Average Coulombic Efficiency Research Articles

Graphitized Layers Encapsulated Carbon Nanofibers as Li-Free Anode for Hybrid Li-Ion/Metal Batteries.

Hard carbon, the Li-free anode for hybrid Li-ion/metal batteries (LIB/LMBs), has great potential for enhancing fast charging capability, energy density, and battery lifespan. However, low initial Coulombic efficiency (ICE) and Li dendrite growth are crucial factors constraining its development. In this work, graphitized layers encapsulated carbon nanofibers (G-CF) are fabricated via Joule heating within 10 s. The Csp2 structure in graphitized layers reduces side reactions with the electrolyte, promotes LiC compound formation, and improves Li ions/metal reversibility. The inner amorphous carbon structure boosts fast charging capability. As a result, the G-CF anode attains an 85.2% high ICE and exhibits long-term cycling stability. Under 2 C fast charging, it maintains an average Coulombic efficiency of 99.94% and a 500 mAh g-1 capacity after 200 cycles. Moreover, when the N/P ratio is 0.5, the G-CF||NCM811full cell has an ICE of 84.5% and provides a capacity of 530.8 mAh g-1 and an energy density of 365.9Wh kg-1 at 1C. The G-CF||LFP full cell can also provide a capacity of 541.0 mAh g-1 under the same N/P ratio. A 30 mAh pouch cell can stably cycle over 100 times. This heterogeneous hard carbon design paves a revolutionary path for manufacturing high-efficiency Li-free anodes for hybrid LIB/LMBs.

A "Flexible" Solvent Molecule Enabling High-Performance Lithium Metal Batteries.

Localized high-concentration electrolytes (LHCEs) exhibit good performance in lithium metal batteries. However, understanding how the intermolecular interactions between solvents and diluents regulate the solvation structure and interfacial layer structure remains limited. Here, we reported an LHCE in which strong hydrogen bonding between diluents and solvents alters the conformation and polarity of "flexible" solvent molecules, thereby effectively regulating the solvation structure of Li+ ion and promoting the formation of robust electrode interfaces. The endpoint H of the "flexible" chain O-CH-CH3 of the 2,5-dimethyltetrahydrofuran (2,5-THF) solvent and the F of the benzotrifluoride (BTF) diluent form strong hydrogen bonds, which expand the bond angle of the 2,5-THF molecule. The expanded bond angle increases the steric hindrance of the 2,5-THF and decreases its polarity. This leads to an increase in the anion content within the solvation structure, which in turn enhances the performance of both the lithium anode and the sulfurized polyacrylonitrile (SPAN) cathode. As a result, the lithium anode shows a Coulombic efficiency (CE) of as high as 99.4%. The assembled Li||SPAN battery exhibits impressive stability with an average CE of 99.8% over 700 cycles. Moreover, the Li||SPAN pouch cell can be stably cycled with a high energy density of 301.4 Wh kg-1.

Synergistic Electrode and Electrolyte Polarities Lead to Outstanding Organic Potassium‐based Batteries

AbstractOrganic materials are promising as battery electrodes due to their flexible design, low cost, and sustainability. Although high electrolyte concentrations are known to suppress organic cathode dissolution, the organic cathode solubility depends on the interplay between the electrode and electrolyte polarities, which remains unexplored. Here, we elucidate the delicate interplay of electrode and electrolyte polarities to achieve stable cycling of organic cathode. Notably, we demonstrate that the solubility of low‐polar organic cathodes initially increases and subsequently decreases in electrolytes with increasing polarity. In contrast, high‐polar organic cathodes display increasing solubility in electrolytes with increasing polarity. When the polarities of the organic cathodes and the electrolyte are tuned, the batteries show high‐capacity retention and Coulombic efficiency. For example, polyaniline||potassiated graphite (KC8) pouch cells deliver 2500 cycles with an average Coulombic efficiency of 99.85 %. These new insights into low‐ and high‐polar organic cathode behavior in electrolytes lay a theoretical foundation for designing new organic battery electrodes and optimizing their electrolyte formulation.

