Self-Adaptive Liquid Film: Dynamic Realization of Dendrite-Free Zn Deposition Toward Ultralong-Life Aqueous Zn Battery.

The poor reversibility and stability of Zn metal anode (ZMA) caused by uncontrolled Zn deposition behaviors and serious side reactions severely impeded the practical application of aqueous Zn metal battery. Herein, a liquid-dynamic and self-adaptive protective layer (LSPL) was constructed on the ZMA surface for inhibiting dendrites and by-products formation. Interestingly, the outer LSPL consists of liquid perfluoropolyether (PFPE), which can dynamically adapt volume change during repeat cycling and inhibit side reactions. Moreover, it can also decrease the de-solvation energy barrier of Zn2+ by strong interaction between C-F bond and foreign Zn2+ , improving Zn2+ transport kinetics. For the LSPL inner region, in-situ formed ZnF2 through the spontaneous chemical reaction between metallic Zn and part PFPE can establish an unimpeded Zn2+ migration pathway for accelerating ion transfer, thereby restricting Zn dendrites formation. Consequently, the LSPL-modified ZMA enables reversible Zn deposition/dissolution up to 2000 h at 1 mA cm-2 and high coulombic efficiency of 99.8% at 4 mA cm-2 . Meanwhile, LSPL@Zn||NH4 V4 O10 full cells deliver an ultralong cycling lifespan of 100 00 cycles with 0.0056% per cycle decay rate at 10 A g-1 . This self-adaptive layer provides a new strategy to improve the interface stability for next-generation aqueous Zn battery.

Multicomponent Hybridization Transition Metal Oxide Electrode Enriched with Oxygen Vacancy for Ultralong-Life Supercapacitor.

Transition metal oxide electrode materials for supercapacitors suffer from poor electrical conductivity and stability, which are the research focus of the energy storage field. Herein, multicomponent hybridization Ni-Cu oxide (NCO-Ar/H2 -10) electrode enriched with oxygen vacancy and high electrical conductivity including the Cu0.2 Ni0.8 O, Cu2 O and CuO is prepared by introducing Cu element into Ni metal oxide with hydrothermal, annealing, and plasma treatment. The NCO-Ar/H2 -10 electrode exhibits high specific capacity (1524 F g-1 at 3 A g-1 ), good rate performance (72%) and outstanding cyclic stability (109% after 40,000 cycles). The NCO-Ar/H2 -10//AC asymmetric supercapacitor (ASC) achieves high energy density of 48.6 Wh kg-1 at 799.6 W kg-1 while exhibiting good cycle life (117.5% after 10,000 cycles). The excellent electrochemical performance mainly comes from the round-trip valence change of Cu+ /Cu2+ in the multicomponent hybridization enhance the surface capacitance during the redox process, and the change of electronic microstructure triggered by a large number of oxygen vacancies reduce the adsorption energy of OH- ions of thin nanosheet with crack of surface edge, ensuring electron and ion-transport processes and remitting the structural collapse of material. This work provides a new strategy for improving the cycling stability of transition metal oxide electrode materials.

In Situ Induced Lattice-Matched Interfacial Oxygen-Passivation-Layer Endowing Li-Rich and Mn-Based Cathodes with Ultralong Life.

The high capacity of Li-rich and Mn-based (LRM) cathode materials is originally due to the unique hybrid anion- and cation redox, which also induces detrimental oxygen escape. Furthermore, the counter diffusion of released oxygen (into electrolyte) and induced oxygen vacancies (into the interior bulk phase) that occurs at the interface will cause uncontrolled phase collapse and other issues. Therefore, due to its higher working voltage (>4.7 V) than the activation voltage of lattice oxygen in LRM (≈4.5 V), the anion-redox-free and structurally consistent cobalt-free LiNi0.5 Mn1.5 O4 (LNMO) is selected to in situ construct a robust, crystal-dense and lattice-matched oxygen-passivation-layer (OPL) on the surface of LRM particles by the electrochemical delithiation to protect the core layered components. As expected, the modified sample displays continuously decreasing interfacial impedance and high specific capacity of 135.5 mAh g-1 with a very small voltage decay of 0.67 mV per cycle after 1000 cycles at 2 C rate. Moreover, the stress accumulation during cycling is mitigated effectively. This semicoherent OPL strengthens the surface stability and interrupts the counter diffusion of oxygen and oxygen vacancies in LRM cathode materials, which would provide guidance for designing high-energy-density layered cathode materials.

Countering the Segregation of Transition-Metal Ions in LiMn1/3 Co1/3 Ni1/3 O2 Cathode for Ultralong Life and High-Energy Li-Ion Batteries.

