In Situ Polymerization Bi-Functional Gel Polymer Electrolyte for High Performance Quasi-Solid-State Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are expected to be the next-generation energy storage system due to the ultrahigh theoretical energy density and low cost. However, the notorious shuttle effect of higher-order polysulfides and the uncontrollable lithium dendrite growth are the two biggest challenges for commercially viable Li-S batteries. Herein, these two main challenges are solved by in situ polymerization of bi-functional gel polymer electrolyte (GPE). The initiator (SiCl4) not only drives the polymerization of 1,3-dioxolane (DOL) but also induces the construction of a hybrid solid electrolyte interphase (SEI) with inorganic-rich compositions on the Li anode. In addition, diatomaceous earth (DE) is added and anchored in the GPE to obtain PDOL-SiCl4-DE electrolyte through in situ polymerization. Combined with density functional theory (DFT) calculations, the hybrid SEI provides abundant adsorption sites for the deposition of Li+, inhibiting the growth of lithium dendrites. Meanwhile, the shuttle effect is greatly alleviated due to the strong adsorption capacity of DE toward lithium polysulfides. Therefore, the Li/Li symmetric cell and Li-S full cell assembled with PDOL-SiCl4-DE exhibit excellent cycling stability. This study offers a valuable reference for the development of high performance and safe Li-S batteries.

Diagnostic Protocols for Evaluating the Degradation Mechanisms in Gel-Polymer Lithium Batteries.

Gel polymer electrolytes (GPEs) present a promising alternative to standard liquid electrolytes (LE) for Lithium-ion Batteries (LIBs) and Lithium Metal Batteries bridging the advantages of both liquid and solid polymer electrolytes. However, their cycle life still lags behind that of standard LIBs, and their degradation mechanisms remain poorly understood. A significant challenge is the need for specific diagnostic protocols to systematically study the degradation mechanisms of GPE-based cells. Challenges include the separation of cell components and effective washing, as well as the study of the solid electrolyte interfaces, all complicated by the semi-solid nature of GPEs. This paper provides a brief review of existing literature and proposes a comprehensive set of diagnostic tools for dismantling and evaluating the degradation of GPE-based LIBs. Finally, these methods and recommendations are applied to LiNi0.5Mn1.5O4 (LNMO)-graphite cells, revealing electrolyte oxidation as a major source of cell degradation.

An Advanced Gel Polymer Electrolyte for Solid-State Lithium Metal Batteries.

All-solid-state lithium metal batteries (LMBs) are regarded as one of the most viable energy storage devices and their comprehensive properties are mainly controlled by solid electrolytes and interface compatibility. This work proposes an advanced poly(vinylidene fluoride-hexafluoropropylene) based gel polymer electrolyte (AP-GPEs) via functional superposition strategy, which involves incorporating butyl acrylate and polyethylene glycol diacrylate as elastic optimization framework, triethyl phosphate and fluoroethylene carbonate as flameproof liquid plasticizers, and Li7La3Zr2O12 nanowires (LLZO-w) as ion-conductive fillers, endowing the designed AP-GPEs/LLZO-w membrane with high mechanical strength, excellent flexibility, low flammability, low activation energy (0.137 eV), and improved ionic conductivity (0.42 × 10-3 S cm-1 at 20 °C) due to continuous ionic transport pathways. Additionally, the AP-GPEs/LLZO-w membrane shows good safety and chemical/electrochemical compatibility with the lithium anode, owing to the synergistic effect of LLZO-w filler, flexible frameworks, and flame retardants. Consequently, the LiFePO4/Li batteries assembled with AP-GPEs/LLZO-w electrolyte exhibit enhanced cycling performance (87.3% capacity retention after 600 cycles at 1 C) and notable high-rate capacity (93.3 mAh g-1 at 5 C). This work proposes a novel functional superposition strategy for the synthesis of high-performance comprehensive GPEs for LMBs.

Phytic Acid Customized Hydrogel Polymer Electrolyte and Prussian Blue Analogue Cathode Material for Rechargeable Zinc Metal Hydrogel Batteries.

