Ultralong Lifespan Research Articles

In Situ Ions Induced Formation of KxF-Rich SEI Layers toward Ultrastable Life of Potassium-Ion Batteries.

Engineering F-rich solid electrolyte interphase (SEI) layers is regarded as an effective strategy to enable the long-term cycling stability of potassium-ion batteries (KIBs). However, in the conventional KPF6 carbonate electrolytes, it is challenging to form F-containing SEI layers due to the inability of KPF6 to decompose into KxF. Herein, AlCl3 is employed as a novel additive to change the chemical environment of the KPF6 carbonate electrolyte. First, due to the large charge-to-radius ratio of Al3+, the Al-containing groups in the electrolyte can easily capture F from PF6 - and accelerate the formation of KxF in SEI layer. In addition, AlCl3 also reacts with trace H2O or solvents in the electrolytes to form Al2O3, which can further act as a HF scavenger. Upon incorporating AlCl3 into conventional KPF6 carbonate electrolyte, the hard carbon (HC) anode exhibits an ultra-long lifespan of 10000 cycles with a high coulombic efficiency of ≈100%. When coupled with perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), the full cell exhibits a high capacity retention of 81% after 360 cycles-significantly outperforming cells using conventional electrolytes. This research paves new avenues for advancing electrolyte engineering towards developing durable batteries tailored for large-scale energy storage applications.

Ultrastable Electrolytic Zn-I2 Batteries Based on Nanocarbon Wrapped by Highly Efficient Single-Atom Fe-NC Iodine Catalysts.

Aqueous Zn-iodine (Zn-I2) conversion batteries with iodine redox chemistry suffers the severe polyiodide shuttling and sluggish redox kinetics, which impede the battery lifespan and rate capability. Herein, an ultrastable Zn-I2 battery is introduced based on single-atom Fe-N-C encapsulated high-surface-area carbon (HC@FeNC) as the core-shell cathode materials, which accelerate the I-/I3 -/I° conversion significantly. The robust chemical-physical interaction between polyiodides and Fe-N4 sites tightly binds the polyiodide ions and suppresses the polyiodide shuttling, thereby significantly enhancing the coulombic efficiency. As a result, the core-shell HC@FeNC cathode endows the electrolytic Zn-I2 battery with an excellent capacity, remarkable rate capability, and an ultralong lifespan over 60000 cycles. More importantly, a practical 253Wh kg-1 pouch cell shows good capacity retention of 84% after 100 cycles, underscoring its considerable potential for commercial Zn-I2 batteries.

Dual-Defect Engineering Strategy Enables High-Durability Rechargeable Magnesium-Metal Batteries

HighlightsMVOH/rGO cathode with dual defect of Mg2+ pre-intercalation defect (P-Mgd) and surface oxygen defect (Od) is prepared.The dual defect of Od and P-Mgd in MVOH/rGO lamellar structure effectively enhances Mg2+ migration kinetics, structural stability, and electronic conductivity.The Mg foil//MVOH/rGO full cell achieves an ultralong lifespan of 850 cycles at 0.1 A g−1 and powers an orange light-emitting diode.

An environmentally friendly and scalable manufacturing route to the high performance composite polymer electrolytes for lithium-metal batteries

Environmentally friendly manufacturing of flexible all-solid-state electrolytes in large-scale and low cost is important for market entering of lithium metal batteries. Herein, a simple and practical solvent-free route to the high performance composite polymer electrolyte is proposed by infiltrating the hot-molten polyether polymer (F127)/Li-salt (LiTFSI) slurry into a thin cellulose fibrous membrane. The good compatibility between the slurry and cellulose membrane allows the formation of a highly dense F127/LiTFSI/cellulose composite electrolyte with a thin thickness of 28 μm. The solvent-free feature without side-reaction as well as the good mechanical stability of such electrolyte makes great significance to ensure the safety and stability of the batteries. Therefore, its Li symmetric cell can stably operate with an ultralong lifespan of more than 3600 h without dendritic growth of metal lithium, and the LiFePO4//Li cell can also deliver an excellent cycling stability with an initial capacity of 130.1 mAh g−1 and a capacity retention of 84.11 % after more than 260 cycles at 0.5C and 60 °C. Additionally, the performance of high-loading cathode full cell and the flexible pouch cell further confirm its excellent stability and safety for practical use.

