Low Coulombic Efficiency Research Articles

Influence of Chloride and Electrolyte Stability on Passivation Layer Evolution at the Negative Electrode of Mg Batteries Revealed byoperandoEQCM-D.

Rechargeable magnesium batteries are promising for future energy storage. However, among other challenges, their practical application is hindered by low coulombic efficiencies of magnesium plating and stripping. Fundamental processes such as the formation, structure, and stability of passivation layers and the influence of different electrolyte components on them are still not fully understood. In this work, we gain unique insights into the initial Mg plating and stripping cycles by comparing Mg bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2)- and Mg tetrakis(hexafluoroisopropyloxy)borate (Mg[B(hfip)4]2)-based electrolytes, each with and without MgCl2, on gold electrodes by highly sensitive operando electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) applying hydrodynamic spectroscopy. With the stable Mg[B(hfip)4]2-based electrolytes, highly efficient and interphase-free cycling is possible and passivation layers are attributed to electrolyte contaminants. These are forming and degrading during the so-called initial conditioning process. With the more reactive Mg(TFSI)2-based electrolyte, thick passivation layers with small pores are growing during cycling. We demonstrate that the addition of chloride lowers the amount of passivated Mg deposits in these electrolytes and accelerates the currentless dissolution of the passivation layer. This has a positive effect since we observe the most efficient cycling and uniform deposition when no interphase is present on the electrode.

Influence of Chloride and Electrolyte Stability on Passivation Layer Evolution at the Negative Electrode of Mg Batteries Revealed by operando EQCM‐D

Rechargeable magnesium batteries are promising for future energy storage. However, among other challenges, their practical application is hindered by low coulombic efficiencies of magnesium plating and stripping. Fundamental processes such as the formation, structure, and stability of passivation layers and the influence of different electrolyte components on them are still not fully understood. In this work, we gain unique insights into the initial Mg plating and stripping cycles by comparing Mg bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2)‐ and Mg tetrakis(hexafluoroisopropyloxy)borate (Mg[B(hfip)4]2)‐based electrolytes, each with and without MgCl2, on gold electrodes by highly sensitive operando electrochemical quartz crystal microbalance with dissipation monitoring (EQCM‐D) applying hydrodynamic spectroscopy. With the stable Mg[B(hfip)4]2‐based electrolytes, highly efficient and interphase‐free cycling is possible and passivation layers are attributed to electrolyte contaminants. These are forming and degrading during the so‐called initial conditioning process. With the more reactive Mg(TFSI)2‐based electrolyte, thick passivation layers with small pores are growing during cycling. We demonstrate that the addition of chloride lowers the amount of passivated Mg deposits in these electrolytes and accelerates the currentless dissolution of the passivation layer. This has a positive effect since we observe the most efficient cycling and uniform deposition when no interphase is present on the electrode.

Design, perspectives, and challenges of modification strategies for alkali metal anodes

Abstract. The alkali metal anode has emerged as a focal point of research due to its extremely low oxidation-reduction potential and high theoretical specific capacity. However, challenges such as unstable solid electrolyte interphase (SEI), infinite volume expansion, and uncontrollable dendrite growth result in low coulombic efficiency and irreversible losses during the deposition and stripping processes. To address these issues, various effective strategies have been proposed to protect the alkali metal anode and achieve dendrite-free growth. In this review, we summarize recent advancements in enhancement strategies for alkali metal anodes, including the construction of three-dimensional current collectors and interface engineering. Specifically, we delve into the development of carbon-based current collectors with various dimensions and structures and the application of interface engineering techniques to tackle the challenges of unstable SEI, volume changes, and dendrite growth. Furthermore, we explore advanced characterization techniques that provide deeper insights into the reaction mechanisms and behavior of these enhancement strategies. Finally, we discuss the current limitations and future research directions in protecting alkali metal anodes, aiming to provide valuable insights into the study of dendrite growth and the development of effective protection strategies for alkali metal anodes.

