中国科学技术大学 焦龙--中文主页--论文发表.pdf 
中国科学技术大学 焦龙--中文主页--论文发表.pdf
ll Article Metal-organic frameworks for nanoconfinement of chlorine in rechargeable lithium-chlorine batteries Yan Xu, Long Jiao, Jiale Ma, ..., Zhenyu Li, Hai-Long Jiang, Wei Chen zyli@ustc.edu.cn (Z.L.) jianglab@ustc.edu.cn (H.-L.J.) weichen1@ustc.edu.cn (W.C.) Highlights Metal-organic frameworks with functional groups are developed for Li-Cl2 batteries The Li-Cl2 battery exhibits good electrochemical performance at both room and low temperatures The storage mechanism of Cl2 is studied by low-dose TEM and cryo-TEM Rechargeable Li-Cl2 batteries are an emerging and promising high-energy battery technology. We develop metal-organic frameworks (MOFs) with functional groups for the nanoconfinement of chlorine by chemisorption in the Li-Cl2 battery. The functional MOFs boost the storage capability of Cl2 and LiCl, contributing to excellent electrochemical performance for the Li-Cl2 battery in a wide temperature range. The charge storage mechanism of the functional MOFs is revealed by a combination of low-dose HRTEM, cryo-TEM, and XPS. Xu et al., Joule 7, 515–528 March 15, 2023 ª 2023 Elsevier Inc. https://doi.org/10.1016/j.joule.2023.02.010 ll Article Metal-organic frameworks for nanoconfinement of chlorine in rechargeable lithium-chlorine batteries Yan Xu,1 Long Jiao,2 Jiale Ma,3 Pan Zhang,4 Yongfu Tang,4 Lingmei Liu,5 Ying Liu,5 Honghe Ding,6 Jifei Sun,1 Mingming Wang,1 Zhenyu Li,2,3,* Hai-Long Jiang,2,* and Wei Chen1,7,* SUMMARY CONTEXT & SCALE Metal-organic frameworks (MOFs) with functional groups are developed for the nanoconfinement of chlorine by chemisorption in a rechargeable Li-Cl2 battery. Predicted by theoretical calculations, highly porous MOF functionalized with –NH2 groups, namely UiO66-NH2, is screened out as a model to apply in the Li-Cl2 battery. The Li-Cl2 battery using NH2-functionalized MOF (Li-Cl2@MOF) demonstrates high specific capacities of up to 2,000 mAh/g and is highly stable for 500 cycles under a specific capacity of 1,000 mAh/g at room temperature. It also exhibits superior low-temperature performance, displaying a high voltage of 3.5 V and a Coulombic efficiency (CE) of 99.7% with 300 stable cycles under a capacity of 1,000 mAh/g at 25 C. Furthermore, the Li-Cl2@MOF cell exhibits a high areal capacity of 4.4 mAh/cm2 in coin cells and a CE of 99% for over 120 cycles in large-scale pouch cells. This work provides opportunities for the promising application of functionalized MOFs as cathodes in rechargeable Li-Cl2 batteries. Rechargeable Li-Cl2 batteries are considered one of the cuttingedge battery energy storage systems. We propose and demonstrate metal-organic frameworks (MOFs) with functional groups to facilitate the storage of Cl2 by chemisorption in the Li-Cl2 battery. The designed Li-Cl2@MOF battery delivers high specific capacities up to 2,000 mAh/g with excellent rate capability and cycle stability. Even at low temperatures, it still exhibits a high voltage of 3.5 V and a CE of 99.7% with 300 stable cycles under a capacity of 1,000 mAh/g. Low-dose highresolution transmission electron microscopy, cryogenic transmission electron microscopy, and X-ray photoelectron spectroscopy are utilized to reveal the storage mechanism on nanoconfinement of Cl2 and LiCl by the functionalized MOFs in the Li-Cl2@MOF battery. INTRODUCTION The development of high-energy batteries is highly desirable for meeting the ever-growing demand for energy storage.1–3 Rechargeable Li-Cl2 batteries were developed by Dai et al. in 2021 based on primary lithium-thionyl chloride (LiSOCl2) batteries, which delivered a high specific capacity of 1,200 mAh/g and a high output voltage of 3.6 V, and considered one of the cutting-edge battery energy storage systems.4 A rechargeable Li-Cl2 battery typically consists of a Li metal anode, a SOCl2-based nonaqueous electrolyte, and a Cl2 storage cathode material, such as microporous carbon with a high surface area4 and graphite flakes with tunnels.5 The solid product of LiCl is generated on the cathode during the discharge process in Li-Cl2 cell, which is oxidized to Cl2 during the recharge process. Recently, other halogen cells, such as Na-Cl25 and K-Br2 cells,6 have been developed. We take the Li-Cl2 cell as the research target due to its high energy density among the halogen cells. However, several challenges need to be overcome to realize the practical application of the Li-Cl2 cells. First, the supply of Cl2 to the reaction is limited due to the weak physical adsorption of porous carbon to Cl2 molecules. Second, the excessive generation of LiCl into the carbon pores tends to block the tunnels for Li+ transportation and Cl2 diffusion, impeding further electrochemical reactions. In addition, the shuttle effect of unbonded Cl2 can cause battery decay, particularly at a high output capacity. Therefore, the cathode materials with highly porous structures are critical to overcome the above issues concerning the Li-Cl2 batteries. Joule 7, 515–528, March 15, 2023 ª 2023 Elsevier Inc. 515 ll Article Further improvements can be made by modification of the pore structures with polarities that can interact with Cl atoms. Metal-organic frameworks (MOFs) with high porosity and versatile functionalities