Side Reactions Research Articles

Coupling Solvation Structure Regulation and Interface Engineering via Reverse Micelle Strategy Toward Highly Stable Zn Metal Anode

AbstractThe stability of aqueous Z inc (Zn) ion energy storage devices is significantly compromised by the instability at the electrode/electrolyte interface, which can result in the growth of Zn dendrites, self‐corrosion, and various other side reactions. Regulating the Zn‐ion （Zn2+) solvation structure through electrolyte additives has been proved to be effective strategy in stabilizing the Zn anode, but the influence of free water on the solvation structure is often lacking in‐depth exploration. Herein, the piperazine‐N,N‐bis(2‐hydroxypropanesulfonic acid) sodium salt (POPSO‐Na) is presented as a multifunctional electrolyte additive, which enhances the stability of the Zn anode by modulating the deposition and stripping environment of Zn2⁺ and limiting the presence of free water in the electrolyte during cycling. Theoretical calculation and experimental results demonstrate that the POPSO‐Na additive can not only replace the structural water around Zn2+ to destroy the original solvation sheath, but also form reverse micelle interface structure to hinder the proton transition and constrain the free water in the electrolyte. Thus, the Zn||Zn battery utilizing the ZnSO4+POPSO‐Na electrolyte exhibits an impressive cycle life of 1600 h at a current density of 1 mA cm−2, achieving an average Coulomb efficiency (CE) of ≈100%, which is significantly better than that observed with the ZnSO4 electrolyte. Moreover, the Zn||Cu battery with ZnSO4+POPSO‐Na electrolyte achieves high stability even after cycling for over 2000 h.

Stereocatalytic Effect of CeO2 for the Synthesis of trans‐3‐Penten‐2‐ol

AbstractThe transformation of biobased alkanediols over heterogeneous catalysts is a major object. Here, a series of catalysts were prepared for 2,4‐pentanediol dehydration to 3‐penten‐2‐ol. Ceria‐based catalysts had a unique property of showing high efficiency. More importantly, a stereocatalytic effect was observed for CeO2, yielding trans‐3‐penten‐2‐ol with a high selectivity. Raman, XPS, TPD, and TPR were carried out to clarify the catalyst structure, and the relationship between the catalyst structure and catalytic performance were studied. The amount of Lewis acid sites can hardly be correlated with the total concentrations of the oxygen vacancies. It was suggested that the geometry structure of the active sites played a crucial role in trans‐3‐penten‐2‐ol production. The oxygen vacancies originating from CeO2 consisted of active sites with a geometrical structure, which were different from those created by Pr doping CeO2. In addition, the Pr doping enhanced the oxygen migration, which resulted in side reactions, consequently, giving a lower selectivity to trans‐3‐penten‐2‐ol.

Improving Oxygen-Redox-Active Layered Oxide Cathodes for Sodium-Ion Batteries Through Crystal Facet Modulation and Fluorinated Interfacial Engineering.

Layered oxides with active oxygen redox are attractive cathode materials for sodium-ion batteries (SIBs) due to high capacity but suffer from rapid capacity/voltage deterioration and sluggish reaction kinetics stemming from lattice oxygen release, interfacial side reactions, and structural reconstruction. Herein, a synergistic strategy of crystal-facet modulation and fluorinated interfacial engineering is proposed to achieve high capacity, superior rate capability, and long cycle stability in Na0.67Li0.24Mn0.76O2. The synthesized single-crystal Na0.67Li0.24Mn0.76O2 (NLMO{010}) featuring increased {010} active facet exposure exhibits faster anionic redox kinetics and delivers a high capacity (272.4 mAh g-1 at 10mA g-1) with superior energy density (713.9Wh kg-1) and rate performance (116.4 mAh g-1 at 1 A g-1). Moreover, by incorporating N-Fluorobenzenesulfonimide (NFBS) as electrolyte additive, the NLMO{010} cathode retains 84.6% capacity after 400 cycles at 500mA g-1 with alleviated voltage fade (0.27mV per cycle). Combined in situ analysis and theoretical calculations unveil dual functionality of NFBS, which results in thin yet durable fluorinated interfaces on the NLMO{010} cathode and hard carbon anode and scavenges highly reactive oxygen species. The results indicate the importance of fast-ion-transfer facet engineering and fluorinated electrolyte formulation to enhance oxygen redox-active cathode materials for high-energy-density SIBs.