Large-Scale Integration of the Ion-Reinforced Phytic Acid Layer Stabilizing Magnesium Metal Anode.

Rechargeable magnesium batteries (RMBs) have garnered significant attention for their potential in large-scale energy storage applications. However, the commercial development of RMBs has been severely hampered by the rapid failure of large-sized Mg metal anodes, especially under fast and deep cycling conditions. Herein, a concept proof involving a large-scale ion-reinforced phytic acid (PA) layer (100 cm × 7.5 cm) with an excellent water-oxygen tolerance, high Mg2+ conductivity, and favorable electrochemical stability is proposed to enable rapid and uniform plating/stripping of Mg metal anode. Guided by even distributions of Mg2+ flux and electric field, the as-prepared large-sized PA-Al@Mg electrode (5.8 cm × 4.5 cm) exhibits no perforation and uniform Mg plating/stripping after cycling. Consequently, an ultralong lifespan (2400 h at 3 mA cm-2 with 1 mAh cm-2) and high current tolerance (300 h at 9 mA cm-2 with 1 mAh cm-2) of the symmetric cell using the PA-Al@Mg anode could be achieved. Notably, the PA-Al@Mg//Mo6S8 full cell demonstrates exceptional stability, operating for 8000 cycles at 5 C with a capacity retention of 99.8%, surpassing that of bare Mg (3000 cycles, 74.7%). Moreover, a large-sized PA-Al@Mg anode successfully contributes to the stable pouch cell (200 and 750 cycles at 0.1 and 1 C), further confirming its significant potential for practical utilization. This work provides valuable theoretical insights and technological support for the practical implementation of RMBs.

Lamellar Nanoporous Metal/Intermetallic Compound Heterostructure Regulating Dendrite-Free Zinc Electrodeposition for Wide-Temperature Aqueous Zinc-Ion Battery.

Aqueous zinc-ion batteries are attractive post-lithium battery technologies for grid-scale energy storage because of their inherent safety, low cost and high theoretical capacity. However, their practical implementation in wide-temperature surroundings persistently confronts irregular zinc electrodeposits and parasitic side reactions on metal anode, which leads to poor rechargeability, low Coulombic efficiency and short lifespan. Here, this work reports lamellar nanoporous Cu/Al2Cu heterostructure electrode as a promising anode host material to regulate high-efficiency and dendrite-free zinc electrodeposition and stripping for wide-temperatures aqueous zinc-ion batteries. In this unique electrode, the interconnective Cu/Al2Cu heterostructure ligaments not only facilitate fast electron transfer but work as highly zincophilic sites for zinc nucleation and deposition by virtue of local galvanic couples while the interpenetrative lamellar channels serving as mass transport pathways. As a result, it exhibits exceptional zinc plating/stripping behaviors in aqueous hybrid electrolyte of diethylene glycol dimethyl ether and zinc trifluoromethanesulfonate at wide temperatures ranging from 25 to -30°C, with ultralow voltage polarizations at various current densities and ultralong lifespan of >4000 h. The outstanding electrochemical properties enlist full cell of zinc-ion batteries constructed with nanoporous Cu/Al2Cu and ZnxV2O5/C to maintain high capacity and excellent stability for >5000 cycles at 25 and -30°C.

Selenium-Doped Sulfurized Polyacrylonitrile Hybrid Cathodes with Ultrahigh Sulfur Content for High-Performance Solid-State Lithium Sulfur Batteries.

