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2023, Vol. 79, No. 4　Online: 15 April 2023

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Synergic effect of covalent and chemical sulfur fixation enhancing the immobilization-conversion of polysulfides in lithium-sulfur batteries Ruili Gao, Qian Zhang, Hui Wang, Fanghui Wang, Jianwei Ren, Xuyun Wang, Xianguo Ma, Rongfang Wang 2023, 79(4): 1-11.  DOI: 10.1016/j.jechem.2022.12.042 Abstract ( 11 )   PDF (3175KB) ( 11 )   Lithium-sulfur batteries (LSBs) are promising as the next generation energy storage options. However, their wide applications have been technically challenged by the diffusion losses of polysulfides and poly-sulfide shuttle effect. In this work, the small organic molecules of 2,5-dichloropyrazine (2,5-DCP) were combined with Co-doped carbon (CoANAC) flakes to achieve the synergic effect of the covalent and chemical sulfur fixation, so as that the immobilization-conversion of polysulfides in LSBs was greatly enhanced. More specifically, the nucleophilic substitution of the 2,5-DCP additive in the electrolyte with polysulfides formed the CAS bonds. Through the further covalent N-Li bonds between the N atoms in 2,5-DCP and polysulfides, sulfur fixation was achieved in the form of solid organosulfur. Meanwhile, the CoANAC flakes served as the sulfur cathode to chemically anchor the polysulfides. The interaction mech-anism between CoANAC/2,5-DCP and polysulfides was explored by the density functional theory (DFT) calculations and in-situ infrared spectroscopy. The results showed that the optimal ‘‘with 2,5-DCP” sample-assembled LSB exhibited an initial discharge specific capacity of 1244 mA h g-1 at 0.2C, and a capacity decay rate of 0.053% per cycle was displayed after 800 cycles at 1C. The good cycling stability with a high sulfur-loaded electrode sample suggested that the synergic effect of covalent/chemical sulfur fixation enabled the enhancement of polysulfides immobilization-conversion in LSBs.

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A class of Ga-Al-P-based compounds with disordered lattice as advanced anode materials for Li-ion batteries Yanhong Li, Peixun Xiong, Lei Zhang, Songliu Yuan, Wenwu Li 2023, 79(4): 12-21.  DOI: 10.1016/j.jechem.2022.12.036 Abstract ( 8 )   PDF (10468KB) ( 3 )   Phosphides possess large reversible capacity, small voltage hysteresis, and high energy efficiency, thus promising to be new anode candidates to replace commercial graphite for Li-ion batteries (LIBs). Through a facile mechanochemistry method, we prepare a novel ternary phosphide of Ga0.5Al0.5P whose crystalline structure is determined to be a cation-disordered cubic zinc sulfide structure according to XRD refinement. As an anode for LIBs, the Ga0.5Al0.5P delivers a reversible capacity of 1,352 mA h g-1 at 100 mA g-1 with an initial Coulombic efficiency (ICE) up to 90.0% based on a reversible Li-storage mech-anism integrating intercalation and subsequent conversion processes as confirmed by various character-izations techniques including in-situ XRD, ex-situ Raman, and XPS and electrochemical characterizations. Graphite-modified Ga0.5Al0.5P exhibits a long-lasting cycling stability of retaining 1,182 mA h g-1 after 300 cycles at 100 mA g-1, and 625 mA h g-1 after 800 cycles at 2,000 mA g-1, and a high-rate perfor-mance of remaining 342 mA h g-1 at 20,000 mA g-1. The outstanding electrochemical performances can be attributed to enhanced reaction kinetics enabled by the capacitive behaviors and the faster Li-ion diffusion enabled by the cation-mixing. Importantly, by tuning the cationic ratio, we develop a novel series of cation-mixed compounds of Ga1/3Al2/3P, Ga1/4Al3/4P, Ga1/5Al4/5P, Ga2/3Al1/3P, Ga3/4Al1/4P, and Ga4/5Al1/5P, which demonstrate large capacity, high ICE, and suitable anode potentials. Broadly, these compounds with disordered lattices probably present novel physicochemical properties, and high elec-trochemical performances, thus providing a new perspective for new materials design.

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Synthesis of high density and low freezing point jet fuels range cycloalkanes with cyclopentanone and lignin-derived vanillins Xinghua Zhang, Miaojia Song, Jianguo Liu, Qi Zhang, Lungang Chen, Longlong Ma 2023, 79(4): 22-30.  DOI: 10.1016/j.jechem.2022.12.017 Abstract ( 18 )   PDF (1073KB) ( 7 )   In this work, a ‘‘cyclopentanone-vanillin” strategy was proposed for the preparation of jet fuel range cycloalkanes from lignocellulose-derived ketones and lignin-derived aldehydes via aldol condensation and hydrodeoxygenation (HDO). Ethanolamine lactate ionic liquid (LAIL) exhibited excellent catalytic activity in the aldol condensation of cyclopentanone and vanillin. Desired mono-condensation and bi-condensation products were obtained with yield of 95.2% at 100 °C. It is found that the synergy effects between amino group of ethanolamine and hydroxyl group of lactic acid play a key role in the aldol con-densation. The condensation products were converted into cycloalkanes by HDO over 5%Pd/Nb2O5 cata-lyst. The density of the obtained HDO products is 0.89 g/cm3 and the freezing point is lower than —60 °C. These results suggest that the resulted cycloalkanes can be used as additives to improve the density and low-temperature fluidity of the jet fuels.

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Creation of cytochrome P450 catalysis depending on a non-natural cofactor for fatty acid hydroxylation Qing Li, Xiaojia Guo, Xueying Wang, Junting Wang, Li Wan, Haizhao Xue, Zongbao K. Zhao 2023, 79(4): 31-36.  DOI: 10.1016/j.jechem.2022.12.021 Abstract ( 6 )   PDF (794KB) ( 4 )   Cytochrome P450 enzymes catalyze diverse oxidative transformations at the expense of reduced nicoti-namide adenine dinucleotide phosphate (NADPH), however, their applications remain limited largely because NADPH is cost-prohibitive for biocatalysis at scale yet tightly regulated in host cells. A highly challenging task for P450 catalysis has been to develop an alternative and biocompatible electron-donating system. Here we engineered P450 BM3 to favor reduced nicotinamide cytosine dinucleotide (NCDH) and created non-natural cofactor-dependent P450 catalysis. Two outstanding mutants were identified with over 640-fold NCDH preference improvement and good catalytic efficiencies of over 15,000 M-1 s-1 for the oxidation of the fatty acid probe 12-(para-nitrophenoxy)-dodecanoate. Molecular docking analysis indicated that these mutants bear a compacted cofactor entrance. Upon fus-ing with an NCD-dependent formate dehydrogenase, fused proteins functioned as NCDH-specific P450 catalysts by using formate as the electron donor. Importantly, these mutants and fusions catalyzed NCDH-dependent hydroxylation of fatty acids with similar chain length preference to those by natural P450 BM3 in the presence of NADPH and also similar regioselectivity for subterminal hydroxylation of lauric acid. As P450 BM3 and its variants are catalytically powerful to take diverse substrates and convey different reaction paths, our results offer an exciting opportunity to devise advanced cell factories that convey oxidative biocatalysis with an orthogonal reducing power supply system.