Length and Sequence-Selective Polymer Synthesis Templated by a Combination of Covalent and Noncovalent Base-Pairing Interactions.

Information can be encoded and stored in sequences of monomer units organized in linear synthetic polymers. Replication of sequence information is of fundamental importance in biology; however, it represents a challenge for synthetic polymer chemistry. A combination of covalent and noncovalent base pairs has been used to achieve high-fidelity templated synthesis of synthetic polymers that encode information as a sequence of different side-chain recognition units. Dialkyne building blocks were attached to the template by using ester base pairs, and diazide building blocks were attached to the template by using H-bond base pairs. Copper-catalyzed azide-alkyne cycloaddition reactions were used to zip up the copy strand on the template, and the resulting duplex was cleaved by hydrolyzing the covalent ester base pairs. By using recognition-encoded melamine oligomers with either three phosphine oxide or three 4-nitrophenol recognition units to form the noncovalent base pairs, exceptionally high affinities of the diazides for the template were achieved, allowing the templated polymerization step to be carried out at low concentrations, which promoted on-template intramolecular reactions relative to competing intermolecular processes. Two different templates, a 7-mer and an 11-mer, were used in the three-step reaction sequence to obtain the sequence-complementary copy strands with minimal amounts of side reaction.

Bio-Inspired Core-Shell Structured Electrode Particles with Protective Mechanisms for Lithium-Ion Batteries.

Lithium-ion batteries (LIBs), as predominant energy storage devices, are applied to electric vehicles, which is an effective way to achieve carbon neutrality. However, the major obstructions to their applications are two dilemmas: enhanced cyclic life and thermal stability. Taking advantage of bio-inspired core-shell structures to optimize the self-protective mechanisms of the mercantile electrode particles, LIBs can improve electrochemical performance and thermal stability simultaneously. The favorable core-shell structures suppress volume expansion to stabilize electrode-electrolyte interfaces (EEIs), mitigate direct contact between the electrode material and electrolyte, and promote electrical connectivity. They possess wide operating temperatures, high-voltage resistance, and inhibit short circuits. During cycling, the cathode and anode generate a cathode-electrolyte interface (CEI) and a solid-electrolyte interface (SEI), respectively. Applying multitudinous coating approaches can generate multifarious bio-inspired core-shell structured electrode particles, which is helpful for the generation of the EEIs, self-healing the surface cracks, and maintaining the structural integrities of electrodes. The protected shells act as barriers to minimize unwanted side reactions and enhance thermal stability. These in-depth understandings of the bio-inspired evolution for electrode particles can inspire further enhancements in LIB lifetime and thermal safety, especially for bio-inspired core-shell structured electrodes possessing high-performance protective mechanisms.

The Interaction Between Fluorinated Additives and Imidazolyl Ionic Liquid Electrolytes in Lithium Metal Batteries: A First‐Principles Study

ABSTRACTThis investigation employs first‐principles calculations to explore the interaction between imidazolium ionic liquids (ILs) and fluoride additives on lithium metal surface. Our focus lies in the comprehensive analysis of three distinct categories of fluorinated additives, each differing in their degree of fluorination. The computations reveal that fluorination plays a significant role in determining both the ionic conductivity and the formation of the solid–electrolyte interphase (SEI) film. Specifically, heightened fluorination enhances the oxidative stability of the system but diminishes the strength of solvent binding, resulting in the formation of larger salt/anion clusters and a decrease in ionic conductivity. Conversely, increased fluorination facilitates the interaction between fluorinated additives and the lithium metal surface, thereby aiding in the formation of a stable SEI film characterized by an abundance of inorganic LiF components. This is important as it serves to suppress dendrite growth and mitigate interface side reactions. Considering the combined influences of ionic conductivity and film formation, 1FP is suggested as the optimal candidate for pyridine‐based additive systems, with FEC preferred for cyclic ester‐based additive systems and BC for chain ester‐based additive systems. This study provides theoretical references for the design of ionic liquid‐fluorinated additive electrolyte systems that can protect the lithium metal anode.

