Chloride Ion Batteries Research Articles

Unravelling rechargeable zinc-copper batteries by a chloride shuttle in a biphasic electrolyte

The zinc-copper redox couple exhibits several merits, which motivated us to reconstruct the rechargeable Daniell cell by combining chloride shuttle chemistry in a zinc chloride-based aqueous/organic biphasic electrolyte. An ion-selective interface was established to restrict the copper ions in the aqueous phase while ensuring chloride transfer. We demonstrated that the copper-water-chloro solvation complexes are the descriptors, which are predominant in aqueous solutions with optimized concentrations of zinc chloride; thus, copper crossover is prevented. Without this prevention, the copper ions are mostly in the hydration state and exhibit high spontaneity to be solvated in the organic phase. The zinc-copper cell delivers a highly reversible capacity of 395 mAh g−1 with nearly 100% coulombic efficiency, affording a high energy density of 380 Wh kg−1 based on the copper chloride mass. The proposed battery chemistry is expandable to other metal chlorides, which widens the cathode materials available for aqueous chloride ion batteries.

A Room‐TemperatureChloride‐Conducting Metal–Organic Crystal [Al(DMSO)6]Cl3 for Potential Solid‐State Chloride‐Shuttle Batteries

The growing demand for substitutes of lithium chemistries in battery leads to a surge in budding novel anion‐based electrochemical energy storage, where the chloride ion batteries (CIBs) take over the role. The application of CIBs is limited by the dissolution and side reaction of chloride‐based electrode materials in a liquid electrolyte. On the flipside, its solid‐state electrolytes are scarcely reported due to the challenge in realizing fast Cl− conductivity. The present study reports [Al(DMSO)6]Cl3, a solid‐state metal–organic material, allows chloride ion transfer. The strong Al‐Cl bonds in AlCl3 are broken down after coordinating of Al3+ by ligand DMSO, and Cl− in the resulting compound is weakly bound to complexions [Al(DMSO)6]3+, which may facilitate Cl− migration. By partial replacement of Cl− with , the room‐temperature ionic conductivity of as‐prepared electrolyte is increased by one order of magnitude from 2.172 × 10−5 S cm−1 to 2.012 × 10−4 S cm−1. When they are assembled with Ag (anode)/Ag–AgCl (cathode) electrode system, reversible electrochemical redox reactions occur on both sides, demonstrating its potential for solid‐state chloride ion batteries. The strategy by weakening the bonding interaction using organic ligands between Cl− and central metallic ions may provide new ideas for developing solid chloride‐ion conductors.

Computational high-throughput screening of layered double hydroxides as cathodes for chloride ion batteries

The chloride-ion battery (CIB) based on the anion transfer plays an essential role in developing new battery technologies. As a rare anion intercalated layered material, layered double hydroxide (LDHs) has attracted considerable attention as promising cathodes for CIBs. However, driven by the great compositional diversity, developing a general methodology to effective design and assess the usability of unexploited LDHs for CIBs is still a challenging issue. Herein, a computational high-throughput screening is performed among MII3MIII/IV LDHs (MII = Ni and Co; MIII/IV = Ni, Co, Fe, V, Cr and Ti). When designated as the only guest in LDHs gallery, Cl atoms tend to absorb above the O atoms without MIII/IV around and adsorption energy increases with the order of Ti > Cr > V > Fe > Co > undoped hydroxides. During the chlorination reaction, a special ClHOMIII/IV electron transfer chain is proposed for the first time. Furthermore, Cl storage performance for 11 cathodes were evacuated by the theoretical voltage in a full CIB system. The results indicates Ti-containing LDHs is the most encouraging cathodes, which is verified by the experimental measurement. This work provides a clear guidance and a theoretical insight into the anion insertion electrochemistry for LDHs materials.

FeOCl Nanoparticle-Embedded Mesocellular Carbon Foam as a Cathode Material with Improve d Electrochemical Performance for Chloride-Ion Batteries.

