Tuning Proton Insertion Chemistry for Sustainable Aqueous Zinc-Ion Batteries.

Rechargeable aqueous zinc-ion batteries (ZIBs) have emerged as an alternative to lithium-ion batteries due to their affordability and high level of safety. However, their commercialization is hindered by the low mass loading and irreversible structural changes of the cathode materials during cycling. Here, a disordered phase of a manganese nickel cobalt dioxide cathode material derived from wastewater via a coprecipitation process is reported. When used as the cathode for aqueous ZIBs , the developed electrode delivers 98% capacity retention at a current density of 0.1 A g-1 and 72% capacity retention at 1 A g-1 while maintaining high mass loading (15 mg cm-2 ). The high performance is attributed to the structural stability of the Co and Ni codoped phase; the dopants effectively suppress Jahn-Teller distortion of the manganese dioxide during cycling, as revealed by operando X-ray absorption spectroscopy. Also, it is found that the Co and Ni co-doped phase effectively inhibits the dissolution of Mn2+ , resulting in enhanced durability without capacity decay at first 20 cycles. Further, it is found that the performance of the electrode is sensitive to the ratio of Ni to Co, providing important insight into rational design of more efficient cathode materials for low-cost, sustainable, rechargeable aqueous ZIBs.

A Single-Atom Fe-N-C Catalyst with Ultrahigh Utilization of Active Sites for Efficient Oxygen Reduction.

Fe-N-C single-atom catalysts (SACs) are emerging as a promising class of electrocatalysts for the oxygen reduction reaction (ORR) to replace Pt-based catalysts. However, due to the limited loading of Fe for SACs and the inaccessibility of internal active sites, only a small portion of the sites near the external surface are able to contribute to the ORR activity. Here, this work reports a metal-organic framework-derived Fe-N-C SAC with a hierarchically porous and concave nanoarchitecture prepared through a facile but effective strategy, which exhibits superior electrocatalytic ORR activity with a half-wave potential of 0.926 V (vs RHE) in alkaline media and 0.8 V (vs RHE) in acidic media while maintaining excellent stability. The superior ORR activity of the as-designed catalyst stems from the unique architecture, where the hierarchically porous architecture contains micropores as Fe SAC anchoring sites, meso-/macro-pores as accessible channels, and concave shell for increasing external surface area. The unique architecture has dramatically enhanced the utilization of previously blocked internal active sites, as confirmed by a high turnover frequency of 3.37 s-1 and operando X-ray absorption spectroscopy analysis with a distinct shift of adsorption edge.

A Nonstoichiometric Niobium Oxide/Graphite Composite for Fast-Charge Lithium-Ion Batteries.

Electrification of transportation has spurred the development of fast-charge energy storage devices. High-power lithium-ion batteries require electrode materials that can store lithium quickly and reversibly. Herein, the design and construction of a Nb2 O5-δ /graphite composite electrode that demonstrates remarkable rate capability and durability are reported. The presence of graphite enables the formation of a dominant Nb12 O29 phase and a minor T-Nb2 O5 phase. The high rate capability is attributed to the enhanced electronic conductivity and lower energy barriers for fast lithium diffusion in both Nb12 O29 and T-Nb2 O5 , as unraveled by density functional theory calculations. The excellent durability or long cycling life is originated from the coherent redox behavior of Nb ions and high reversibility of lithium intercalation/deintercalation, as revealed by operando X-ray absorption spectroscopy analysis. When tested in a half-cell at high cycling rates, the composite electrode delivers a specific capability of 120 mAh g-1 at 80 C and retains over 150 mAh g-1 after 2000 cycles at 30 C, implying that it is a highly promising anode material for fast-charging lithium-ion batteries.

Oxygen Vacancy Diffusion and Condensation in Lithium-Ion Battery Cathode Materials.

Oxygen vacancies (OV) are native defects in transition metal (TM) oxides and their presence has a critical effect on the physicochemical properties of the oxide. Metal oxides are commonly used in lithium-ion battery (LIB) cathodes and there is still a lack of understanding of the role of OVs in LIB research field. Here, we report on the behavior of OVs in a single-crystal LIB cathode during the non-equilibrium states of charge and discharge. We found that microcrack evolution in a single crystal occurs due to OV condensation in specific crystallographic orientations generated by the continuous migration of OVs and TM ions. Moreover, understanding the effects of the presence and diffusion of OVs in metal oxides enables the elucidation of most of the conventional mechanisms of capacity fading in LIBs and provides new insights for new electrochemical applications.