Progress of silicon and graphene composites in lithium-ion battery anodes

As society progresses, the need for high-power, long-life energy supply devices gradually increases. Lithium-ion batteries (LIBs) with large energy reserves and high power have recently become the preferred choice. The anode of LIBs plays a crucial role in battery performance, safety, and cycle life. Typically, graphite materials are used for LIBs anodes. Still, they have drawbacks such as low first-time Coulombic efficiency, capacity degradation, safety issues, short cycle life, insufficient gram capacity, and purity and side reactions, which limit the application of LIBs. Therefore, new harmful electrode materials are in demand. Graphene and silicon are both environmentally friendly and sustainable materials. They both have the advantages of high theoretical capacity and high energy density, which are critical materials for developing LIBs. Combining the two can exert a synergistic effect and jointly improve the cycle stability of the battery. In this paper, we review the preparation methods of graphene and silicon composites in recent years, including mechanical ball milling and hydrothermal and thermal reduction methods. In addition, graphene and silicon composites have been explored for LIBs applications.

Fluorine-Doping Carbon-Modified Si/SiOx to Effectively Achieve High-Performance Anode.

To address the significant challenges encountered by silicon-based anodes in high-performance lithium-ion batteries (LIBs), including poor cycling stability, low initial coulombic efficiency (ICE), and insufficient interface compatibility, this work innovatively prepares high-performance Si/SiOx@F-C composites via in situ coating fluorine-doping carbon layer on Si/SiOx surface through high-temperature pyrolysis. The Si/SiOx@F-C electrodes exhibit superior LIB performance with a high ICE of 79%, exceeding the 71% and 43% demonstrated by Si/SiOx@C and Si/SiOx, respectively. These electrodes also show excellent rate performance, maintaining a capacity of 603 mAhg-1 even under a high current density of 5000 mAg-1. Notably, the Si/SiOx@F-C electrode sustains a high reversible capacity of 829 mAh g-1 at 1000mA g-1 over 1400 cycles, and 588 mAhg-1 at 3000 mAg-1 even over 2400 cycles, capacity retention of up to 82.12%. Comprehensive characterization and analysis of the fluorine-doped carbon layer reveal its role in enhancing electrical conductivity and preventing structural degradation of the material. The abundant fluorine in the coating layer significantly increases the LiF concentration in the solid electrolyte interface (SEI) film, improving interfacial compatibility and overall lithium storage performance. This method is both straightforward and effective, providing a promising blueprint for the broader application of Si-based anodes in advanced lithium batteries.

Three-dimensional Covalent Organic Framework with Dense Lithiophilic Sites as Protective Layer to Enable High-Performance Lithium Metal Battery.

Lithium (Li) metal batteries with remarkable energy densities are restrained by short lifetime and low Coulombic efficiency (CE), resulting from the accumulative Li dendrites and dead Li during cycling. Here, we prepared a new three-dimensional (3D) covalent organic framework (COF) with dense lithiophilic sites (heteoatom weight contents of 32.32wt%) as an anodic protective layer of Li metal batteries. The 3D COF was synthesized using a [6+4] synthesis strategy by inducing flexible 6-connected cyclotriphosphazene derivative aldehyde and 4-connected porphyrin-based tetraphenylamines. Both phosphazene and porphyrin rings in the COF served as electron-rich and lithiophilic sites, enhancing a homogeneous Li+ flux via 3D direction towards highly smooth and compact Li deposition. The Li/Por-PN-COF-Cu cells achieved a record average CE of 99.1% for 320 cycles with smooth Li deposition. Meanwhile, the abundant lithiophilic sites can promote fast Li+ transport with Li+ transference number of 0.87, enabling LiFePO4 full cell with stable stripping/plating processes even at a harsh rate of 5 C. Theoretical calculations revealed that the strong interaction force between Li+ and the COF facilitated the dissolution of Li+ from the electrolyte, and the low migration barrier of 1.08 eV indicated a favorable interaction between the Li+ ions and the π-electron system.

Three‐dimensional Covalent Organic Framework with Dense Lithiophilic Sites as Protective Layer to Enable High‐Performance Lithium Metal Battery