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Data-driven short circuit resistance estimation in battery safety issues Yikai Jia, Jun Xu 2023, 79(4): 37-44.  DOI: 10.1016/j.jechem.2022.12.035 Abstract ( 20 )   PDF (1367KB) ( 9 )   Developing precise and fast methods for short circuit detection is crucial for preventing or mitigating the risk of safety issues of lithium-ion batteries (LIBs). In this paper, we developed a Convolutional Neural Networks (CNN) based model that can quickly and precisely predict the short circuit resistance of LIB cells during various working conditions. Cycling tests of cells with an external short circuit (ESC) are pro-duced to obtain the database and generate the training/ testing samples. The samples are sequences of voltage, current, charging capacity, charging energy, total charging capacity, total charging energy with a length of 120 s and frequency of 1 Hz, and their corresponding short circuit resistances. A big database with ~6 × 105 samples are generated, covering various short circuit resistances (47 ~ 470 X), current loading modes (Constant current-constant voltage (CC-CV) and drive cycle), and electrochemical states (cycle numbers from 1 to 300). Results show that the average relative absolute error of five random sam-ple splits is 6.75 %±2.8 %. Further parametric analysis indicates the accuracy estimation benefits from the appropriate model setups: the optimized input sequence length (~120 s), feature selection (at least one total capacity-related variable), and rational model design, using multiple layers with different kernel sizes. This work highlights the capabilities of machine learning algorithms and data-driven methodolo-gies in real-time safety risk prediction for batteries.

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Deciphering the potassium storage phase conversion mechanism of phosphorus by combined solid-state NMR spectroscopy and density functional theory calculations Huixin Chen, Lingyi Meng, Hongjun Yue, Chengxin Peng, Qiaobao Zhang, Guiming Zhong, Ding Chen 2023, 79(4): 45-53.  DOI: 10.1016/j.jechem.2022.11.060 Abstract ( 9 )   PDF (2137KB) ( 4 )   Phosphorus is the potential anode material for emerging potassium-ion batteries (PIBs) owing to the highest specific capacity and relatively low operation plateau. However, the reversible delivered capac-ities of phosphorus-based anodes, in reality, are far from the theoretical capacity corresponding to the formation of K3P alloy. And, their underlying potassium storage mechanisms remain poorly understood. To address this issue, for the first time, we perform high-resolution solid-state 31P NMR combined with XRD measurements, and density functional theory calculations to yield a systemic quantitative under-standing of (de)potassiation reaction mechanism of phosphorus anode. We explicitly reveal a previously unknown asymmetrical nanocrystalline-to-amorphous transition process via rP↔(K3P11, K3P7, beta-K4P6)↔(alpha-K4P6)↔(K1—xP, KP, K4—xP3, K1+xP)↔(amorphous K4P3, amorphous K3P) that are proceed along with the electrochemical potassiation/depotassiation processes. Additionally, the corresponding K-P alloys intermediates, such as the amorphous phases of K4P3, K3P, and the nonstoichiometric phases of ‘‘K1—xP”, ‘‘K1+xP”, ‘‘K4—xP3” are experimentally detected, which indicating various complicated K-P alloy species are coexisted and evolved with the sluggish electrochemical reaction kinetics, resulting in lower capacity of phosphorus-based anodes. Our findings offer some insights into the specific multi-phase evo-lution mechanism of alloying anodes that may be generally involved in conversion-type electrode mate-rials for PIBs.

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Interpretable hybrid machine learning demystifies the degradation of practical lithium-sulfur batteries Zhi Wei Seh 2023, 79(4): 54-55.  DOI: 10.1016/j.jechem.2022.12.003 Abstract ( 7 )   PDF (323KB) ( 2 )

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Revealing the potential of apparent critical current density of Li/garnet interface with capacity perturbation strategy Zhihao Guo, Xinhai Li, Zhixing Wang, Huajun Guo, Wenjie Peng, Guangchao Li, Guochun Yan, Qihou Li, Jiexi Wang 2023, 79(4): 56-63.  DOI: 10.1016/j.jechem.2022.12.047 Abstract ( 5 )   PDF (1495KB) ( 4 )   Apparent critical current density (jaAC) of garnet all-solid-state lithium metal symmetric cells (ASSLSCs) is a fundamental parameter for designing all-solid-state lithium metal batteries. Nevertheless, how much the possible maximum apparent current density that a given ASSLSC system can endure and how to reveal this potential still require study. Herein, a capacity perturbation strategy aiming to better measure the possible maximum jaAC is proposed for the first time. With garnet-based plane-surface structure ASSLSCs as an exemplification, the jaAC is quite small when the capacity is dramatically large. Under a per-turbed capacity of 0.001 mA h cm-2, the jaAC is determined to be as high as 2.35 mA cm-2 at room tem-perature. This investigation demonstrates that the capacity perturbation strategy is a feasible strategy for measuring the possible maximum jaAC of Li/ solid electrolyte interface, and hopefully provides good refer-ences to explore the critical current density of other types of electrochemical systems.

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Sulfur vacancies-induced ‘‘Electron Bridge” in Ni4Mo/Sv-ZnxCd1-xS regulates electron transfer for efficient H2-releasing photocatalysis Xin Zhang, Manyi Gao, Longyu Qiu, Jie Sheng, Weiwei Yang, Yongsheng Yu 2023, 79(4): 64-71.  DOI: 10.1016/j.jechem.2023.01.001 Abstract ( 8 )   PDF (1857KB) ( 5 )   Despite the existence of plentiful photocatalyst heterojunctions, their separation efficiency and charge flow precision remain low on account of lacking interfacial modulation. Herein, through a defect-induced heterojunction constructing strategy, Ni4Mo alloys were in-situ grown on the unsaturated coordinated sulfur atoms of sulfur vacancies-rich ZCS (Sv-ZCS) via interfacial Ni-S covalent bonds. The experimental and theoretical results reveal that these unsaturated sulfur atoms induced by sulfur vacan-cies vastly facilitate to anchor more Ni-Mo nanoparticles and form abundant Ni-S covalent bonds, mean-while, these sulfur vacancies could form dual internal electric field (IEF) and work with Ni-S covalent bonds as ‘‘Electron Bridge” to further accelerate photoelectrons transfer, as well as promote the activation of water molecules and the desorption of hydrogen proton. Accordingly, the optimized Ni4Mo/Sv-ZCS composite achieves an improved photocatalytic hydrogen evolution (PHE) rate of 94.69 mmol h-1 g-1 without an evident decrease after 6 cycles of photocatalytic tests, which is 21.2 and 1.94 times higher than those of Pt/ZCS and Ni4Mo/ZCS, respectively. This tactic opens a new way for optimizing ZnxCd1-xS-based heterojunctions by constructing sulfur vacancies and covalent bonds as ‘‘Electron Bridge” to enhance the activity of PHE.

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Anomalous metastable hcp Ni nanocatalyst induced by non-metal N doping enables promoted ammonia borane dehydrogenation Ping Li, Yuqi Huang, Quhua Huang, Ran Chen, Jixin Li, Shuanghong Tian 2023, 79(4): 72-82.  DOI: 10.1016/j.jechem.2022.12.048 Abstract ( 4 )   PDF (3405KB) ( 2 )   Developing high-performing non-noble transition metal catalysts for H2 evolution from chemical hydro-gen storage materials is of great significance for the hydrogen economy system, yet challenging. Herein, we present for the first time that anomalous metastable hexagonal close-packed Ni nanoparticles induced by heteroatom N doping encapsulated in carbon (N-hcp-Ni/C) can exhibit admirable catalytic performance for ammonia borane (AB) dehydrogenation, prominently outperforming conventional fcc Ni counterpart with similar morphology and favorably presenting the state-of-the-art level. Comprehensive experimental and theoretical studies unravel that unusual hcp phase engineering of Ni together with N doping could induce charge redistribution and modulate electronic structure, thereby facilitating H2O adsorption and expediting H2O dissociation (rate-determining step). As a result, AB dehy-drogenation can be substantially boosted with the assistance of N-hcp-Ni/C. Our proposed strategy high-lights that unconventional crystal phase engineering coupled with non-metal heteroatom doping is a promising avenue to construct advanced transition metal catalysts for future renewable energy technologies.