A Tailored Bifunctional Electrocatalyst: Boosting Oxygen Reduction/Evolution Catalysis via Electron Transfer Between N-Doped Graphene and Perovskite Oxides.

Fabricating perovskite oxide/carbon material composite catalysts is a widely accepted strategy to enhance oxygen reduction reaction/oxygen evolution reaction (ORR and OER) catalytic activities. Herein, synthesized, porous, perovskite-type Sm0.5 Sr0.5 CoO3-δ hollow nanofibers (SSC-HF) are hybridized with cross-linked, 3D, N-doped graphene (3DNG). This rationally designed hybrid catalyst, SSC-HF-3DNG (SSC-HG), exhibits a remarkable enhancement in ORR/OER activity in alkaline media. The synergistic effects between SSC and 3DNG during their ORR and OER processes are firstly revealed by density functional theory calculations. It suggests that electron transport from 3DNG to O2 and SSC increases the activity of electrocatalytic reactions (ORR and OER) by activating O2 , increasing the covalent bonding of lattice oxygen. This electron transfer-accelerated catalysis behavior in SSC-HG will provide design guidelines for composites of perovskite and carbon with bifunctional catalysts.

Unveiling the Catalytic Origin of Nanocrystalline Yttrium Ruthenate Pyrochlore as a Bifunctional Electrocatalyst for Zn-Air Batteries.

Zn-air batteries suffer from the slow kinetics of oxygen reduction reaction (ORR) and/or oxygen evolution reaction (OER). Thus, the bifunctional electrocatalysts are required for the practical application of rechargeable Zn-air batteries. In terms of the catalytic activity and structural stability, pyrochlore oxides (A2[B2-xAx]O7-y) have emerged as promising candidates. However, a limited use of A-site cations (e.g., lead or bismuth cations) of reported pyrochlore catalysts have hampered broad understanding of their catalytic effect and structure. More seriously, the catalytic origin of the pyrochlore structure was not clearly revealed yet. Here, we report the new nanocrystalline yttrium ruthenate (Y2[Ru2-xYx]O7-y) with pyrochlore structure. The prepared pyrochlore oxide demonstrates comparable catalytic activities in both ORR and OER, compared to that of previously reported metal oxide-based catalysts such as perovskite oxides. Notably, we first find that the catalytic activity of the Y2[Ru2-xYx]O7-y is associated with the oxidations and corresponding changes of geometric local structures of yttrium and ruthenium ions during electrocatalysis, which were investigated by in situ X-ray absorption spectroscopy (XAS) in real-time. Zn-air batteries using the prepared pyrochlore oxide achieve highly enhanced charge and discharge performance with a stable potential retention for 200 cycles.

Integrated Hierarchical Cobalt Sulfide/Nickel Selenide Hybrid Nanosheets as an Efficient Three-dimensional Electrode for Electrochemical and Photoelectrochemical Water Splitting.

Developing highly active electrocatalysts for photoelectrochemical water splitting is critical to bring solar/electrical-to-hydrogen energy conversion processes into reality. Herein, we report a three-dimensional (3D) hybrid electrocatalyst that is constructed through in situ anchoring of Co9S8 nanosheets onto the surface of Ni3Se2 nanosheets vertically aligned on an electrochemically exfoliated graphene foil. Benefiting from the synergistic effects between Ni3Se2 and Co9S8, the highly conductive graphene support, and large surface area, the novel 3D hybrid electrode delivers superior electrocatalytic activity toward water reduction in alkaline media, featuring overpotentials of -0.17 and -0.23 V to achieve current densities of 20 and 50 mA cm-2, respectively, demonstrating an electrocatalytic performance on the top of the Ni3Se2- and Co9S8-based electrocatalysts as reported in literature. Experimental investigations and theoretical calculations confirm that the remarkable activity of the obtained material results from the unique 3D hierarchical architecture and interface reconstruction between Ni3Se2 and Co9S8 through Ni-S bonding, which leads to charge redistribution and thus lowers the energy barrier of hydrogen desorption in the water splitting process. Further integration of the 3D hybrid electrode with a macroporous silicon photocathode enables highly active and sustainable sunlight-driven water splitting in both basic media and real river water. The overall water splitting with 10 mA cm-2 at a low voltage of 1.62 V is achieved using our hybrid as both anode and cathode catalysts, which surpasses that of the Ir/C-Pt/C couple (1.60 V) for sufficiently high overpotentials.