Zinc anode deterioration in aqueous electrolytes, and Zn dendrite growth is a major concern in the operation of aqueous rechargeable Zn metal batteries (AZMBs). To tackle this, the replacement of aqueous electrolytes with a zinc hydrogel polymer electrolyte (ZHPE) is presented in this study. This method involves structural modifications of the ZHPE by phytic acid through an ultraviolet (UV) light-induced photopolymerization process. The high membrane flexibility, high ionic conductivity (0.085 S cm-1), improved zinc corrosion overpotential, and enhanced electrochemical stability value of ≈2.3 V versus Zn|Zn2+ show the great potential of ZHPE as an ideal gel electrolyte for rechargeable zinc metal hydrogel batteries (ZMHBs). This is the first time that the dominating effect of chelation of phytic acid with M2+ center over H-bonding with water is described to tune the gel electrolyte properties for battery applications. The ZHPE shows ultra-high stability over 360 h with a capacity of 0.50 mAh cm-2 with dendrite-free plating/stripping in Zn||Zn symmetric cell. The fabrication of the ZMHB with a high-voltage zinc hexacyanoferrate (ZHF) cathode shows a high-average voltage of ≈1.6 V and a comparable capacity output of 63 mAh g-1 at 0.10 A g-1 of the current rate validating the potential application of ZHPE.

In Situ-Initiated Poly-1,3-dioxolane Gel Electrolyte for High-Voltage Lithium Metal Batteries.

To realize high-energy-density Li metal batteries at low temperatures, a new electrolyte is needed to solve the high-voltage compatibility and fast lithium-ion de-solvation process. A gel polymer electrolyte with a small-molecular-weight polymer is widely investigated by combining the merits of a solid polymer electrolyte (SPE) and liquid electrolyte (LE). Herein, we present a new gel polymer electrolyte (P-DOL) by the lithium difluoro(oxalate)borate (LiDFOB)-initiated polymerization process using 1,3-dioxolane (DOL) as a monomer solvent. The P-DOL presents excellent ionic conductivity (1.12 × 10-4 S cm-1) at -20 °C, with an oxidation potential of 4.8 V. The Li‖LiCoO2 cell stably cycled at 4.3 V under room temperature, with a discharge capacity of 130 mAh g-1 at 0.5 C and a capacity retention rate of 86.4% after 50 cycles. Moreover, a high-Ni-content LiNi0.8Co0.1Mn0.1O2 (NCM811) cell can steadily run for 120 cycles at -20 °C, with a capacity retention of 88.4%. The underlying mechanism of high-voltage compatibility originates from the dense and robust B- and F-rich cathode interface layer (CEI) formed at the cathode interface. Our report will shed light on the real application of Li metal batteries under all-climate conditions in the future.

Highly tough slide-crosslinked gel polymer electrolyte for stable lithium metal batteries.

Gel polymer electrolytes (GPEs) hold great promise for the practical application of lithium metal batteries. However, conventional GPEs hardly resists lithium dendrites growth and maintains long-term cycling stability of the battery due to its poor mechanical performance. Inspired by the slide-ring structure of polyrotaxanes (PRs), herein we developed a dynamic slide-crosslinked gel polymer electrolyte (SCGPE) with extraordinary stretchability of 970.93% and mechanical strength of 1.15 MPa, which is helpful to buffer the volume change of electrodes and maintain mechanical integrity of the battery structure during cycling. Notably, the PRs structures can provide fast ion transport channels to obtain high ionic conductivity of 1.73×10-3 S cm-1 at 30°C. Additionally, the strong polar groups in SCGPE restrict the free movement of anions to achieve high lithium-ion transference number of 0.71, which is favorable to enhance Li+ transport dynamics and induce uniform Li+ deposition. Benefiting from these features, the constructed Li|SCGPE-3|LFP cells exhibit ultra-long and stable cycle life over 1000 cycles and high-capacity retention (89.6% after 1000 cycles). Even at a high rate of 16C, the cells deliver a high capacity of 79.2 mAh g-1. The slide-crosslinking strategy in this work provides a new perspective on the design of advanced GPEs for LMBs.

Interface-Compatible Gel-Polymer Electrolyte Enabled by NaF-Solubility-Regulation toward All-Climate Solid-State Sodium Batteries.