The solid-state lithium sulfur battery (SSLSB) is an attractive next-generation energy storage system by reason of its remarkably high energy density and safety. However, the SSLSB still faces critical challenges, such as sluggish reaction kinetics, mismatched interface, and undesirable reversible capacity. Herein, a high-performance SSLSB is reported using sulfurized polyacrylonitrile with rich selenium-doped sulfur (Se/S-S@pPAN) as a cathode and poly(ethylene oxide)/Li7La3Zr1.4Ta0.6O12 (PEO-LLZTO) as an electrolyte. The sulfur content of the cathode up to 60.9 wt % can be achieved by dispersing selenium sulfide (SeSx) species in the sulfurized polyacrylonitrile (S@pPAN) skeleton at a molecular level. Selenium as a eutectic accelerator can be uniformly distributed in the composite through the Se-S bond and can accelerate the reaction kinetics. The PEO-LLZTO hybrid solid-state electrolyte (SSE) displays an attractive electrochemical performance and provides an intimate contact with electrodes. At 60 °C, Se/S-S@pPAN delivers an impressive discharge capacity of 1042 mAh g-1 at 0.1C and 445 mAh g-1 at 1C. Additionally, the LiFePO4 cathodes combined with PEO-LLZTO deliver a high reversible capacity (158.9 mAh g-1, 1C) and an ultralong lifespan (a capacity retention of 80%, 1000 cycles) at 1C. The synergetic design of the high-performance sulfur cathode and the organic/inorganic hybrid electrolyte is crucial for enabling the high-performance SSLSB.

Microwave-Assisted Hydrothermal Synthesis of Na3V2(PO4)2F3 Nanocuboid@Reduced Graphene Oxide as an Ultrahigh-Rate and Superlong-Lifespan Cathode for Fast-Charging Sodium-Ion Batteries.

Na3V2(PO4)2F3 (NVPF) has been regarded as a favorable cathode for sodium-ion batteries (SIBs) due to its high voltage and stable structure. However, the limited electronic conductivity restricts its rate performance. NVPF@reduced graphene oxide (rGO) was synthesized by a facile microwave-assisted hydrothermal approach with subsequent calcination to shorten the hydrothermal time. NVPF nanocuboids with sizes of 50-150 nm distributed on rGO can be obtained, delivering excellent electrochemical performance such as a longevity life (a high capacity retention of 85.6% after 7000 cycles at 10 C) and distinguished rate capability (116 mAh g-1 at 50 C with a short discharging/charging time of 1.2 min). The full battery with a Cu2Se anode represents a capacity of 116 mAh g-1 at 0.2 A g-1. The introduction of rGO can augment the electronic conductivity and advance the Na+ diffusion speed, boosting the cycling and rate capability. Besides, the small lattice change (3.3%) and high structural reversibility during the phase transition process between Na3V2(PO4)2F3 and NaV2(PO4)2F3 testified by in situ X-ray diffraction are also advantageous for Na storage behavior. This work furnishes a simple method to synthesize polyanionic cathodes with ultrahigh rate and ultralong lifespan for fast-charging SIBs.

Stable Zinc Anode Facilitated by Regenerated Silk Fibroin-modified Hydrogel Protective Layer.

Inherent dendrite growth and side reactions of zinc anode caused by its unstable interface in aqueous electrolytes severely limit the practical applications of zinc-ion batteries (ZIBs). To overcome these challenges, a protective layer for Zn anode inspired by cytomembrane structure is developed with PVA as framework and silk fibroin gel suspension (SFs) as modifier. This PVA/SFs gel-like layer exerts similar to the solid electrolyte interphase, optimizing the anode-electrolyte interface and Zn2+ solvation structure. Through interface improvement, controlled Zn2+ migration/diffusion, and desolvation, this buffer layer effectively inhibits dendrite growth and side reactions. The additional SFs provide functional improvement and better interaction with PVA by abundant functional groups, achieving a robust and durable Zn anode with high reversibility. Thus, the PVA/SFs@Zn symmetric cell exhibits an ultra-long lifespan of 3150 h compared to bare Zn (182 h) at 1.0 mAh cm-2-1.0 mAh cm-2, and excellent reversibility with an average Coulombic efficiency of 99.04% under a large plating capacity for 800 cycles. Moreover, the PVA/SFs@Zn||PANI/CC full cells maintain over 20 000 cycles with over 80% capacity retention under harsh conditions at 5 and 10 A g-1. This SF-modified protective layer for Zn anode suggests a promising strategy for reliable and high-performance ZIBs.

