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New epoxy functionalized 4-methyl-4-glycidylmorpholin bis[(trifluoromethyl)-sulfonyl]imide (MGM[TFSI]) ionic liquids were developed for mitigating water reactivity and constructing inorganic SEI layer, thus achieving uniform zinc deposition and reduce hydrogen evolution in ZIBs. [Display omitted] • Developed a novel ether-functionalized MGM[TFSI] ionic liquid to mitigate water reactivity in aqueous Zn-ion batteries. • MGM[TFSI] suppresses dendrite growth and water-induced reactions. • The MGM[TFSI] additive greatly improves the reversibility of Zn deposition. Despite the high safety and low cost associated with aqueous Zn-ion batteries (ZIBs), uncontrolled Zn dendrite growth and parasitic reactions induced by water significantly diminish their stability. Herein, a new epoxy functionalized ionic liquid, 4-methyl-4-glycidylmorpholin bis[(trifluoromethyl) sulfonyl ]imide (MGM[TFSI]), has been developed to mitigate water reactivity for stable ZIBs. It was found that the MGM+ cation disrupts the hydrogen bond network of water, hindering its adsorption on Zn anodes, thereby suppressing water decomposition and enhancing anode stability. Additionally, preferential adsorption of MGM+ cations on the Zn anode surface mitigates tip effects, suppresses dendrite growth, and promotes the formation of a ZnF 2 solid electrolyte interphase layer, effectively isolating the anode from the bulk electrolyte. As a result, benefiting from the well-designed MGM+-based electrolyte, Zn//Zn cells achieve significantly enhanced cycling stability, lasting over 2000 h at 1 mA cm−2 with 1 mAh cm−2. Furthermore, Zn//MnO 2 full cells deliver remarkable stability, retaining approximately 89 % of their initial capacity after 3000 cycles at 5 A/g. This work proposes that the MGM[TFSI] additive can effectively regulate the interfacial chemistry of the Zn anode, providing an opportunity to design advanced electrolytes for highly reversible ZIBs and beyond. [ABSTRACT FROM AUTHOR]

Aqueous zinc ion batteries (AZIBs) have stimulated extensive attention due to their environmental friendliness and low cost. Unfortunately, the inevitable dendrite growth and corrosion on the zinc (Zn) anode severely hinder the practical application of AZIBs. Herein, an amino acid containing an imidazole group is introduced as an effective additive to address these issues. The dynamic conversion of amino acid and protonated amino acid creates a pH buffer function that regulates solution pH in real time, inhibits hydrogen evolution reaction (HER), and eliminates notorious by‐products. In addition, the protonated amino acid is preferentially adsorbed on the Zn anode, preventing contact of the active water with the Zn surface and promoting homogeneous Zn deposition. Thus, the amino acid‐based electrolyte promotes dendrite free plating/stripping with a Coulombic efficiency up to 99.67% and cycle lifetime of 2600 h. In particular, a depth of discharge of up to 87% can be achieved with an ultra‐high areal capacity of 24 mAh cm−2. The developed Zn||CVO full cell also exhibits better electrochemical performance than that without additives. This work provides an effective and convenient approach for safe and efficient Zn‐ion batteries. [ABSTRACT FROM AUTHOR]

A polycarbonyl polymer PNAQI was synthesized by a simple solvothermal method, the strong nucleophilic carbonyl oxygen on PNAQI can coordinate with zinc ions to induce uniform deposition of zinc and inhibit the growth of zinc dendrite, thereby demonstrating a long cycle life exceeding 1000 h at current density of 1.0 mA cm−2 and a capacity of 1.0 mAh cm−2. [Display omitted] • A polycarbonyl polymer PNAQI was synthesized by a simple hydrothermal method. • The strong nucleophilic carbonyl oxygen on PNAQI can coordinate with zinc ions to achieve the purpose of charge storage. • C O on PNAQI can induce uniform deposition of zinc and inhibit the growth of zinc dendrite, thereby effectively stabilizing zinc anodes. • The polycarbonyl polymer PNAQI coating exhibits low nucleation overpotential, excellent cycling performance, high coulombic efficiency, and excellent rate performance. The Zn anode of aqueous zinc ion batteries (AZIBs) have suffered from a series of rampant side reactions such as dendrite growth and corrosion, which seriously affect the reversibility and stability of Zn anodes. Herein, a polycarbonyl polymer poly(1,4,5,8-naphthalene tetracarboxylic anhydride anthraquinone) imine (PNAQI) as the protective coating is synthesized through a simple solvothermal method with the raw materials of the equimolar 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA) and 2, 6-aminoanthraquinone (2,6-DAAQ). A series of characterizations such as contact angle measurement and ex-situ XRD analysis confirm that it can effectively prevent some side reactions. Moreover, C O on PNAQI can regulate the uniform distribution of zinc, thereby preventing the occurrence of zinc dendrites. Finally, the PNAQI@Zn//PNAQI@Zn symmetrical cell demonstrates a long cycle life exceeding 1000 h at current density of 1.0 mA cm−2 and a capacity of 1.0 mAh cm−2. The result significantly outperforms the cycling performance of the cell with bare zinc anode. Especially, the full battery of PNAQI@Zn//NH 4 V 4 O 10 demonstrates an excellent capacity retention and prolonged cycle life (96.9 mAh/g after 1000 cycles at 1.0 A/g) compared to Zn//NH 4 V 4 O 10. This work provides an effective, simple and low-cost solution for developing high-performance AZIBs. [ABSTRACT FROM AUTHOR]