Gel-polymer electrolyte (GPE) is a pragmatic choice for high-safety sodium batteries but still plagued by interfacial compatibility with both cathode and anode simultaneously. Here, salt-in-polymer fibers with NaF salt inlaid in polylactide (PLA) fiber network was fabricated via electrospinning and subsequent in situ forming gel-polymer electrolyte in liquid electrolytes. The obtained PLA-NaF GPE achieves a high ion conductivity (2.50×10-3 S cm-1) and large Na+ transference number (0.75) at ambient temperature. Notably, the dissolution of NaF salt occupies solvents leading to concentrated-electrolyte environment, which facilitates aggregates with increased anionic coordination (anion/Na+ >1). Aggregates with higher HOMO realize the preferential oxidation on the cathode so that inorganic-rich and stable CEI covers cathode' surface, preventing particles' breakage and showing good compatibility with different cathodes (Na3V2(PO4)3, Na2+2xFe2-x(SO4)3, Na0.72Ni0.32Mn0.68O2, NaTi2(PO4)3). While, passivated Na anode induced by the lower LUMO of aggregates, and the lower surface tension between Na anode and PLA-NaF GPE interface, leading to the dendrites-free Na anode. As a result, the assembled Na || Na3V2(PO4)3 cells display excellent electrochemical performance at all-climate conditions.

In-Situ Cross-linked F- and P-Containing Solid Polymer Electrolyte for Long-Cycling and High-Safety Lithium Metal Batteries with Various Cathode Materials.

The practical application of lithium metal batteries (LMBs) has been hindered by limited cycle-life and safety concerns. To solve these problems, we develop a novel fluorinated phosphate cross-linker for gel polymer electrolyte in high-voltage LMBs, achieving superior electrochemical performance and high safety simultaneously. The fluorinated phosphate cross-linked gel polymer electrolyte (FP-GPE) by in-situ polymerization method not only demonstrates high oxidation stability but also exhibits excellent compatibility with lithium metal anode. LMBs utilizing FP-GPE realize stable cycling even at a high cut-off voltage of 4.6 V (vs Li/Li+) with various high-voltage cathode materials. The LiNi0.6Co0.2Mn0.2O2|FP-GPE|Li battery exhibits an ultralong cycle-life of 1200 cycles with an impressive capacity retention of 80.1 %. Furthermore, the FP-GPE-based batteries display excellent electrochemical performance even at practical conditions, such as high cathode mass loading (20.84 mg cm-2), ultrathin Li (20 µm), and a wide temperature range of -25 to 80 °C. Moreover, the first reported solid-state 18650 cylindrical LMBs have been successfully fabricated and demonstrate exceptional safety under mechanical abuse. Additionally, the industry-level 18650 cylindrical LiMn2O4|FP-GPE|Li4Ti5O12 cells demonstrate a remarkable cycle-life of 1400 cycles. Therefore, the impressive electrochemical performance and high safety in practical batteries demonstrate a substantial potential of well-designed FP-GPE for large-scale industrial applications.

Gel Polymer Electrolytes with Talc as a Natural Mineral Filler and a Biodegradable Polymer Matrix in Sodium-Ion Batteries.

A gel polymer electrolyte based on poly(vinyl alcohol) (PVA) is used in sodium-ion batteries (SIBs). The use of biodegradable and water-soluble polymer potentially reduces the negative environmental impact. The other components include sodium salt (NaPF6 ), sulfolane (TMS) as a plasticizer and talc. For the first time, natural and abundant talc has been used as an inert filler in a gel polymer electrolyte. The best results were obtained for moderate amounts of filler (1 and 3 wt%). Then, an increase in the conductivity, transference numbers, and thermal stability of the membranes was observed. Moreover, the presence of talc had a positive effect on the cyclability of the hard carbon electrode. The discharge capacity after 50 cycles of HC|1 % T_TMS|Na and HC|3 % T_TMS|Na was 243 and 225 mAh g-1 , respectively. The use of talc in gel polymer electrolytes containing sodium ions improves the safety and efficiency of SIBs.

Glass Fiber Reinforced Epoxy-Amine Thermosets and Solvate IL: Towards New Composite Polymer Electrolytes for Lithium Battery Applications.