Gradient Distribution of Zincophilic Sites for Stable Aqueous Zinc-Based Flow Batteries with High Capacity.

Current collectors, as reaction sites, play a crucial role ininfluencing various electrochemical performances in emerging cost-effective zinc-based flow batteries (Zn-based FBs). 3D carbon felts (CF) are commonly used but lack effectiveness in improving Zn metal plating/stripping. Here, a current collector with gravity-induced gradient copper nanoparticles (CF-G-Cu NPs) is developed, integrating gradient conductivity and zincophilicity to regulate Zn deposition and suppress side reactions. The CF-G-Cu NPs electrode modulates Zn nucleation and growth via the zincophilic Cu/CuZn5 alloy has been confirmed by density functional theory (DFT) calculations. Finite element simulation demonstrates the gradient internal structure effectively optimizes the local electric/current field distribution to regulate the Zn2+ flux, improving bottom-up plating behavior for Zn metal and mitigating top-surface dendrite growth. As a result, Zn-based asymmetrical FBs with CF-G-Cu NPs electrodes achieve an areal capacity of 30 mAhcm-2 over 640h with Coulombic efficiency of 99.5% at 40mAcm-2. The integrated Zn-Iodide FBs exhibit a competitive long-term lifespan of 2910h (5800 cycles) with low energy efficiency decay of 0.062% per cycle and high cumulative capacity of 112800 mAhcm-2 at a high current density of 100mAcm-2. This gradient distribution strategy offers a simple mode for developing Zn-based FB systems.

Constructing Dual Schottky Junctions for High‐Performance Zinc Anode

AbstractAqueous zinc ion batteries provide new solutions for achieving environmentally friendly and safe energy storage devices. Unfortunately, the further application is hampered by the growth of zinc dendrites caused by uneven zinc deposition, hydrogen evolution and other side interfacial reactions at the zinc anode. Herein, a multifunctional Bi‐Bi2O3 hybrid artificial interface layer is constructed on the surface of the zinc anode using an in situ conversion reaction. Among them, the Bi‐Bi2O3 Schottky structure not only significantly accelerates the migration of Zn2+ through its built‐in electric field, but also effectively improves the hydrogen evolution barrier (ΔGH*), thereby suppressing side reactions. Moreover, the Schottky contact formed between the interface layer and the metal zinc interface also regulates the electronic distribution state on the zinc surface and optimizes the deposition process of Zn2+, ensuring a more uniform and orderly zinc deposition process. Based on the synergistic effect of dual Schottky junctions, symmetric batteries achieve stable cycling for 2000 h under the conditions of 1.0 mA cm−2 and 1.0 mAh cm−2. The full cell assembled with α‐MnO2 as the cathode maintains capacity of 112.7 mAh g−1 after 1000 cycles at 1 A g−1 with a capacity retention rate of 84%.

Multifunctional Amphoteric Additive Alanine Enables High-Performance Wide-pH Zn Metal Anodes.