Enhancing Zn Deposition Reversibility on MXene Current Collectors by Forming ZnF2-Containing Solid-Electrolyte Interphase for Anode-Free Zinc Metal Batteries.

Anode-free aqueous zinc metal batteries (AZMBs) offer significant potential for energy storage due to their low cost and environmental benefits. Ti3C2Tx MXene provides several advantages over traditional metallic current collectors like Cu and Ti, including better Zn plating affinity, lightweight, and flexibility. However, self-freestanding MXene current collectors in AZMBs remain underexplored, likely due to challenges with Zn deposition reversibility. This study investigates the combination of a Ti3C2Tx self-freestanding film with advanced electrolyte engineering, specifically examining the effects of Li-salt and propylene carbonate (PC) as additives on Zn plating reversibility. While using Li+ ions as an additive alone facilitates uniform Zn deposition on bulk metals through the electrostatic shielding effect, the addition of Li-salt negatively impacts Zn plating uniformity on Ti3C2Tx. Meanwhile, using PC additive alone forms an organic SEI layer on Ti3C2Tx and causes Zn agglomeration. The use of both additives together results in a ZnF2-containing hybrid SEI layer with improved interfacial kinetics, promoting more uniform Zn deposition. This approach achieves an average Coulombic efficiency (CE) of 96.8% over 150 cycles (a maximum CE of 97.8%). The study highlights the strategic difference in electrolyte design, emphasizing the need for tailored approaches to optimize Zn deposition on MXenes, contrasting with traditional metallic current collectors.

Selective Interface Engineering with Large π‐Conjugated Molecules Enables Durable Zn Anodes

Undesirable dendrite growth and side reactions at the electrical double layer (EDL) of Zn/electrolyte interface are critical challenges limiting the performance of aqueous zinc ion batteries. Through density functional theory calculations, we demonstrate that grafting large π‐conjugated molecules (e.g. bilirubin, biliverdin, lumirubin, and hemoglobin) onto Zn surface induces preferential adsorption on non‐(002) facets, leading to interfacial charge redistribution, upshifted Zn d‐band center, and enhanced H+ fixation capability. Among these, bilirubin (BR) is identified as the most effective, preferentially adsorbing onto non‐Zn(002) facets to inhibit hydrogen evolution reaction and promote Zn(002) planar growth during plating. This approach results in average Coulombic efficiency of 99.86% over 4000 cycles in Zn||BR‐1@Cu cells and prolonged lifespan exceeding 1600 h in BR‐1@Zn||BR‐1@Zn cells at 10 mA cm−2 and 1 mAh cm−2. Even under harsh condition of 25 mA cm−2 and 10 mAh cm−2, BR‐1@Zn||BR‐1@Zn cell maintains a lifespan of over 400 h. Furthermore, BR‐1@Zn||MnO2 and BR‐1@Zn||NVO full cells achieve 76.4% and 86.1% capacity retention after 800 and 1400 cycles at 1.0 A g−1, respectively. This study underscores the importance of grafting large π‐conjugated molecules to allow selective Zn(002) exposure, Zn d‐band center upshift, and EDL structure regulation, paving the way towards durable Zn anodes.

Selective Interface Engineering with Large π-Conjugated Molecules Enables Durable Zn Anodes.