have been applied in various battery systems to improve their electrochemical performance.7–12 The tuning of pore size, geometry, and chemical functionality of MOFs can realize many targeted applications, such as gas storage and separation for Li-air battery,4,13–15 and shuttle effect suppression for Li-S batteries.16–23 For example, Li et al. reported that MOFs with rich defects could lead to a significant oxygen enrichment in the framework.13 Tarascon et al. demonstrated a mesoporous MOF with polarized surfaces, where mesopores with small apertures could suppress the migration of polysulfide species in Li-S batteries.20 Compared with porous carbon materials, MOFs possess several distinct advantages,24–27 including high porosity with uniform pores, adjustable pore sizes, and controllable functionalization of the organic linkers. The functionalized organic linkers make MOFs having a high affinity to some specific gases. For example, Lu et al. demonstrated that the introduction of –NH2 groups in CAU-1-NH2 MOF has successfully improved the capability of CO2 capture in Li-air battery.28 Yaghi et al. also verified the capture capability of – NH2 groups of CAU-1-NH2@polydopamine MOF to CO2 molecules.29 Inspired by the successful application of MOFs in Li-air battery, we speculate that MOFs may be potential good candidates for the cathode Cl2/LiCl reactions in the Li-Cl2 battery. One of the critical enablers of using MOFs in Li-Cl2 battery is to design MOFs with high porosity and functional groups for the confinement of LiCl and Cl2. Considering that both LiCl and Cl2 are Lewis acids, we further speculate that MOFs constructed by organic ligands with Lewis basic functional groups may be promising candidates for the storage of LiCl and Cl2. In this work, we propose to apply highly porous MOFs with Lewis basic functional groups in Li-Cl2 batteries to improve the Cl2/LiCl conversion reactions. Guided by the theoretical prediction using first-principles calculations, MOFs with –NH2 functional groups are screened out for the applications in the Li-Cl2 battery (referred to as Li-Cl2@MOF battery). It is revealed by cryo-TEM and low-dose high-resolution TEM (HRTEM) that UiO-66-NH2 is stable during cycling, and XPS verify the strong affinity of the –NH2 groups to Cl2 and LiCl, thereby boosting their redox reaction kinetics. Our designed Li-Cl2@MOF cell delivers a highly rechargeable specific capacity of up to 2,000 mAh/g and is stable over 500 cycles under a high capacity of 1,000 mAh/g. Moreover, the Li-Cl2 cell exhibits excellent low-temperature electrochemical performance down to 40 C, as well as high areal capacities in coin cells and extended capacities in large-scale pouch cells, demonstrating its practical energy storage applications. This work demonstrates that functional MOFs can provide an innovative pathway to the performance improvement of rechargeable Li-Cl2 batteries. 1Department of Applied Chemistry, School of Chemistry and Materials Science, Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China 2Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China 3Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China 4Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, China 5Multi-scale Porous Materials Center, Institute of RESULTS AND DISCUSSION Prediction of –NH2 groups functionalized MOFs for Li-Cl2 batteries We screened a series of MOFs for deployment in the Li-Cl2 battery. Given the electrochemical stability, Zr-based MOF was chosen as the main framework in our work. Furthermore, considering the synthetic availability, UiO-66 MOF was used as the base MOF. We then carried out density functional theory (DFT)-based first-principles calculations to determine the adsorption energy of Cl atom on several Lewis base groups, including –NH2, –Cl, –OH, and –OCH3 groups. As shown in Figures 1A and S1, the adsorption energies of UiO-66, UiO-66-NH2, UiO-66-Cl, UiO-66-OH, 516 Joule 7, 515–528, March 15, 2023 Advanced Interdisciplinary Studies & School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China 6National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230026, China 7Lead contact *Correspondence: zyli@ustc.edu.cn (Z.L.), jianglab@ustc.edu.cn (H.-L.J.), weichen1@ustc.edu.cn (W.C.) https://doi.org/10.1016/j.joule.2023.02.010 ll Article Adsorption energy (eV) A B 0.0 -0.14 eV -0.4 -0.8 Adsorption -0.75 eV -1.2 -1.6 -2.0 -0.14 eV -0.39 eV -1.67 eV UiO-66-NH2 UiO-66-Cl UiO-66-OH UiO-66-OCH3 UiO-66 of Cl atom UiO-66-NH2 D C UiO-66 UiO-66-NH2 E MOF Li Charge Discharge Li+ Charge Li+ Cl2 Li+ LiCl Discharge MOF：UiO-66-NH2 Figure 1. The prediction of functional MOFs for Li-Cl2 batteries (A) DFT calculation of adsorption energy of UiO-66-NH2 , UiO-66-Cl, UiO-66-OH, UiO-66-OCH3 , and UiO-66 to Cl atoms. (B–D) (B) DFT calculation of adsorption process of UiO-66-NH 2 to Cl atoms. The charge density plot of (C) UiO-66-NH 2 and (D) UiO-66 to Cl atoms. Atoms of Zr, O, C, N, and H are colored in blue, red, brown, blue gray, and white, respectively. (E) Schematic diagram of the Li-Cl 2 @MOF (UiO-66-NH 2 ) cell and the cathode Cl2 /LiCl reaction mechanism. and UiO-66-OCH3 to Cl atom were 0.14, 1.67, 0.75, 0.14, and 0.39 eV, respectively, which indicates that the –NH2 group has the strongest