Chloride-ion batteries (CIBs) have been regarded as a promising alternative battery technology to lithium-ion batteries because of their abundant resources, high theoretical volumetric energy density, and high safety. However, the research on chloride-ion batteries is still in its infancy. Exploring appropriate cathode materials with desirable electrochemical performance is in high demand for CIBs. Herein, the FeOCl nanocrystal embedded in a mesocellular carbon foam (MCF) has been prepared and developed as a high-performance cathode material for CIBs. The MCF with uniform and large mesocells (15.7-31.2 nm) interconnected through uniform windows (15.2-21.5 nm) can provide high-speed pathways for electron and chloride-ion transport and accommodate the strain caused by the volume change of FeOCl during cycling. As a result, the optimized FeOCl@MCF cathode exhibits the highest discharge capacity of 235 mAh g-1 (94% of the theoretical capacity) among those of the previously reported metal (oxy)chloride cathodes for CIBs. A reversible capacity of 140 mAh g-1 after 100 cycles is retained. In contrast, only 18 mAh g-1 was kept for the FeOCl cathode.

Introducing high-valence molybdenum to stimulate lattice oxygen in a NiCo LDH cathode for chloride ion batteries.

Layered double hydroxides (LDHs) have been intensively investigated as promising cathodes for the new concept chloride ion battery (CIB) with multiple advantages of high theoretical energy density, abundant raw materials and unique dendrite-free characteristics. However, driven by the great compositional diversity, a complete understanding of interactions between metal cations, as well as a synergetic effect between metal cations and lattice oxygen on LDH host layers in terms of the reversible Cl-storage capability, is still a crucial but elusive issue. In this work, we synthesized a series of chloride-inserted trinary Mox-doped NiCo2-Cl LDH (x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5) with gradient oxygen vacancies as enhanced cathodes toward CIBs. The combination of advanced spectroscopic techniques and theoretical calculations reveals that the Mo dopant facilitates oxygen vacancy formation and varies the valence states of coordinated transition metals, which can not only tune the electronic structure effectively and promote Cl-ion diffusion, but improve the redox activity of LDHs. The optimized Mo0.3NiCo2-Cl LDH delivers a reversible discharge capacity of 159.7 mA h g-1 after 300 cycles at 150 mA g-1, which is almost a triple enhancement compared to that of NiCo2Cl LDH. The superior Cl-storage of trinary Mo0.3NiCo2Cl LDH is attributed to the reversible intercalation/deintercalation of chloride ions in the LDH gallery along with the oxidation state changes in Ni0/Ni2+/Ni3+, Co0/Co2+/Co3+ and Mo4+/Mo6+ couples. This simple vacancy engineering strategy provides critical insights into the significance of the chemical interaction of various components on LDH laminates and aims to effectively design more LDH-based cathodes for CIBs, which can even be extended to other halide-ion batteries like fluoride ion batteries and bromide ion batteries.

A nickel-based metal-organic framework as a new cathode for chloride ion batteries with superior cycling stability.

Chloride ion batteries (CIBs) have drawn growing attention as attractive candidates for large-scale energy storage technology because of their high theoretical energy densities (2500 W h L-1), dendrite-free characteristics and abundance of chloride-containing materials available worldwide. However, the further development of CIBs is greatly limited by sluggish Cl- diffusion and distinct structural variation of cathode materials, resulting in severe decayed capacity and inferior rate performance. Metal-organic framework (MOF) materials possess regular pores/channels and flexible structural designability to accommodate charge carrier ions, but the application of MOFs in anion-type batteries has not been reported. Here, we demonstrate the first example of Ni(dpip) with two different opening sizes of tubular channels serving as the cathode for high performance CIBs. The Ni-based MOF exhibited a stable reversible capacity of 155 mA h g-1 with an admirable low capacity decay of 0.026% per cycle over 500 cycles and superior kinetics with a 10-10 cm2 s-1 average diffusion coefficient for chloride ions as well. The high performance of the Ni(dpip) cathode results from the synergetic redox couples of Ni metal nodes and N-ligands, the unique double-channel structure for reversible Cl-storage, and the low chloride diffusion energy barrier. This work switches on the new application of MOF-based materials as cathodes for CIBs.