Undesirable dendrite growth and side reactions at the electrical double layer (EDL) of Zn/electrolyte interface are critical challenges limiting the performance of aqueous zinc ion batteries. Through density functional theory calculations, we demonstrate that grafting large π-conjugated molecules (e.g. bilirubin, biliverdin, lumirubin, and hemoglobin) onto Zn surface induces preferential adsorption on non-(002) facets, leading to interfacial charge redistribution, upshifted Zn d-band center, and enhanced H+ fixation capability. Among these, bilirubin (BR) is identified as the most effective, preferentially adsorbing onto non-Zn(002) facets to inhibit hydrogen evolution reaction and promote Zn(002) planar growth during plating. This approach results in average Coulombic efficiency of 99.86% over 4000 cycles in Zn||BR-1@Cu cells and prolonged lifespan exceeding 1600 h in BR-1@Zn||BR-1@Zn cells at 10 mA cm-2 and 1 mAh cm-2. Even under harsh condition of 25 mA cm-2 and 10 mAh cm-2, BR-1@Zn||BR-1@Zn cell maintains a lifespan of over 400 h. Furthermore, BR-1@Zn||MnO2 and BR-1@Zn||NVO full cells achieve 76.4% and 86.1% capacity retention after 800 and 1400 cycles at 1.0 A g-1, respectively. This study underscores the importance of grafting large π-conjugated molecules to allow selective Zn(002) exposure, Zn d-band center upshift, and EDL structure regulation, paving the way towards durable Zn anodes.

Salt-in-presalt electrolyte solutions for high-potential non-aqueous sodium metal batteries.

Room-temperature non-aqueous sodium metal batteries are viable candidates for cost-effective and safe electrochemical energy storage. However, they show low specific energy and poor cycle life as the use of conventional organic-based non-aqueous electrolyte solutions enables the formation of interphases that cannot prevent degradations at the positive and negative electrodes. Here, to promote the formation of inorganic NaF-rich interphases on both negative and positive electrodes, we propose the salt-in-presalt (SIPS) electrolyte formulation strategy. In SIPS, sodium bis(fluorosulfonyl)imide (NaFSI) salt is dissolved in the liquid precursor of the sodium bis(trifluoromethylsulfonyl)imide (NaTFSI) salt, that is, N,N-dimethyltrifluoromethane-sulfonamide, called PreTFSI. The prepared 0.5 M NaFSI in PreTFSI (SIPS5) electrolyte solution shows an electrochemical stability up to 6.7 V versus Na|Na+ and enables a Na stripping/plating average Coulombic efficiency of 99.7% at 2.0 mA cm-2 and 4.0 mAh cm-2 in Na||Al cell configuration. By testing SIPS5 in Na metal and 'anode-less' coin and pouch cell configurations using NaNi0.6Mn0.2Co0.2O2 or sulfurized polyacrylonitrile as positive electrode active materials, we demonstrate the ability of the SIPS strategy to deliver improved specific discharge capacity and capacity retentions at high cell potentials and moderate applied specific currents for cell cycle life up to 1,000 cycles.

Anode-Free Zinc-Bromine Batteries Enabled by a Simple Prenucleation Strategy.

The design of anode-free zinc (Zn) batteries with high reversibility at high areal capacity has received significant attention recently, which is quietly challenging yet. Here, a Zn alloyed interface through electroplating is introduced, providing homogeneous Zn prenucleation sites to stabilize subsequent Zn nucleation and plating. By employing Zn-Cu alloy as a module, the complementary simulations and characterizations confirm that the prenucleation alloyed interfaces achieve a homogeneous electric field distribution and greatly enhance the stability of the Zn anode. Accordingly, the Zn//Zn-Cu@Cu half-cells show a long cycle life of over 900h and an average Coulombic efficiency (CE) of 99.8% at an areal capacity of10 mAh cm-2. The assembled anode-free zinc-bromine (Zn-Br2) battery exhibits an attractive stable cycling of 11 000 cycles at 1 mAh cm-2, while over 1000 cycles at the higher areal capacity of 10 mAh cm-2. Excitingly, the Zn-Br2 pouch cell with a capacity of 1000 mAh operates stably over 50 cycles, and achieves successful integration with photovoltaic systems. This anode-free Zn-Br2 batteries constructed through a prenucleation strategy offer new insights into the potential for large-scale energy storage applications.

A Robust Dual-Layered Solid Electrolyte Interphase Enabled by Cation Specific Adsorption-Induced Built-In Electrostatic Field for Long-Cycling Solid-State Lithium Metal Batteries.