To effectively use (Li) lithium metal anodes, it is becoming increasingly necessary to create membranes with high lithium conductivity, electrochemical and thermal stabilities, as well as adequate mechanical properties. Composite gel polymer electrolytes (CGPE) have emerged as a promising strategy, offering improved ionic conductivity and structural performance compared to polymer electrolytes. In this study, a simple and scalable approach was developed to fabricate a crosslinked polyethylene oxide (PEO)-based membrane, comprising two different glass fiber reinforcements, in terms of morphology and thickness. The incorporation of a solvated ionic liquid into the developed membrane enhances the ionic conductivity and reduces flammability in the resulting CGPE. Galvanostatic cycling experiments demonstrate favorable performance of the composite membrane in symmetric Li cells. Furthermore, the CGPE demonstrated electrochemical stability, enabling the cell to cycle continuously for more than 700 h at a temperature of 40 °C without short circuits. When applied in a half-cell configuration with lithium iron phosphate (LFP) cathodes, the composite membrane enabled cycling at different current densities, achieving a discharge capacity of 144 mAh·g-1. Overall, the findings obtained in this work highlight the potential of crosslinked PEO-based composite membranes for high-performance Li metal anodes, with enhanced near room temperature conductivity, electrochemical stability, and cycling capability.

Starch-Based Superabsorbent Hydrogel with High Electrolyte Retention Capability and Synergistic Interface Engineering for Long-Lifespan Flexible Zinc-Air Batteries.

The advent of wearable electronics has strongly stimulated advanced research into the exploration of flexible zinc-air batteries (ZABs) with high theoretical energy density, high inherent safety, and low cost. However, the half-open battery structure and the high concentration of alkaline aqueous environment pose great challenges on the electrolyte retention capability and the zinc anode stability. Herein, a starch-based superabsorbent hydrogel polymer electrolyte (SSHPE) with high ionic conductivity, electrolyte absorption and retention capabilities, strong alkaline resistance and high zinc anode stability has been designed and applied in ZABs. Experimental and calculational analyses probe into the root of the superiority of SSHPEs, confirming the significance of the carboxyl functional groups along their polymer chains. These features endow the as-fabricated ZAB a long cycle life of 300 h, much longer than that with commonly used poly(vinyl alcohol)-based electrolyte.

Nanofiber Composite for Improved Water Retention and Dendrites Suppression in Flexible Zinc-Air Batteries.

Water loss of the gel polymer electrolytes (GPEs) and dendrites growth on Zn anode are overriding obstacles to applying flexible zinc-air batteries (ZABs) for wearable electronic devices. Nearly all previous efforts aim at developing novel GPEs with enhanced water retention and therefore elongate their lifespan. Herein, a facile interface engineering strategy is proposed to retard the water loss of GPE from the half-open structured air cathode. In detail, the poly(ethylene vinyl acetate)/carbon powder (PEVA-C) nanofiber composite interface layer with features of hydrophobicity, high conductivity, air permeability, and flexibility are prepared on the carbon cloth and set up between the GPE and electrode. The as-assembled ZAB with simple alkaline PVA GPE exhibits an impressive cycle life of 230 h, which outperforms ZAB without the PEVA-C nanofibers interface layer by 14 times. Additionally, the growth of Zn dendrites can be suppressed due to the tardy water loss of GPE.

Ionic Liquid Functionalized Gel Polymer Electrolytes for Stable Lithium Metal Batteries.

Metallic lithium (Li) is regarded as the ideal anode material in lithium-ion batteries due to its low electrochemical potential, highest theoretical energy density and low density. There are, however, still significant challenges to be addressed such as Li-dendrite growth and low interfacial stability, which impede the practical application of Li metal anodes. In order to circumvent these shortcomings, herein, we present a gel polymer electrolyte containing imidazolium ionic liquid end groups with a perfluorinated alkyl chain (F-IL) to achieve both high ionic conductivity and Li ion transference number by fundamentally altering the solubility of salt within the gel electrolyte through Lewis-acidic segments in the polymer backbone. Moreover, the presence of F-IL moieties decreased the binding affinity of Li cation towards the glycol chains, enabling a rapid transfer of Li cation within the gel network. These structural features enabled the immobilization of anions on the ionic liquid segments to alleviate the space-charge effect while promoting stronger anion coordination and weaker cation coordination in the Lewis-acidic polymers. Accordingly, we realized a high Li ion conductivity (9.16×10-3  S cm-1 ) and high Li ion transference number of 0.69 simultaneously, along with a good electrochemical stability up to 4.55 V, while effectively suppressing Li dendrite growth. Moreover, the gel polymer electrolyte exhibited stable cycling performance of the Li|Li symmetric cell of 9 mAh cm-2 for more than 1800 hours and retained 86.7 % of the original capacity after 250 cycles for lithium-sulfur (Li-S) full cell.

Unique aqueous Li-ion/sulfur chemistry with high energy density and reversibility.