adsorption preference to the Cl atom. Therefore, UiO-66-NH2 MOF was selected for the LiCl2 battery in this work. Considering that the unit cells of UiO-66 with 440 atoms and UiO-66-NH2 with 488 atoms are large, a part of the structure, which contains one benzene ring and two roundish Zr6O8(COO)12 clusters (Figure S2), was taken into investigation for the adsorption of Cl. For the Cl atom adsorption process in UiO-66-NH2 MOF, Cl can spontaneously occupy the H position of the –NH2 group and push it to the neighboring O (Figure 1B). By contrast, as depicted in Figure S3, Cl stays at the non-bonded state in UiO-66 when the –NH2 group is absent. The state of chemical bond formation can be verified by the charge density difference plot in Figures 1C and 1D, where the charge transfer locates at the space between Cl–N–C in UiO-66-NH2, whereas the charge transfer region is limited around Cl in UiO-66, further indicating the strong chemisorption between –NH2 group and Cl. Therefore, the existence of the -NH2 groups in UiO-66-NH2 can effectively enhance the adsorption of Cl, which is believed to promote the LiCl/Cl2 reactions in the Li-Cl2 batteries. The structure of the Li-Cl2@MOF cell was depicted in Figure 1E, in which a Li metal anode, a porous UiO-66-NH2 MOF cathode, and a Li+-conductive electrolyte were composed. The highly porous UiO-66-NH2 MOF functionalized with the –NH2 Joule 7, 515–528, March 15, 2023 517 ll groups was synthesized based on a previous report with some modifications.30 Due to the affinity of UiO-66-NH2 MOF to Cl2 and LiCl molecules, its storage capacity to Cl2 and LiCl molecules can be much enhanced. During the first discharge process, Li metal dissolves into Li+ ions on the anode and SOCl2 solvent is decomposed into a solid product of LiCl (2SOCl2 + 4Li+ + 4e / SO2 + S + 4LiCl), which is stored in the micropores of the UiO-66-NH2 MOF cathode. During the recharge process, Li+ ions in the electrolyte deposit onto the Li metal, and LiCl is oxidized to Cl2, which is stored in the micropores by the chemisorption between the Cl2 and –NH2 groups in the UiO-66-NH2 cathode. In the following discharge process, Cl2 is reduced to LiCl (1/2Cl2 + e / Cl ) to complete the battery cycling. Characterization of pristine UiO-66-NH2 MOF Different characterization tools were applied to investigate the functional MOFs. The synthesized UiO-66-NH2 was first confirmed by X-ray diffraction (XRD). As shown in Figure 2A, all patterns match very well with the UiO-66 MOF. Furthermore, the morphology and structure of pristine UiO-66-NH2 were characterized by cryo-TEM and its electron diffraction pattern. As shown in Figure 2B, the UiO-66-NH2 showed an octahedral nanoparticular structure with particle size in the range of 300–600 nm. The inset image showed a typical electron diffraction pattern of the crystal along the <110> zone axis. The sharp diffraction spots of the pristine UiO-66-NH2 indicated the good crystallinity of the UiO-66-NH2 sample. In addition, (111) and (002) planes of the crystalline UiO-66-NH2, which are two of the strongest peaks in the XRD pattern of UiO-66-NH2 (Figure 2A), further indicate the successful synthesis of UiO-66-NH2. The lattice planes of (113), (133), (024), (224), and (135) in UiO-66NH2 can be detected by electron diffraction in different areas (Figure S4). Moreover, the porous structure of UiO-66-NH2 was characterized by N2 adsorption/desorption at 77 K, which exhibited a sharp increase at a low relative pressure (P/P0 < 0.05) and, then, a platform characteristic of the type-I isotherms (Figure 2C). The fitted pore size of UiO-66-NH2 from the N2 adsorption isotherm was calculated to be 1.2 nm (Figure 2D), illustrating its microporous feature. The Brunauer–Emmett–Teller (BET) surface area of UiO-66-NH2 was as high as 1,036 m2/g. The porous structure and large surface area in UiO-66-NH2 can provide ample reaction sites for LiCl and Cl2 redox reactions. It is well-recognized that the characterization of MOFs at the atomic level is extremely difficult due to their electron-beam sensitivity. In our work, HRTEM images were obtained under an extremely low-dose condition (Figure 2E). Using a 0.03 e/Å2/s cumulative electron dose, we have caught the structural features of UiO-66-NH2 (Figure 2E), which is hard to be obtained by room temperature TEM. Figure 2E is a representative denoised low-dose HRTEM image of UiO-66-NH2 along the <110> direction. To make the image contrast more interpretable, contrast transfer function (CTF) correction was performed according to the method reported in the previous literature.31 In the CTF-corrected image of the pristine UiO-66-NH2 (Figure 2F), Zr6O8 clusters are clearly identified, which is in good agreement with UiO-66-NH2 crystal structure from the <110> direction. Interestingly, we found the missing linkers in this image, but the contrasts of the horizontally arranged ligands are not presented. As a consequence, the adjacent opposing triangleshaped channels are vertically merged into rhombus-shaped channels, indicating the rich defects in the UiO-66-NH2 structure. Electrochemical performance of the Li-Cl2@MOF cell at room temperature In light of the reaction mechanism of Cl2/LiCl redox in UiO-66-NH2, a Li-Cl2@MOF cell was assembled to evaluate