Ultralong‐Life Chloride Ion Batteries Achieved by the Synergistic Contribution of Intralayer Metals in Layered Double Hydroxides

Abstract

Chloride ion batteries (CIBs) are a promising type of energy storage device due to their high theoretical volumetric energy density and abundant reserves of chlorine-containing precursors. However, the unsatisfactory cycling performance and structural instability of cathode materials hinder their practical application. In this work, layered double hydroxides (LDHs), which consist of a trimetallic NiVAl hydroxide host matrix and interlayer Cl − , are demonstrated to be high-performance cathode materials for CIBs. The Ni 2 V 0.9 Al 0.1 -Cl LDH is capable of delivering a high initial capacity of 312.2 mAh g −1 at 200 mA g −1 and an ultralong life over 1000 cycles (with a capacity higher than 113.8 mAh g −1 ). Such a long cycling life exceeds that of any reported CIBs. The remarkable Cl − -storage performance of the Ni 2 V 0.9 Al 0.1 -Cl LDH is ascribed to the synergetic contributions from V m+ (high redox activity), Ni 2+ (favorable electronic structure), and inactive Al 3+ (enhances the structural stability), which is revealed by a comprehensive study that utilizes synchrotron X-ray absorption near-edge structure experiments, kinetic investigations, and theoretical calculations. This study provides an effective strategy to achieve superior rechargeable batteries, which are applicable to large-scale energy storage and power grids.room-temperature chloride ion batteries (CIBs) based on Cl − shuttling [6][7][8][9][10] have attracted intensive attention as a result of their large theoretical volumetric energy density (up to 2500 Wh L −1 ). [11] In addition, the abundance of chloride-containing materials and their availability worldwide not only lower the costs but also enable manufacturing all over the world. Another key advantage of CIBs is their dendritefree feature, which is derived from the simple migration of Cl − , making CIB systems more secure and suitable for large-scale energy storage. [12] Since the first proof that the reversible shuttle of chloride ions between a metal chloride cathode (BiCl 2 , CoCl 2 , and VCl 3 ) and a lithium anode was proposed by Zhao et al., [5] metal oxychlorides [6,13] and chloride-doped organic polymers, [14,15] such as PPy and PANI, have been subsequently demonstrated as possible electrode materials in CIBs. Although some progress has been made in CIB cathode materials during the past few years, it is still at the initial stage compared with the development of metal-ion batteries. One urgent issue to be solved is their short cycling life; i.e., most of these cathode materials can only sustain dozens of charge/discharge cycles with a moderate capacity of ≈40−100 mAh g −1 . Therefore, exploiting suitable Cl − -hosting cathode materials with a simultaneous high capacity and long cycling life is a top priority for the development of rechargeable CIBs.Layered double hydroxides (LDHs), whose structure can be generally expressed by the formula [M II 1−x M III x (OH) 2 ] (A n− ) x/n ·mH 2 O (M II and M III are divalent and trivalent metals respectively, and A n− is an interlayer anion co...

High-performance, long lifetime chloride ion battery using a NiFe–Cl layered double hydroxide cathode

“…of the NiFe-CO 3 LDH sample with Ni/Fe ratio of 2/1 indicates a well-dened carbonate-intercalated LDH with a basal plane spacing of $7.42Å. 33 Aer ion-exchange, all Bragg reections in the XRD pattern can be indexed to a rhombohedral unit cell, reections indexed as (003), (006), (110), and (113) were observed at 2q ¼ 11.54 , 23.22 , 59.80 , and 61.14 respectively. The XRD showed no evidence for the presence of any crystalline impurity phases.…”

A review of halide charge carriers for rocking‐chair and dual‐ion batteries

“…After the work on CoFe-Cl LDH, Yin et al 70 continued their exploration of LDH materials for rechargeable CIBs and reported the use of a trimetallic NiVAl LDH with interlayer Cl − (Ni 2 V 0.9 Al 0.1 -Cl LDH) as a new high-performance CIB cathode. The Ni 2 V 0.9 Al 0.1 -Cl LDH was found to possess an ultralong cycle life of >1000 cycles at 200 mA•g −1 with a capacity higher than 113 mAh•g −1 (Figure 6A).…”

All‐Solid‐State Chloride‐Ion Battery with Inorganic Solid Electrolyte

“…These materials exhibited good cycle performance; however, the theoretical capacities were low because the metal oxychlorides have a small number of reaction electrons compared with the corresponding metal chloride (Table S1). Polymer and layered double hydroxides have been reported as cathode materials; however, these materials tend to have low theoretical capacity compared with metal chlorides [15–17] …”