Solid-state lithium (Li) metal batteries (SSLMBs) are considered as one of the most promising next-generation battery technologies due to their high energy density and intrinsic safety. However, interfacial issues such as side reactions and Li dendrite growth severely hinder the practical application of SSLMBs. In this contribution, we proposed a cationic built-in electrostatic field to drive the generation of an anion-derived dual-layered solid electrolyte interphase (SEI). The specific adsorption of tributylmethyl-phosphonium bis(trifluoromethanesulfonyl)imide (TMPB) cations onto negatively charged Li anode surface significantly prevents interfacial side reactions between vulnerable polyethylene oxide (PEO) and Li metal. More importantly, the formed cationic built-in electrostatic field induces the targeted trapping of Li-salt anions onto the Li metal surface, leading to the generation of an anion-derived dual-layered SEI, composed of a mechanically flexible organic-rich surface layer and a Li-ion conductive inorganic-rich bottom layer. As a result, the Li||Li cell demonstrated an extended lifespan of over 1900 hours with the reduced polarization voltage. The Li||LiFePO4 full cell also exhibited excellent cycling stability, maintaining an average Coulombic efficiency of 99.69% over 200 cycles at 0.5 C. This work provides valuable insights into mitigating interfacial degradation and promoting uniform Li deposition through surface electrostatic field regulation.

Synergistic Electrode and Electrolyte Polarities Lead to Outstanding Organic Potassium-based Batteries.

Organic materials are promising as battery electrodes due to their flexible design, low cost, and sustainability. Although high electrolyte concentrations are known to suppress organic cathode dissolution, the organic cathode solubility depends on the interplay between the electrode and electrolyte polarities, which remains unexplored. Here, we elucidate the delicate interplay of electrode and electrolyte polarities to achieve stable cycling of organic cathode. Notably, we demonstrate that the solubility of low-polar organic cathodes initially increases and subsequently decreases in electrolytes with increasing polarity. In contrast, high-polar organic cathodes display increasing solubility in electrolytes with increasing polarity. When the polarities of the organic cathodes and the electrolyte are tuned, the batteries show high-capacity retention and Coulombic efficiency. For example, polyaniline||potassiated graphite (KC8) pouch cells deliver 2500 cycles with an average Coulombic efficiency of 99.85%. These new insights into low- and high-polar organic cathode behavior in electrolytes lay a theoretical foundation for designing new organic battery electrodes and optimizing their electrolyte formulation.

Rapid Na+ Transport Pathway and Stable Interface Design Enabling Ultralong Life Solid‐State Sodium Metal Batteries

AbstractSodium‐metal batteries (SMBs) using solid‐state polymer electrolytes (SPEs) show impressive superiority in energy density and safety. As promising candidates for SPEs, solid‐state plastic crystal electrolytes (SPCE) based on succinonitrile (SN) plastic crystal could achieve high ion conductivity and wide voltage window. Nonetheless, the notorious SN decomposition reaction on the electrode/electrolyte interface seriously challenges the stable operation of the battery. To address this drawback, we commence with the structural engineering of the polymer chain segments in SPCE and employ intermolecular interactions to optimize the composition of solid electrolyte interface (SEI). Moreover, this study emphasizes the importance of polymer network design in optimizing the migration behavior of sodium ions in SPCE. The assembled sodium symmetric cells display a high critical current density of up to 2.7 mA cm−2 and stable cycling performance for 700 hours at 0.5 mA cm−2. Furthermore, the Na/SPCE‐9/Na3V2(PO4)3 maintains a discharge specific capacity of up to 76.8 mAh g−1 at 10 C and shows impressive long‐cycle stability, retaining 86.2 % of initial capacity over 5000 cycles with an average coulombic efficiency of 99.9 %. Our work presents a high‐performance SPCE with intrinsic safety, providing valuable insights for the future design of solid‐state SMBs.

Rapid Na+ Transport Pathway and Stable Interface Design Enabling Ultralong Life Solid-State Sodium Metal Batteries.