A polymer electrolyte for rechargeable chloride ion batteries

• A poly(diallyl dimethyl ammonium chloride) (PDDAC) is proposed as an new electrolyte for chloride ion batteries. • The chloride ion conductivity is significantly varied by PEG plasticizer. • Chloride ion conductivity of 2.63 × 10 −5 S cm −1 is obtained at 303 K. • The chloride ion conducting capability is evidenced in a chloride ion battery. Chloride-ion batteries (CIBs) based on shuttling of chloride ion have recently attracted attention because of the safety, abundant resources, and high theoretical energy density. Herein, a polymer of poly(diallyl dimethyl ammonium chloride) (PDDAC) plasticized by poly(ethylene glycol) (PEG) is proposed as an new electrolyte for chloride ion batteries. The ionic conductivity of polymer electrolyte is significantly varied by the amount of plasticizer. A flexible, transparent polymer film with 70 wt% of PEG (Mw = 300) shows the highest chloride ion conductivity (2.63 × 10 −5 S cm −1 ) at 303 K. The chloride ion conducting capability is also evidenced in a lithium free chloride ion battery with CuCl as a cathode and Mg as an anode.

Inverse design and high-throughput screening of TM-A (TM: Transition metal; A: O, S, Se) cathodes for chloride-ion batteries

Transition metal oxychlorides (TMOCl) are one of the most attractive cathode materials for chloride ion batteries (CIBs) due to their layered framework and high stability in organic electrolytes. However, the conversion reaction of TMOCl at low Cl− content is harmful to the cycle performance and energy density of CIBs. In order to eliminate the conversion reaction, high-throughput screening combined with an inverse design method is applied to search Cl-free layered materials among the TM-A (A = O, S, Se) compounds. After a comprehensive evaluation of layered characteristics, thermodynamic and dynamic stability, FeSe and its chloride FeSeCl are found to both have layered ground state structures. The stable Fe-Se framework prevents the material from decomposing or reconstructing during Cl− extraction. Compared to the reported TMOCl cathodes, the discharge process from FeSeCl to FeSe is a constant intercalation reaction, which leads to a flat voltage platform, high reaction reversibility, and low reaction energy barrier. The extended Se-4p orbital ensures excellent electronic conductivity. In addition, the spacious Cl− channels in FeSeCl and FeSe result in low Cl− diffusion barriers of 0.28 and 0.13 eV, respectively, which is significantly improved compared to the reported TMOCl materials.

Well‐dispersed FeOCl Nanosheets as High‐performance Chloride Ion Battery Cathode Material

AbstractThermal decomposition method has been widely used to synthesize FeOCl materials with simple process and low requirements for devices. However, the FeOCl particles show nonuniform size and are easy to grow up together with the rapid reaction. The formed aggregates contribute to the poor cyclic stability for chloride ion battery. Herein, NaCl template was developed to fabricate FeOCl nanosheets with uniform size of thermal decomposition method. When the Fe: Na molar ratio reached 1 : 10, the FeOCl nanosheets showed good dispersity and high chlorine content. The FeOCl‐1‐10‐NaCl cathode delivered a maximum discharge capacity of 145 mAh g−1 and an excellent capacity retention (80 %) over 50 cycles, due to the high particle dispersion in electrode slurry. With the amount of NaCl template increasing, the FeOCl‐1‐40‐NaCl cathode delivered a high initial discharge capacity of 173 mAh g−1, as a result of the low contact resistance and charge transfer resistance.

Cuprous Chloride as a New Cathode Material for Room Temperature Chloride Ion Batteries

AbstractChloride ion batteries (CIBs) are regarded as promising energy storage devices due to their high theoretical energy density, sustainability, and abundant resources. However, the development of CIBs is still limited by the proper cathode materials and electrolyte due to the dissolution issue of active material during the electrochemical reaction. Herein, a stable room temperature rechargeable CIB coupled with CuCl cathode in a tributylmethylammonium chloride based liquid electrolyte is reported. Chloride ion shuttle behavior is evidenced in two different cells, in which lithium foil, and CuCl are used as the anode and cathode, respectively. The CuCl cathode delivers an initial discharge capacity of 278 mAh g−1 and a reversible capacity of 70 mAh g−1 is still retained after 100 cycles at a current density of 5 mA g−1. This study indicates that CuCl would be a promising cathode for CIBs with good cycling stability.

Polyxylylviologen Chloride as an Organic Electrode Material for Efficient Reversible Chloride-Ion Storage

Organic molecules such as viologens with a nitrogen redox center show promise as efficient anion storage materials in rechargeable batteries. However, the high solubility of viologens in liquid electrolytes limits their wide electrochemical application. Herein, an insoluble polymerized polyxylylviologen chloride (PXVCl2) is first developed as a chloride ion storage electrode in chloride ion batteries. The as-prepared PXVCl2 electrode exhibits a competitive discharge capacity of 140 mA h g–1 (86% of the theoretical discharge capacity) compared to that of the previously reported organic conducting polymer electrodes. The incorporation of graphene in the PXVCl2 material achieves significant improvements in reaction reversibility and rate capability of the PXVCl2 electrode. Importantly, the nitrogen redox reactions based on chloride ion transfer of the PXVCl2 electrode are demonstrated.