Aqueous zinc-ion batteries (AZIBs) are a promising solution for large-scale energy storage due to their safety and cost-effectiveness. However, challenges like zinc dendrite growth and electrolyte corrosion hinder their practical use. Surface engineering methods have shown potential in stabilizing the zinc metal anode interface. In this study, we propose a successful approach by combining 2D g-C3N4 nanosheets with 3D ZIF8 nanoparticles to form a g-C3N4@ZIF8 artificial interface. The 3D ZIF8 support on the 2D g-C3N4 enables precise regulation of Zn2+ flux and efficient charge transfer, leading to improved electrochemical performance. Density functional theory confirms ZIF8's superior adsorption energy compared to g-C3N4. Strategically anchoring 3D ZIF8 nanoparticles within 2D g-C3N4 allows robust 3D diffusion of Zn2+, preventing dendrite formation and enabling dendrite-free Zn deposition. This structural design can enhance the performance of symmetric cells with an ultralong cycling lifespan of up to 6200 h at 0.25 mA cm−2/0.25 mA h cm−2 and superior rate capability, even at 40 mA cm−2. When combined with a V2O5 nanopaper cathode, our assembled AZIBs exhibit stable long-term performance. This research paves the way for more efficient and reliable AZIBs for large-scale energy storage.

N, F-enriched inorganic/organic composite solid electrolyte interphases (SEI) were constructed to stabilize lithium metal anodes by the in-situ formation of LiF and Li 3 N components as well as organic polyvinyl alcohol (PVA) layer serves as a flexible buffer. [Display omitted] The practical application of lithium metal batteries is considered to be one of the most promising successors for lithium-ion batteries due to their ability to meet the high-energy storage demands of modern society. However, their application is still hindered by the unstable solid electrolyte interphase (SEI) and uncontrollable dendrite growth. In this study, we propose a robust composite SEI (C-SEI) that consists of a fluorine doped boron nitride (F-BN) inner layer and an organic polyvinyl alcohol (PVA) outer layer. Both theoretical calculations and experimental results demonstrate that the F-BN inner layer induces the formation of favourable components (LiF and Li 3 N) at the interface, promoting rapid ionic transport and inhibiting electrolyte decomposition. The PVA outer layer acts as a flexible buffer in the C-SEI, ensuring the structural integrity of the inorganic inner layer during lithium plating and stripping. The C-SEI modified lithium anode shows a dendrite-free performance and stable cycle over 1200 h, with an ultralow overpotential (15 mV) at 1 mA cm−2 in this study. This novel approach also enhances the stability of capacity retention rate by 62.3% after 100 cycles even in anode-free full cells (C-SEI@Cu||LFP). Our findings suggest a feasible strategy for addressing the instability inherent in SEI, showing great prospects for the practical application of lithium metal batteries. [ABSTRACT FROM AUTHOR]

Sodium metal, with a high theoretical specific capacity of 1165 mAh g−1, is the ultimate anode for sodium batteries, yet how to deal with the inhomogeneous and dendritic sodium deposition and the infinite relative dimension change of sodium metal anodes during sodium depositing/stripping is still challenging. Here, a facile fabricated sodiuphilic 2D N‐doped carbon nanosheets (N‐CSs) are proposed as sodium host material for sodium metal batteries (SMBs) to prevent dendrite formation and eliminate volume change during cycling. Revealing from combined in situ characterization analyses and theoretical simulations, the high nitrogen content and porous nanoscale interlayer gaps of the 2D N‐CSs can not only concede dendrite‐free sodium stripping/depositing but also accommodate the infinite relative dimension change. Furthermore, N‐CSs can be easily process into N‐CSs/Cu electrode via traditional commercial battery electrode coating equipment that pave the way for large‐scale industrial applications. On account of the abundant nucleation sites and sufficient deposition space, N‐CSs/Cu electrodes demonstrate a superior cycle stability of more than 1500 h at a current density of 2 mA cm−2 with a high coulomb efficiency of more than 99.9% and ultralow nucleation overpotential, which enable reversible and dendrites‐free SMBs and shed light on further development of SMBs with even higher performance. [ABSTRACT FROM AUTHOR]

