Overpotential Deposition Research Articles

Deciphering Lithium Deposition Behavior in Elemental Alloy Anodes for Lithium Metal Batteries.

Lithium (Li) dendrite is one of the most fatal obstacles for developing practical high energy Li metal batteries, while Li alloy substrates, with strong lithiophilicity, have attracted increasing interest for directing uniform Li deposition. However, most of the previous research studies associated Li dendrite inhibition closely with high adsorption energy. Yet, the Li deposition process is not solely about the adsorption of an isolated Li atom, where a comprehensive understanding of the interfacial lattice mismatch and the Li atom diffusion should also be taken into account. Here, we explore the Li deposition behavior from adhesion work, representing interfacial stability and bonding strength, and both Li adsorption and diffusion. It is found that the overpotential of Li deposition is inversely related to adhesion work, while uniform Li deposition requires a high adsorption energy and low Li atom diffusion barrier. These detailed relationships may offer guidance for subsequent substrate development.

Functional organic 7,7,8,8‐tetracyanoquinodimethane artificial layers for the dendrite suppressed lithium metal anodes

AbstractThe large‐scale industrialization of lithium metal (Li), as a potential anode for a high energy density energy storage system, has been hindered by dendrite growth. The construction of an artificial solid electrolyte interphase layer featuring high ionic and low electronic conductivity has been verified to be a high‐performance strategy to confine the dendrite growth and promote the Li anode stability. Therefore, a functional organic protective layer is homogeneously deposited on the Li anode surface via an in situ chemical reaction between tetracyanoquinodimethane (TCNQ) and Li. The as‐synthesized Lin‐TCNQ organic film could efficiently trap non‐uniform Li deposition and restrain dendrite propagation. Particularly, an asymmetric M‐TCNQ‐Li|Cu cell with the Lin‐TCNQ layer breezed through a high Coulombic efficiency of 91.15% after 100 cycles at 1.0 mA cm−2. The M‐TCNQ‐Li|NCM622 cell delivered a high capacity of 143.40 mAh g−1 at 0.2 C and maintained a good cyclic stability of 110.44 mAh g−1 after 160 cycles. The analysis results of spectroscopic tests further demonstrate that the Lin‐TCNQ with the enhanced absorption energy is conducive to lithiophilicity and decreases the overpotential of Li deposition.

Initial stages of silver electrodeposition on a model Pt(111) single-crystal substrate from ethaline

Deep eutectic solvents (DES) are a new class of solvents with unique properties that are very promising media for the electroplating of metals and alloys. Knowledge about the regularities of metal electrodeposition is noticeably promoted by studies on model single crystal electrodes with a known well-ordered surface structure. In this work, we investigate the regularities of under- and overpotential deposition (upd and opd, respectively) of silver from a silver chloride solution in ethaline on a Pt(111) single crystal surface. For a better understanding of the occurring processes, we employ a complex approach involving electrochemical and in situ and ex situ microscopic techniques. We show that the process of gradual surface poisoning is observed on Pt(111) in the potential range in which no massive solvent degradation is yet observed. We also observe that the extent of this process largely depends on the employed potential of contact between the electrode and the solution and the studied potential range.The presence of Ag upd on Pt(111) in ethaline is demonstrated using voltammetric and in situ STM data. The available results and charge analysis are used to compare the Ag upd processes in ethaline and in aqueous solutions. We discuss the number of Ag adlayers on Pt(111), the effect of the potential of initial contact of the electrode with the solution and cycling history, and the possibility of anion upd and formation of coadsorbate between Ag adatoms and upd chloride anions (chlorine adatoms). We also demonstrate that upd Ag is not completely desorbed until high anodic potentials, where it seems to catalyze the solvent oxidation. Phase deposition of silver from ethaline on Pt(111) starts at almost zero overpotentials, which is probably related to the presence of the already deposited Ag adlayer. Even at very low overpotentials the deposit includes both large planar 2D crystallites and 3D crystallites formed on the surface defects and at the edges of the flat deposit islands. As the overpotential grows, the epitaxiality is gradually lost; the deposit becomes unshaped and the amount of 3D crystallites and their height increase.