Interfacial pH fluctuation is one of the primary reasons for issues related to Zn metal anodes. Herein, polar amphoteric alanine, as a multifunctional electrolyte additive, is designed to regulate the electric double layer (EDL) and solvation structure. Alanine with self-adaptation capability to pH can stabilize electrolyte pH. Due to more negative adsorption energy, alanine preferentially adsorbs on the Zn surface and repels water molecules within the EDL. Alanine-enriched EDL effectively shields the surface tips, homogenizes interfacial electric field distribution, and promotes preferential deposition of horizontal flaky Zn. Alanine-enriched EDL limits the contact between water and the Zn anode. Alanine additive decreases the quantity of water molecules in the Zn2+ solvation sheath and disrupts H-bond networks in the electrolyte. Consequently, a dense and textured Zn deposition is achieved. Corrosion and side reactions are suppressed. Cycling stability of symmetrical cells attains 2700h at 3mAcm-2/1mAhcm-2 and 2050h at 5mAcm-2/1mAhcm-2. Average coulombic efficiency reaches 99.8% over 4500 cycles at 5mAcm-2/1mAhcm-2. Even within KOH alkaline electrolytes, alanine additive still improves the cycling lifespan of symmetrical cells to 100h at 0.5mAcm-2/0.5mAhcm-2.

Strengthen Water O−H Bond in Electrolytes for Enhanced Reversibility and Safety in Aqueous Aluminum Ion Batteries

AbstractAqueous aluminum‐ion batteries present a promising prospect for large‐scale energy storage applications, owing to the abundance, inherent safety, and the high theoretical capacity of aluminum. However, their voltage output and energy density are significantly hindered by challenges such as complex hydrogen evolution and uncontrollable solvation reactions. In this work, we demonstrate that water decomposition is restrain by increasing the electron density of water protons and increasing the dissociation energy of H2O through robust dipole interactions with highly polar dimethylformamide (DMF) molecules. Moreover, the incorporation of dimethyl methylphosphonate (DMMP) flame retardant effectively addresses the flammability risk arising from a substantial presence of organic additives The in‐depth study with experimental and theoretical simulations reveals that the water‐poor solvation structure with reduced water activity is achieved, which can (i) effectively mitigate undesired solvated H2O‐mediated side reactions on the Al anode; (ii) boost the de‐solvation kinetics of Al3+ while preventing cathode structural distortion; (iii) reduce the flammability of hybrid electrolytes. As a proof of concept, the Al//AlxMnO2 full cell employing a hybrid electrolyte demonstrate enhanced stability (deliver 335 mAh g−1 while retaining 71 % capacity for 400 cycles) compared to those with pure electrolyte.

Research on aging mechanism and capacity attenuation of automotive lithium-ion batteries

In order to investigate the internal mechanism and the variation law of capacity attenuation of LIBs, a simplified electrochemical model of the LIBs was established using the nickel-cobalt-aluminum LIBs as the research object, and the aging model of solid electrolyte interface SEI growth and lithium evolution was added to simulate the electrochemical behavior of the batteries. The results showed that the porosity of the anode/diaphragm reduced continually at the start of the cycle, while the SEI film grew continuously. The loss of active materials accelerated as the number of cycles increased, while the side reaction of lithium development continued. Finally, the aging mechanism was confirmed by using microscopic morphology. The results show that the negative particles are obviously crushed and contain white deposited substances. The formation of these compounds increases the oxygen content, reduces the carbon content, reduces the porosity of the electrode, increases the overpotential of the electrolyte transport, and becomes the main reason for the attenuation of the battery life. Finally, the positive particles expand and break, which leads to the sudden reduction of the battery capacity. This study determined the evolution process of aging mechanism in the whole life cycle, and provided a theoretical basis for the establishment of mechanism aging model.

Polyethylene Glycol-Protected Zinc Microwall Arrays for Stable Zinc Anodes.