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Photoinduced Cu+/Cu2+ interconversion for enhancing energy conversion and storage performances of CuO based Li-ion battery Qiuman Zhang, Meng Wei, Qianwen Dong, Qiongzhi Gao, Xin Cai, Shengsen Zhang, Teng Yuan, Feng Peng, Yueping Fang, Siyuan Yang 2023, 79(4): 83-91.  DOI: 10.1016/j.jechem.2022.11.029 Abstract ( 16 )   PDF (2390KB) ( 7 )   Pursuing appropriate photo-active Li-ion storage materials and understanding their basic energy stor-age/conversion principle are pretty crucial for the rapidly developing photoassisted Li-ion batteries (PA-LIBs). Copper oxide (CuO) is one of the most popular candidates in both LIBs and photocatalysis. While CuO based PA-LIBs have never been reported yet. Herein, one-dimensional (1D) CuO nanowire arrays in situ grown on a three-dimensional (3D) copper foam support were employed as dual-functional photoanode for both ‘solar-to-electricity’ and ‘electricity-to-chemical’ energy conversion in the PA-LIBs. It is found that light energy can be indeed stored and converted into electrical energy through the assembled CuO based PA-LIBs. Without external power source, the photo conversion effi-ciency of CuO based photocell reaches about 0.34%. Impressively, at a high current density of 4000 mA g-1, photoassisted discharge and charge specific capacity of CuO based PA-LIBs respectively receive 64.01% and 60.35% enhancement compared with the net electric charging and discharging pro-cess. Mechanism investigation reveals that photogenerated charges from CuO promote the interconver-sion between Cu2+ and Cu+ during the discharging/charging process, thus forcing the lithium storage reaction more completely and increasing the specific capacity of the PA-LIBs. This work can provide a general principle for the development of other high-efficient semiconductor-based PA-LIBs.

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Fiber swelling to improve cycle performance of paper-based separator for lithium-ion batteries application Zhenghao Li, Wei Wang, Xinmiao Liang, Jianlin Wang, Yonglin Xu, Wei Li 2023, 79(4): 92-100.  DOI: 10.1016/j.jechem.2022.08.030 Abstract ( 8 )   PDF (2520KB) ( 3 )   It is well established that paper-based separators display short-circuit risk in lithium-ion batteries due to their intrinsic micron-sized pores. In this research, we have adjusted pore structure of paper by fiber swelling in liquid electrolyte. Specifically, the paper-based separator is prepared by propionylated sisal fibers through a wet papermaking process. Scanning electron microscope (SEM) and multi-range X-ray nano-computed tomography (CT) images display strong swelling of modified fibers after electrolyte absorption, which can effectively decrease the pore size of separator. Due to the high electrolyte uptake (817 wt%), paper-based separator exhibits ionic conductivity of 2.93 mS cm-1. 7Li solid-state NMR spec-troscopy and Gaussian simulation reveal that the formation of local high Li+ ion concentration in the sep-arator and its low absorption energy with Li+ ion (62.2 kcal mol-1) is conducive to the ionic transportation. In particular, the assembled Li/separator/LiFePO4 cell displays wide electrochemical sta-bility window (5.2 V) and excellent cycle performance (capacity retention of 96.6% after 100 cycles at 0.5 C) due to the reduced side reactions as well as enhanced electrolyte absorption and retention capacity by propionylation. Our proposed strategy will provide a novel perspective to design high-performance bio-based separators to boost the development of clean and sustainable energy economy.

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Interlayer and intralayer co-modified flexible V2CTX MXene@SWCNT films for high-power Li-ion capacitors Wanli Wang, Min Feng, Enze Hu, Zhaowei Hu, Cheng Fan, Huifang Li, Peng Wang, Xiaojun Wang, Zhiming Liu 2023, 79(4): 101-109.  DOI: 10.1016/j.jechem.2022.08.034 Abstract ( 5 )   PDF (1740KB) ( 2 )   As an emerging member of the two-dimensional (2D) material family, V2CTX MXene shows great poten-tial in the application of lithium-ion capacitors (LICs) due to its unique structure and excellent electrical conductivity. However, severe nanosheets stacking and intra-layer transport barriers have limited the further development of V2CTX MXene-based materials. Herein, we prepared K+ ions and -O functional group co-modified V2CTX MXene (VCT-K) and further incorporated it with single-walled carbon nanotube (SWCNT), obtaining freestanding V2CTX composite films (VCT-K@C) with the 3D conductive network. Significantly, K+ ions were introduced into V2CTX MXene to stabilize the interlayer structure and prevent the aggregation of nanosheets, the terminal group of -O was controllably modified on the surface of MXene to improve the Li+ ions storage reversible capacities and the SWCNT acted as the bridge between MXene nanosheets to opens up the channels for ion/electron transportation in the longitudinal direction. Benefited from the synergistic effect of VCT-K and SWCNT, the VCT-K@C exhibits superior reversible specific capacities of 671.8 mA h g-1 at 0.1 A g-1 and 318 mA h g-1 at 1.0 A g-1. Furthermore, the assem-bled LICs with VCT-K@C anode coupling activated carbon (AC) cathode deliver an outstanding power den-sity of 19.0 kW kg-1 at 67.4 Wh kg-1, a high energy density of 140.5 Wh kg-1 at 94.8 W kg-1 and a stable capacitance retention of 86% after 6000 cycles at 10 A g-1. Such unique structures and excellent electro-chemical properties are expected to pave the way for the large-scale application in LICs of MXene-based materials.

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Durable semi-crystalline interphase engineering to stabilize high voltage Ni-rich cathode in dilute ether electrolyte Zhuangzhuang Cui, Shunqiang Chen, Qingshun Nian, Yecheng Li, Yawei Chen, Bing-Qing Xiong, Zihong Wang, Zixu He, Shuhong Jiao, Xiaodi Ren 2023, 79(4): 110-117.  DOI: 10.1016/j.jechem.2022.12.049 Abstract ( 5 )   PDF (2771KB) ( 2 )   Ethers are promising electrolyte solvents for secondary Li metal batteries because of their excellent reduction stability. However, their oxidation stability has been mostly relying on the high concentration approach, and limited progress has been made on building effective interphase to protect the cathode from the corrosion of the electrolyte. In this work, we construct a semi-crystalline interfacial layer on the surface of Li(Ni0.8Co0.1Mn0.1)O2 cathode that can achieve improved electrochemical stability in the highly corrosive chemical environment formed by the decomposition of ether molecules. Different from traditional brittle crystalline interphases, the optimized semi-crystalline layer with low modulus and high ionic conductivity can effectively relieve electrode strain and maintain the integrity of the interface layer. Due to this design, the continuous oxidation decomposition of ether-based electrolytes could be significantly suppressed and the battery shows outstanding cycling stability (84% capacity retention after 300 cycles). This article provides a solution to address the oxidation instability issue of ether-based electrolytes.