Multifunctional Water Additive Enabling Stable Cycling of Chloride‐Free Magnesium Metal Batteries Based on Carbonate Electrolyte

AbstractRechargeable magnesium batteries (RMBs) face with the challenge of interphase passivation between electrolytes and Mg anodes. Compared with ether electrolytes, carbonate solvents possess the superior electrochemical stability at cathode side, but their incompatibility with Mg metal, high viscosity, and desolvation energy barrier restrict their practical utilization in RMBs. Herein, the “unwanted‐impurity” water with high concentration is revisited and employed as multifunctional additive in carbonate electrolyte to improve the reversibility of RMBs. Water additive enables the localized deep eutectic effect, reduces the viscosity of carbonate electrolyte, and improves the Mg ion conductivity. The water molecules also participate the solvation sheath of Mg ions, resulting in the reduction of Mg deposition overpotential and inhibition of parasitic reaction. Furthermore, the co‐intercalated water molecules in V2O5 cathode layers enable the stabilization of intercalation structure and supply of additional magnesiophilic sites. Cooperated with the binder‐decorated Mg powder anode, the propylene carbonate electrolyte with water additive endows Mg||Mg symmetric cells and Mg||V2O5 full cells with satisfactory cycling performance and high‐voltage stability. This work revisits the impact of impurity water and provides a practical strategy for the utilization of conventional low‐cost carbonate electrolyte family, broadening the design and formulation of electrolytes for chlorine‐free and high‐voltage RMBs.

New Electrochemical Approach for Synthesis of Nanoporous Silver

Cu-Ag alloy films were electrodeposited on Au substrates to serve as precursor alloys for synthesizing finely-structured nanoporous Ag (NPS) structures. Two innovative approaches, surface limited redox replacement (SLRR) and defect mediated growth (DMG) along with overpotential deposition (OPD), were comparatively utilized to fabricate Cu-Ag alloy films. The electrolyte for these novel approaches contained Pb2+ ions to serve either as a sacrificial metal to be replaced by the co-depositing Cu and Ag (in SLRR) or as mediating metal to facilitate the 2D growth of both alloy constituents (in DMG). The resulting alloy films from both approaches displayed superior uniformity and miscibility compared to the OPD alloy, as evidenced by electrochemical scanning electron microscopy (SEM) and X-ray diffraction characterization routines. In a subsequent step, NPS structures were generated through the de-alloying of as-deposited Cu-Ag alloys, as illustrated by SEM imaging that revealed ligament and pore sizes with a thickness in the ballpark of 40 nm. Also, surface area measurements done by a Pb underpotential deposition assay suggested a surface enhancement ratio nearly five times higher than that of flat Ag. Furthermore, various de-alloying potentials were assessed to determine the optimal de-alloying potential for the best outcome of the de-alloying process.

Control of Ag deposition for improvement of specular reflection in Ag deposition-based electrochemical mirror through modulation of electrolysis condition

The reflection behavior of an Ag deposition-based reversible electrochemical mirror is determined by the morphology of the electrodeposited Ag. This study demonstrates the control of the morphology of Ag deposits through the modulation of the electrolysis conditions, specifically the applied potential and Ag+ ions concentration, without increasing the amount of Ag deposits. By applying a potential with a sufficiently large deposition overpotential for continuous deposition on the electrode surface, the deposited Ag formed a flat surface, resulting in high reflectivity. Considering the concentration dependence of Ag+ ions, the diffusion of Ag+ ions to the electrode significantly affected the resulting morphology of the deposits. At higher Ag+ concentrations, the time for the transition to a diffusion-limited process increased because Ag+ ions were close to the working electrode. Therefore, a flat Ag layer was obtained due to the promotion of three-dimensional deposition, including the in-plane growth.

Diverse Hierarchical Meso/Nanoporous Pt Film Electrocatalysts Prepared via Hydrogen Adsorption-Assisted Dynamic Soft Templating.

In this study, we present an innovative approach for creating hierarchical meso/nanoporous Pt films using dynamic soft templating. The fabrication process, called dynamic soft templating, involves Pt electrodeposition within a specialized bicontinuous microemulsion (BME) system characterized by a sophisticated three-dimensional network comprising water and oil phases, surfactants, and cosurfactants. Pt electrodeposition exclusively occurs in the water phase of the BME. This results in a porous Pt film exhibiting a nanostructure mirroring the oil solution/water solution nanostructure (solution/solution structure) of the BME, the size of which can be tailored by adjusting the BME composition. Through a simultaneous interplay of Pt electrodeposition and overpotential deposition of hydrogen (H-OPD, dissociative adsorption of water), potential-dependent Pt mesostructures are dynamically shaped. As a result, we achieve diverse morphologies in the form of hierarchical meso/nanoporous Pt films. The potential applications of the films are evaluated as electrocatalysts for the methanol oxidation reaction (MOR), and it was found that the electrocatalytic performances seem to be sensitive to nanoporosity and not relevant to mesoporosity.