Highly Reversible Zn-Air Batteries Enabled by Tuned Valence Electron and Steric Hindrance on Atomic Fe-N4-C Sites.

The bifunctional oxygen electrocatalyst is the Achilles' heel of achieving robust reversible Zn-air batteries (ZABs). Herein, durable bifunctional oxygen electrocatalysis in alkaline media is realized on atomic Fe-N4-C sites reinforced by NixCo3-xO4 (NixCo3-xO4@Fe1/NC). Compared with that of pristine Fe1/NC, the stability of the oxygen evolution reaction (OER) is increased 10 times and the oxygen reduction reaction (ORR) performance is also improved. The steric hindrance alters the valence electron at the Fe-N4-C sites, resulting in a shorter Fe-N bond and enhanced stability of the Fe-N4-C sites. The corresponding solid-state ZABs exhibit an ultralong lifespan (>460 h at 5 mA cm-2) and high rate performance (from 2 to 50 mA cm-2). Furthermore, the structural evolution of NixCo3-xO4@Fe1/NC before and after the OER and ORR as well as charge-discharge cycling is explored. This work develops an efficient strategy for improving bifunctional oxygen electrocatalysis and possibly other processes.

H2O-Mg2+ Waltz-Like Shuttle Enables High-Capacity and Ultralong-Life Magnesium-Ion Batteries.

Mg-ion batteries (MIBs) are promising next-generation secondary batteries, but suffer from sluggish Mg2+ migration kinetics and structural collapse of the cathode materials. Here, an H2O-Mg2+ waltz-like shuttle mechanism in the lamellar cathode, which is realized by the coordination, adaptive rotation and flipping, and co-migration of lattice H2O molecules with inserted Mg2+, leading to the fast Mg2+ migration kinetics, is reported; after Mg2+ extraction, the lattice H2O molecules rearrange to stabilize the lamellar structure, eliminating structural collapse of the cathode. Consequently, the demo cathode of Mg0.75V10O24·nH2O (MVOH) exhibits a high capacity of 350mAhg-1 at a current density of 50mAg-1 and maintains a capacity of 70mAhg-1 at 4Ag-1. The full aqueous MIB based on MVOH delivers an ultralong lifespan of 5000 cycles The reported waltz-like shuttle mechanism of lattice H2O provides a novel strategy to develop high-performance cathodes for MIBs as well as other multivalent-ion batteries.

Dendrite‐Free Zinc Anode via Oriented Plating with Alkaline Earth Metal Ion Additives

AbstractThe cost‐effectiveness and environmentally friendly nature of aqueous zinc‐ion batteries (ZIBs) have garnered significant attention. Nevertheless, obstacles such as dendrite growth and side reactions have hindered their practical application. Here, an alkaline earth metal ion, strontium ions (Sr2+), is chosen as a dual‐functional electrolyte additive to improve the reversibility of ZIBs. Importantly, Sr2+ ions adsorb on the anode surface, creating a dynamic electrostatic shield layer, thus regulating the Zn2+ deposition behavior and suppressing side reactions. Meanwhile, Sr2+ ions prefer to adsorb on (002) and (110) planes of Zn, thus inducing the preferential deposition of (100) crystal plane and achieving dendrite‐free zinc anode. Consequently, the assembled Zn||Zn symmetric battery delivers an ultralong lifespan of 3500 h, and the Zn||Ti asymmetric battery shows a superior Coulombic efficiency of 99.8% for Zn stripping/plating at 2 mA cm−2. Further, the Zn||NH4V4O10 battery presents an excellent retention of 97.7% over 800 cycles under 2 A g−1. This research introduces a novel alkaline earth metal ion electrolyte additive and establishes its persistent dynamic electrostatic shielding effect and preferentially oriented (100) plane plating, ensuring dendrite‐free zinc deposition. These findings chart a course for further exploration of unexplored alkaline earth elements in enhancing metal battery technologies.