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Recycling of spent lithium-ion batteries as a sustainable solution to obtain raw materials for different applications V.M. Leal, J.S. Ribeiro, E.L.D. Coelho, M.B.J.G. Freitas 2023, 79(4): 118-134.  DOI: 10.1016/j.jechem.2022.08.005 Abstract ( 12 )   PDF (1960KB) ( 11 )   Lithium-ion batteries (LIBs) containing graphite as anode material and LiCoO2, LiMn2O4, and LiNixMnyCozO2 as cathode materials are the most used worldwide because of their high energy density, capacitance, dura-bility, and safety. However, such widespread use implies the generation of large amounts of electronic waste. It is estimated that more than 11 million ton of LIBs waste will have been generated by 2030. Battery recycling can contribute to minimizing environmental contamination and reducing production costs through the recovery of high-value raw materials such as lithium, cobalt, and nickel. The most com-mon processes used to recycle spent LIBs are pyrometallurgical, biometallurgical, and hydrometallurgical. Given the current scenario, it is necessary to develop environmentally friendly methods to recycle batteries and synthesize materials with multiple technological applications. This study presents a review of indus-trial and laboratory processes for recycling spent LIBs and producing materials that can be used in new bat-teries, energy storage devices, electrochemical sensors, and photocatalytic reactions.

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Promoting and controlling electron transfer of furfural oxidation efficiently harvest electricity, furoic acid, hydrogen gas and hydrogen peroxide Denghao Ouyang, Daihong Gao, Jinpeng Hong, Zhao Jiang, Xuebing Zhao 2023, 79(4): 135-147.  DOI: 10.1016/j.jechem.2022.10.036 Abstract ( 10 )   PDF (2176KB) ( 5 )   Conventional chemical oxidation of aldehydes such as furfural to corresponding acids by molecular oxy-gen usually needs high pressure to increase the solubility of oxygen in aqueous phase, while electro-chemical oxidation needs input of external electric energy. Herein, we developed a liquid flow fuel cell (LFFC) system to achieve oxidation of furfural in anode for furoic acid production with co-production of hydrogen gas. By controlling the electron transfer in cathode for reduction of oxygen, efficient gener-ation of electricity or production of H2O2 were achieved. Metal oxides especially Ag2O have been screened as the efficient catalyst to promote the oxidation of aldehydes, while liquid redox couples were used for promoting the kinetics of oxygen reduction. A novel alkaline-acidic asymmetric design was also used for anolyte and catholyte, respectively, to promote the efficiency of electron transfer. Such an LFFC system achieves efficient conversion of chemical energy of aldehyde oxidation to electric energy and makes full use the transferred electrons for high-value added products without input of external energy. With (VO2)2SO4 as the electron carrier in catholyte for four-electron reduction of oxygen, the peak output power density (Pmax) at room temperature reached 261 mW/cm2 with furoic acid and H2 yields of 90% and 0.10 mol/mol furfural, respectively. With anthraquinone-2-sulfonate (AQS) as the cathodic electron carrier, Pmax of 60 mW/cm2 and furoic acid, H2 and H2O2 yields of 0.88, 0.15 and 0.41 mol/mol furfural were achieved, respectively. A new reaction mechanism on furfural oxidation on Ag2O anode was pro-posed, referring to one-electron and two-electron reaction pathways depending on the fate of adsorbed hydrogen atom transferred from furfural aldehyde group.

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Selenium-doped cathode materials with polyaniline skeleton for lithium-organosulfur batteries Rong Zou, Wenwu Liu, Fen Ran 2023, 79(4): 148-157.  DOI: 10.1016/j.jechem.2022.12.027 Abstract ( 5 )   PDF (2541KB) ( 2 )   Sulfur-containing polymer (SCP) is considered as an outstanding cathode material for lithium-sulfur bat-teries. However, undesirable soluble polysulfides may shuttle in electrolyte, concluding long-chain Li2Sn (n > 4) and short-chain Li2Sn (n ≤ 4), as well as the sluggish conversion kinetics are yet to be solved to enhance the performance of lithium-sulfur batteries. Here Se-doped sulfurized polyaniline with adjusted sulfur-chain —Sx— (x ≤ 6) contribute to ensure the absence of long-chain polysulfides, and the skeleton with quinoid imine can endow strongly adsorption towards short-chain polysulfides by the reversible transition between deprotonated/protonated imine (—NH+ = and —N =), which offer double insurance against suppressing ‘‘shuttle effect”. Furthermore, Se atoms are doped into sulfurized polysulfides to accelerate the redox conversion and take a frontier orbital theory-oriented view into catalytic mecha-nism. Se-doped sulfurized polyaniline as active materials for lithium-organosulfur batteries delivers good electrochemical performance, including high rate, reversible specific capacity (680 mA h g-1 at 0.1 A g-1), and lower capacity decay rate only of 0.15% with near 100% coulomb efficiency during long-term cycle. This work provides a valuable guiding ideology and promising solution for the chemistry-oriented struc-ture design and practical application for lithium-organosulfur batteries.

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Dual-functional marigold-like ZnxCd1-xS homojunction for selective glucose photoreforming with remarkable H2 coproduction Fuyan Kang, Cai Shi, Yeling Zhu, Malin Eqi, Junming Shi, Min Teng, Zhanhua Huang, Chuanling Si, Feng Jiang, Jinguang Hu 2023, 79(4): 158-167.  DOI: 10.1016/j.jechem.2022.11.043 Abstract ( 11 )   PDF (2645KB) ( 2 )   The global commitment to pivoting to sustainable energy and products calls for technology development to utilize solar energy for hydrogen (H2) and value-added chemicals production by biomass photoreform-ing. Herein, a novel dual-functional marigold-like ZnxCd1-xS homojunction has been the production of lac-tic acid with high-yield and H2 with high-efficiency by selective glucose photoreforming. The optimized Zn0.3Cd0.7S exhibits outstanding H2 generation (13.64 mmol h-1 g-1), glucose conversion (96.40%), and lactic acid yield (76.80%), over 272.80 and 19.21 times higher than that of bare ZnS (0.05 mmol h-1 g-1) and CdS (0.71 mmol h-1 g-1) in H2 generation, respectively. The marigold-like morphology provides abundant active sites and sufficient substrates accessibility for the photocatalyst, while the specific role of the homojunction formed by hexagonal wurtzite (WZ) and cubic zinc blende (ZB) in photoreforming biomass has been demonstrated by density functional theory (DFT) calculations. Glucose is converted to lactic acid on the WZ surface of Zn0.3Cd0.7S via the photoactive species .O-2, while the H2 is evolved from protons (H+) in H2O on the ZB surface of Zn0.3Cd0.7S. This work paves a promising road for the production of sustainable energy and products by integrating photocatalysis and biorefine.

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Recent progress of inverted organic-inorganic halide perovskite solar cells Dongyang Li, Yulan Huang, Zhiwei Ren, Abbas Amini, Aleksandra B. Djurišić, Chun Cheng, Gang Li 2023, 79(4): 168-191.  DOI: 10.1016/j.jechem.2022.12.029 Abstract ( 64 )   PDF (6406KB) ( 36 )   In recent years, inverted perovskite solar cells (IPSCs) have attracted significant attention due to their low-temperature and cost-effective fabrication processes, hysteresis-free properties, excellent stability, and wide application. The efficiency gap between IPSCs and regular structures has shrunk to less than 1%. Over the past few years, IPSC research has mainly focused on optimizing power conversion efficiency to accelerate the development of IPSCs. This review provides an overview of recent improvements in the efficiency of IPSCs, including interface engineering and novel film production techniques to overcome critical obstacles. Tandem and integrated applications of IPSCs are also summarized. Furthermore, pro-spects for further development of IPSCs are discussed, including the development of new materials, methods, and device structures for novel IPSCs to meet the requirements of commercialization.

