of ASSBs. It is found that the inclusion of various carbon conductive agents in composite cathode leads to inferior kinetic performance of the cathode despite expectedly enhanced electrical conductivity of the composite. We observe that the poor kinetic performance is attributed to a large interfacial impedance which is gradually developed upon the inclusions of the various carbon conductive agents regardless of their physical differences. The analysis through X-ray Photoelectron Spectroscopy suggests that the carbon additives in the composite cathode stimulate the electrochemical decomposition of LGPS electrolyte degrading its surface during cycling, indicating the large interfacial resistance stems from the undesirable decomposition of the electrolyte at the interface.

Despite their high specific capacity, sodium layered oxides suffer from severe capacity fading when cycled at higher voltages. This key issue must be addressed in order to develop high-performance cathodes for sodium ion batteries (SIBs). Herein, we present a comprehensive study on the influence of Al doping of Mn sites on the structural and electrochemical properties of a P2-Na 0.5 Mn 0.5-x Al x Co 0.5 O 2 (x = 0, 0.02, or 0.05) cathode for SIBs. Detailed structural, morphological, and electrochemical investigations were carried out using X-ray diffraction, cyclic voltammetry, and galvanostatic charge-discharge measurements, and some new insights are proposed. Rietveld refinement confirmed that Al doping caused TMO 6 octahedra (TM = transition metal) shrinkage, resulting in wider interlayer spacing. After optimizing the aluminum concentration, the cathode exhibited remarkable electrochemical performance, with better stability and improved rate performance. Electrochemical impedance spectroscopy (EIS) measurements were performed at various states of charge to probe the surface and bulk effects of Al doping. The material presented here exhibits exceptional stability over 100 cycles within a 1.5-4.3 V window and outperforms several other Mn-Co-based cathodes for SIBs. This study presents a facile method for designing structurally stable cathodes for SIBs.

The development of a high-performance oxygen evolution reaction (OER) catalyst is pivotal for the practical realization of a water-splitting system. Although an extensive search for OER catalysts has been performed in the past decades, cost-effective catalysts remain elusive. Herein, an amorphous cobalt phyllosilicate (ACP) with layered crystalline motif prepared by a room-temperature precipitation is introduced as a new OER catalyst; this material exhibits a remarkably low overpotential (η ≈ 367 mV for a current density of 10 mA cm -2 ). A structural investigation using X-ray absorption spectroscopy reveals that the amorphous structure contains layered motifs similar to the structure of CoOOH, which is demonstrated to be responsible for the OER catalysis based on density functional theory calculations. However, the calculations also reveal that the local environment of the active site in the layered crystalline motif in the ACP is significantly modulated by the silicate, leading to a substantial reduction of η of the OER compared with that of CoOOH. This work proposes amorphous phyllosilicates as a new group of efficient OER catalysts and suggests that tuning of the catalytic activity by introducing redox-inert groups may be a new unexplored avenue for the design of novel high-performance catalysts., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Shedding new light on conventional batteries sometimes inspires a chemistry adoptable for rechargeable batteries. Recently, the primary lithium-sulfur dioxide battery, which offers a high energy density and long shelf-life, is successfully renewed as a promising rechargeable system exhibiting small polarization and good reversibility. Here, we demonstrate for the first time that reversible operation of the lithium-sulfur dioxide battery is also possible by exploiting conventional carbonate-based electrolytes. Theoretical and experimental studies reveal that the sulfur dioxide electrochemistry is highly stable in carbonate-based electrolytes, enabling the reversible formation of lithium dithionite. The use of the carbonate-based electrolyte leads to a remarkable enhancement of power and reversibility; furthermore, the optimized lithium-sulfur dioxide battery with catalysts achieves outstanding cycle stability for over 450 cycles with 0.2 V polarization. This study highlights the potential promise of lithium-sulfur dioxide chemistry along with the viability of conventional carbonate-based electrolytes in metal-gas rechargeable systems.