Sabatier effect based adsorption-desorption coordination via cationized chitosan for enhancing ion kinetics in zinc anodes

Interface engineering through a Sabatier effect-based adsorption–desorption coordination via cationized chitosan offers a promising approach to counteract dendritic growth, hydrogen evolution, and sluggish Zn2+ kinetics. The adsorption effect in zinc ion batteries is important for maintaining a balanced distribution of zinc ions and reducing dendrite formation. However, an excessive emphasis on the adsorption effect often neglects the desorption process of zinc ions, leading to a decrease in overall ion reaction kinetics. Herein, an adsorption–desorption synergic coating called CGP@Zn was systematically designed on zinc anodes to serve as both a Zn2+ adsorption and desorption regulator and a functional protective interface. The CGP@Zn coating exhibited zincophilic and negatively charged amino and hydroxy functional groups, which facilitated the transport of Zn2+ ions and repelled free SO42- anions. Moreover, the positively charged N+ component of the CGP@Zn coating exhibited a strong desorption effect, guaranteeing the voluble retransfer of Zn2+ and promoting intensive kinetics. Collaborating with the functional interface layer, the CGP@Zn anode demonstrated a significantly high ionic transfer number of 0.72. Furthermore, CGP@Zn symmetrical cells showed an impressive ultralong lifespan of over 5000 h with an extremely low polarization voltage of ≈80 mV at 1 mA cm−2 and 2 mAh cm−2. More encouragingly, the MnO2-based full batteries endowed with the CGP interface layer achieved a capacity of 206 mAh g -1 with a retention of 91.8 % over 500 cycles at 1C. This study offers a new perspective for designing high-performance aqueous batteries via coordination of adsorption–desorption.

Self-mixing anti-corrosive Zn-In powder composite anode with ultra-long lifespan for aqueous zinc-ion battery

Appropriate design of electrode structure and chemistry for Zn metal anode is important to the kinetics and electrochemical stability of Zn in aqueous batteries. Herein, In modified Zn powder electrode with carbon nanofibers as the stable electric conductive matrix provides an effective approach to simultaneously enhance reaction kinetics and inhibit H2 generation reactions. The designed Zn–In powder electrode presents self-mixing In distribution within the electrode during cycling thus enabling superior anti-corrasion and stable conductive network that significantly alters the Zn deposition behavior. Instant 3D Zn deposition with super-fast interfacial kinetics is achieved due to favorable Zn nucleation and growth as well as suppressed side reactions. Stable cycling of over 6300 h is achieved, which is 30-fold longer lifespan than Zn foil anode. Even at 5 mA cm−2, 5 mAh cm−2 (depth of discharge: 31.1%), Zn–In powder anode still presents stable cycling of over 500 h and low polarization voltage. Ultra-long cycle life of over 20,000 cycles can be achieved for full cells using Zn–In powder electrode paired with V2O5 cathode. Modified composite Zn powder electrode provides an effective and practical approach to address the electrochemical stability of Zn-based anodes in rechargeable cells.

Ultrafast Non-Volatile Floating-Gate Memory Based on All-2D Materials.