the effect of UiO-66-NH2 on the conversion reactions 518 Joule 7, 515–528, March 15, 2023 Article ll Article A Intensity (a.u.) (111) B UiO-66-NH2 (002) 2 1/nm 5 10 15 20 2 Theta (degree) 25 Incremental Pore Volume (cm3/g) Quantity Adsorbed (cm3/g STP) D 400 300 200 100 UiO-66-NH2 0.0 0.2 0.4 0.6 0.8 Relative Pressure (P/P0) (002) 500 nm 30 C 0 (111) (111) 0.10 0.08 0.06 0.04 0.02 UiO-66-NH2 0.00 0 1.0 4 8 12 16 Pore Width (nm) 20 F E Zr cluster 20 nm Micropore 4 nm Figure 2. Materials characterizations of UiO-66-NH2 as a functional MOF for Li-Cl2 batteries (A) XRD of pristine UiO-66-NH 2 . (B) Cryo-TEM of pristine UiO-66-NH 2 . Inset: electron diffraction pattern of pristine UiO-66-NH 2 . Scale bar: 500 nm. Inset scale bar: 2 1/nm. (C) N 2 gas adsorption/desorption isotherms at 77 K. (D) The fitted pore size of UiO-66-NH 2 from N 2 adsorption/desorption isotherm. (E) Low-dose HRTEM image of pristine UiO-66-NH 2 . Scale bar: 20 nm. (F) CTF-corrected image from (E). Inset: A UiO-66-NH 2 model. Orange, red, blue, and cyan spheres represent C, O, N, and Zr atoms, respectively. Scale bar: 4 nm. of LiCl and Cl2. First, the UiO-66-NH2 electrode was characterized by scanning electron microscopy (SEM) and the corresponding energy dispersive X-ray spectroscopy (EDX). As shown in Figures S5 and S6, the UiO-66-NH2 MOF was uniformly distributed on the conductive carbon, as the C, N, O, and Zr elements were evenly distributed. As shown in Figure S7, the first cycle discharge capacity of the assembled LiCl2@MOF cell was as high as 7,550 mAh/g, which is much superior to the reported literature (3,309 mAh/g).4 The improved first cycle-specific capacity indicated the much-improved active sites of UiO-66-NH2 to accommodate LiCl. Furthermore, a high capacity of 1,000 mAh/g was used to charge the Li-Cl2@MOF cell to evaluate the storage capacity of UiO-66-NH2. The Li-Cl2@MOF cell exhibited a long cycle Joule 7, 515–528, March 15, 2023 519 ll Article 150 mA/g 1200 100 900 1000 mA/g 80 600 UiO-66-NH2 UiO-66 300 0 60 Room temperature 0 100 200 300 400 40 500 Coulombic efficiency (%) Specific capacity (mAh/g) A Cycle number C D 4.0 3.5 3.5 3.0 2.5 30th cycle 100th cycle 200th cycle 2.0 0 0.13 V 3.0 2.5 2.0 100 mA/g 500 1000 1500 2000 Specific capacity (mAh/g) 0 200 400 600 800 1000 Specific capacity (mAh/g) F 1200 100 900 600 150 mA/g 300 450 600 750 900 1100 300 80 300 60 0 40 60 0 15 30 Cycle number 45 Coulombic efficiency (%) E Specific capacity (mAh/g) 4.0 Voltage (V) 4.0 Voltage (V) Voltage (V) B 3.5 300 mA/g 600 mA/g 750 mA/g 900 mA/g 1100 mA/g 3.0 2.5 2.0 0 150 300 450 Specific capacity (mAh/g) Accumulated specific capacity (mAh/g) Maximium discharge capacity (mAh/g) Porous carbon 25 °C Current density (mA/g) Porous carbon This work Coulombic efficiency Cycle life This work -40 °C - 25 °C Figure 3. Electrochemical performance of the Li-Cl2@MOF battery at room temperature (A) Cycling performance of Li-Cl2 @MOF cells at a current density of 1,000 mA/g. (B) Corresponding voltage profiles of the Li-Cl 2 @MOF cell in different cycles. (C) Voltage profiles of the Li-Cl2 @MOF cell under the specific capacities from 500 to 2,000 mAh/g. (D and E) (D) Voltage profiles and (E) Cycling performance of the Li-Cl 2 @MOF cell under the current densities from 150 to 1,100 mA/g. (F) Comparison of this work with the previously reported porous carbon in terms of accumulated specific capacity, current density, cycle life, working temperature range, Coulombic efficiency, and maximum specific capacity. stability of over 500 cycles and a high output specific capacity of 980 mAh/g after 500 cycles with a high cycling CE up to 99.7% (Figure 3A), indicating the excellent storage capacity of UiO-66-NH2 and the superb stability of its structure. Additionally, an ultra-flat discharge voltage plateau was well maintained within 200 cycles at 3.5 V (Figure 3B), further suggesting the high stability of the UiO-66-NH2 structure. To investigate the importance of the –NH2 groups, UiO-66 containing no such –NH2 groups was used as a control sample to assemble the Li-Cl2 battery. As shown in Figure 3A, the specific capacity of the Li-Cl2 cell using UiO-66 fades to merely 600 mAh/g within only 10 cycles, indicating its limited Cl2/LiCl conversion capability due to the lack of the –NH2 groups to trap Cl2 and LiCl. Furthermore, the Li-Cl2 cell was assembled using ketjenblack as the cathode. As shown in 520 Joule 7, 515–528, March 15, 2023 Article ll Figure S8, although the BET surface area of ketjenblack was as high as 1,348 m2/g, the CE of the Li-Cl2 cell was merely 95% at the initial cycles, which dropped dramatically to 74% within 100 cycles and to 54% within 200 cycles at the current density of 450 mA/g, further indicating the importance of the -NH2 groups in the functional MOF design. The cycling performance of the Li-Cl2@MOF cell under different charge capacities was further evaluated. As shown in Figures 3C and S9, the cell was cyclable at 500–2,000 mAh/g, and the CE was maintained at 100% when the capacity was between 500 and 1,500 mAh/g. Even at the ultra-high capacity of 2,000 mAh/g, the CE still can reach up to 96%. As shown in Figure 3C, the overpotential of Li-Cl2@MOF cell was as low as 0.13 V with a charge voltage of 3.80 V and a