Electron‐Deficient Sites Constructed by Boron Doping Induce Homogenous Zn Deposition in Alkaline Zinc–Iron Flow Batteries

AbstractAlkaline zinc‐iron flow batteries (ZFBs) have recently attracted renewed attention. However, the critical issues with zinc anodes, such as dendrite formation, side reactions, and labile plating or stripping, have yet to be adequately addressed. Here, an attempt is made to overcome these challenges by designing Boron‐doped carbon‐felt (B–CF) electrodes rich in electron‐deficient sites and defects. The fabricated B–CF provides improved adsorption of negatively charged Zn(OH)42−, robust Zn nucleation sites, and lower Zn nucleation and deposition overpotentials, leading to homogeneous Zn deposition morphology. Uniform Zn deposition enables the prevention of undesirable dendrite growth and parasitic reactions. As a result, the constructed alkaline ZFBs achieve a high average Coulombic efficiency of ≈99.85% and energy efficiency of 88% with uniform Zn deposition during 300 cycles (40 mA cm−2). This work expands the understanding of the electrode design strategy for achieving favorable Zn plating/stripping.

Constructing zinc-tin alloy interface for highly stable alkaline zinc anode

Aqueous alkaline zinc batteries have received widespread attention owing to its higher electrode potential and faster reaction kinetics compared to in mild aqueous electrolyte. However, Zn metal anode in alkaline electrolyte usually suffers more severe corrosion, passivation, and hydrogen evolution reaction. Herein, an interface chemical regulation strategy employs to in-situ construct a Zn-Sn alloy layer during cycling. The K2[Sn(OH)6] has been introduced into the electrolyte as the deposition overpotential of Zn and Sn in alkaline electrolyte is approximate leading to their simultaneously plating. The Zn-Sn alloy layer not only prevents Zn anode corrosion and suppresses the dendrite growth but also promotes the reaction kinetics. Therefore, the Zn||Zn cell exhibits a long life of 400 h in alkaline electrolyte about 20 times of that in without K2[Sn(OH)6] electrolyte. Moreover, the N-NCP@PQx||Zn full cell displays a superior cycle performance of 4000 cycles with 93% capacity retention at 2 A/g.

Efficient manufacture of high-performance electroplated diamond wires utilizing Cr-coated diamond micro-powder

The slicing of silicon ingots using electroplated diamond wires is a fundamental process in the creation of semiconductor devices such as chips and photovoltaic cells. Composite electroplating, a process that uses nickel (Ni) plating to fix diamond particles onto a steel wire, is a critical step in the manufacturing of these diamond wires. In this work, chromium (Cr)-coated diamond was used to achieve rapid and high-quality composite electroplating, thereby aiding the production of high-performance diamond wire saws. The Cr-coated diamond micro-powder was prepared utilizing vacuum slow evaporation technology at a temperature of 850 °C. This resulted in a uniform and firm Cr coating that was firmly bonded to the diamond surface via Cr3C2. Subsequent electrochemical tests were conducted in the composite electroplating bath. Linear scanning voltammetric curves revealed that the Cr-coated diamond was capable of inducing a more positive shift in the overpotential of Ni deposition, thus enhancing the reaction beyond that of uncoated diamond micro-powder. Additionally, the electrochemical impedance spectra indicated a decrease in charge transfer resistance during composite electroplating, attributable to the conductivity of the Cr-coated diamond. Electroplated diamond wires incorporating Cr-coated diamond demonstrated a greater abrasive density per unit length. SEM results showed that Ni was able to deposit on the Cr-coated diamond surface, resulting in the abrasives being completely covered by the Ni plating. The Cr-coated diamond wire exhibits a stronger resistance to abrasive detachment after cutting, which could increase the diamond-protrusion of the wire. The utilization of Cr-coated diamond micro-powder as an abrasive is anticipated to enhance the manufacturing efficiency of diamond wires and improve product quality, thereby promoting advancements in hard and brittle material processing technology.