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Heteroatom dopant strategy triggered high-potential plateau to non- graphitized carbon with highly disordered microstructure for high- performance sodium ion storage Peilin Zhang, Chen Huang, Mingzhen Xiu, Siyu Zhu, Weiwei Wang, Bo Zhu, Likang Qin, Yizhong Huang, Luyang Chen 2023, 79(4): 192-200.  DOI: 10.1016/j.jechem.2022.12.025 Abstract ( 10 )   PDF (2775KB) ( 6 )   Non-graphitized carbon (NGC) has been extensively utilized as carbonaceous anode in sodium-ion bat-teries (SIBs). However, more optimization to achieve competitive capacity and stability is still challenging for SIBs. In the study, the dopant strategy is utilized to construct nitrogen/sulfur-doped non-graphitized carbon (N-NGC or S-NGC) shell decorated on three-dimensional graphene foam (GF) as a self-support electrode. The highly disordered microstructures of heteroatom doped carbons are produced by applying a low-temperature pyrolysis treatment to precursors containing nitrogen and sulfur. The DFT calculations of Na-ion adsorption energies at diverse heteroatom sites show marginal-S, pyrrolic N and pyridinic N with more intensive Na-ion adsorption ability than middle-S, C@O and pristine carbon. The N-NGC with dominant small graphitic regions delivers adsorption ability to Na-ion, while the S-NGC with significant single carbon lattice stripes demonstrates redox reaction with Na-ion. Evidently, in comparison with only adsorption-driven slope regions at high potential for N-NGC, the redox reaction-generated potential-plateau enables non-graphitized S-NGC superior discharge/charge capacity and cycle-stability in the slope region. This work could provide deep insight into the rational design of non-graphitized carbon with rich microstructure and composition.

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Moderately concentrated electrolyte enabling high-performance lithium metal batteries with a wide working temperature range Sisi Wang, Zhichen Xue, Fulu Chu, Zengqiang Guan, Jie Lei, Feixiang Wu 2023, 79(4): 201-210.  DOI: 10.1016/j.jechem.2022.12.060 Abstract ( 9 )   PDF (2018KB) ( 7 )   The electrolyte integrated with lithium metal anodes is subjected to the issues of interfacial compatibility and stability, which strongly influence the performances of high-energy lithium metal batteries. Here, we report a new electrolyte recipe viz. a moderately concentrated electrolyte comprising of 2.4 M lithium bis (fluorosulfonyl)imide (LiFSI) in a cosolvent mixture of fluorinated ethylene carbonate (FEC) and dimethyl carbonate (DMC) with relatively high ion conductivity. Owing to the preferential decomposition of LiFSI and FEC, an inorganic-rich interphase with abundant Li2O and LiF nanocrystals is formed on lithium metal with improved robustness and ion transfer kinetics, enabling lithium plating/stripping with an extremely low overpotential of ~ 8 mV and the average CE of 97%. When tested in Li||LiFePO4 cell, this electrolyte provides long-term cycling with a capacity retention of 98.3% after 1000 cycles at 1 C and an excellent rate performance of 20 C, as well as an areal capacity of 1.35 mA h cm-2 at the cathode areal loading of 9 mg cm-2. Moreover, the Li||LiFePO4 cell exhibits excellent wide-temperature performances (-40 ~ 60 ℃), including long-term cycling stability over 2600 cycles without visible capacity fading at 0 ℃, as well as extremely high average CEs of 99.6% and 99.8% over 400 cycles under —20 ℃ and 45 ℃.

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Battery impedance spectrum prediction from partial charging voltage curve by machine learning Jia Guo, Yunhong Che, Kjeld Pedersen, Daniel-Ioan Stroe 2023, 79(4): 211-221.  DOI: 10.1016/j.jechem.2023.01.004 Abstract ( 10 )   PDF (2188KB) ( 4 )   Electrochemical impedance spectroscopy (EIS) is an effective technique for Lithium-ion battery state of health diagnosis, and the impedance spectrum prediction by battery charging curve is expected to enable battery impedance testing during vehicle operation. However, the mechanistic relationship between charging curves and impedance spectrum remains unclear, which hinders the development as well as optimization of EIS-based prediction techniques. In this paper, we predicted the impedance spectrum by the battery charging voltage curve and optimized the input based on electrochemical mechanistic analysis and machine learning. The internal electrochemical relationships between the charging curve, incremental capacity curve, and the impedance spectrum are explored, which improves the physical interpretability for this prediction and helps define the proper partial voltage range for the input for machine learning models. Different machine learning algorithms have been adopted for the verification of the proposed framework based on the sequence-to-sequence predictions. In addition, the predictions with different partial voltage ranges, at different state of charge, and with different training data ratio are evaluated to prove the proposed method have high generalization and robustness. The experimental results show that the proper partial voltage range has high accuracy and converges to the findings of the electrochemical analysis. The predicted errors for impedance spectrum are less than 1.9 mΩ with the proper partial voltage range selected by the corelative analysis of the electrochemical reactions inside the batteries. Even with the voltage range reduced to 3.65-3.75 V, the predictions are still reliable with most RMSEs less than 4 mΩ.

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Heterogeneous isomorphism hollow SiGe nanospheres with porous carbon reinforcing for superior electrochemical lithium storage Peibo Gao, Huimin Wu, Wenhao Liu, Shuang Tian, Jinglin Mu, Zhichao Miao, Pengfei Zhou, Huanian Zhang, Tong Zhou, Jin Zhou 2023, 79(4): 222-231.  DOI: 10.1016/j.jechem.2022.12.001 Abstract ( 7 )   PDF (2641KB) ( 4 )   Silicon is emerging as a promising next-generation lithium-ion battery anode because of its high theoret-ical capacity and low cost. However, the poor cyclability and inferior rate performance hinder its large-scale applications. Here, hollow silicon/germanium (H-SiGe) nanospheres with a binary-active compo-nent and heterogeneous structure combined with porous carbon (pC) reinforcing are synthesized as lithium-ion battery anodes. Experimental studies demonstrate that the H-SiGe/pC anodes possess tiny volume expansion, high ion/electron conductivity, and stable electrode interface. Theoretical calculations confirm that through the replacement of Si using Ge with rational component control, the diffusion energy barrier of lithium will be reduced and lithium storage ability can be improved because of the slight charge polarization. Benefiting from these unique merits, the H-SiGe/pC anodes display a high ini-tial specific capacity of 2922.2 mA h g-1 at 0.1 A g-1, superior rate capability (59.4% capacity retention from 0.5 to 8 A g-1), and excellent cycling stability (81% retention after 700 cycles at 5 A g-1 at 1.0-1.2 mg cm-2). An outstanding stability is preserved even at a high loading of 3.2 mg cm-2 with an improved reversible capacity of 429.1 mA h g-1 after 500 cycles at 4 A g-1. Furthermore, the full-cell with the prelithiated H-SiGe/pC anode and LiFePO4 cathode exhibits an impressive capacity performance.