discharge voltage of 3.67 V when cycling at the current density of 100 mA/g, further indicating the fast Cl2/LiCl gas/solid conversion reaction kinetics promoted by the functional MOF structure. To investigate the reaction kinetics of the Li-Cl2@MOF cell, the cycling performance of the Li-Cl2@MOF cell under different current densities was also investigated. When the current density increased from 150 to 1,100 mA/g, the decrease of the discharge voltage plateau was negligible, and the discharge voltages were maintained at 3.5 V, suggesting the fast reduction kinetics from Cl2 to LiCl due to the strongly bonded Cl2 with UiO-66-NH2 (Figure 3D). Meanwhile, the charge voltage was merely increased from 3.81 to 3.96 V (Figure 3D) when the current density was increased from 150 to 1,100 mA/g, indicating that the oxidation kinetics from LiCl to Cl2 was also fast due to the strong binding of LiCl with UiO-66-NH2. As shown in Figure 3E, the Li-Cl2@MOF cell delivered specific capacities of around 500 mAh/g at the current densities from 300 to 1,100 mA/g, when the charge capacity is 500 mAh/g. It is noted that the CE is a little bit higher than 100% at the first several cycles under a current density of 150 mA/g, which can be ascribed to the extra decomposition of SOCl2 during the initial cell activation process. When charging the battery at a fixed specific capacity of 500 mAh/g, the corresponding CE is maintained at 100% even at a high current density of 1,100 mA/g. Encouragingly, compared with the reported Li-Cl2 cell by porous carbon, our Li-Cl2@MOF cell showed much superior electrochemical performance in the aspects of accumulated specific capacity, current density, and working temperature range, which is summarized in Figure 3F. Specifically, our Li-Cl2@MOF cell showed a cumulative capacity of up to 500,000 mAh/g, which is about 8 times higher than the reported Li-Cl2 cell by porous carbon. Particularly, the cycling current density can be improved from 100 to 1,000 mA/g, which is 10 times higher than the reported Li-Cl2 cell by porous carbon. In addition, the operating temperature range of our Li-Cl2@MOF cell was enlarged from 40 C to 25 C, which can be applied to more application situations. These advantages suggest the great promises of the MOFs with functional groups as cathodes for high-energy Li-Cl2 batteries. Low-temperature electrochemical behaviors of the Li-Cl2@MOF cell To explore the feasibility of the Li-Cl2@MOF cells to be applied in extreme weather, we carried out their electrochemical performance measurements under low temperatures. Figures 4A and 4B show the electrochemical performance of the Li-Cl2@MOF cells under temperatures from 0 C to 40 C. At 0 C, the discharge capacity of the Li-Cl2@MOF cells is about 1,022 mAh/g when the charge capacity was set at 1,000 mAh/g. When the temperature was reduced to 10 C, the Li-Cl2@MOF cells can provide a high capacity of 1,000 mAh/g. With the temperature further decreased to 40 C, the Li-Cl2@MOF cells can still deliver a capacity of 989 mAh/g. The CE can Joule 7, 515–528, March 15, 2023 521 ll Article B 80 900 0 °C 600 -20 0 60 -40 -30 40 300 0 -10 20 Li-Cl2@MOF 0 20 40 60 Cycle number 3.5 3.0 0 °C -20 °C -40 °C 2.5 2.0 0 80 C -10 °C -30 °C 250 500 750 1000 Specific capacity (mAh/g) D 900 80 450 mA/g 60 600 40 300 0 -25 °C Li-Cl2@MOF 0 75 150 Cycle number 225 20 300 4.0 Voltage (V) 100 1200 Coulombic efficiency (%) Specific capacity (mAh/g) 4.5 4.0 Voltage (V) 100 1200 Coulombic efficiency (%) Specific capacity (mAh/g) A 3.5 3.0 30th cycle 100th cycle 200th cycle 300th cycle 2.5 2.0 0 -25 °C 200 400 600 800 1000 Specific capacity (mAh/g) Figure 4. Low-temperature electrochemical performance of Li-Cl2@MOF batteries (A and B) (A) Cycling performance and (B) voltage profiles of Li-Cl 2 @MOF cell under different temperatures from 0 C to 40 C. (C and D) (C) Cycling performance and (D) voltage profiles of Li-Cl 2 @MOF cell under the temperature of 25 C. be maintained at 102%, 100%, 99.6%, 99.7%, and 98.9% under the temperatures of 0 C, 10 C, 20 C, 30 C, and 40 C, respectively, which indicated the good reversibility of the Li-Cl2@MOF cells under low temperatures. When the temperature returned to 0 C, the discharge capacity returned to nearly 1,000 mAh/g, suggesting a good temperature tolerance of the Li-Cl2@MOF cells. The discharge plateau of the Li-Cl2@MOF cell was 3.50 V at 0 C (Figure 4B), which is comparable with that at room temperature (Figure 3C). When the temperature decreased to 30 C, the discharge plateau merely dropped by 0.14 V, which indicated the reaction kinetics from Cl2 to LiCl was fast even at low temperatures, further verifying the strong binding of Cl2 with UiO-66-NH2. It is worth mentioning that the polarization in the charge process with the temperature decrease was higher than that in the discharge process, which indicated that the solid to gas reaction kinetics from LiCl to Cl2 is impacted greater by temperature than the gas to solid reaction kinetics from Cl2 to LiCl. In addition to the excellent rate capability performance, the longterm cycling stability of the Li-Cl2@MOF cells was also evaluated at 25 C. The Li-Cl2@MOF cells provide an ultra-high first discharge capacity of 7,190 mAh/g (Figure S10) and a high specific