Abstract Sodium metal, with a high theoretical specific capacity of 1165 mAh g−1, is the ultimate anode for sodium batteries, yet how to deal with the inhomogeneous and dendritic sodium deposition and the infinite relative dimension change of sodium metal anodes during sodium depositing/stripping is still challenging. Here, a facile fabricated sodiuphilic 2D N‐doped carbon nanosheets (N‐CSs) are proposed as sodium host material for sodium metal batteries (SMBs) to prevent dendrite formation and eliminate volume change during cycling. Revealing from combined in situ characterization analyses and theoretical simulations, the high nitrogen content and porous nanoscale interlayer gaps of the 2D N‐CSs can not only concede dendrite‐free sodium stripping/depositing but also accommodate the infinite relative dimension change. Furthermore, N‐CSs can be easily process into N‐CSs/Cu electrode via traditional commercial battery electrode coating equipment that pave the way for large‐scale industrial applications. On account of the abundant nucleation sites and sufficient deposition space, N‐CSs/Cu electrodes demonstrate a superior cycle stability of more than 1500 h at a current density of 2 mA cm−2 with a high coulomb efficiency of more than 99.9% and ultralow nucleation overpotential, which enable reversible and dendrites‐free SMBs and shed light on further development of SMBs with even higher performance.

Lithium (Li) metal is considered a hopeful anode for next-generation Li-ion batteries thanks to its ultra-high theoretical specific capacity, extra-low theoretical density, and low negative potential. However, the uncontrolled growth of Li dendrites and volume fluctuation during plating/stripping processes severely hamper its commercial application. Herein, ZnS seeds sealed in N, P, S co-doped carbon hollow rhombic dodecahedra (ZnS@NPS-C HRD) is fabricated as a superlithiophilic host for Li metal anodes (LMAs) to solve the above problems. In addition, the Li nucleation and deposition mechanism on ZnS@NPS-C HRD is investigated by in situ optical microscopy, ex-situ X-ray diffraction, scanning electron microscopy, and theoretical calculations. Owing to the synergistic strategy of ZnS seeds-inducing nucleation and Li-limited growth, the as-prepared composite exhibits stability for 300 cycles in asymmetric cells and a long lifespan over 1100 h in symmetric cells. Moreover, the ZnS@NPS-C HRD@Li|LiFePO 4 full cell demonstrates a reversible capacity of 100.91 mAh g -1 after 400 cycles at 1 C., (© 2024 Wiley‐VCH GmbH.)

Solid-state battery has been considered as ultimate form of lithium-ion batteries due to high safety and extreme temperature tolerance, but the solid-state electrolyte fails to meet the requirements which are often suffered from low ionic conductivity, weak mechanical properties, and poor interfacial contact with the electrode simultaneously. In this paper, we report preparation of a new polymer cross-linking PVDF nanofibrous-based quasi solid-state electrolyte (P-PVDF) by in situ polymerization of melamine and epoxy-ended amino-terminated polyoxypropylene with LiPF6-based liquid electrolyte in framework of PVDF nanofiber. The polymer cross-linking PVDF nanofiber not only improves mechanical strength for polymer electrolyte but also contributes to the one-off formation of a homogenous solid electrolyte interface to suppressing dendrite lithium. The ether-dominated polymer chains provide ionic transportation channel induced high ionic conductivity (1.35 mS/cm). In comparison with liquid electrolyte, the P-PVDF polymer electrolyte exhibits significantly enhanced rate behavior with retention rate of 75% (61% for the liquid elelctrolyte) at 8 °C, cycling stability of 92% initial capacities (80% for liquid electrolyte) after 200 cycles. [ABSTRACT FROM AUTHOR]