High-voltage layered lithium transition-metal oxides are very promising cathodes for high-energy Li-ion batteries. However, these materials often suffer from a fast degradation of cycling stability due to structural evolutions. It seriously impedes the large-scale application of layered lithium transition-metal oxides. In this work, an ultralong life LiMn1/3 Co1/3 Ni1/3 O2 microspherical cathode is prepared by constructing an Mn-rich surface. Its capacity retention ratio at 700 mA g(-1) is as large as 92.9% after 600 cycles. The energy dispersive X-ray maps of electrodes after numerous cycles demonstrate that the ultralong life of the as-prepared cathode is attributed to the mitigation of TM-ions segregation. Additionally, it is discovered that layered lithium transition-metal oxide cathodes with an Mn-rich surface can mitigate the segregation of TM ions and the corrosion of active materials. This study provides a new strategy to counter the segregation of TM ions in layered lithium transition-metal oxides and will help to the design and development of high-energy cathodes with ultralong life.

A High-Rate and Ultralong-Life Sodium-Ion Battery Based on NaTi2 (PO4 )3 Nanocubes with Synergistic Coating of Carbon and Rutile TiO2.

Highly regular NaTi2 (PO4 )3 nanocubes with synergistic nanocoatings of rutile TiO2 and carbon are prepared as an electrode material for sodium-ion batteries. It exhibits a high rate and ultralong life performance simultaneously, and a capacity retention of 89.3% after 10 000 cycles is achieved.

Efficient Polytelluride Anchoring for Ultralong-Life Potassium Storage: Combined Physical Barrier and Chemisorption in Nanogrid-in-Nanofiber.

Metal tellurides (MTes) are highly attractive as promising anodes for high-performance potassium-ion batteries. The capacity attenuation of most reported MTe anodes is attributed to their poor electrical conductivity and large volume variation. The evolution mechanisms, dissolution properties, and corresponding manipulation strategies of intermediates (K-polytellurides, K-pTex) are rarely mentioned. Herein, we propose a novel structural engineering strategy to confine ultrafine CoTe2 nanodots in hierarchical nanogrid-in-nanofiber carbon substrates (CoTe2@NC@NSPCNFs) for smooth immobilization of K-pTex and highly reversible conversion of CoTe2 by manipulating the intense electrochemical reaction process. Various in situ/ex situ techniques and density functional theory calculations have been performed to clarify the formation, transformation, and dissolution of K-pTex (K5Te3 and K2Te), as well as verifying the robust physical barrier and the strong chemisorption of K5Te3 and K2Te on S, N co-doped dual-type carbon substrates. Additionally, the hierarchical nanogrid-in-nanofiber nanostructure increases the chemical anchoring sites for K-pTex, provides sufficient volume buffer space, and constructs highly interconnected conductive microcircuits, further propelling the battery reaction to new heights (3500 cycles at 2.0 A g-1). Furthermore, the full cells further demonstrate the potential for practical applications. This work provides new insights into manipulating K-pTex in the design of ultralong-cycling MTe anodes for advanced PIBs.

Entropy Engineering Constrain Phase Transitions Enable Ultralong-life Prussian Blue Analogs Cathodes.

Prussian blue analogs (PBAs) are considered as one of the most potential electrode materials in capacitive deionization (CDI) due to their unique 3D framework structure. However, their practical applications suffer from low desalination capacity and poor cyclic stability. Here, an entropy engineering strategy is proposed that incorporates high-entropy (HE) concept into PBAs to address the unfavorable multistage phase transitions during CDI desalination. By introducing five or more metals, which share N coordination site, high-entropy hexacyanoferrate (HE-HCF) is constructed, thereby increasing the configurational entropy of the system to above 1.5R and placing it into the high-entropy category. As a result, the developed HE-HCF demonstrates remarkable cycling performance, with a capacity retention rate of over 97% after undergoing 350 ultralong-life cycles of adsorption/desorption. Additionally, it exhibits a high desalination capacity of 77.24 mg g-1 at 1.2 V. Structural characterization and theoretical calculation reveal that high configurational entropy not only helps to restrain phase transition and strengthen structural stability, but also optimizes Na+ ions diffusion path and energy barrier, accelerates reaction kinetics and thus improves performance. This research introduces a new approach for designing electrodes with high performance, low cost, and long-lasting durability for capacitive deionization applications.

Ultrastable Cu2+ Intercalation Chemistry Based on a Niobium Sulfide Nanosheet Cathode for Advanced Aqueous Storage Devices.

Exploring stable and durable cathodes for cost-effective reversible aqueous batteries is highly desirable for grid-scale energy storage applications, but significant challenges remain. Herein, we disclosed an ultrastable Cu2+ intercalation chemistry in mass-produced exfoliated NbS2 nanosheets to build ultralong lifespan aqueous batteries with cost advantages. Anisotropic interplanar expansion of NbS2 lattices balanced dynamic Cu2+ incorporation and the highly reversible redox reaction of Nb4+/Nb(4-δ)+ couple were illuminated by operando synchrotron X-ray diffraction and energy dispersive X-ray absorption spectroscopy, affording an extraordinary capacity of approximately 317 mAh g-1 at 1 A g-1 and a good stability of 92.2% capacity retention after 40000 cycles at 10 A g-1. Impressively, a budget NbS2||Fe hybrid ion cell involving an aqueous electrolyte/Fe-metal anode is established and provides a reliable energy supply of 225.4 Wh kg-1 at 750 W kg-1, providing insights for building advanced aqueous battery systems for large-scale applications.