capacity of 996 mAh/g when the charge capacity was set at 1,000 mAh/g for a lifespan of 300 cycles with nearly 100% of the capacity retention (Figure 4C). In addition, the Li-Cl2@MOF cells showed a maintained discharge plateau of 3.5 V at 25 C within 200 cycles (Figure 4D), which demonstrated their practical long-term application at low temperatures. Investigation of reaction mechanism of the Li-Cl2@MOF cell The reaction mechanism of the –NH2 groups to the Cl2/LiCl conversion reactions is illustrated in Figure 5A. Typically, Cl2 interacted with the –NH2 groups by chemisorption, spontaneously H atom was pushed to the neighboring O and its position in the – NH2 groups was occupied (Figure S3). During the discharge process, the bonded Cl2 was supplied to the reduction reaction to form LiCl, and during the charge process, the formed Cl2 was trapped by the –NH2 groups to suppress its shuttle effect. To investigate the reaction mechanism of the improvements by using UiO-66-NH2 in 522 Joule 7, 515–528, March 15, 2023 ll Article Cl2 2 292 C=O 288 C Pristine Discharge to 2 V Charge to 500 mAh/g Charge to 1000 mAh/g 284 280 412 408 Binding energy (eV) + 2e- E D C 1s C-OH π-π* satellite 296 2LiCl = 2Li+ + Cl C-C 404 C-NH2 N 1s 400 396 Binding energy (eV) CTF-corrected image F Discharge to 2 V Charge to 1000 mAh/g Intensity (a.u.) LiCl Pristine Discharge to 2V Charge to 500 mAh/g Charge to 1000 mAh/g Intensity (a.u.) B Intensity (a.u.) A Micropore LiCl (111) (200) (220) Ni (311) (222) (400) Ni Ni 10 nm Zr cluster 2 nm 30 40 50 60 2 Theta (degree) 70 80 Figure 5. The working mechanism of Li-Cl2@MOF batteries (A) The schematic diagram of redox reaction of Cl 2 /LiCl. (B and C) (B) C 1s and (C) N 1s XPS spectra of UiO-66-NH 2 cathode under the states of pristine, discharge to 2 V, charge to 500 mAh/g and charge to 1,000 mAh/g. (D) Low-dose HRTEM image of UiO-66-NH 2 discharged to 150 mAh/g. Scale bar: 10 nm. (E) CTF-corrected image from (D). Scale bar: 2 nm. (F) XRD pattern of UiO-66-NH 2 cathode under the states of discharge to 2 V and charge to 1,000 mAh/g. the Li-Cl2 cell, XPS, XRD, and low-dose HRTEM were applied to analyze the cycled UiO-66-NH2 cathode. XPS was conducted to verify the bond interaction between the Cl atom and UiO-66-NH2. As shown in Figure 5B, the C 1s spectrum can be deconvoluted into the C–C group (284.8 eV), C–OH group (286.6 eV), C=O group (289.0 eV), and p-p* satellite structure (292.7 eV), in which the p-p* satellite structure is ascribed to the extended delocalized electrons in the aromatic ring. The C–C and C=O groups are ascribed to the carbon in the aromatic ring and carbonyl group of 2-amino-1,4-benzenedicarboxylate. Compared with the pristine UiO-66-NH2 MOF, the C–C group in the aromatic ring kept unchanged in the UiO-66-NH2 MOF in the states of discharge to 2 V, charge to 500 mAh/g, and charge to 1,000 mAh/g, which indicated that the electron state in the aromatic ring was negligibly changed when the Cl atom was adsorbed. The C–OH group emerged in the states of discharge to 2 V, charge to 500 mAh/g and charge to 1,000 mAh/g compared with the C–O group in the pristine UiO-66-NH2, suggesting the proton transfer to the C–O group, which is identical to the computational results. The –NH2 groups connected to the benzene ring can be detected in the N 1s XPS (400.7 eV) (Figure 5C). Both N 1s peak (400.7 eV) ascribed to the C–NH2 group and the p-p* satellite peak in C 1s moved to the lower energy after the Cl atom was adsorbed in the states of discharge to 2 V, charge to 500 mAh/g, and charge to 1,000 mAh/g, indicating that the electron on C–NH2 was transferred to the Cl atom due to the adsorption of Cl2/LiCl, which is consistent with the computational results. Both the C 1s and N 1s XPS results verified that Cl2/LiCl bonded with the –NH2 groups while pushing one proton in the –NH2 group to the neighboring O in the C–O group. Joule 7, 515–528, March 15, 2023 523 ll It is known that the stability of electrode materials significantly affected the battery performance. Thus, we performed low-dose HRTEM imaging of the UiO-66-NH2 cathode discharged to 150 mAh/g to check its structural stability. As shown in Figure 5D, the crystalline structure of the cycled UiO-66-NH2 MOF was retained, indicating stable and reliable characteristics of UiO-66-NH2 MOF in the Li-Cl2 cell. The CTF-corrected image obtained from Figure 5D further verified that the channel structure was maintained in the cycled UiO-66-NH2 MOF (Figure 5E). XRD was conducted on UiO-66-NH2 MOF in the same state, but no peak shift can be observed (Figure S11), further indicating the stability of UiO-66-NH2 MOF. The discharge products in the UiO-66-NH2 cathode under the states of discharge to 2 V and charge to 1000 mAh/g were investigated by XRD. As shown in Figure 5F, the diffraction peaks of 30.3 , 35.2 , 50.4 , 60 , 62.8 , and 73.4 can be assigned to the (111), (200), (220), (311), (222), and (400) planes of LiCl, respectively, which indicated the formation of crystalline LiCl. In light of the XPS, XRD, and low-dose HRTEM results, we identified that both the highly porous structure and the stable functional group are responsible for boosting the electrochemical performance of the Li-Cl2 cell. Electrochemical performance of