Lithium (Li) metal batteries with remarkable energy densities are restrained by short lifetime and low Coulombic efficiency (CE), resulting from the accumulative Li dendrites and dead Li during cycling. Here, we prepared a new three‐dimensional (3D) covalent organic framework (COF) with dense lithiophilic sites (heteoatom weight contents of 32.32wt%) as an anodic protective layer of Li metal batteries. The 3D COF was synthesized using a [6+4] synthesis strategy by inducing flexible 6‐connected cyclotriphosphazene derivative aldehyde and 4‐connected porphyrin‐based tetraphenylamines. Both phosphazene and porphyrin rings in the COF served as electron‐rich and lithiophilic sites, enhancing a homogeneous Li+ flux via 3D direction towards highly smooth and compact Li deposition. The Li/Por‐PN‐COF‐Cu cells achieved a record average CE of 99.1% for 320 cycles with smooth Li deposition. Meanwhile, the abundant lithiophilic sites can promote fast Li+ transport with Li+ transference number of 0.87, enabling LiFePO4 full cell with stable stripping/plating processes even at a harsh rate of 5 C. Theoretical calculations revealed that the strong interaction force between Li+ and the COF facilitated the dissolution of Li+ from the electrolyte, and the low migration barrier of 1.08 eV indicated a favorable interaction between the Li+ ions and the π‐electron system.

A highly water-soluble phenoxazine quaternary ammonium compound catholyte for pH-neutral aqueous organic redox flow batteries

The pH-neutral aqueous redox flow battery (ARFB) is one of the most attractive flow batteries due to its non-corrosiveness, low-cost, and wider electrochemical stability window compared to those with acidic or alkaline electrolytes. However, there are few families of organic redox-active molecules available as catholyte materials for pH-neutral ARFBs. Herein, through incorporation of quaternary ammonium moiety into the redox-active phenoxazine nucleus, an organic catholyte material, N, N, N-trimethyl-2-(10H-phenoxazin-10-yl) ethan-1-aminium chloride (NEt-POZ) is achieved for pH-neutral ARFBs. The NEt-POZ has a high redox potential of 0.79 V versus SHE and rapid redox kinetics (0.23 cm s−1) as well as high water-solubility (∼2.6 M in H2O). Paired with a methyl viologen (MV) anolyte in the pH-neutral aqueous electrolyte, a viologen-phenoxazine ARFB full cell is assembled, which shows an open circuit voltage of ∼1.23 V. However, the results of long-term cycling experiments indicate low Coulomb efficiency and rapid declining capacity of the NEt-POZ catholyte. The mechanism analysis unveils that the unstable doubly oxidized tri-cations (NEt-POZ3+) formed via the disproportionation of radical di-cations (NEt-POZ2+) in solution readily react with chloride anions to form poly-chlorinated derivatives, which precipitate from the catholyte due to their poor water solubility, leading to a rapid decrease in capacity. When there is no chloride present in the electrolyte solution, highly reactive NEt-POZ3+ cations can interact with other counter-anions (such as sulfate and carbonate ions) and even water to form complex adducts.

Pre-lithiation synergized with magnesiothermic reduction to enhance the performance of SiO anode for Advanced lithium-ion batteries

Due to its high theoretical specific capacity, micron-sized silicon monoxide (SiO) is regarded as one of the most competitive anode materials for lithium-ion batteries with high specific energy density. However, originating from the low initial Coulombic efficiency (ICE) and large volume expansion, its large-scale application is seriously hindered. Herein, an easy-to-implement solid-state pre-lithiation method synergized with the magnesiothermic reduction process was performed to enhance the ICE of SiO and a common bimetallic hydride was used as a prelithiation reagent. Moreover, the effects of different pre-lithiation reagent amounts on the physical and electrochemical properties of SiOx are investigated. Notably, the SiOx-LA@C composite anchored by in-situ generated LiAl(SiO3)2 shows a more stable microstructure and excellent electrochemical properties, which delivers an ultrahigh ICE of 89.4 % and an excellent initial capacity of 1864.4 mAh g−1. Furthermore, the full cells were successfully assembled by using the prepared anodes, which exhibit relatively stable cycle performance over 150 cycles. This work suggests a safe and feasible route to enhance the ICE of SiOx for the applicable SiO-based anode materials.

Understanding and Mastering Multiphysical Fields Toward Dendrite‐Free Aqueous Zinc Batteries

AbstractAqueous zinc batteries (AZBs) have emerged as promising candidates for next‐generation grid‐scale energy storage due to their excellent safety, environmental friendliness, and abundance of Zn metal. However, undesired dendrite growth on Zn anodes, resulting from uneven Zn plating/stripping, leads to poor durability and low Coulombic efficiency, posing significant challenges for the practical application of AZBs. Multiple physical fields, the intrinsic driving force governing the distribution of electrons and ions, significantly impact Zn deposition behavior. The underlying mechanisms and regulation strategies related to this phenomenon has not been fully reviewed. This comprehensive review focuses on revealing the key physical fields influencing Zn deposition (including ionic flux, electric field, stress field, and temperature field) and summarizes the most effective control methods. Each approach is thoroughly scrutinized, highlighting its operational mechanisms, benefits, and limitations. Furthermore, the challenges and potential pathways for developing durable Zn anodes are outlined. Through in‐depth analysis of the influences of multiphysical fields on Zn deposition behavior, this review sets the foundation for enhancing the performance of Zn anodes, thereby supporting the advancement of Zn batteries commercialization.