Aqueous zinc-ion batteries promise good commercial application prospects due to their environmental benignity and easy assembly under atmospheric conditions, positioning them as a viable alternative to lithium-ion batteries. However, some inherent issues, such as chaotic zinc dendrite growth and inevitable side reactions, challenge the commercialization progress. In this work, we imprint highly ordered zinc microwall arrays to regulate the electric field toward uniform Zn deposition. Afterward, coating a polyethylene glycol protection layer on the zinc microwalls aims to passivate the surface defects that rise unintentionally by mechanical imprinting. Polyethylene glycol can also boost oriented Zn deposition along the (002) plane and inhibit hydrogen gas production, further enhancing the stability of such three-dimensional (3D) hybrid anodes. Compared to the messy electric field near the polyethylene glycol-protected Zn foil, the uniform electric field provided by these 3D hybrid anodes can regulate the Zn deposition behaviors, enabling a longer lifespan and thus certifying the necessity of adding 3D microstructures. Additionally, 3D microstructures can offer a larger surface area than that of the planar Zn foil, providing more reaction sites and higher specific capacity. In this case, the 3D hybrid electrode exhibits a good initial capacity of approximately 120 mA h/g at a current density of 5 A/g and a nice retention of more than 80% after 800 cycles. The proposed scheme paves the way for a long-term stable 3D zinc anode solution with promising application prospects.

Co Cluster-Modified Ni Nanoparticles with Superior Light-Driven Thermocatalytic CO2 Reduction by CH4

Excessive fossil burning causes energy shortages and contributes to the environmental crisis. Light-driven thermocatalytic CO2 reduction by methane (CRM) provides an effective strategy to conquer these two global challenges. Ni-based catalysts have been developed as candidates for CRM that are comparable to the noble metal catalysts. However, they are prone to deactivation due to the thermodynamically inevitable coking side reactions. Herein, we reported a novel Co-Ni/SiO2 nanocomposite of Co cluster-modified Ni nanoparticles, which greatly enhance the catalytic durability for light-driven thermocatalytic CRM. It exhibits high production rates of H2 (rH2) and CO (rCO, 22.8 and 26.7 mmol min−1 g−1, respectively), and very high light-to-fuel efficiency (ƞ) is achieved (26.8%). Co-Ni/SiO2 shows better catalytic durability than the referenced catalyst of Ni/SiO2. Based on the experimental results of TG-MS, TEM, and HRTEM, we revealed the origin of the significantly enhanced light-driven thermocatalytic activity and durability as well as the novel photoactivation. It was discovered that the focused irradiation markedly reduces the apparent activation energy of CO2 on the Co-Ni/SiO2 nanocomposite, thus significantly enhancing the light-driven thermocatalytic activity.

Salt-Concentrated Electrolyte Constructing High Elasticity Modulus Interphase for Li-Rich Layered Oxide Cathode.

Stable electrolytes are urgently required for lithium-ion batteries based on lithium-rich layered oxides (LLOs), which generally suffer from fast capacity and voltage decay at high voltages up to 4.8 V. Herein, we report a salt-concentrated electrolyte consisting of 4 M lithium hexafluorophosphate (LiPF6) salt in ester solvents of fluoroethylene carbonate (FEC) and dimethyl carbonate (DMC) to alleviate the above challenges. The solvent structure in the 4 M electrolyte shows more volatile DMC integrated with Li+ and more free antioxidative FEC compared with a 1 M electrolyte, broadening the operation voltage. Simultaneously, this electrolyte endows a thin yet high elasticity modulus LiF-rich interphase on the LLOs surface, which can effectively prevent diverse side reactions and transition metal migration, consequently improving the electrochemical performance with a voltage decay of only 0.46 mV/cycle and capacity retention of 80.3% after 500 cycles. This simple and effective approach boosts the development of high-energy-density batteries using LLOs.

Surface Reconstruction Reduces Internal Stress of Ni-Rich Cathode Particles.