Leveraging the most recent success in expanding the electrochemical stability window of aqueous electrolytes, in this work we create a unique Li-ion/sulfur chemistry of both high energy density and safety. We show that in the superconcentrated aqueous electrolyte, lithiation of sulfur experiences phase change from a high-order polysulfide to low-order polysulfides through solid-liquid two-phase reaction pathway, where the liquid polysulfide phase in the sulfide electrode is thermodynamically phase-separated from the superconcentrated aqueous electrolyte. The sulfur with solid-liquid two-phase exhibits a reversible capacity of 1,327 mAh/(g of S), along with fast reaction kinetics and negligible polysulfide dissolution. By coupling a sulfur anode with different Li-ion cathode materials, the aqueous Li-ion/sulfur full cell delivers record-high energy densities up to 200 Wh/(kg of total electrode mass) for >1,000 cycles at ∼100% coulombic efficiency. These performances already approach that of commercial lithium-ion batteries (LIBs) using a nonaqueous electrolyte, along with intrinsic safety not possessed by the latter. The excellent performance of this aqueous battery chemistry significantly promotes the practical possibility of aqueous LIBs in large-format applications.

MCM-41/PVA Composite as a Separator for Zinc-Air Batteries.

Membrane separators are one of the critical components in zinc-air batteries (ZABs). In the control of mass transfer, and hence, electrochemical reaction, membrane separators have an important role to play. This work addresses the issue of battery performance in a ZAB via a new composite membrane separator based on polyvinyl alcohol (PVA). To enhance the electrolyte uptake and ionic conductivity, mesoporous Mobil Composition of Matter No. 41 (MCM-41) is incorporated as a filler in the membrane while maintaining its integrity. The presence of MCM-41 is seen to reduce the number of cycles of secondary ZABs due to the uninvited drawbacks of increased zincate crossover and reduced triple phase boundary at the air cathode, which is pivotal for oxygen reduction reaction. Overall, results suggest that the application of the MCM-41/PVA composite has the potential for use as a separator in high-capacity primary ZABs.

Characteristics of Dye-Sensitized Solar Cell Assembled from Modified Chitosan-Based Gel Polymer Electrolytes Incorporated with Potassium Iodide.

In the present work, phthaloyl chitosan (PhCh)-based gel polymer electrolytes (GPEs) were prepared using dimethylformamide (DMF) as a solvent, ethyl carbonate (EC) as a co-solvent, and a set of five quaternaries of potassium iodide (KI) as a doping salt, which is a mixed composition of iodine (I2). The prepared GPEs were applied to dye-sensitized solar cells (DSSC) to observe the effectiveness of the electrolyte, using mesoporous TiO2, which was sensitized with N3 dye as the sensitizer. The incorporation of the potassium iodide-based redox couple in a polymer electrolyte is fabricated for dye-sensitized solar cells (DSSCs). The number of compositions was based on the chemical equation, which is 1:1 for KI:I2. The electrical performance of prepared GPE systems have been assessed using electrical impedance spectroscopy (EIS), and dielectric permittivity. The improvement in the ionic conductivity of PhCh-based GPE was observed with the rise of salt concentration, and the maximum ionic conductivity (4.94 × 10-2 S cm-1) was achieved for the 0.0012 mol of KI:I2. The study of dielectric permittivity displays that ions with a high dielectric constant are associated with a high concentration of added ions. Furthermore, the gel polymer electrolyte samples were applied to DSSCs to detect the conversion effectiveness of the electrolytes. For electrolytes containing various content of KI:I2 the highest conversion efficiency (η%) of DSSC obtained was 3.57% with a short circuit current density (Jsc) of 20.33 mA cm-2, open-circuit voltage (Voc) of 0.37 V, fill factor (FF) of 0.47, as well as a conductivity of 2.08 × 10-2 S cm-1.

A Newly Designed Composite Gel Polymer Electrolyte Based on Poly(Vinylidene Fluoride-Hexafluoropropylene) (PVDF-HFP) for Enhanced Solid-State Lithium-Sulfur Batteries.