The explosive growth of massive-data storage and the demand for ultrafast data processing require innovative memory devices with exceptional performance. 2D materials and their van der Waal heterostructures with atomically sharp interfaces hold great promise for innovations in memory devices. Here, this work presents non-volatile, floating-gate memory devices with all functional layers made of 2D materials, achieving ultrafast programming/erasing speeds (20ns), high extinction ratios (up to 108), and multi-bit storage capability. These devices also exhibit long-term data retention exceeding 10 years, facilitated by a high gate-coupling ratio (GCR) and atomically sharp interfaces between functional layers. Additionally, this work demonstrates the realization of an "OR" logic gate on a single-device unit by synergistic electrical and optical operations. The present results provide a solid foundation for next-generation ultrahigh-speed, ultralong lifespan, non-volatile memory devices, with a potential for scale-up manufacturing and flexible electronics applications.

Dilute Aqueous-Aprotic Electrolyte Towards Robust Zn-Ion Hybrid Supercapacitor with High Operation Voltage and Long Lifespan

HighlightsA novel aqueous/aprotic electrolyte with low salt concentration (i.e., 0.5 m Zn(CF3SO3)2+1 m LiTFSI) demonstrated an expanded electrochemical window, which can simultaneously stabilize Zn metal anode and increase the operation voltage of Zn-ion hybrid supercapacitors.The coordination shell of the electrolyte induced by acetonitrile and LiTFSI can not only suppress the Zn corrosion and hydrogen evolution reaction but also promote the cathodic stability and ion migration, which is depicted by the density functional theory simulations together with experimental characterizations.The Zn-ion hybrid supercapacitor based on the developed electrolyte can operate within 0–2.2 V in a wide temperature range with an ultra-long lifespan (> 120,000 cycles).

Defect‐Driven Reconstruction of Na‐Ion Diffusion Channels Enabling High‐Performance Co‐Doped TiO2 Anodes for Na‐Ion Hybrid Capacitors

AbstractNa‐ion hybrid capacitors (NICs) are known for their potential to integrate high power and energy density along with superior lifespan into a single energy storage device. However, the practical implementation of NICs is delayed due to their inadequate energy densities (<100 Wh kg−1), which is a result of the lack of anodes with rapid Na‐ion diffusion kinetics to match the cathodes. To accelerate Na‐ion diffusion kinetics, cobalt‐doped TiO2 (CoxTi1−xOy) nanosheet anodes with reconstructed low‐energy barrier channels for Na‐ion transfer are designed. Crystal defects, including nanointerfaces, Ti interstitials, and oxygen vacancies, are intentionally introduced to the CoxTi1−xOy structure to improve its conductivity and induce pseudocapacitive‐type Na‐ion storage. Moreover, these crystal defects subtly alter the Na‐ion transfer pathways in the bulk CoxTi1−xOy and reduce the energy barrier, as confirmed by density functional theory (DFT) simulations. Rapid Na‐ion diffusion kinetics can minimize the kinetics discrepancy between anodes and cathodes, presenting great potential for achieving high‐performance anodes for NIC applications. When integrated with activated carbon/reduced graphene oxide composite (AC/rGO) cathodes, the fabricated NICs demonstrate remarkable energy density (164 Wh kg−1 at 31 W kg−1), power density (8307 W kg−1 at 56 Wh kg−1), and an ultralong lifespan (83% capacity retention after 15000 cycles).

Phase Inversion‐Induced Porous Polymer Coating for High Rate and Stable Zinc Anode

AbstractPolymer coatings are emerged as promising candidates for zinc anode artificial solid electrolyte interphase (ASEI) owing to their barrier effect and zincophilicity. However, the poor ionic conductivity of conventional polymer coatings limits their application. Herein, inspired by epidermis function, a porous poly(methylmethacrylate) (PMMA) coating is fabricated to stabilize Zn anode via a novel phase inversion method. The modified Zn anode delivers a remarkable lifespan of over 4000 h at 1 mA cm−2, 1 mAh cm−2, and 120 h at 20 mA cm−2, 20 mAh cm−2 in symmetrical cells. Moreover, porous PMMA‐Zn||NVO full cell also exhibits an excellent cycling stability over 500 cycles at 1 A g−1 as well as an ultralong lifespan exceeding 5000 cycles at 5 A g−1. The excellent cycling stability and rate performance are mainly attributed to the avoided side reactions by the coating protection, as well as the enhanced diffusion and reaction kinetics derived from the good zincophilicity and porous structure of porous PMMA. The facile and universal method for fabricating porous polymer ASEI provides a new insight for the application of conventional polymer materials in Zn anode protection.