Tungsten Oxytetrachloride as a Positive Electrode for Chloride‐Ion Batteries

Rechargeable chloride‐ion batteries (CIBs) are a new emerging battery technology that can potentially provide high theoretical volumetric capacities at lower cost and higher abundance. However, research on CIBs is in its early stages, and the current challenge lies in finding suitable electrodes and electrolytes. Herein, tungsten oxychloride is introduced for the first time as a cathode candidate for use in CIB. WOCl4 enables the reversible transfer of nearly one Cl− per formula unit during electrochemical cycling, corresponding to an initial discharge capacity of 120 mAh g−1. A reversible capacity of 90 mAh g−1 (75%) is retained after 50 cycles. Postmortem analysis of cycled electrodes by X‐ray diffraction, X‐ray photoelectron spectroscopy, and Raman spectroscopy reveals the reversible chloride‐ion transfer between the electrodes through a conversion mechanism. This work paves the way for the use of tungsten chloride‐based electrode materials for battery applications.

Ammonium escorted chloride chemistry in stabilizing aqueous chloride ion battery

The blue ocean has attracted great expectations since it can provide sustainable and green energies. We propose and demonstrate a feasible strategy for a novel seawater-based chloride ion battery (CIB). Moreover, a new approach has been proposed to synthetically improve the reaction kinetics on both electrodes in CIB by introducing ammonium ions (NH4+) to the aqueous NaCl electrolyte. In particular, a seawater-based CIB has been developed with an initial discharge specific capacity of 123.7 mAh g−1 at a specific charge current 500 mA g−1 with a stable cyclability and excellent rate capability. The superior electrochemical performance of the CIB can be contributed to the Janus effect on promoting Cl− capture/release from both electrodes, hence enhancing AgCl/Ag conversion and more electrons transferred from trivalent bismuth to low valence state.

A high capacity aqueous zinc-based chlorine ion battery improved by zinc selenide-modified anode

Chloride ion battery (CIB) is a novel anionic battery first reported in 2013. The high open circuit voltage and high theoretical capacity have attracted wide attention. However, its low cycle life imposes restrictions on its application. Since the electrochemical performance of zinc anode in chloride ion batteries is different from zinc ion batteries, we attempted to modify the zinc anode with kinds of strategies or addictives to match the zinc electrode with the zinc-free electrolyte and finally found the positive influence of ZnSe. The zinc selenide-modified anode improved the capacity to 177.4mAh g−1 and expanded the cycle life to 2500 times. Besides, our work may also have reference significance for other zinc based batteries. The mechanism of anode was analyzed using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) as well as high-definition scanning electron microscopy (HD SEM) and simulated by adsorption models. The electrochemical performance of the anode was tested by cyclic voltammetry (CV) and the full cell was test on BTS4000 battery program-control test system.

A novel type of chloride ion battery that can change the structure of electric vehicle

Chloride ion battery (CIB) is considered as one of the potential objects to replace lithium ion battery because of its high discharge platform and high theoretical capacity. However, traditional CIB still has many problems because it can not solve the problem of matching the positive and negative active materials with the electrolyte. The main performance is poor cycle life, and low battery capacity, and it cannot meet the needs of real life. In our work, we first propose the application of graphite paper as cathode material and aqueous electrolyte in CIB, and reconstruct a new system of CIB. With zinc anode, the cycle life of the battery is more than 4000 times, and the cycle life of the electrolyte is more than 10,000 times under the promotion of lithium salt. At the same time, we synthesize flexible-solid-electrolyte, and first assemble flexible CIB, which broadens the application field of CIB. The breakthrough of flexible chloride ion battery changes the structure of the battery, which can be applied to the car as a part of the car shell to save the material cost. Secondly, chloride ion battery in high temperature environment do not produce safety hazards, which greatly improves the safety. • A novel rechargeable chloride ion battery. • The cycle life of battery is more than 10,000 times. • Graphite paper is stabilized as the cathode of the battery. • Flexible-solid-electrolyte was synthesized and flexible chloride ion battery was assembled.