Anode‐Free Solid‐State Rechargeable Batteries: Mechanisms, Challenges, and Design Strategies

Anode‐free solid‐state alkali metal batteries (AFSSAMBs) have emerged as promising high‐performance battery systems, attracting significant scientific interest due to their exceptional safety, high theoretical energy density, and cost‐effectiveness. Recently, extensive research efforts have focused on addressing the key issues impeding their practical deployment, primarily centered around severe dendrite growth, unstable electrolyte‐electrode interface, and low Coulombic efficiency. Despite this progress, a comprehensive framework for the fundamental understanding of AFSSAMBs is still lacking. This paper presents a comprehensive concept, outlining detailed construction, mechanisms, challenges, and strategies of AFSSAMBs. First, the basic configuration and internal mechanisms of AFSSAMBs are summarized. Subsequently, we discuss the existing challenges hindering the cycling lifespan of AFSSAMBs, offering several promising approaches to overcome these obstacles. In the end, insightful perspectives and viewpoints are briefly proposed on the further developments of AFSSAMBs.

Structural stability and enhanced electrochemical performance of Co-free Li-rich layered Mn-based Li1.2Mn0.6Ni0.2O2 cathodes via F doping at the O site of lithium-ion batteries

Li-rich Mn-based Co-free layered oxides (LLOs) are promising cathode materials for lithium-ion batteries (LIBs). However, they exhibit capacity loss and low initial Coulombic efficiency. Herein, an F-doped Li1.2Mn0.6Ni0.2O1.9F0.10 material has been prepared by the high-temperature solid-state method, with numerous oxygen vacancies on the surface to accelerate Li + transport. The electrochemical performance of Li1.2Mn0.6Ni0.2O1.9F0.10 considerably improved after the treatment. A high-capacity retention of 86.9 % after 100 charge/discharge cycles at 1C was achieved for Li1.2Mn0.6Ni0.2O1.9F0.10. Results revealed that F doping replaces part of O2−, forming more force between the TM-F bonds (compared to the TM-O bond), which inhibits the cation mixing phenomenon. The layered structure stability of the material is improved after F doping, and the migration energy barrier of Li+ is reduced, which promotes the migration of Li+, thereby improving the electrochemical performance of Li1.2Mn0.6Ni0.2O2.

Charge-Compensation-Driven Failure Mechanism of Ni Redox in Fe-Rich Ni/Fe/Mn-Based O3-Type Layered Oxide Sodium-Ion Cathodes.

For cathode materials of sodium-ion batteries, O3-type Ni/Fe/Mn-based (Na-NFM) layered oxides have garnered extensive attention because of high economic viability, environmental friendliness, and the potential for high energy density. Among them, Fe-rich compositions exhibit higher initial charge capacity and lower bill-of-material costs, while they fade rapidly and exhibit low initial coulombic efficiency, hindering their commercialization prospects. In this work, we investigate the failure of Fe-rich Na-NFM materials through X-ray absorption spectroscopy methods. The results reveal a combined failure mechanism that encompasses not only the conventional theory of Fe migration but also an abnormal Ni-redox deterioration, which has not yet been reported. More factors related to the failure of Fe-rich Na-NFM layered oxides are discussed in detail. These findings are expected to inspire targeted research efforts toward Fe-rich Na-NFM materials, thereby accelerating the practical application of sodium-ion batteries.

Molecular Engineering Chemical Pre-lithiation Reagent with Low Redox Potential for Graphite Anode Enables High Coulombic Efficiency.