Regulation of fiber surface nucleation kinetics via ordered nitrogen-rich carbon dots

Three dimensional (3D) carbon-based current collectors have attracted much attentions as host for Li metal anodes (LMAs) owing to their lightweight, flexible, and wide sources etc. However, the lithiophobic nature of carbon makes it difficult to achieve low nucleation overpotential and dendrite-free Li deposition. Herein, carbon dots (CDs) with nitrogen (N)-rich were introduced to modify carbonized cotton fiber (CCF) coated by reduced graphene oxide (CD@RGCCF). Coating graphene oxide (GO) increases the active site of cotton fiber (CF), which facilitates the growth of CDs on the surface of CF fiber. The introduction of ordered structure CDs drives fast migration of Li+ in the “highway-like” channels and induces the uniform nucleation of Li in the initial stage. As a result, the obtained CD@RGCCF decreases the nucleation overpotential of Li, and achieves dendrite-free Li deposition. the CD@RGCCF|Li half cells exhibit extending cycling life over 5000 h with a voltage hysteresis of 10.5 mV at 2 mA cm−2. As coupled with the LiFePO4 (LFP), the Li@CD@RGCCF||LFP composite anode enables a high reversible specific capacity and improved cycle stability. This work provides a low-cost modification method for carbon substrate to realize dendritic-free LMAs.

Dendrite-free electrolyte for Zn/LiFePO4 batteries operating at low-temperature

Zinc-ion batteries, known for safety and efficiency, are a hotspot in electrochemical energy storage field. Nonetheless, the emergence of dendrites on zinc anodes during electrochemical cycles can lead to capacity attenuation and even failure, particularly under low temperatures. In this study, we develop a novel dendrite-free and low-temperature resistant Zn(ClO4)2/Li2SO4/Dimethyl sulfoxide (DMSO) hybrid electrolyte by using DMSO as a hydrogen bond acceptor and solvation regulator. Our research demonstrates that, by reducing the desolvation energy barrier of the Zn2+ solvation sheath and the nucleation overpotential of Zn deposition, DMSO effectively inhibits zinc dendrites and side reactions. Furthermore, DMSO disrupts hydrogen bonding between water molecules, preventing electrolyte freezing at low temperatures. As a result, at 0.5 mA cm−2, the Zn||Zn symmetric device using this hybrid electrolyte exhibits consistent operation for over 4000 h even at -25 °C, featuring a minimal deposition/dissolution overpotential of approximately 0.045 mV. Additionally, at -20 °C, the Zn||Zn(ClO4)2-Li2SO4-DMSO||LiFePO4 battery demonstrates stable cycling for over 600 cycles at 0.6 C (1 C = 170 mA g− 1), delivering a capacity of 103 mA h g−1.

Ion Sieve Interface Assisted Zinc Anode with High Zinc Utilization and Ultralong Cycle Life for 61 Wh/kg Mild Aqueous Pouch Battery.

The cycling stability of a thin zinc anode under high zinc utilization has a critical impact on the overall energy density and practical lifetime of zinc ion batteries. In this study, an ion sieve protection layer (ZnSnF@Zn) was constructed in situ on the surface of a zinc anode by chemical replacement. The ion sieve facilitated the transport and desolvation of zinc ions at the anode/electrolyte interface, reduced the zinc deposition overpotential, and inhibited side reactions. Under a 50% zinc utilization, the symmetrical battery with this protection layer maintained stable cycling for 250 h at 30 mA cm-2. Matched with high-load self-supported vanadium-based cathodes (18-20 mg cm-2), the coin battery with 50% zinc utilization possessed an energy density retention of 94.3% after 1000 cycles at 20 mA cm-2. Furthermore, the assembled pouch battery delivered a whole energy density of 61.3 Wh kg-1, surpassing the highest mass energy density among reported mild zinc batteries, and retained 76.7% of the energy density and 85.3% (0.53 Ah) of the capacity after 300 cycles.

Modified Ion Migration via Multi-Ion Competitive Transportation for Stable Aqueous Zn Metal Batteries.

The application of metal batteries is seriously affected by active ions transport and deposition stability during operation. This article takes water-based Zn metal electrodes as an example to analyze the factors that affect ion distribution and the impact of ion distribution on electrodeposition morphology through electrochemical model simulation calculation, in situ observation and electrochemical experiment: 1) high concentration will reduce the concentration polarization and the overpotential; 2) The passage of active ions through channels are facilitated by small anion (Cl-) rather than bigger one (SO4 2-), which means small deposition overpotential; 3) The transportability-reaction properties of cations (Zn2+, Li+, Na+ and H+) depends on their concentration, solvent coordination structure, and the energy changes during redox reactions. Based on the diffusion and reaction properties, a Li+ coupled Zn2+ electrolyte is designed to achieve the rapid transportation of doped ions to cover uneven growth sites and maintain a stable interface for the steady deposition of active Zn2+, guiding the interface design for high stability metal batteries in addition to the traditional addition of organic solvents.