Dynamically Ion‐Coordinated Bipolar Organodichalcogenide Cathodes Enabling High‐Energy and Durable Aqueous Zn Batteries

AbstractBipolar organic cathode materials (OCMs) implementing cation/anion storage mechanisms are promising for high‐energy aqueous Zn batteries (AZBs). However, conventional organic functional group active sites in OCMs usually fail to sufficiently unlock the high‐voltage/capacity merits. Herein, we initially report dynamically ion‐coordinated bipolar OCMs as cathodes with chalcogen active sites to solve this issue. Unlike conventional organic functional groups, chalcogens bonded with conjugated group undergo multielectron‐involved positive‐valence oxidation and negative‐valence reduction, affording higher redox potentials and reversible capacities. With phenyl diselenide (PhSe‐SePh, PDSe) as a proof of concept, it exhibits a conversion pathway from (PhSe)− to (PhSe‐SePh)0 and then to (PhSe)+ as unveiled by characterization and theoretical simulation, where the diselenide bonds are periodically broken and healed, dynamically coordinating with ions (Zn2+ and OTF−). When confined into ordered mesoporous carbon (CMK‐3), the dissolution of PDSe intermediates is greatly inhibited to obtain an ultralong lifespan without voltage/capacity compromise. The PDSe/CMK‐3 || Zn batteries display high reversibility capacity (621.4 mAh gPDSe−1), distinct discharge plateau (up to 1.4 V), high energy density (578.3 Wh kgPDSe−1), and ultralong lifespan (12 000 cycles) at 10 A g−1, far outperforming conventional bipolar OCMs. This work sheds new light on conversion‐type active site engineering for high‐voltage/capacity bipolar OCMs towards high‐energy AZBs.

Dynamically Ion-Coordinated Bipolar Organodichalcogenide Cathodes Enabling High-Energy and Durable Aqueous Zn Batteries.

Bipolar organic cathode materials (OCMs) implementing cation/anion storage mechanisms are promising for high-energy aqueous Zn batteries (AZBs). However, conventional organic functional group active sites in OCMs usually fail to sufficiently unlock the high-voltage/capacity merits. Herein, we initially report dynamically ion-coordinated bipolar OCMs as cathodes with chalcogen active sites to solve this issue. Unlike conventional organic functional groups, chalcogens bonded with conjugated group undergo multielectron-involved positive-valence oxidation and negative-valence reduction, affording higher redox potentials and reversible capacities. With phenyl diselenide (PhSe-SePh, PDSe) as a proof of concept, it exhibits a conversion pathway from (PhSe)- to (PhSe-SePh)0 and then to (PhSe)+ as unveiled by characterization and theoretical simulation, where the diselenide bonds are periodically broken and healed, dynamically coordinating with ions (Zn2+ and OTF-). When confined into ordered mesoporous carbon (CMK-3), the dissolution of PDSe intermediates is greatly inhibited to obtain an ultralong lifespan without voltage/capacity compromise. The PDSe/CMK-3 || Zn batteries display high reversibility capacity (621.4 mAh gPDSe -1), distinct discharge plateau (up to 1.4 V), high energy density (578.3 Wh kgPDSe -1), and ultralong lifespan (12 000 cycles) at 10 A g-1, far outperforming conventional bipolar OCMs. This work sheds new light on conversion-type active site engineering for high-voltage/capacity bipolar OCMs towards high-energy AZBs.