Graphite (Gr) is a low-cost and high-stability anode for lithium-ion batteries (LIBs). However, Gr anode exhibits an obstinate drawback of low initial Coulombic efficiency (ICE), owing to the active lithium loss for the solid electrolyte interphase (SEI) layer. Herein, a straightforward and effective chemical pre-lithiation strategy is proposed to compensate for the lithium loss. A molecular engineering phenanthrene-based lithium-arene complex (Ph-based LAC) reagent is designed by density functional theory (DFT) calculations. The engineering Ph-based reagent enhances the stability of the π-electron system and the electron-donating capacity, resulting in a reduced redox potential to facilitate lithium transfer. The electrochemical distinct of the Ph-based reagent is illustrated, the prelithiation process in a low Li-insertion platform, and the lithiation degree is controllable with the dipping time (ICE = 102%, 3min). Notably, a denser and homogeneous SEI layer has pre-formed to enhance the Li+ transport and interface stability. Moreover, the lithium-ion full batteries assemble with LiFePO4 and NCM811 cathode, which exhibits high ICE (96.5% and 90.3%) and energy density (310 and 333Whkg-1). These findings present a facile and controllable pre-lithiation strategy to compensate for the lithium of LIBs, providing new valuable insights into the design and optimization of battery manufacture.

Dynamic Processes at the Electrode‐Electrolyte Interface: Implications for Lithium Deposition Stability

AbstractLithium (Li) metal is a promising negative electrode material for high‐energy‐density rechargeable batteries, owing to its exceptional specific capacity, low electrochemical potential, and low density. However, challenges such as dendritic Li deposits, leading to internal short‐circuits, and low Coulombic efficiency hinder the widespread adoption of lithium‐metal batteries (LMBs). These issues stem from the morphological instability of Li deposition, influenced by dynamic processes at the electrolyte|Li interface. Understanding the interplay between electrolyte properties, interfacial kinetics, and Li deposition stability is crucial yet challenging due to their simultaneous occurrence and the complexity of the solid electrolyte interphase (SEI) layer. This review discusses three key dynamic processes influencing Li deposition: desolvation of Li+ ions, transport through the SEI, and electrochemical reduction. The effects of electrolyte properties on these processes and their interplay with electroplating stability are discussed, highlighting contradictions in the literature and proposing explanations for the discrepancies. Despite numerous reviews on SEI structure and composition effects, this article emphasizes the kinetic aspects at interfaces, aiming to provide clarity and direction for future research in achieving stable Li deposition in LMBs.

Modification of Lithium‐Rich Manganese Oxide Materials: Coating, Doping and Single Crystallization

AbstractThe increasing demand for portable electronics, electric vehicles and energy storage devices has spurred enormous research efforts to develop high‐energy‐density advanced lithium‐ion batteries (LIBs). Lithium‐rich manganese oxide (LRMO) is considered as one of the most promising cathode materials because of its high specific discharge capacity (>250 mAh g−1), low cost, and environmental friendliness, all of which are expected to propel the commercialization of lithium‐ion batteries. However, practical applications of LRMO are still limited by low coulombic efficiency, significant capacity and voltage decay, slow reaction kinetics, and poor rate performance. This review focus on recent advancements in the modification methods of LRMO materials, systematically summarizing surface coating with different physical properties (e. g., oxides, metal phosphates, metal fluorides, carbon, conductive polymers, lithium compound coatings, etc.), ion doping with different doping sites (Li sites, TM sites, O sites, etc.), and single crystal structures. Finally, the current states and issues, key challenges of the modification of LRMO are discussed, and the perspectives on the future development trend base on the viewpoint of the commercialization of LRMO are also provided.

Organic Electrolyte Additives for Aqueous Zinc Ion Batteries:Progress and Outlook.

Aqueous zinc ion batteries (AZIBs) are considered one of the most prospective new-generation electrochemical energy storage devices with the advantages of high specific capacity, good safety, and high economic efficiency. Nevertheless, the enduring problems of low Coulombic efficiency (CE) and inadequate cycling stability of zinc anodes, originating from dendrites, hydrogen precipitation and passivation, are closely tied to their thermodynamic instability in aqueous electrolytes, which significantly shortens the cycle life of the battery. Electrolyte additives can solve the above difficulties and are important for the advancement of affordable and reliable AZIBs. Organic electrolyte additives have attracted widespread attention due to their unique properties, however, there is a lack of systematic discussion on the performance and mechanism of action of organic electrolyte additives. In this review, a comprehensive overview of the application of organic electrolyte additives in AZIBs is presented. The role of organic electrolyte additives in stabilizing zinc anodes is described and evaluated. Finally, further potential directions and prospects for improving and directing organic electrolyte additives for AZIBs are presented.