Developing high-performance solid-state electrolytes is crucial for the innovation of next-generation lithium-sulfur batteries. Herein, a facile method for preparation of a novel gel polymer electrolyte (GPE) based on poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) is reported. Furthermore, Li1.5 Al0.5 Ti1.5 (PO4 )3 (LATP) nanoparticles as the active fillers are uniformly embedded into the GPE to form the final PVDF-HFP/LATP composite gel polymer electrolyte (CPE). Impressively, the obtained CPE demonstrates a high lithium ion transference number of 0.51 and improved electrochemical stability as compared to commercial liquid electrolyte. In addition, the assembled solid-sate Li-S battery with the composite gel polymer electrolyte membrane presents a high initial capacity of 918 mAh g-1 at 0.05 C, and better cycle performance than the counterparts with liquid electrolyte. Our designed PVDF-HFP/LATP composite can be a promising electrolyte for next-generation solid-state batteries with high cycling stability.

An Ultrahigh Modulus Gel Electrolytes Reforming the Growing Pattern of Li Dendrites for Interfacially Stable Lithium-Metal Batteries.

Gel polymer electrolytes (GPEs) have aroused intensive attention for their moderate comprehensive performances in lithium-metal batteries (LMBs). However, GPEs with low elastic moduli of MPa magnitude cannot mechanically regulate the Li deposition, leading to recalcitrant lithium dendrites. Herein, a porous Li7 La3 Zr2 O12 (LLZO) framework (PLF) is employed as an integrated solid filler to address the intrinsic drawback of GPEs. With the incorporation of PLF, the composite GPE exhibits an ultrahigh elastic modulus of GPa magnitude, confronting Li dendrites at a mechanical level and realizing steady polarization at high current densities in Li||Li cells. Benefiting from the compatible interface with anodes, the LFP|PLF@GPE|Li cells deliver excellent rate capability and cycling performance at room temperature. Theoretical models extracted from the topology of solid fillers reveal that the PLF with unique 3D structures can effectively reinforce the gel phase of GPEs at the nanoscale via providing sufficient mechanical support from the load-sensitive direction. Numerical models are further developed to reproduce the multiphysical procedure of dendrite propagation and give insights into predicting the failure modes of LMBs. This work quantitatively clarifies the relationship between the topology of solid fillers and the interface stability of GPEs, providing guidelines for designing mechanically reliable GPEs for LMBs.

Noncombustible gel polymer electrolyte inspired by bio-radicalchemistry for high voltage and high safety Ni-rich lithium batteries.

For high energy density lithium-ion batteries (LIBs) with nickel-rich ternary cathodes, the chemical degradation of electrolytes caused by free radical reactions and the hazards of thermal runaway have always been significant challenges. Inspired by the free radical scavenging of living organisms and multiphase synergistic flame retardant mechanism, we innovatively designed and prepared a multifunctional flame retardant HCCP-TMP that combines flame retardancy and free radical scavenging by combining hindered amine and cyclophosphazene. Only 1 wt% HCCP-TMP can make the polyacrylate-based gel polymer electrolyte (GPE) incombustible. Moreover, the equipped NCM811//Graphite pouch cells don't exhibit combustion behavior after thermal runaway and can resist mechanical abuse. Based on the above noncombustible GPE, the NCM811//Li battery exhibits capacity retention rate of 82.2 % after 100 cycles at a current density of 2 C and in the voltage range of 3.0-4.7 V, exhibiting excellent cyclability under high voltage. This simple molecular design simultaneously improves the fire safety and high voltage stability, demonstrating enormous application potential in the field of advanced LIBs with high safety and high energy density.

Immobile polyanionic backbone enables a 900-µm-thick electrode for compact energy storage with unprecedented areal capacitance.

Thickening of electrodes is crucial for maximizing the proportion of active components and thus improving the energy density of practical energy storage cells. Nevertheless, trade-offs between electrode thickness and electrochemical performance persist because of the considerably increased ion transport resistance of thick electrodes. Herein, we propose accelerating ion transport through thick and dense electrodes by establishing an immobile polyanionic backbone within the electrode pores; and as a proof of concept, gel polyacrylic electrolytes as such a backbone are in situ synthesized for supercapacitors. During charge and discharge, protons rapidly hop among RCOO- sites for oriented transport, fundamentally reducing the effects of electrode tortuosity and polarization resulting from concentration gradients. Consequently, nearly constant ion transport resistance per unit thickness is achieved, even in the case of a 900-µm-thick dense electrode, leading to unprecedented areal capacitances of 14.85 F cm-2 at 1 mA cm-2 and 4.26 F cm-2 at 100 mA cm-2. This study provides an efficient method for accelerating ion transport through thick and dense electrodes, indicating a significant solution for achieving high energy density in energy storage devices, including but not limited to supercapacitors.