Enhanced Intrinsic Catalytic Activity of λ-MnO2 by Electrochemical Tuning and Oxygen Vacancy Generation.

Chemically prepared λ-MnO2 has not been intensively studied as a material for metal-air batteries, fuel cells, or supercapacitors because of their relatively poor electrochemical properties compared to α- and δ-MnO2 . Herein, through the electrochemical removal of lithium from LiMn2 O4 , highly crystalline λ-MnO2 was prepared as an efficient electrocatalyst for the oxygen reduction reaction (ORR). The ORR activity of the material was further improved by introducing oxygen vacancies (OVs) that could be achieved by increasing the calcination temperature during LiMn2 O4 synthesis; a concentration of oxygen vacancies in LiMn2 O4 could be characterized by its voltage profile as the cathode in a lithiun-metal half-cell. λ-MnO2-z prepared with the highest OV exhibited the highest diffusion-limited ORR current (5.5 mA cm(-2) ) among a series of λ-MnO2-z electrocatalysts. Furthermore, the number of transferred electrons (n) involved in the ORR was >3.8, indicating a dominant quasi-4-electron pathway. Interestingly, the catalytic performances of the samples were not a function of their surface areas, and instead depended on the concentration of OVs, indicating enhancement in the intrinsic catalytic activity of λ-MnO2 by the generation of OVs. This study demonstrates that differences in the electrochemical behavior of λ-MnO2 depend on the preparation method and provides a mechanism for a unique catalytic behavior of cubic λ-MnO2 .

Metal-free Ketjenblack incorporated nitrogen-doped carbon sheets derived from gelatin as oxygen reduction catalysts.

Electrocatalysts facilitating oxygen reduction reaction (ORR) are vital components in advanced fuel cells and metal-air batteries. Here we report Ketjenblack incorporated nitrogen-doped carbon sheets derived from gelatin and apply these easily scalable materials as metal-free electrocatalysts for ORR. These carbon nanosheets demonstrate highly comparable catalytic activity for ORR as well as better durability than commercial Vulcan carbon supported Pt catalysts in alkaline media. Physico-chemical characterization and theoretical calculations suggest that proper combination of graphitic and pyridinic nitrogen species with more exposed edge sites effectively facilitates a formation of superoxide, [O2(ad)](-), via one-electron transfer, thus increasing catalytic activities for ORR. Our results demonstrate a novel strategy to expose more nitrogen doped edge sites by irregular stacked small sheets in developing better electrocatalysts for Zn-air batteries. These desirable architectures are embodied by an amphiphlilic gelatin mediated compatible synthetic strategy between hydrophobic carbon and aqueous water.

Nb1.60Ti0.32W0.08O5-δ as negative electrode active material for durable and fast-charging all-solid-state Li-ion batteries.

Li-based all-solid-state batteries (ASSBs) are considered feasible candidates for the development of the next generation of high-energy rechargeable batteries. However, ASSBs are detrimentally affected by a limited rate capability and inadequate performance at high currents. To circumvent these issues, here we propose the use of Nb1.60Ti0.32W0.08O5-δ (NTWO) as negative electrode active material. NTWO is capable of overcoming the limitation of lithium metal as the negative electrode, offering fast-charging capabilities and cycle stability. Physicochemical and electrochemical characterizations of NTWO in combination with the Li6PS5Cl (LPSCl) solid-state electrolyte demonstrate that the formation of LiWS2 at the electrode|electrolyte interphase is the main responsible for the improved battery performance. Indeed, when an NTWO-based negative electrode and LPSCl are coupled with a LiNbO3-coated LiNi0.8Mn0.1Co0.1O2-based positive electrode, the lab-scale cell is capable of maintaining 80% of discharge capacity retention after 5000 cycles at 45 mA cm-2 at 60 °C and 60 MPa.