Stress-Dispersed Nanoconstruction of CoMoP Anode: Improved Na-Storage Stability and Reversibility.

Metal phosphide anode materials encounter poor reversibility of the discharge product (metal and Na3P) and large volume variation, resulting in low initial Coulombic efficiency (ICE) and severe capacity degradation. Herein, a bimetallic phosphide (CoMoP) with three-dimensional ordered porous (3DOP) nanoconstruction was fabricated, which presents a reduced Gibbs free energy change (ΔG) of redox reaction between Co-Mo/Na3P and CoMoP and improved conductivity compared to CoP and MoP. Additionally, the 3DOP architecture could disperse stress and reduce strain during cycling, thus improving structural stability of CoMoP. In situ and ex situ characterizations and electrochemical measurements suggest that 3DOP CoMoP exhibits highly reversible sodium storage with an ICE of 58% at 0.1 A g-1, enhanced reaction dynamics, and good cycling stability with around 0.04% capacity decay per cycle at 1 A g-1 after 1000 cycles. Consequently, this work offers a new perspective to solve issues of reversibility of redox chemistry and volume expansion for secondary batteries.

Electrolyte Reconfiguration by Cation/Anion Cross‐coordination for Highly Reversible and Facile Sodium Storage

Hard carbon (HC) materials are promising anodes for sodium‐ion batteries (SIBs) owing to low cost, high specific capacity and low working potential. However, the poor compatibility of the electrolyte with HC leads to low initial coulombic efficiency (ICE) and sluggish Na+ transport kinetics. Here, we propose an electrolyte reconfiguration strategy based on the hard and soft acid and base (HSAB) theory by introducing methyltriphenylphosphonium bromide (MTPPB). MTPPB can realize a spontaneous cross‐coordination solvation structure with NaPF6 by selective affinity, synchronously optimizing the interfacial chemistry and sodium storage process. The advantages of the chemical π‐π bridging of MTPP+‐HC and interaction of MTPP+‐PF6− contribute to preferential and oriented reduction of PF6−, forming a low‐resistance supramolecular SEI. Additionally, Na+‐Br− coordination weakens the Na+‐solvent interactions, facilitating Na+ de‐solvation kinetics. Consequently, the HC||Na cell achieves a superior ICE of 96.6%, desirable rate capability under 25 °C and invisible capacity decay after 500 cycles at 1 C under −20 °C. The Na4Fe3(PO4)2P2O7||HC pouch battery displays a high ICE of 90.3% and a 15% increment of energy density under 25 °C. This work provides a guidance through electrolyte reconfiguration engineering for designing practical HC‐based SIBs with high energy/power density and long‐life span in the extended operating‐temperature range.

Electrolyte Reconfiguration by Cation/Anion Cross-coordination for Highly Reversible and Facile Sodium Storage.

Hard carbon (HC) materials are promising anodes for sodium-ion batteries (SIBs) owing to low cost, high specific capacity and low working potential. However, the poor compatibility of the electrolyte with HC leads to low initial coulombic efficiency (ICE) and sluggish Na+ transport kinetics. Here, we propose an electrolyte reconfiguration strategy based on the hard and soft acid and base (HSAB) theory by introducing methyltriphenylphosphonium bromide (MTPPB). MTPPB can realize a spontaneous cross-coordination solvation structure with NaPF6 by selective affinity, synchronously optimizing the interfacial chemistry and sodium storage process. The advantages of the chemical π-π bridging of MTPP+-HC and interaction of MTPP+-PF6- contribute to preferential and oriented reduction of PF6-, forming a low-resistance supramolecular SEI. Additionally, Na+-Br- coordination weakens the Na+-solvent interactions, facilitating Na+ de-solvation kinetics. Consequently, the HC||Na cell achieves a superior ICE of 96.6%, desirable rate capability under 25 °C and invisible capacity decay after 500 cycles at 1 C under -20 °C. The Na4Fe3(PO4)2P2O7||HC pouch battery displays a high ICE of 90.3% and a 15% increment of energy density under 25 °C. This work provides a guidance through electrolyte reconfiguration engineering for designing practical HC-based SIBs with high energy/power density and long-life span in the extended operating-temperature range.