the Li-Cl2@MOF pouch cell To meet the requirements for the practical application, the Li-Cl2@MOF cell in large areal capacity was assembled in the coin-type cell. As shown in Figure 6A, the LiCl2@MOF cell showed a stable performance up to 150 cycles at a high areal capacity of 4.4 mAh/cm2 with a negligible capacity degradation, which indicated the superb capability of the UiO-66-NH2 MOF to the Cl2 and LiCl reactions. To further demonstrate the superiority of our Li-Cl2@MOF cell, large-scale pouch cells were assembled with an electrode area of 20 cm2 (4.0 cm 3 5.0 cm). The as-prepared pouch cell was cycled at a current density of 150 mA/g with a charge capacity of 38 mAh (Figure 6B). Under such conditions, the pouch cell delivered over 120 stable cycles, and the Coulombic efficiency can be maintained over 99%. It is worth mentioning that the voltage profiles of the pouch cell showed a similar discharge plateau at 3.64 V to the coin cell (Figure 6C), demonstrating its promising practical utilization. Although the Li-Cl2@MOF pouch cell showed advantages in the discharge voltage, output specific capacity, and cycle stability compared with other Li-based batteries, the electrolyte utilization should be further optimized, and cell engineering is needed to tackle the corrosion issues of SOCl2 and Cl2. Conclusion In conclusion, we applied the first-principles calculations to predict UiO-66-NH2 as a functional MOF to be used as a cathode material in the rechargeable Li-Cl2 batteries, in which the highly stable, porous structure and functional groups are critical to boost the battery electrochemical performance. The working mechanism of the UiO-66-NH2 MOF structure to enrich the Cl2/LiCl reactions was revealed by a combination of cryo-TEM, low-dose HRTEM and XPS. Our designed Li-Cl2@MOF full cell showed high capacities of up to 2,000 mAh/g and over 500 stable cycles at a specific capacity of 1,000 mAh/g at room temperature. The Li-Cl2@MOF cell also exhibited excellent electrochemical performance at low temperatures, delivering a maintained CE of 99.7% with a discharge plateau of 3.5 V and 300 stable cycles under a capacity of 1,000 mAh/g at 25 C. Moreover, the Li-Cl2@MOF cells achieved a high areal capacity of 4.4 mAh/cm2 and a large-scale pouch cell fabrication, showing their practical energy storage applications. This study opens new avenues to the development of rechargeable Li-Cl2 batteries with high capacity and excellent stability under a wide temperature range. However, the exploration of rechargeable Li-Cl2 batteries is still in its very early stage, and further 524 Joule 7, 515–528, March 15, 2023 Article ll Article 100 75 4 50 2 0 0 30 60 Cycle number 90 150 C 100 45 75 30 50 15 0 120 Li-Cl2@MOF pouch cell 0 20 40 60 80 Cycle number 100 25 120 4.0 Voltage (V) B 60 Capacity (mAh) 25 Li-Cl2@MOF coin cell Coulombic efficiency (%) 6 Coulombic efficiency (%) Areal capacity (mAh/cm2) A 3.5 3.0 36th cycle 58th cycle 100th cycle 2.5 2.0 0 10 20 30 40 Capacity (mAh) Figure 6. Electrochemical performance of the Li-Cl2@MOF pouch cell (A) The cycling stability of Li-Cl2 @MOF cell at a large areal capacity of 4.4 mAh/cm 2 . (B) Cycling performance and (C) voltage profiles of the Li-Cl 2 @MOF pouch cell with a charge capacity of 38 mAh at a current density of 150 mA/g. Scale bar in (B), 2 cm. optimizations are needed to enhance the practical energy density for widespread applications. EXPERIMENTAL PROCEDURES Resource availability Lead contact Further information and requests for resources and materials should be directed to and will be fulfilled by the lead contact, Wei Chen (Weichen1@ustc.edu.cn). Materials availability This study did not generate new unique materials. Synthesis of UiO-66-NH2. UiO-66-NH2 was synthesized according to a previously reported study.32 In brief, zirconium tetrachloride (ZrCl4, 1.5 g), 2-amino-1,4benzenedicarboxylic acid (NH2-BDC, 1.07 g), acetic acid (CH3COOH, 44 mL), and deionized water (7.5 mL) were added into dimethylformamide (DMF, 100 mL) and then reacted at 120 C for 15 min under vigorous stirring in an oil bath. The as-synthesized UiO-66-NH2 was washed with DMF and methanol in sequence. Finally, the resulting product, which is a yellow solid, was dried overnight at 60 C under vacuum. Preparation of electrolyte. The electrolyte was prepared according to a reported study by Zhu et al.4 Briefly, 1.088 g AlCl3 with 4 wt % LiTFSI and 4 wt % LiFSI were added into a 20 mL vial, and then 2 mL SOCl2 was added and stirred for 5 min. Finally, a light-yellow solution can be obtained. Li-Cl2@MOF coin cell assembly. The nonaqueous Li-Cl2@MOF coin-type battery was assembled in an Ar-filled glovebox with O2 and H2O concentrations under 0.3 ppm. Lithium foil was used as anode, and a volume of 100 mL electrolyte was added Joule 7, 515–528, March 15, 2023 525 ll with glass fiber separator. The cathodes were prepared by mixing 60 mg UiO-66NH2 MOF, 30 mg ketjenblack, and 10 mg poly(tetrafluoroethylene) (PTFE) dissolved in alcohol to form a slurry. The resulting slurry was uniformly drop casted onto Ni foam, and then the cathode was dried in an oven at 60 C for 12 h. The mass loading of the cathode active material is in the range of 0.7–5 mg/cm2. The electrochemical performance of the