A High-Rate, Durable Cathode for Sodium-Ion Batteries: Sb-Doped O3-Type Ni/Mn-Based Layered Oxides.

O3-Type layered oxides are widely studied as cathodes for sodium-ion batteries (SIBs) due to their high theoretical capacities. However, their rate capability and durability are limited by tortuous Na+ diffusion channels and complicated phase evolution during Na+ extraction/insertion. Here we report our findings in unravelling the mechanism for dramatically enhancing the stability and rate capability of O3-NaNi0.5Mn0.5-xSbxO2 (NaNMS) by substitutional Sb doping, which can alter the coordination environment and chemical bonds of the transition metal (TM) ions in the structure, resulting in a more stable structure with wider Na+ transport channels. Furthermore, NaNMS nanoparticles are obtained by surface energy regulation during grain growth. The synergistic effect of Sb doping and nanostructuring greatly reduces the ionic migration energy barrier while increasing the reversibility of the structural evolution during repeated Na+ extraction/insertion. An optimized NaNMS-1 electrode delivers a reversible capacity of 212.3 mAh g-1 at 0.2 C and 74.5 mAh g-1 at 50 C with minimal capacity loss after 100 cycles at a low temperature of -20 °C. Such electrochemical performance is superior to most of the reported layered oxide cathodes used in rechargeable SIBs.

Evaluation of the Volumetric Activity of the Air Electrode in a Zinc-Air Battery Using a Nitrogen and Sulfur Co-doped Metal-free Electrocatalyst.

While numerous oxygen electrocatalysts have been reported to enhance zinc-air battery (ZAB) performance, highly efficient electrocatalysts for the oxygen electrocatalysis need to be developed for broader commercialization of ZABs. Furthermore, areal (instead of volumetric) power density has been used to benchmark the performance of ZABs, often causing ambiguities or confusions. Here, we propose a methodology for evaluating the performance of a ZAB using the volumetric (rather than the areal) power density by taking into consideration the air electrode thickness. A nitrogen and sulfur co-doped metal-free oxygen reduction electrocatalyst (N-S-PC) is used as a model catalyst for this new metric. The electrocatalyst exhibited a half-wave potential of 0.88 V, which is similar to that of the Pt/C electrocatalyst (0.89 V) due to the effects of co-doping and a highly mesoporous structure. In addition, the use of volumetric activity allows fair comparison among different types of air electrodes. The N-S-PC-loaded air electrode demonstrated a higher peak power density (5 W cm-3) than the carbon felt or paper electrode in the ZAB test under the same testing conditions.

Fully Conjugated Phthalocyanine Copper Metal-Organic Frameworks for Sodium-Iodine Batteries with Long-Time-Cycling Durability.

Rechargeable sodium-iodine (Na-I2 ) batteries are attracting growing attention for grid-scale energy storage due to their abundant resources, low cost, environmental friendliness, high theoretical capacity (211 mAh g-1 ), and excellent electrochemical reversibility. Nevertheless, the practical application of Na-I2 batteries is severely hindered by their poor cycle stability owing to the serious dissolution of polyiodide in the electrolyte during charge/discharge processes. Herein, the atomic modulation of metal-bis(dihydroxy) species in a fully conjugated phthalocyanine copper metal-organic framework (MOF) for suppression of polyiodide dissolution toward long-time cycling Na-I2 batteries is demonstrated. The Fe2 [(2,3,9,10,16,17,23,24-octahydroxy phthalocyaninato)Cu] MOF composited with I2 (Fe2 -O8 -PcCu/I2 ) serves as a cathode for a Na-I2 battery exhibiting a stable specific capacity of 150 mAh g-1 after 3200 cycles and outperforming the state-of-the-art cathodes for Na-I2 batteries. Operando spectroelectrochemical and electrochemical kinetics analyses together with density functional theory calculations reveal that the square planar iron-bis(dihydroxy) (Fe-O4 ) species in Fe2 -O8 -PcCu are responsible for the binding of polyiodide to restrain its dissolution into electrolyte. Besides the monovalent Na-I2 batteries in organic electrolytes, the Fe2 -O8 -PcCu/I2 cathode also operates stably in other metal-I2 batteries like aqueous multivalent Zn-I2 batteries. Thus, this work offers a new strategy for designing stable cathode materials toward high-performance metal-iodine batteries.