Self‐Assembled Lithiophilic Interface with Abundant Nickel‐Bis(Dithiolene) Sites Enabling Highly Durable and Dendrite‐Free Lithium Metal Batteries

AbstractDespite its ultrahigh theoretical capacity and ultralow redox electrochemical potential, the practical application of lithium metal anodes is still hampered by severe dendrite growth and unstable solid electrolyte interphase (SEI). Herein, a self‐assembled lithiophilic interface (SALI) for regulating Li electroplating behavior is constructed by introducing a meticulously synthesized Ni‐bis(dithiolene)‐based molecule (NiS4‐COOH) into a hybrid fluorinated ester‐ether electrolyte. The NiS4‐COOH molecules with carboxyl functional groups can spontaneously anchor on the Li metal surface to form a SALI, whose abundant Ni‐bis(dithiolene) sites can effectively reduce the initial Li deposition overpotential and guide the subsequent uniform Li electrodeposition. Moreover, due to the interaction between the coordination unsaturated Ni atom and the negatively charged PF6−, the NiS4‐COOH additive can significantly change the ionic coordination environment in the electrolyte, which is greatly conducive to suppressing PF6− decomposition, optimizing SEI composition and accelerating Li‐ion transfer. Consequently, the NiS4‐COOH‐modified electrolyte leads to impressive electrochemical performance of Li||LiFePO4 and Li||LiNi0.8Co0.1Mn0.1O2 batteries, delivering ultrahigh Coulombic efficiencies, considerable capacity retention, and good rate performance even at high areal active material loadings. This study presents the great potential of SALIs derived from multifunctional metal‐organic hybrid electrolyte additives toward high‐specific‐energy Li metal batteries.

Lithium metal deposition under the geometrical confinement effect: Dendritic copper foam current collector

Dendrite-free lithium is the ultimate goal in achieving the commercial application of lithium metal anode. In this paper, Dendritic Copper Foam Current Collector (DCFC) is prepared by an electrometallurgy method to realize the homogeneous deposition of lithium metal. The deposition behavior of Cu and Li on different interfaces was studied. Firstly, the Cu dendrites constructed on the surface of Cu foam are induced and formed by the potential oscillation generated by the hydrogen evolution reaction. Secondly, the heterogeneous nucleation model reveals that the reason for the dendrite-free lithium deposition on the dendritic copper foam is the geometrical confinement effect. Compared with commercial copper foam, DCFC with hierarchical structure significantly reduces the nucleation energy and deposition overpotential of lithium metal. The in situ optical microscope observation and finite element simulation results confirm our ideas. Electrochemically, DCFC works stably after 1200 h at a lower potential of 36 mV in a DCFC@Li symmetric battery, which is much superior to 75 mV for just 340 h in Cu foam. The ideal collector with a dendritic structure has broad prospects for the practical application of lithium metal anode.

Thin and strong Janus separator based on nanocellulose and Ti3C2Tx for dendrite-free aqueous zinc-ion batteries

Glass fiber separators are commonly used for aqueous zinc-ion batteries (AZIBs), whereas easily leading to Zn dendrites and parasitic reactions. Although various strategies have been proposed to address this issue, most of those modified separators still suffer from large thickness and poor mechanical properties. Herein, wheat straw-derived nanocellulose is combined with Ti3C2Tx to form a Janus separator, which is merely 32 μm in thickness and owns remarkable strength and modulus of 215.3 MPa and 8.8 GPa, respectively. In addition, the Ti3C2Tx layer brings about Maxwell–Wagner and low lattice mismatch effects, which can facilitate Zn2+ ion transfer, accelerate desolvation procedure, enhance interfacial charge transport, reduce nucleation overpotential, promote homogeneous and horizontal Zn deposition, and inhibit side reactions. With the use of such Janus separator, the Zn//Zn cell provides a high cumulative plating capacity of 2500 mAh cm−2, and the Cu//Zn cell achieves a large average Coulombic efficiency of 98.95 % over 1000 cycles. Furthermore, the Janus separator renders Zn//MnO2 battery with great rate capability and excellent cycling stability. This work offers new insights into separator modifications for AZIBs towards practical applications.