A new potassium dual-ion hybrid supercapacitor based on battery-type Ni(OH)2 nanotube arrays and pseudocapacitor-type V2O5-anchored carbon nanotubes electrodes.

Hybrid supercapacitors (HSCs) with the characteristics of high energy density, long cycle life and without altering their power density need to be developed urgently. Herein, a novel dual-ion hybrid supercapacitors (DHSCs) with Ni(OH)2 nanotube arrays (NTAs) as positive electrode and V2O5 directly grown on freestanding carbon nanotubes (CNTs) as negative electrode is assembled. In charging mechanism of DHSCs, K+ are inserted into the V2O5 negative while OH- react with Ni(OH)2 positive; during discharge, the K+ and OH- are released from V2O5 negative and Ni(OH)2 positive, respectively, and return back to the electrolyte, which is quite different from traditional metal ion or alkaline supercapacitors. Because of the merits combining dual-ion mechanism and HSCs, the DHSC displays excellent capacity retention of âˆ¼ 81.4% after 10,000 cycles, high energy density of âˆ¼ 25.4 µWh cm-2 and high power density of âˆ¼ 4.66 mW cm-2, indicating the potential applications in the further on flexible wearable electronics.

Tuning Surface Energy of Zn Anodes via Sn Heteroatom Doping Enabled by a Codeposition for Ultralong Life Span Dendrite-Free Aqueous Zn-Ion Batteries.

Aqueous Zn-ion batteries (AZBs) have been considered as one of the most promising large-scale energy storage systems, owing to the advantages of raw material abundance, low cost, and eco-friendliness. However, the severe growth of Zn dendrites leads to poor stability and low Coulombic efficiency of AZBs. Herein, to effectively inhibit the growth of Zn dendrites, a new strategy has been proposed, i.e., tuning the surface energy of the Zn anode. This strategy can be achieved by in situ doping of Sn heteroatoms in the lattice of metallic Zn via codeposition of Sn and Zn with a small amount of the SnCl2 electrolyte additive. Density functional theory calculations have suggested that Sn heteroatom doping can sharply decrease the surface free energy of the Zn anode. As a consequence, driven by the locally strong electric field, metallic Sn tends to deposit at the tips of the Zn anode, thus decreases the surface energy and growth of Zn at the tips, resulting in a dendrite-free Zn anode. The positive effect of the SnCl2 additive has been demonstrated in both the Zn∥Zn symmetric battery and the Zn/LFP and Zn/HATN full cell. This novel strategy can light a new way to suppress Zn dendrites for long life span Zn-ion batteries.

High-Power and Ultralong-Life Aqueous Zinc-Ion Hybrid Capacitors Based on Pseudocapacitive Charge Storage.

Rechargeable aqueous zinc-ion hybrid capacitors and zinc-ion batteries are promising safe energy storage systems. In this study, amorphous RuO2·H2O for the first time was employed to achieve fast and ultralong-life Zn2+ storage based on a pseudocapacitive storage mechanism. In the RuO2·H2O||Zn zinc-ion hybrid capacitors with Zn(CF3SO3)2 aqueous electrolyte, the RuO2·H2O cathode can reversibly store Zn2+ in a voltage window of 0.4-1.6 V (vs. Zn/Zn2+), delivering a high discharge capacity of 122 mAh g-1. In particular, the zinc-ion hybrid capacitors can be rapidly charged/discharged within 36 s with a very high power density of 16.74 kW kg-1 and a high energy density of 82 Wh kg-1. Besides, the zinc-ion hybrid capacitors demonstrate an ultralong cycle life (over 10,000 charge/discharge cycles). The kinetic analysis elucidates that the ultrafast Zn2+ storage in the RuO2·H2O cathode originates from redox pseudocapacitive reactions. This work could greatly facilitate the development of high-power and safe electrochemical energy storage.

Self-Assembled 3D Hierarchical Porous Bi2MoO6 Microspheres toward High Capacity and Ultra-Long-Life Anode Material for Li-Ion Batteries.

Three-dimensional (3D) hierarchical porous Bi2MoO6 microspheres (HPBMs) were successfully prepared and used as the anode material in Li-ion batteries (LIBs) for the first time. The HPBMs showed a high capacity (>830 mAh·g-1, 734.5 mAh·cm-2), high rate capability (20 A·g-1, 177.7 mAh·g-1), and superior long cycle life (>2700 cycles) in the temperature range 5-55 °C without adding any other conductive carbon materials, such as graphene and carbon nanotubes. This can be reasonably attributed to their substantially high surface area, 3D hierarchical porous structure, and homogeneous conductive matrix composed of metallic nanoparticles. HPBMs surprisingly showed a high reversible discharge capacity of 537.2 mAh·g-1 (475.4 mAh·cm-2) and an average discharge voltage >3.0 V even when coupled with LiCoO2 in a full cell. The results highlight the feasibility of HPBMs as anode material for LIBs.