Excess-Li Localization Triggers Chemical Irreversibility in Li- and Mn-Rich Layered Oxides.

Li- and Mn-rich layered oxides (LMRs) have emerged as practically feasible cathode materials for high-energy-density Li-ion batteries due to their extra anionic redox behavior and market competitiveness. However, sluggish kinetics regions (<3.5 V vs Li/Li+ ) associated with anionic redox chemistry engender LMRs with chemical irreversibility (first-cycle irreversibility, poor rate properties, voltage fading), which limits their practical use. Herein, the structural origin of this chemical irreversibility is revealed through a comparative study involving Li1.15 Mn0.51 Co0.17 Ni0.17 O2 with relatively localized and delocalized excess-Li in its lattice system. Operando fine-interval X-ray absorption spectroscopy is used to simultaneously observe the interplay between transition-metal-oxygen (TM-O) redox chemistry and TM migration behavior in real time. Density functional theory calculations show that excess-Li localization in the LMR structure attenuates TM-O covalency and stability, leading to overall chemical irreversibility. Hence, the delocalized excess-Li system is proposed as an alternative design for practically feasible LMR cathodes with restrained TM migration and sustainable O-redox chemistry.

Towards maximized volumetric capacity via pore-coordinated design for large-volume-change lithium-ion battery anodes.

To achieve the urgent requirement for high volumetric energy density in lithium-ion batteries, alloy-based anodes have been spotlighted as next-generation alternatives. Nonetheless, for the veritable accomplishment with regards to high-energy demand, alloy-based anodes must be evaluated considering several crucial factors that determine volumetric capacity. In particular, the electrode swelling upon cycling must be contemplated if these anodes are to replace conventional graphite anodes in terms of volumetric capacity. Herein, we propose macropore-coordinated graphite-silicon composite by incorporating simulation and mathematical calculation of numerical values from experimental data. This unique structure exhibits minimized electrode swelling comparable to conventional graphite under industrial electrode fabrication conditions. Consequently, this hybrid anode, even with high specific capacity (527 mAh g-1) and initial coulombic efficiency (93%) in half-cell, achieves higher volumetric capacity (493.9 mAh cm-3) and energy density (1825.7 Wh L-1) than conventional graphite (361.4 mAh cm-3 and 1376.3 Wh L-1) after 100 cycles in the full-cell configuration.

Atomically dispersed nickel-nitrogen-sulfur species anchored on porous carbon nanosheets for efficient water oxidation.

Developing low-cost electrocatalysts to replace precious Ir-based materials is key for oxygen evolution reaction (OER). Here, we report atomically dispersed nickel coordinated with nitrogen and sulfur species in porous carbon nanosheets as an electrocatalyst exhibiting excellent activity and durability for OER with a low overpotential of 1.51 V at 10 mA cm-2 and a small Tafel slope of 45 mV dec-1 in alkaline media. Such electrocatalyst represents the best among all reported transition metal- and/or heteroatom-doped carbon electrocatalysts and is even superior to benchmark Ir/C. Theoretical and experimental results demonstrate that the well-dispersed molecular S|NiNx species act as active sites for catalyzing OER. The atomic structure of S|NiNx centers in the carbon matrix is clearly disclosed by aberration-corrected scanning transmission electron microscopy and synchrotron radiation X-ray absorption spectroscopy together with computational simulations. An integrated photoanode of nanocarbon on a Fe2O3 nanosheet array enables highly active solar-driven oxygen production.

Influence of Surface Charges/Chemistry on the Catalysis of Perovskite Complexes.