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Electrode structure enabling dendrite inhibition for high cycle stability quasi-solid-state lithium metal batteries Kaiming Wang, Ao Yu, Zhiyi Zhou, Fei Shen, Manni Li, Liang Zhang, Weichang Guo, Yifei Chen, Le Shi, Xiaogang Han 2023, 79(4): 232-241.  DOI: 10.1016/j.jechem.2022.12.009 Abstract ( 9 )   PDF (3247KB) ( 4 )   ithium (Li) metal batteries (LMBs) are widely regarded as the ultimate choice for the next generation of high-energy-density batteries. However, the uncontrollable growth of Li dendrites formed by inhomoge-neous deposition seriously hinders its commercialization. Although many studies have achieved signifi-cant results in inhibiting the formation of Li dendrites, it is still impossible to eradicate them completely. Therefore, regulating the deposition behavior, such as the growth direction of unevenly deposited Li, is preferable to unilaterally suppressing them in some cases. Here we report a structured anode that can confine the deposited Li within holes and tune it to become vertical-up/horizontal-centripetal mixed growth mode by optimizing the electric field/Li+ concentration gradient. The Li+ adsorbed by the poly (amic acid) (PAA) insulating layer coated on the anode surface can form the Li+ concentration gradient pointing to the center of the hole. Combined with the special electric field formed by the hole structure, it is favorable for the Li+ to move into the vertically arrayed holes and simultaneously deposit on the bot-tom and walls. Furthermore, both in-situ and ex-situ observations confirm that the growth mode is chan-ged and the Li deposition morphology is denser, which can greatly delay capacity fading and prolong cycle life in both liquid and quasi-solid-state LMBs. All the results show that the novel anode provides a new perspective for deep research into solid-state LMBs.

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Optimization of perovskite/carbon interface performance using N-doped coal-based graphene quantum dots and its mechanism analysis Qixu Hu, Xiaoyu Yang, Ying Qi, Peng Wei, Jian Cheng, Yahong Xie 2023, 79(4): 242-252.  DOI: 10.1016/j.jechem.2022.12.014 Abstract ( 9 )   PDF (2936KB) ( 6 )   Optimizing the interfacial properties between perovskite and carbon electrodes has always been an important way to improve the photoelectric conversion efficiency (PCE) of carbon-based perovskite solar cells (C-PSCs) and facilitate their commercialization. In this paper, nitrogen-doped graphene quantum dots (N-GQDs) with fluorescent properties were successfully prepared using inexpensive coal as raw material by a facile and environmentally friendly chemical reagent oxidation. The results show that the electron-rich pyridinic nitrogen in N-GQDs can act as Lewis bases to form coordination bonds with uncoordinated lead ions by sharing electron pairs, thereby reducing the defect density and nonradiative recombination of photo-generated electron-hole, and extending lifetime of charge carriers. In addition, due to the passivation of N-GQDs, the hysteresis effect of the device is significantly reduced and the long-term stability is also improved. By optimizing the concentration, the PCE of C-PSCs achieved a max-imum of 14.31%, which was improved by 20.25% compared with 11.90% of the pristine C-PSCs. This work provides a facile, environmentally friendly and efficient strategy for improving the overall performance of C-PSCs using inexpensive coal-based N-GQDs.

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In situ formed cross-linked polymer networks as dual-functional layers for high-stable lithium metal batteries Lei Shi, Wanhui Wang, Chunjuan Wang, Yang Zhou, Yuezhan Feng, Tiekun Jia, Fang Wang, Zhiyu Min, Ji Hu, Zhigang Xue 2023, 79(4): 253-262.  DOI: 10.1016/j.jechem.2022.12.007 Abstract ( 17 )   PDF (1933KB) ( 6 )   Lithium-metal anodes (LMAs) have been recognized as the ultimate anodes for next-generation batteries with high energy density, but stringent assembly-environment conditions derived from the poor moisture stability dramatically hinder the transformation of LMAs from laboratory to industry. Herein, an in situ formed cross-linked polymer layer on LMAs is designed and constructed by a facile thiol-acrylate click chemistry reaction between poly(ethylene glycol) diacrylate (PEGDA) and the crosslinker containing multi thiol groups under UV irradiation. Owing to the hydrophobic nature of the layer, the treated LMAs demon-strate remarkable humid stability for more than 3 h in ambient air (70% relative humidity). The coating humid-resistant protective layer also possesses a dual-functional characterization as solid polymer elec-trolytes by introducing lithium bis(trifluoromethanesulfonyl)imide in the system in advance. The intimate contact between the polymer layer and LMAs reduces interfacial resistance in the assembled Li/LiFePO4 or Li/LiNi0.8Co0.1Mn0.1O2 full cell effectively, and endows the cell with an outstanding cycle performance.

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In-situ constructing Cu1Bi1 bimetallic catalyst to promote the electroreduction of CO2 to formate by synergistic electronic and geometric effects Houan Ren, Xiaoyu Wang, Xiaomei Zhou, Teng Wang, Yuping Liu, Cai Wang, Qingxin Guan, Wei Li 2023, 79(4): 263-271.  DOI: 10.1016/j.jechem.2023.01.017 Abstract ( 5 )   PDF (2258KB) ( 3 )   Electrochemical CO2 reduction to formate is a potential approach to achieving global carbon neutrality. Here, Cu1Bi1 bimetallic catalyst was prepared by a co-precipitation method. It has a ginger like composite structure (CuO/CuBi2O4) and exhibited a high formate faradaic efficiency of 98.07% at -0.98 V and a large current density of -56.12 mA cm-2 at -1.28 V, which is twice as high as Bi2O3 catalyst. Especially, high selectivity (FE-HCOO > 85%) is maintained over a wide potential window of 500 mV. In-situ Raman mea-surements and structure characterization revealed that the reduced Cu1Bi1 bimetallic catalyst possesses abundant Cu-Bi interfaces and residual Bi-O structures. The abundant Cu-Bi interface structures on the catalyst surface can provide abundant active sites for CO2RR, while the Bi-O structures may stabilize the CO2*- intermediate. The synergistic effect of abundant Cu-Bi interfaces and Bi-O species promotes the efficient synthesis of formate by following the OCHO* pathway.

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In situ formed LiF-Li3N interface layer enables ultra-stable sulfide electrolyte-based all-solid-state lithium batteries Ming Wu, Mengqi Li, Yuming Jin, Xinshuang Chang, Xiaolei Zhao, Zhi Gu, Gaozhan Liu, Xiayin Yao 2023, 79(4): 272-278.  DOI: 10.1016/j.jechem.2023.01.007 Abstract ( 33 )   PDF (2243KB) ( 10 )   Sulfide solid electrolytes are promising for high energy density and safety in all-solid-state batteries due to their high ionic conductivity and good mechanical properties. However, the application of sulfide solid electrolytes in all-solid-state batteries with lithium anode is restricted by the side reactions at lithium/ electrolytes interfaces and the growth of lithium dendrite caused by nonuniform lithium deposition. Herein, a homogeneous LiF-Li3N composite protective layer is in situ formed via a manipulated reaction of pentafluorobenzamide with Li metal. The LiF-Li3N layer with both high interfacial energy and interfa-cial adhesion energy can synergistically suppress side reactions and inhibit the growth of lithium den-drite, achieving uniform deposition of lithium. The critical current densities of Li10GeP2S12 and Li6PS5Cl are increased to 3.25 and 1.25 mA cm-2 with Li@LiF-Li3N layer, which are almost triple and twice as those of Li-symmetric cells in the absence of protection layer, respectively. Moreover, the Li@LiF-Li3N/ Li10GeP2S12/Li@LiF-Li3N cell can stably cycle for 9000 h at 0.1 mA cm-2 under 0.1 mA h cm-2, and Li@LiF-Li3N/Li6PS5Cl/Li@LiF-Li3N cell achieves stable Li plating/stripping for 8000 h at 0.1 mA cm-2 under 10 mA h cm-2. The improved dynamic stability of lithium plating/stripping in Li@LiF-Li3N/Li10GeP2S12 or Li6PS5Cl interfaces is proved by three-electrode cells. As a result, LiCoO2/electrolytes/Li@LiF-Li3N batteries with Li10GeP2S12 and Li6PS5Cl exhibit remarkable cycling stability of 500 cycles with capacity retentions of 93.5% and 89.2% at 1 C, respectively.