With the demand for high-energy-storage devices, the rechargeable metal-oxygen battery has attracted attention recently. Sodium-oxygen batteries have been regarded as the most promising candidates because of their lower-charge overpotential compared with that of lithium-oxygen system. However, conflicting observations with different discharge products have inhibited the understanding of precise reactions in the battery. Here we demonstrate that the competition between the electrochemical and chemical reactions in sodium-oxygen batteries leads to the dissolution and ionization of sodium superoxide, liberating superoxide anion and triggering the formation of sodium peroxide dihydrate (Na2O2·2H2O). On the formation of Na2O2·2H2O, the charge overpotential of sodium-oxygen cells significantly increases. This verification addresses the origin of conflicting discharge products and overpotentials observed in sodium-oxygen systems. Our proposed model provides guidelines to help direct the reactions in sodium-oxygen batteries to achieve high efficiency and rechargeability.

Perovskite solar cells (PSCs) are the most promising candidates as next-generation solar energy conversion systems. To design a highly efficient PSC, understanding electronic properties of mesoporous metal oxides is essential. Herein, we explore the effect of Nb doping of TiO2 on electronic structure and photovoltaic properties of PSCs. Light Nb doping (0.5 and 1.0 at %) increased the optical band gap slightly, but heavy doping (5.0 at %) distinctively decreased it. The relative Fermi level position of the conduction band is similar for the lightly Nb-doped TiO2 (NTO) and the undoped TiO2 whereas that of the heavy doped NTO decreased by as much as ∼0.3 eV. The lightly doped NTO-based PSCs exhibit 10 % higher efficiency than PSCs based on undoped TiO2 (from 12.2 % to 13.4 %) and 52 % higher than the PSCs utilizing heavy doped NTO (from 8.8 % to 13.4 %), which is attributed to fast electron injection/transport and preserved electron lifetime, verified by transient photocurrent decay and impedance studies., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Fabricating inorganic-organic hybrid perovskite solar cells (PSCs) on plastic substrates broadens their scope for implementation in real systems by imparting portability, conformability and allowing high-throughput production, which is necessary for lowering costs. Here we report a new route to prepare highly dispersed Zn2SnO4 (ZSO) nanoparticles at low-temperature (<100 °C) for the development of high-performance flexible PSCs. The introduction of the ZSO film significantly improves transmittance of flexible polyethylene naphthalate/indium-doped tin oxide (PEN/ITO)-coated substrate from ∼75 to ∼90% over the entire range of wavelengths. The best performing flexible PSC, based on the ZSO and CH3NH3PbI3 layer, exhibits steady-state power conversion efficiency (PCE) of 14.85% under AM 1.5G 100 mW·cm(-2) illumination. This renders ZSO a promising candidate as electron-conducting electrode for the highly efficient flexible PSC applications.

In recent studies of inorganic materials for energy applications, surface modification processes have been shown to be among the most effective methods to enhance the performance of devices. Here, we demonstrate a facile nano-decoration method which is generally applicable to anatase TiO2 nanostructures, as well as a nano-decorated hierarchical TiO2 nanostructure which improves the energy conversion efficiency of a dye-sensitized solar cell (DSSC). Using a facile sol-gel method, 0-D, 1-D, and 2-D type anatase TiO2 nanostructures were decorated with 200 nm long anatase TiO2 nanorods to create various hierarchical nanostructures. A structural analysis reveals that the branched nanorod has a highly crystalline anatase phase with anisotropic growth in the [001] longitudinal direction. When one of the hierarchical structures, a chestnut bur-like nanostructure, was employed in a dye-sensitized solar cell as a scattering layer, offering increased dye-loading properties, preserving a sufficient level of light-scattering ability and preserving superior charge transport and recombination properties as well, the energy conversion efficiency of the cell improved by 19% (from 7.16% to 9.09%) compared to a cell with a 0-D TiO2 sphere as a scattering layer. This generally applicable anatase nanorod-decorating method offers potential applications in various energy-conversion applications, especially in DSSCs, quantum-dot solar cells, photoelectrochemical water-splitting devices, photocatalysis, and lithium ion batteries.

Herein, we report on the synthesis of phase-pure rutile walnut-like TiO(2) (W-TiO(2)) spheres composed of single-crystalline nanorod-building blocks using a surfactant-free non-aqueous acidic modified "benzyl alcohol route". Based on the various HCl concentration- and reaction time-dependent experiments, an effect of hydrochloric acid on the phase formation mechanism in a non-aqueous system is suggested. As anodes for Li-ion batteries, the W-TiO(2) sphere electrodes exhibited superior cycling performance at a rate of 0.2 C without any conducting layers coated onto the anodes; this result is attributed to their high crystallinity and large surface area.