[Display omitted] • A low-cost separator (CNF + LMS) composes of cellulose nanofibers and lithium magnesium silicate (LMS) has been prepared. • CNF + LMS separator can promote the de-solvation process and facilitate the uniform zinc deposition. • CNF + LMS separator can suppress the zinc dendrites and side reactions. • CNF + LMS separator can be utilized to improve the electrochemical performance of full batteries. Aqueous zinc-ion batteries (ZIBs) are promising as the next-generation energy storage system due to their inherent safety and low cost, but challenges relating to H 2 O-induced side reactions and dendrite growth of the zinc anode are restricting its practical application. Herein, a low-cost separator (CNF + LMS) composed of cellulose nanofibers (CNF) and lithium magnesium silicate (LMS) has been prepared to eliminate the obstacles through accelerating the de-solvation process and facilitating the homogeneous zinc deposition. As verified by the experimental results and theoretical calculations, the battery with CNF + LMS separator shows a lower de-solvation activation energy (44.13 kJ mol−1) and faster de-solvation kinetics due to the superior water adsorption capacity of LMS molecules. Additionally, the CNF + LMS separator also presents superior wettability, large tensile strength, and excellent ionic conductivity, thus enabling dendrite‐free zinc deposition, long cycling life (1000 h at 1 mA cm−2; 500 h at 5 mA cm−2), superior Coulombic efficiency (99.12 % at 1 mA cm−2). The CNF + LMS separator, which cost as low as ¥ 6.36 per m2, can also be utilized in Zn||VO 2 full battery and pouch cell to boost their electrochemical performance. Considering the facile preparation, low cost and practical feasibility, the CNF + LMS separator offers a new opportunity for developing practical ZIBs. [ABSTRACT FROM AUTHOR]

Zinc-ion batteries (ZIBs) are promising energy storage system owing to the low cost and high safety features. As the most-used anode material, zinc metal always encounters poor coulombic efficiency (CE) and cycling stability, because of the serious zinc dendrite and harmful side reactions on Zn surface. Here, a solid-phase non-adhesive homogeneous Nano-Si layer has been embedded on the Zn surface (Zn-Si) via an ultra-facile grinding method. The Nano-Si layer can regulate an even electric field distribution to achieve a homogeneous zinc deposition, and it also can greatly lower the charge transfer resistance and nucleation energy barrier of Zn2+ to facilitate the zinc deposition, thus achieving a dendrites-free and long-life Zn anode. Encouragingly, the zinc symmetrical battery with Zn-Si anode delivers a superior CE of 99.6 % in 1000 cycles under 5 mA cm−2, and a stable cycle lifespan of 3600 h under 1 mA cm−2 with much lower polarization potential (42 mV), outperforming the symmetrical battery with pure Zn anode (455 h, 59 mV) and various previously reported strategies. Additionally, the effectiveness of Nano-Si layer is further proved in the Zn-Si/MnO 2 battery, which presents a greatly improved capacity retention and cycling performance. [Display omitted] • Zn-Si anode has been prepared via a facile grinding process with sandpaper and Nano-Si powder. • Zn-Si anode shows lower the charge transfer resistance and nucleation energy overpotential. • Zn-Si can prevent the formation of zinc dendrites and by-products. • Zn-Si anode can further improve the electrochemical performance of full battery. [ABSTRACT FROM AUTHOR]

Aqueous zinc-ion batteries, as one of the promising substitutes for lithium-ion batteries, have received increasing attention due to their high safety, low cost, and non-toxicity. Nevertheless, the inevitable growth of zinc dendrites, hydrogen evolution, and side reactions on the Zn anode greatly hinder the further application of zinc-ion batteries. The current solutions mainly focused on electrolyte regulation, artificial interface layer introduction, and zinc alloy anode construction. MXene, as a novel generation of two-dimensional layered transition metals carbides/ nitrides, has been widely investigated in a variety of metal ion batteries in the last decade owing to excellent physical and chemical properties. Herein, we constructed an ion-sieving Janus separator for the aqueous zinc-ion battery by spraying Ti 3 C 2 T x MXene ink on one side of the commercial glass fiber separator. Because of the advantages of MXene such as high conductivity, abundant surface functional groups, and highly matched lattice constants with the Zn anode, the composite separator can homogenize the surface electric field of the Zn anode, optimize the flux of Zn2+, and induce the uniform deposition of Zn2+. Most importantly, a unique ion sieving function was realized in the electrolyte because of the intrinsic electro-negativity of the MXene layer. The concentration of H+ and SO 4 2- on the Zn anode side is largely reduced, and the hydrogen evolution and side reactions are greatly inhibited. Thus, for symmetrical cells, an ultralong cycling lifespan up to 2500 h and superior rate capability with dendrite-free deposition behavior were achieved. When further applying the Janus separator to aqueous zinc-ion batteries combined with the fabricated α-MnO 2 cathode, Zn anode, and 2 M ZnSO 4 + 0.2 M MnSO 4 electrolyte, a superb capacity retention rate (85.7%) upon cycling for 500 cycles at 1.0 A g−1 was obtained. This ion-sieving separator possesses the giant potential for zinc-ion batteries. • The symmetrical cell with Janus separator can cycle stably for more than 2500 h, with a low voltage hysteresis (25.1 mV). • The MXene endows the Janus separator Ion sieving function, which can significantly inhibit the side reactions. • The extremely low nucleation over potential (15.5 mV) and the dendrite-free behavior of zinc ion batteries were realized. • The Zn-Ti asymmetric cell with Janus separator exhibits a steady Coulombic efficiency up to 95.3% after 200 cycles. • The Zn-MnO 2 full cells with Janus separator maintain a higher reversible capacity. [ABSTRACT FROM AUTHOR]