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Monodispersed ultrathin twisty PdBi alloys nanowires assemblies with tensile strain enhance C2+ alcohols electrooxidation Xianzhuo Lao, Ze Li, Likang Yang, Ben Zhang, Wanneng Ye, Aiping Fu, Peizhi Guo 2023, 79(4): 279-290.  DOI: 10.1016/j.jechem.2022.12.056 Abstract ( 6 )   PDF (3256KB) ( 4 )   Direct alcohol fuel cells (DAFCs) are powered by the alcohol electro-oxidation reaction (AOR), where an electrocatalyst with an optimal electronic structure can accelerate the sluggish AOR. Interestingly, strain engineering in hetero-catalysis offers a promising route to boost their catalytic activity. Herein, we report on a class of monodispersed ultrathin twisty PdBi alloy nanowires (TNWs) assemblies with face-centered structures that drive AORs. These thin nanowire structures expose a large number of reactive sites. Strikingly, Pd6Bi1 TNWs show an excellent current density of 2066, 3047, and 1231 mA mg-1 for oxida-tion of ethanol, ethylene glycol, and glycerol, respectively. The ‘‘volcano-like” behaviors observed on PdBi TNWs for AORs indicate that the maximum catalytic mass activity is a well balance between active inter-mediates and blocking species at the interface. This study offers an effective and universal method to build novel nanocatalysts in various applications by rationally designing highly efficient catalysts with specific strain.

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Pressure-induced growth of coralloid-like FeF2 nanocrystals to enable high-performance conversion cathode Yulin Xu, Wenjing Xiong, Jiaqi Huang, Xinglin Tang, Hongqiang Wang, Wei Liu, Dan Xiao, Yong Guo, Yongzhi Zhang 2023, 79(4): 291-300.  DOI: 10.1016/j.jechem.2023.01.006 Abstract ( 7 )   PDF (2461KB) ( 5 )   Fluoride ferrous (FeF2) is viewed as a promising conversion cathode material for next-generation lithium-ion batteries (LIBs) due to its high theoretical specific capacity and low cost. Unfortunately, issues such as poor intrinsic conductivity, iron dissolution, and phase separation hinder the application of FeF2 in high-energy cathodes. Here, a pressure-induced morphology control method is designed to prepare coralloid-like FeF2 nanocrystals with nitrogen-rich carbon coating (c-FeF2@NC). The coralloid-like interconnected crystal structure of c-FeF2@NC contributes to reducing interfacial resistance and enhancing the topotactic transformation during the conversion reaction, and the nitrogen-rich carbon (NC) coating can enhance interfacial stability and kinetic performance. When used as a conversion cathode for LIBs, c-FeF2@NC exhibits a high initial reversible capacity of 503.57 mA h g-1 and excellent cycling stability of 497.61 mA h g-1 with a low capacity decay of 1.19 % over 50 cycles at 0.1 A/g. Even at 1 A/g, a stable capacity of 263.78 mA h g-1 can still be retained after 200 cycles. The capability of c-FeF2@NC as a con-version cathode for sodium-ion batteries (SIBs) was also evaluated to expand its field of application. Furthermore, two kinds of full batteries have been assembled by employing c-FeF2@NC as cathodes and quantitative limited-Li (LLi) and pre-lithiated reduced graphene oxide (PGO) as anodes, respectively, to envisage the feasibility of practical applications of conversion materials.

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Investigation on step overcharge to self-heating behavior and mechanism analysis of lithium ion batteries Fengling Yun, Shiyang Liu, Min Gao, Xuanxuan Bi, Weijia Zhao, Zenghua Chang, Minjuan Yuan, Jingjing Li, Xueling Shen, Xiaopeng Qi, Ling Tang, Yi Cui, Yanyan Fang, Lihao Guo, Shangqian Zhao, Xiangjun Zhang, Shigang Lu 2023, 79(4): 301-311.  DOI: 10.1016/j.jechem.2022.12.033 Abstract ( 10 )   PDF (3618KB) ( 4 )   To obtain intrinsic overcharge boundary and investigate overcharge mechanism, here we propose an innovative method, the step overcharge test, to reduce the thermal crossover and distinguish the over-charge thermal behavior, including 5% state of charge (SOC) with small current overcharge and resting until the temperature equilibrium under adiabatic conditions. The intrinsic thermal response and the self-excitation behaviour are analysed through temperature and voltage changes during the step over-charge period. Experimental results show that the deintercalated state of the cathode is highly correlated to self-heating parasitic reactions. Before reaching the upper limit of Negative/Positive (N/P) ratio, the temperature changes little, the heat generation is significantly induced by the reversible heat (endother-mic) and ohmic heat, which could balance each other. Following that the lithium metal is gradually deposited on the surface of the anode and reacts with electrolyte upon overcharge, inducing self-heating side reaction. However, this spontaneous thermal reaction could be ‘‘self-extinguished”. When the lithium in cathode is completely deintercalated, the boundary point of overcharge is about 4.7 V (~148% SOC, >40 °C), and from this point, the self-heating behaviour could be continuously triggered until thermal runaway (TR) without additional overcharge. The whole static and spontaneous process lasts for 115 h and the side reaction heat is beyond 320,000 J. The continuous self-excitation behavior inside the battery is attributed to the interaction between the highly oxidized cathode and the solvent, which leads to the dissolution of metal ions. The dissolved metal ions destroy the SEI (solid electrolyte interphase) film on the surface of the deposited Li of anode, which induces the thermal reaction between lithium metal and the solvent. The interaction between cathode, the deposited Li of anode, and solvent promotes the temperature of the battery to rise slowly. When the temperature of the battery reaches more than 60 °C, the reaction between lithium metal and solvent is accelerated. After the temperature rises rapidly to the melting point of the separator, it triggers the thermal runaway of the battery due to the short circuit of the battery.

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Achieving highly selective electrochemical CO2 reduction to C2H4 on Cu nanosheets Huan Xie, Ruikuan Xie, Zhiyuan Zhang, Yongyu Pang, Yuting Luo, Jiong Li, Bilu Liu, Maria-Magdalena Titirici, Guoliang Chai 2023, 79(4): 312-320.  DOI: 10.1016/j.jechem.2022.11.058 Abstract ( 8 )   PDF (1974KB) ( 39 )   The conversion of CO2 into value-added chemicals coupled with the storage of intermittent renewable electricity is attractive. CuO nanosheets with an average size and thickness of ~ 30 and ~ 20 nm have been developed, which are in situ reduced into Cu nanosheets during electrochemical CO2 reduction reac-tion (ECO2RR). The derived Cu nanosheets demonstrate much higher selectivity for C2H4 production than commercial CuO derived Cu powder, with an optimum Faradaic efficiency of 56.2% and a partial current density of C2H4 as large as 171.0 mA cm-2 in a gas diffusion flow cell. The operando attenuated total reflectance-Fourier transform infrared spectra measurements and density functional theory simulations illustrate that the high activity and selectivity of Cu nanosheets originate from the edge sites on Cu nanosheets with a coordinate number around 5 (4-6), which facilitates the formation of *CHO rather than *COH intermediate, meanwhile boosting the C—C coupling reaction of *CO and *CHO intermediates, which are the critical steps for C2H4 formation.