cells at low temperature and room temperature were tested on the Neware and Landt battery testing systems, respectively. Li-Cl2@MOF pouch cell assembly. The pouch cells were assembled in a dry room. The Ni foam substrate was used as the current collector for cathode and anode with an area of 20 cm2 (4.0 cm 3 5.0 cm). Ni tabs were welded with Ni foam by ultrasonic welding for 1.2 s. The slurry consisting of UiO-66-NH2 MOF, ketjenblack, and PTFE in a mass ratio of 6:3:1 was drop casted onto Ni foam and then dried in an oven at 60 C for 12 h. The mass loading of active material is in the range of 45–56 mg. Li foil was pressed onto the Ni foam directly. The glass fiber separator was cut into pieces of 5.0 cm 3 6.0 cm. The anode, separator, and cathode were stacked up in sequence, and insulating taps were applied to immobilize the electrodes. It is worth to mention that glass plates were placed between aluminum-plastic film and electrode to avoid any possible corrosion of the electrolyte to the aluminum-plastic film. Then the cell was transferred to an Ar-filled glovebox to inject electrolyte. 2.2 mL of electrolyte was added in each pouch cell, and it was finally heating sealed. Characterizations. Powder X-ray diffraction (PXRD) patterns were characterized by a Japan Rigaku MiniFlex 600 equipped with graphite-monochromated Cu Ka radiation. Scanning electron microscope (SEM, JEOL-6700F) was used to characterize the morphologies and EDX of pristine and cycled UiO-66-NH2 cathode. Valence state measurements were obtained by X-ray photoelectron spectroscopy (XPS) equipped with a monochromatic Al Ka source. Room temperature TEM characterizations were carried out using an Cs-corrected environmental transmission electron microscope (ETEM, FEI Titan G2) operated at 300 kV and all cryo-EM experiments were performed on the same instrument with a Fischione sample holder. Low-dose TEM characterizations were carried out using an Cs-corrected transmission electron microscope (FEI Titan) operated at 300 kV. The sample searching, the alignment of crystal zone axis, and prefocusing were performed at a 13,0003 magnification with a dose rate of about 0.03 e/Å2/s. The HRTEM images were obtained by utilizing a Gatan K3 direct-detection camera in the electron-counting mode. The total electron dose used for each image was controlled within 15 e/Å2 to avoid structural damage of the samples. The images were finely processed via CTF correction to be more directly interpretable. Theoretical calculations. Spin-polarized density functional theory calculations were performed by Vienna Ab-initio Simulation Package (VASP)33,34 using projector-augmented wave (PAW) pseudopotentials35 and Perdew-Burke-Ernzerhof (PBE) functional.36 Electrons in the states of (4s, 4p, 5s, and 4d) of Zr, (1s) of H, (2s and 2p) of C and O were considered valence electrons. The cutoff energy of the plane-wave basis was set to be 520 eV. Considering that the unit cells of Ui-66 with 440 atoms and Ui-66-NH2 with 488 atoms are extremely large, a part of the structure, which contains one benzene ring and two roundish Zr6O8(COO)12 clusters (Figure S2), was cut to investigate the adsorption of Cl. The cut site was passivated with additional H atoms. This part of structure was simulated in a 40 3 40 3 40 Å3 cubic box with enough vacuum region, and a single gamma k-point was used. There are 64 O, 30 C, 12 Zr, and 26 H atoms in the UiO-66 system, whereas one H on benzene ring was replaced by the –NH2 group in the UiO-66-NH2 system. The 526 Joule 7, 515–528, March 15, 2023 Article ll Article convergence for electronic energy and structural optimization was set to be 1E 5 eV and 0.02 eV/Å, respectively. Data and code availability The data and code presented in this work are available from the corresponding authors upon reasonable request. SUPPLEMENTAL INFORMATION Supplemental information can be found online at https://doi.org/10.1016/j.joule. 2023.02.010. ACKNOWLEDGMENTS The work was supported by the Fundamental Research Funds for the Central Universities (grant WK2060000040, KY2060000150, and 2022CDJXY-003), the China Postdoctoral Science Foundation (2021M693061), and the National Natural Science Foundation of China (21825302 and 22105028). We acknowledge the support from the USTC Center for Micro and Nanoscale Research and Fabrication, the USTC Supercomputer Center, and BL11U beamline in the National Synchrotron Radiation Laboratory (NSRL) in Hefei, China. AUTHOR CONTRIBUTIONS Y.X. and W.C. conceived the idea and designed the experiments. Y.X. performed the experiments of the main research and wrote the manuscript under the guidance of W.C. L.J. and H.-L.J. synthesized the MOF materials. J.M. and Z.L. performed the theoretical calculations. P.Z., Y.T., L.L., and Y.L. conducted and analyzed the TEM data. H.D., J.S., and M.W. participated in the discussion of the experimental details and the framework of the work. DECLARATION OF INTERESTS A patent application based on this work has been filed. Received: December 14, 2022 Revised: January 18, 2023 Accepted: February 15, 2023 Published: March 15, 2023 REFERENCES 1. Chu, S., and Majumdar, A. (2012). Opportunities and challenges for a sustainable energy future. 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