Sodium-metal batteries (SMBs) using solid-state polymer electrolytes (SPEs) show impressive superiority in energy density and safety. As promising candidates for SPEs, solid-state plastic crystal electrolytes (SPCE) based on succinonitrile (SN) plastic crystal could achieve high ion conductivity and wide voltage window. Nonetheless, the notorious SN decomposition reaction on the electrode/electrolyte interface seriously challenges the stable operation of the battery. To address this drawback, we commence with the structural engineering of the polymer chain segments in SPCE and employ intermolecular interactions to optimize the composition of solid electrolyte interface (SEI). Moreover, this study emphasizes the importance of polymer network design in optimizing the migration behavior of sodium ions in SPCE. The assembled sodium symmetric cells display a high critical current density of up to 2.7 mA cm-2 and stable cycling performance for 700 hours at 0.5 mA cm-2. Furthermore, the Na/SPCE-9/Na3V2(PO4)3 maintains a discharge specific capacity of up to 76.8 mAh g-1 at 10 C and shows impressive long-cycle stability, retaining 86.2 % of initial capacity over 5000 cycles with an average coulombic efficiency of 99.9 %. Our work presents a high-performance SPCE with intrinsic safety, providing valuable insights for the future design of solid-state SMBs.

Entropy‐Repaired Solvation Structure Strategy for High‐Efficiency Phosphate‐Based Localized High‐Concentration Electrolytes in Potassium Batteries

AbstractThe safety and cycling stability of potassium‐ion batteries (PIBs) are deeply associated with potassium‐ion electrolytes. However, due to the weak Lewis acidity of potassium ions, localized high‐concentration electrolytes in PIBs are prone to excessive weak solvation. Herein, we propose an entropy repair strategy for the solvation structure of potassium ions and systematically design a moderately weakly solvated high‐entropy localized high‐concentration electrolyte. The repaired electrolyte can achieve an average stable Coulombic efficiency of 99.4 % on the Cu collector surface. The potassium symmetric battery can be stably cycled for over 10000 h under a high current density of 0.5 mA cm−2 and a large deposition capacity of 1 mAh cm−2. The potassium metal pouch cell, using K1.92Fe[Fe(CN)6]0.94⋅0.5H2O as the cathode, maintains a capacity retention of 87.5 % after 2000 cycles at a current density of 0.5 A g−1. Even when the current density is increased tenfold from 0.1 A g−1, the battery still retains 67.1 % of its capacity. Additionally, due to the introduction of multiple solvents, the potassium metal battery with perylene‐3,4,9,10‐tetracarboxylic dianhydride as the cathode can maintain reversible capacities of 94.0 and 77.3 mAh g−1 and operate stably at ambient temperatures of −20 and −40 °C, respectively.

Long-Life Zinc Anodes via Molecular-Layer-Deposited Inorganic-Organic Hybrid Titanicone Thin Films.

Zinc-ion batteries (ZIBs) have consistently faced challenges related to the instability of the zinc anode. Uncontrolled dendrite growth, hydrogen evolution reaction (HER), and byproduct accumulation on the zinc anode severely affect the cycling life of ZIBs. Herein, inorganic-organic hybrid thin films of titanicones (Ti-based hydroquinone, TiHQ) were fabricated by molecular layer deposition (MLD) technology to modify the zinc metal anode. The MLD-based Zn@TiHQ anode suppresses the dendrite growth on the anode surface, reduces side reactions, and facilitates the desolvation and rapid transport of Zn2+ ions. As a result, it maintains an average Coulombic efficiency (CE) as high as 99.1% over 300 cycles at 0.5 mA cm-2 and 1 mAh cm-2, exhibiting excellent cycling stability for over 2800 h and enhancing the reversible capacity of the Zn@TiHQ||MnO2 full cell. This work demonstrates that the MLD-derived inorganic-organic hybrid TiHQ coating provides a more stable interfacial environment for the zinc anode, opening an avenue for designing high-performance zinc anodes.