High-voltage Ni-rich layered cathode materials are undoubtedly a powerful driving force for high-energy density lithium batteries. However, residual lithium impurities on the surface of Ni-rich materials can cause more severe side reactions under high-voltage, leading to rapid decay. There is still no reliable mechanistic explanation for this phenomenon. It has been detected that residual alkali on the cathode surface under high voltage can cause obvious side reactions. This side reaction will affect the capacity retention of the material and increase the internal stress of the particles. In addition, the surface reconstruction of Ni-rich cathodes is achieved through simple chemical reactions, turning waste into treasure. The newly generated Ti-based layer not only repairs the structure of the nickel-rich material but also optimizes the material from a dynamic perspective. Removing residual lithium components on the cathode surface effectively reduces the hydrolysis and self-catalytic side reactions of PF6 - at the electrolyte cathode interface and suppresses gas generation during cycling, promoting the application of the next generation of high-energy density Ni-rich layered cathode-based lithium batteries with high-voltage.

Constructing a Multifunctional SEI Layer Enhancing Kinetics and Stabilizing Zinc Metal Anode

AbstractZn dendrite growth and parasitic reactions at the interface of zinc anode/electrolyte in aqueous zinc batteries severely hinder its lifespan in application. Herein, the zinc anode is effectively stabilized by introducing trace amounts of 4‐aminobutane‐1‐phosphate (ABPA) into the ZnSO4 electrolyte. The ABPA adsorbs onto the surface of zinc anode and then further decomposes to a high conductive organic/inorganic composite in situ SEI layer including amino, partial carbon chain, and zinc phosphate. In the SEI layer, the residual undecomposed carbon chain promotes the desolvation of Zn2+, the amino induces uniform Zn2+ plating and zinc phosphate facilitates the migration of Zn2+. Thus, this in situ SEI layer not only suppresses water‐related side reactions but also enhances the Zn2+ transport kinetics. As a result, Zn||Zn symmetric cell delivers an ultralong cycle life of over 13 000 cycles at 50 mA cm−2 and 1 mAh cm−2. A high average Coulombic efficiency of 99.72% is achieved in over 1000 cycles in Zn||Cu half‐cell. The Zn||I2 full cell delivers a high‐capacity retention of 91.42% after 40,000 cycles. Moreover, a 49 mAh Zn||I2 pouch cell maintains 80.28% capacity retention over 300 cycles and 61.22% after 1000 cycles.

Boosting Dendrite‐Free Zinc Anode with Strongly Polar Functional Group Terminated Hydrogel Electrolyte for High‐Safe Aqueous Zinc‐Ion Batteries

AbstractAqueous zinc‐ion batteries (AZIBs) have become a promising energy storage device due to their low cost and high security. However, the severe dendrite growth and side reactions on metallic zinc (Zn) anode hamper their commercial implementation. Herein, a strongly electronegative trifluoroborate anion (─BF3−) functionalized polyacrylamide hydrogel (PAME) is well‐designed and constructed as the quasi‐solid‐state electrolyte to overcome these obstacles. The PAME chain segments terminated with strongly polar functional groups promote the conversion of water molecules from free water to bound water through the enhanced hydrogen bonding interaction to alleviate the side reactions. Furthermore, the PAME electrolyte featured with hierarchically porous structure and enhanced electrostatic interaction among the ─BF3− groups, and Zn2+ ions homogenizes the high‐flux Zn ion transport and induce the uniform deposition to restrain dendrite growth. Consequently, the assembled Zn‖PAME‖Zn batteries deliver remarkable cycling stability over 1800 h at 1 mA cm−2 and 900 h at 15 mA cm−2. Additionally, the constructed Zn‖PAME‖MnO2 full cells achieve a reversible capacity of 202 mAh g−1 at 2.0 A g−1 with a capacity retention rate of 91.4% over 500 cycles. This work sheds light on constructing the strongly polar hydrogel electrolyte to boost free‐dendrite Zn anodes for long‐lifespan AZIBs.