Cover Feature: All‐Solid‐State Chloride‐Ion Battery with Inorganic Solid Electrolyte (ChemElectroChem 23/2021)

The Cover Feature illustrates an all-solid-state chloride-ion battery composed of a positive electrode layer, a solid electrolyte layer, and a negative electrode layer. Chloride ions, which are abundant in the sea, shuttle inside the battery during charge-discharge reaction. More information can be found in the Communication by R. Sakamoto et al.

Bismuth chloride@mesocellular carbon foam nanocomposite cathode materials for rechargeable chloride ion batteries

Chloride ion batteries (CIB) are considered to be one of the most promising energy storage devices. As cathode materials for CIBs, metal chlorides have many advantages, such as high theoretical energy density, abundant elemental resources and ideal discharge voltage plateau. However, the dissolution and huge volume change of metal chlorides during cycling lead to considerable short lifespan, which limits their potential application for CIBs. Herein, the bismuth chloride nanocrystal is confined in mesocellular carbon foam matrix by a new vacuum impregnation approach. The mesocellular carbon foam with large interconnected pores (15.7 or 23.2 nm) may buffer the large volume variation of bismuth chloride during charge and discharge, giving rise to significantly enhanced electrochemical performance. The as-prepared bismuth chloride@mesocellular carbon foam cathode delivered an initial discharge capacity of 298 mAh/g and a reversible capacity of 91 mAh/g after 60 cycles. In contrast, the pure bismuth chloride cathode almost cannot discharge after 30 cycles. This is the first report that the metal chloride cathode can achieve a prolonged cycling in CIBs.

Natural Clay-Based Materials for Energy Storage and Conversion Applications.

Among various energy storage and conversion materials, functionalized natural clays display significant potentials as electrodes, electrolytes, separators, and nanofillers in energy storage and conversion devices. Natural clays have porous structures, tunable specific surface areas, remarkable thermal and mechanical stabilities, abundant reserves, and cost‐effectiveness. In addition, natural clays deliver the advantages of high ionic conductivity and hydrophilicity, which are beneficial properties for solid‐state electrolytes. This review article provides an overview toward the recent advancements in natural clay‐based energy materials. First, it comprehensively summarizes the structure, classification, and chemical modification methods of natural clays to make them suitable in energy storage and conversion devices. Then, the particular attention is focused on the application of clays in the fields of lithium‐ion batteries, lithium–sulfur batteries, zinc‐ion batteries, chloride‐ion batteries, supercapacitors, solar cells, and fuel cells. Finally, the possible future research directions are provided for natural clays as energy materials. This review aims at facilitating the rapid developments of natural clay‐based energy materials through a fruitful discussion from inorganic and materials chemistry aspects, and also promotes the broad sphere of clay‐based materials for other utilization, such as effluent treatment, heavy metal removal, and environmental remediation.

High-throughput screening of TMOCl cathode materials based on the full-cell system for chloride-ion batteries

Discharge of the Li–CoOCl full-cell system and the Cl− migration path in CoOCl.

A Review of Battery Materials as CDI Electrodes for Desalination

The world is suffering from chronic water shortage due to the increasing population, water pollution and industrialization. Desalinating saline water offers a rational choice to produce fresh water thus resolving the crisis. Among various kinds of desalination technologies, capacitive deionization (CDI) is of significant potential owing to the facile process, low energy consumption, mild working conditions, easy regeneration, low cost and the absence of secondary pollution. The electrode material is an essential component for desalination performance. The most used electrode material is carbon-based material, which suffers from low desalination capacity (under 15 mg·g−1). However, the desalination of saline water with the CDI method is usually the charging process of a battery or supercapacitor. The electrochemical capacity of battery electrode material is relatively high because of the larger scale of charge transfer due to the redox reaction, thus leading to a larger desalination capacity in the CDI system. A variety of battery materials have been developed due to the urgent demand for energy storage, which increases the choices of CDI electrode materials largely. Sodium-ion battery materials, lithium-ion battery materials, chloride-ion battery materials, conducting polymers, radical polymers, and flow battery electrode materials have appeared in the literature of CDI research, many of which enhanced the deionization performances of CDI, revealing a bright future of integrating battery materials with CDI technology.