A Stable Solid-Electrolyte Interphase Constructed by a Nucleophilic Molecule Additive for the Zn Anode with High Utilization and Efficiency.

The solid-electrolyte interphase (SEI) strongly determines the stability and reversibility of aqueous Zn-ion batteries (AZIBs). In traditional electrolytes, the nonuniform SEI layer induced by severe parasitic reactions, such as the hydrogen evolution reaction (HER), will exacerbate the side reactions on Zn anodes, thus leading to low zinc utilization ratios (ZURs). Herein, we propose to use methoxy ethylamine (MOEA) as a nucleophilic additive, which has a stronger nucleophilic characteristic than water, with the advantage of an abundance of nucleophilic atoms. The Helmholtz plane (HP) on the Zn anode can be manipulated via the adsorption of MOEA, which excludes free water from the HP due to its strong affinity with metallic Zn. Benefiting from the optimization of the HP, side reactions are greatly suppressed, and a smooth SEI layer can be constructed, enabling the Zn anode to work at high ZURs and high areal capacities. Consequently, the Zn||Cu asymmetric cell exhibits an extremely high cumulative plating capacity of 4 Ah cm-2 at 10 mA cm-2 with an average Coulombic efficiency (CE) of 99.8%. The Zn||Zn symmetric cell achieves a maximum ZUR of 80% at an areal capacity of 20 mAh cm-2 for 130 h, accounting for the boosted reversibility of Zn||V2O5 and Zn||AC full cells under low N/P ratios. Our strategy with nucleophilic electrolyte additives opens a path for developing durable aqueous Zn batteries with high ZURs.

Honeycomb-like Superstructure of 3D Sodiophilic Host for Anode-Free Sodium Batteries

Sodium metal batteries (SMBs) have emerged as a promising candidate for large-scale energy storage systems due to their abundance and cost-effectiveness. However, the high reactivity of sodium (Na) inevitably leads to side reactions and it's infinite volume expansion would definitely limit the applications. The anode-free Na batteries (AFNB) significantly enhance energy density by eliminating excess sodium, but bring a few challenges in terms of cycling stability. In this study, we report that honeycomb-like Bi-nanosheets arrays vertically grown on a Cu mesh, this unique 3D superstructure accommodate the volumetric changes and provides abundant sodiophilic nucleation sites. The Na||Cu half-cell battery demonstrates high reversibility of Na plating/stripping with an average coulombic efficiency (CE) of 99.8% at high current density. The Na||Na symmetrical cell exhibits a stable cycle lifespan of over 1000 hours at a significant discharge depth (DOD) of 75%. The NaTi2(PO4)3 (NTP) cathode in AFNB cell with an N/P ratio of 1 displays an initial capacity of 95.18 mA h g-1 for 267 cycles at 1 C, with an outstanding capacity retention of 93.22%. Our work proposes a potential path toward establishing a highly sodiophilic 3D sodium host, thereby promoting its application in high-stability AFNBs.

A bismuth oxide-modified copper host achieving bubble-free and stable potassium metal batteries.

Due to the minimal electrochemical oxidation-reduction potential, the potassium (K) metal anode has emerged as a focal in K-ion batteries. However, the reactivity of the K metal anode leads to significant side reactions, particularly gas evolution. Mitigating gas generation from K metal anodes has been a persistent challenge in the field. In this study, we propose a dual protective layer design through pre-treatment of the K metal anode, employing a Bi2O3 modification layer alongside a stable solid electrolyte interface (SEI) formed during the initial charge-discharge cycle, which significantly suppresses gas evolution. Furthermore, we observe that the Bi2O3 modification layer enhances K nucleation due to its strong potassiophilicity when incorporated into the substrate material. The resultant SEI, consisting of dual inorganic layers of Bi-F and K-F formed through the Bi2O3 modification, effectively mitigates side reactions and gas generation while inhibiting dendrite growth. Utilizing a Cu@BO@K host, we achieve a nucleation overpotential as low as 40 mV, with a stability of 1900 h in a Cu@BO@K‖Cu@BO@K cell and a high average Coulombic efficiency of 99.2% in a Cu@BO@K‖Cu cell at 0.5 mA cm-2/0.5 mA h cm-2. Additionally, Cu@BO@K‖PTCDA also presents a high reversible capacity of 114 mA g-1 at 100 mA g-1 after 200 cycles. We believe that this work presents a viable pathway for mitigating side reactions in K metal anodes.