D‐Electrons of Platinum Alloy Steering CO Pathway for Low‐Charge Potential Li‐CO2 Batteries

AbstractAprotic Li‐CO2 batteries suffer from sluggish solid‐solid co‐oxidation kinetics of C and Li2CO3, requiring extremely high charging potentials and leading to serious side reactions and poor energy efficiency. Herein, we introduce a novel approach to address these challenges by modulating the reaction pathway with tailored Pt d‐electrons and develop an aprotic Li‐CO2 battery with CO and Li2CO3 as the main discharge products. Note that the gas‐solid co‐oxidation reaction between CO and Li2CO3 is both kinetically and thermodynamically more favorable. Consequently, the Li‐CO2 batteries with CoPt alloy‐supported on nitrogen‐doped carbon nanofiber (CoPt@NCNF) cathode exhibit a charging potential of 2.89 V at 50 μA cm−2, which is the lowest charging potential to date. Moreover, the CoPt@NCNF cathode also shows exceptional cycling stability (218 cycles at 50 μA cm−2) and high energy efficiency up to 74.6 %. Comprehensive experiments and theoretical calculations reveal that the lowered d‐band center of CoPt alloy effectively promotes CO desorption and inhibits further CO reduction to C. This work provides promising insights into developing efficient and CO‐selective Li‐CO2 batteries.

Impact of conducting agents on sulfide and halide electrolytes in disordered rocksalt cathode‐based all‐solid‐state batteries

AbstractAll‐solid‐state battery (ASSB) systems have attracted significant attention due to their high energy density and safety compared with conventional batteries. Moreover, the application of Mn‐based cation‐disordered rock‐salt (DRX) that possesses cost‐effectiveness and high energy density on the ASSB system as a cathode is expected to be the superior next‐generation battery system. However, DRX cathodes require high carbon contents due to their low electronic conductivity, leading to challenges in introducing them in ASSB systems, as the high carbon levels can cause electrolyte decomposition which potentially affects overall electrochemical performance. In this work, we applied Mn‐based DRX cathodes to ASSB systems within a voltage range of 1.5–4.8 V and evaluated the suitability of cathode composites using halide and sulfide electrolytes as catholytes, respectively. The experimental results showed that the high carbon contents induced side reactions with the argyrodite, resulting in electrochemical degradation such as the drop of initial discharge voltage and the capacity fading. Meanwhile, cathode composites using a halide electrolyte exhibited relatively enhanced electrochemical performance due to its high oxidation stability regardless of the high amount of carbon contents. Consequently, the electrochemical reactions of the electrolyte, influenced by the content of conductive additives and the type of electrolyte, had a great impact on the performance of ASSB systems. This study provides a deep understanding of the interplaying among solid electrolytes, cathodes, and conductive additives and offers an important foundation for future research and development in ASSB systems.image

Strong Replaces Weak: ​Hydrogen Bond‐Anchored Electrolyte Enabling Ultra‐Stable and Wide‐Temperature Aqueous Zinc‐Ion Capacitors

Despite aqueous electrolytes offer a great opportunity for large‐scale energy storage owing to their safety and cost‐effectiveness, their practical application suffers from the parasitic side reactions and poor temperature adaptability stemming from weak hydrogen‐bond (HB) network in free water. Here, we propose the guiding thought “strong replaces weak” to design hydrogen bond‐anchored electrolyte by introducing sulfolane (SL) for disrupting the regular weak HB network and contributing to superior temperature tolerance. Judiciously combined experimental characterization and theoretical calculation confirm that SL can remodel the primary solvation shell of metal ions, customize stable electrode interface chemistry and restrain the side reactions. Consequently, symmetric supercapacitor constructed by activated carbon (AC) electrodes is able to fully work within a voltage range of 2.4 V and reach high capacitance retention of 89.8% after 60000 cycles. Additionally, Zn anodes exhibit ultra‐stable Zn plating/stripping behaviors and a wide temperature range (‐20 ~ 60 °C), and zinc‐ion capacitor (Zn//AC) also delivers an excellent cycling stability with capacity retention of 99.7% after 55000 cycles, implying that the designed electrolyte has practical application potential in extreme environments. This work proposes a novel critical solvation strategy that paves the route for the construction of ultra‐stable and wide‐temperature aqueous energy storage devices.