Influence of Residual Water Traces on the Electrochemical Performance of Hydrophobic Ionic Liquids for Magnesium-Containing Electrolytes.

A trace amount of water is typically unavoidable as an impurity in ionic liquids, which is a huge challenge for their application in Mg-ion batteries. Here, we employed molecular sieves of different pore diameters (3, 4, and 5 Å), to effectively remove the trace amounts of water from 1-methyl-1-propylpiperidinium bis(trifluoromethylsulfonyl)imide (MPPip-TFSI) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP-TFSI). Notably, after sieving (water content <1 mg ⋅ L-1 ), new anodic peaks arise that are attributed to the formation of different anion-cation structures induced by minimizing the influence of hydrogen bonds. Furthermore, electrochemical impedance spectroscopy (EIS) reveals that the electrolyte resistance decreases by ∼10 % for MPPip-TFSI and by ∼28 % for BMP-TFSI after sieving. The electrochemical Mg deposition/dissolution is investigated in MPPip-TFSI/tetraglyme (1 : 1)+100 mM Mg(TFSI)2 +10 mM Mg(BH4 )2 using Ag/AgCl and Mg reference electrodes. The presence of a trace amount of water leads to a considerable shift of 0.9 V vs. Mg2+/ Mg in the overpotential of Mg deposition. In contrast, drying of MPPip-TFSI enhances the reversibility of Mg deposition/dissolution and suppresses the passivation of the Mg electrode.

Zn anode surface engineering for stable zinc-ion batteries: Carbon dots incorporated mesoporous TiO2 as a coating layer

Uncontrolled Zn dendrites growth and sustained corrosion originating from severe interfacial reactions are the major shortcomings of Zn metal electrodes in aqueous zinc-ion batteries (ZIBs). In order to overcome these obstacles, we designed a protective coating layer to stabilize the zinc anode and regulate the Zn deposition simultaneously. This hybrid layer (TiO2/NCDs) is constructed by mesoporous TiO2 nanosheets and N-doped carbon dots (NCDs), which is prepared by a solvothermal growth under the control of NCDs. On one hand, the TiO2 layer immobilize water molecules effectively, preventing them from the parasitic reactions with Zn electrodes. On the other, NCDs with abundant functional groups (–OH, –COOH, –NH2) provide the zincophilic nucleation sites to endow a small deposition overpotential of 28 mV and guide Zn deposition into a petal structure. Owing to mesoporous protective coating layer, the Zn-TiO2/NCDs anode presents a low voltage hysteresis of 48 mV and a prolonged cycling lifespan of 1500 h at 5 mA cm−2 and 2.5 mAh cm−2. Moreover, aqueous ZIBs assembled with the Zn-TiO2/NCDs anode and the α-MnO2 cathode show outstanding reversibility and good cycling stability, whose capacity retention is up to 90% after 1000 cycles.

Self-assembly formation of solid-electrolyte interphase in gel polymer electrolytes for high performance lithium metal batteries

Lithium-metal batteries (LMBs) using limited-Li anodes are imperative for realizing high-energy storage. Proper solid-electrolyte interphase (SEI) design to control Li-deposition behavior and enhance deposition reversibility is challenging. We engineer the self-assembly formation of SEI in a gel polymer electrolyte (GPE) comprising poly(vinylidene fluoride-co-hexafluoro propylene) (PVDF-co-HFP) dissolved in a LiPF6-LiNO3 dual-salt solution with multiple solvents. The components of this GPE present critical functions: (1) dielectric (PVDF‐co-HFP) dissociates ion pairs to facilitate Li+ transport in the electrolyte and regulate Li+ diffusion in the SEI to lower Li deposition overpotentials, and endows soft characteristics to the SEI; (2) dual-anion PF6−-NO3− in the Li+ solvation sheath facilitates facile Li+ desolvation and formation of rigid and ion-conductive Li3N–LiF-rich SEI. This GPE exhibits higher ionic conductivity and Li+ transference number than the corresponding liquid electrolytes. The capacity retention of an anode-free Cu|GPE|NMC811 battery, i.e., at an anodic-to-cathodic Li ratio (A/C) of 0, reaches 44% after 100 charge-discharge cycles. An LMB with limited-Li at A/C = 2, having energy of 616 Wh kg−1 based on electrode-material mass, exhibits a retention of 85% after 100 cycles. The strategy to regulate Li+-transport and Li-deposition through GPE is promising for realizing the application of LMBs.