Terminally fluorinated ether as a solvent for high-performance lithium metal battery electrolyte.

Terminally fluorinated ether 5FDEE shows exceptional compatibility with LiPF6, enabling high-performance Li-metal batteries. Li‖NMC811 cells with a 1 M LiPF6 in 5FDEE : FEC (9 : 1 v/v) electrolyte demonstrate remarkable cycling stability with an average coulombic efficiency exceeding 99.9% and no capacity fading over 550 cycles at 2.7-4.3 V vs. Li+/Li.

Manipulating Interphase Chemistry for Aqueous Zn Stabilization: The Role of Supersaturation

The limited cycling durability of Zn anode, attributed to the absence of a robust electrolyte‐derived solid electrolyte interphase (SEI), remains the bottleneck for the practical deployment of aqueous zinc batteries. Herein, we highlight the role of local supersaturation in governing the fundamental crystallization chemistry of Zn4SO4(OH)6·xH2O (ZSH) and propose a subtle supersaturation‐controlled morphology strategy to tailor the interphase chemistry of Zn anode. By judiciously creating local high‐supersaturation environment with organic caprolactam to manipulate the precipitation manner of zinc sulfate hydroxide (ZSH), lattice‐lattice matched heterogeneous nucleation of ZSH (001) and Zn (002) is realized in aqueous ZnSO4, producing a dense, pseudo‐coincidence interface capable of functioning as decent SEI. The plating/stripping efficacy of Zn is significantly boosted, as reflected by the great improvement of the initial (from 59.9% to 84.1%) and average (from 94.0% to 99.2%) coulombic efficiency. Accordingly, the cyclic endurance of Zn anode is prolonged from 50 h to over 7000 h at 0.5 mA cm‐2/1 mAh cm‐2, witnessing 140‐fold lifespan extension. Profiting from supersaturation‐mediated Zn stabilization, the performance deterioration of zinc‐vanadium batteries is also alleviated, even with a low N/P ratio of 4.4. This work is anticipated to deepen current understanding on the control of the anodic chemistry.

Manipulating Interphase Chemistry for Aqueous Zn Stabilization: The Role of Supersaturation.

The limited cycling durability of Zn anode, attributed to the absence of a robust electrolyte-derived solid electrolyte interphase (SEI), remains the bottleneck for the practical deployment of aqueous zinc batteries. Herein, we highlight the role of local supersaturation in governing the fundamental crystallization chemistry of Zn4SO4(OH)6·xH2O (ZSH) and propose a subtle supersaturation-controlled morphology strategy to tailor the interphase chemistry of Zn anode. By judiciously creating local high-supersaturation environment with organic caprolactam to manipulate the precipitation manner of zinc sulfate hydroxide (ZSH), lattice-lattice matched heterogeneous nucleation of ZSH (001) and Zn (002) is realized in aqueous ZnSO4, producing a dense, pseudo-coincidence interface capable of functioning as decent SEI. The plating/stripping efficacy of Zn is significantly boosted, as reflected by the great improvement of the initial (from 59.9% to 84.1%) and average (from 94.0% to 99.2%) coulombic efficiency. Accordingly, the cyclic endurance of Zn anode is prolonged from 50 h to over 7000 h at 0.5 mA cm-2/1 mAh cm-2, witnessing 140-fold lifespan extension. Profiting from supersaturation-mediated Zn stabilization, the performance deterioration of zinc-vanadium batteries is also alleviated, even with a low N/P ratio of 4.4. This work is anticipated to deepen current understanding on the control of the anodic chemistry.