Aqueous Zn-based batteries have been regarded as a promising energy storage system due to their high energy/power density, safety, and cost-effectiveness. However, their performance have been severely hindered by the dendrite growth of zinc and water-induced side reactions. Herein, a facial strategy of electrolyte modification with a high concentration of zinc sulfate and lithium iodide (LiI) as additives is proposed to guide the preferential growth along with the Zn (002) plane for the smooth Zn deposition. Compared to the pure zinc sulfate electrolyte, the Zn anode in the modified electrolyte exhibited the ultralong cycling stability for 3000 h at a capacity of 1 mAh cm−2 and 400 h at a higher capacity of 5 mAh cm−2, with low reversible deposition potentials of around 30 and 40 mV, respectively, demonstrating the stable plating/stripping behaviors. More importantly, the cycling stability of the Zn–I 2 battery with the modified electrolyte can still deliver a large specific capacity after 5000 cycles. The strategy presented that the LiI as additive could not only provide an iodine-rich environment to induce the preferential growth of Zn (002) plane, but also eliminate the side corrosion reactions with the help of additional Li-ions, thus leading to the high-performing Zn–I 2 battery. The interface behavior of zinc was regulated by adjusting the composition of electrolyte with LiI additive, which enables the preferential growth of Zn (002) plane to fabricate high-performance zinc-iodine battery. [Display omitted] • LiI as additive could induce the preferential growth of Zn (002) plane. • The competitive coordination of Li-ions with H 2 O eliminate side reactions of zinc. • The presence of iodide ions improves the battery reversibility. [ABSTRACT FROM AUTHOR]

The optimization strategies of electrode and electrolyte currently advocated for zinc dendrite suppression remain challenging for aqueous zinc-ion batteries (ZIBs) due to their complex manufacturing processes and non-economic prices. Here, a cellulose nanofibers-ZrO 2 composite (ZC) separator with easily-fabricated and cost-effective features is developed to stabilize the zinc anode. The ZC separator is designed to enable excellent ionic conductivity (4.59 mS cm−1) and high Zn2+ transfer number (0.69), and the ZrO 2 particles with high dielectric constant (ε = 25) offer a directional electric field via the Maxwell-Wagner polarization effect, which regulates uniform zinc deposition, accelerate the Zn2+ ions diffusion kinetics and repel anions, thus stabilizing zinc anode and suppressing passivation reactions. As a result, ZC separator renders zinc anode with dendrite‐free plating/stripping behavior, high Coulombic efficiency (99.5%) and exceptional cyclability (2000 h under 0.5 mA cm−2). Additionally, this developed composite separator can be extended to other insulating ceramics, or even random combinations. Moreover, the rate capability and cyclability of the as-assembled Zn||ZnSO 4 ||MnO 2 /graphite coin and pouch cells also can be significantly boosted via the ZC separator, accompanied by the remarkable flexibility and integration ability. The ceramics-cellulose separators offer an appealing strategy for constructing advanced zinc anode for large-scale energy storage. A composite separator with excellent ionic conductivity, high Zn2+ transfer number, low-cost and easily-fabricated features is prepared from cellulose nanofibers and ZrO 2 particles, and employed to improve the poor reversibility of Zn anode and hinder the formation of passivated byproduct as well as serious dendrite growth. [Display omitted] ● Dendrites-free zinc anode is obtained using ZrO 2 -cellulose (ZC) separator. ● ZrO 2 particles can offer directional electric field and low nucleation overpotential via Maxwell-Wagner polarization. ● The rate capability and cyclability of Zn||ZnSO 4 ||MnO 2 /graphite batteries can be significantly boosted via the ZC separator. ● The preparation process of ZC separator is facile, cost effective and scalable. [ABSTRACT FROM AUTHOR]