The electrochemical performance of the perovskite complex was discovered to depend greatly on the different locations of the identical particle, which represent different surface charges accordingly. The surface charges were evaluated by Zeta potential (ζ) for the intrinsic BSCF5582 (Ba0.5Sr0.5Co0.8Fe0.2O3 -δ), ball-milled (BM-BSCF5582), and heat-treated in an oxygen atmosphere after ball-milling (48h-O2-BM-BSCF5582), the mean ζ of which represents -11.1, 21.2, and -6.1 mV, respectively, which reflects well on different surface chemistries. When the bonding structures at the different stratified layers and the overall crystalline morphologies were analyzed via X-ray photoelectron spectroscopy and high resolution transmission electron microscopy, respectively, the crystalline- and bonding-structure at the 50 nm depth of BSCF5582 is nearly identical to that of BM-BSCF5582 at the surface. As ball-milling proceeds, not only are particles comminuted but also the amorphous surface is broken open, leading to the revelation of inner and naïve cubic crystalline phase surfaces and affecting the catalytic activities of oxygen evolution reactions and oxygen reduction reactions positively and negatively, respectively, at significant scales.

Highly active bifunctional oxygen electrocatalysts derived from nickel- or cobalt-phytic acid xerogel for zinc-air batteries.

Developing highly efficient non-noble metal electrocatalysts for oxygen electrode reactions is highly desirable for industrial scale application in energy related devices. Herein, two new kinds of Ni (POxN3-x)2/NPC and Co (POxN3-x)2/NPC (NPC: N, P-co-doped carbon) are synthesized through a facile post-treatment of nickel- or cobalt-phytic acid xerogel, followed by an annealing procedure under an argon and ammonia atmosphere at 800 °C. The as-prepared catalysts exhibit outstanding catalytic activities for both the oxygen reduction and evolution reactions, which are comparable to those of Pt/C and IrO2. Furthermore, the primary zinc-air batteries assembled with Ni (POxN3-x)2/NPC and Co (POxN3-x)2/NPC as the cathodes show gravimetric energy densities of 894 and 836 W h kgZn-1, which are superior to that of Pt/C (793 W h kgZn-1). In addition, the rechargeable zinc-air battery assembled with Ni (POxN3-x)2/NPC exhibits an excellent round-trip efficiency, which is shown by a slight increase in the sum of the overpotentials for discharge-charge cycling at a current density of 20 mA cm-2, even after experiencing 33 h of testing. To the best of our knowledge, there are few reports on metaphosphate salts where oxygen is partially replaced by nitrogen as bifunctional oxygen electrode catalysts for zinc-air batteries. This work provides an easy, low-cost and scalable avenue to develop new kinds of catalyst for application in energy devices.

NiFe (Oxy) Hydroxides Derived from NiFe Disulfides as an Efficient Oxygen Evolution Catalyst for Rechargeable Zn-Air Batteries: The Effect of Surface S Residues.

A facile H2 O2 oxidation treatment to tune the properties of metal disulfides for oxygen evolution reaction (OER) activity enhancement is introduced. With this method, the degree of oxidation can be readily controlled and the effect of surface S residues in the resulted metal (oxy)hydroxides for the OER is revealed for the first time. The developed NiFe (oxy)hydroxide catalyst with residual S demonstrates an extraordinarily low OER overpotential of 190 mV at the current density of 10 mA cm-2 after coupling with carbon nanotubes, and outstanding performance in Zn-air battery tests. Theoretical calculation suggests that the surface S residues can significantly reduce the adsorption free energy difference between O* and OH* intermediates on the Fe sites, which should account for the high OER activity of NiFe (oxy)hydroxide catalysts. This work provides significant insight regarding the effect of surface heteroatom residues in OER electrocatalysis and offers a new strategy to design high-performance and cost-efficient OER catalysts.

Understanding voltage decay in lithium-excess layered cathode materials through oxygen-centred structural arrangement.

Lithium-excess 3d-transition-metal layered oxides (Li1+xNiyCozMn1-x-y-zO2, >250 mAh g-1) suffer from severe voltage decay upon cycling, which decreases energy density and hinders further research and development. Nevertheless, the lack of understanding on chemical and structural uniqueness of the material prevents the interpretation of internal degradation chemistry. Here, we discover a fundamental reason of the voltage decay phenomenon by comparing ordered and cation-disordered materials with a combination of X-ray absorption spectroscopy and transmission electron microscopy studies. The cation arrangement determines the transition metal-oxygen covalency and structural reversibility related to voltage decay. The identification of structural arrangement with de-lithiated oxygen-centred octahedron and interactions between octahedrons affecting the oxygen stability and transition metal mobility of layered oxide provides the insight into the degradation chemistry of cathode materials and a way to develop high-energy density electrodes.