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π-Extension and chlorination of non-fullerene acceptors enable more readily processable and sustainable high-performance organic solar cells Ning Su, Jianhua Chen, Mengran Peng, Guoping Li, Robert M. Pankow, Ding Zheng, Junqiao Ding, Antonio Facchetti, Tobin J. Marks 2023, 79(4): 321-329.  DOI: 10.1016/j.jechem.2022.12.002 Abstract ( 5 )   PDF (1992KB) ( 1 )   Organic solar cells (OSCs) processed without halogenated solvents and complex treatments are essential for future commercialization. Herein, we report three novel small molecule acceptors (NFAs) consisting of a Y6-like core but with p-extended naphthalene with progressively more chlorinated end-capping groups and a longer branched chain on the Nitrogen atom. These NFAs exhibit good solubilities in non-chlorinated organic solvents, broad optical absorptions, close p-p stacking distances (3.63-3.84 Å), and high electron mobilities (~10-3 cm2 V-1 s-1). The o-xylene processed and as-cast binary devices using PM6 as the donor polymer exhibit a PCE increasing upon progressive chlorination of the naphthalene end-capping group from 8.93% for YN to 14.38% for YN-Cl to 15.00% for YN-2Cl. Furthermore similarly processed ternary OSCs were fabricated by employing YN-Cl and YN-2Cl as the third component of PM6:CH1007 blends (PCE = 15.75%). Compared to all binary devices, the ternary PM6:CH1007:YN-Cl (1:1:0.2) and PM6:CH1007:YN-2Cl (1:1:0.2) cells exhibit significantly improved PCEs of 16.49% and 15.88%, respectively, which are among the highest values reported to date for non-halogenated solvent processed OSCs without using any additives and blend post-deposition treatments.

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Chemical bonding of perovskite LaFeO3 with Li1.2Mn0.6Ni0.2O2 to moderate anion redox for achieving high cycling stability Xin Zhang, Chaochao Fu, Dong Luo, Xiaoqing Liu, Qiao Wang, Baoyun Li, Guangshe Li, Liping Li 2023, 79(4): 330-339.  DOI: 10.1016/j.jechem.2023.01.013 Abstract ( 3 )   PDF (2331KB) ( 2 )   Oxygen anion redox reaction provides a high theoretical capacity for Li-rich manganese-based cathodes. However, irreversible surface oxygen release often results in further oxygen loss and exacerbates the decomposition of the electrolyte, which could reduce the capacity contribution from the anionic redox and produce more acidic substances to corrode the surface of the material. In this paper, the surface oxy-gen release is suppressed by moderating oxygen anion redox activity via constructing chemical bonds between M (M = Fe and La) in LaFeO3 and surface oxygen anions of Li1.2Mn0.6Ni0.2O2. The constructed interface layer stabilizes the surface lattice oxygen and retards the electrolyte from being attacked by the nucleophilic oxygen generated in the process of oxygen release, as evidenced by Differential Electrochemical Mass Spectrometry (DEMS) and X-ray Photoelectron Spectroscopy (XPS) detections. Moreover, in the charge and discharge process, the formed FeF3, located at the cathode electrolyte inter-facial layer, is conducive to the stability of the cathode surface. The modified Li1.2Mn0.6Ni0.2O2 electrode with 3 wt% LaFeO3 exhibits a high specific capacity of 189.5 mA h g-1 at 1C (200 mA g-1) after 150 cycles with capacity retentions of 96.6%, and 112.6 mA h g-1 (84.7%) at 5C after 200 cycles higher than the pris-tine sample. This study provides a rational design chemical bonding method to suppress the oxygen release from the cathode surface and enhance cyclic stability.

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Tuning desolvation kinetics of in-situ weakly solvating polyacetal electrolytes for dendrite-free lithium metal batteries Peng Wen, Yimin Liu, Jinyan Mao, Xiaotong Liu, Weiping Li, Yang Ren, Yang Zhou, Fei Shao, Mao Chen, Jun Lin, Xinrong Lin 2023, 79(4): 340-347.  DOI: 10.1016/j.jechem.2022.12.058 Abstract ( 7 )   PDF (1709KB) ( 6 )   The host structure of polymers significantly influences ion transport and interfacial stability of elec-trolytes, dictating battery cycle life and safety for solid-state lithium metal batteries. Despite promising properties of ethylene oxide-based electrolytes, their typical clamp-like coordination geometry leads to crowd solvation sheath and overly strong interactions between Li+ and electrolytes, rendering difficult dissociation of Li+ and unfavorable solid electrolyte interface (SEI). Herein, we explore weakly solvating characteristics of polyacetal electrolytes owing to their alternately changing intervals between -O- coor-dinating sites in the main chain. Such structural asymmetry leads to unique distorted helical solvation sheath, and can effectively reduce Li+-electrolyte binding and tune Li+ desolvation kinetics in the in-situ formed polymer electrolytes, yielding anion-derived SEI and dendrite-free Li electrodeposition. Combining with photoinitiated cationic ring-opening polymerization, polyacetal electrolytes can be instantly formed within 5 min at the surface of electrode, with high segmental chain motion and well adapted interfaces. Such in-situ polyacetal electrolytes enabled more than 1300-h of stable lithium elec-trodeposition and prolonged cyclability over 200 cycles in solid-state batteries at ambient temperatures, demonstrating the vital role of molecular structure in changing solvating behavior and Li deposition sta-bility for high-performance electrolytes.

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Li-richening strategy in Li2ZrCl6 lattice towards enhanced ionic conductivity Haochang Zhang, Zhaozhe Yu, Hannan Chen, Yongjian Zhou, Xiao Huang, Bingbing Tian 2023, 79(4): 348-356.  DOI: 10.1016/j.jechem.2023.01.008 Abstract ( 15 )   PDF (1829KB) ( 6 )   All-solid-state Li batteries (ASSLBs) with solid-state electrolytes (SSEs) are exciting candidates for next-generation energy storage and receive considerable attention owing to their reliability. Halide SSEs are promising candidates due to their excellent stability against 4 V-class layered cathodes. Compared with Li3InCl6 or Li3ScCl6, the low ionic conductivity of Li2ZrCl6 (LZC) is a challenge despite its low raw-material cost. Herein, we report a family of Li-Richened chloride, Li2+2xZr1-xMxCl6, which can be used in high-performance ASSLBs owing to its high ionic conductivity (up to 0.62 mS cm-1). The theoretical (ab initio molecular dynamics simulations) and experimental results prove that the strategy of aliovalent substitu-tion with divalent metals to obtain Li-Richened LZC is effective in improving Li+ conductivity in SSEs. By combining Li2.1Zr0.95Mg0.05Cl6 (Mg5-LZC) with a Li-In anode and a LiCoO2 cathode, a room-temperature ASSLBs with excellent long-term cycling stability (88% capacity retention at 0.3C for 100 cycles) and high-rate capability (121 mA h g-1 at 1C) is reported. This exploratory work sheds light on improving the Li+ conductivity of low-cost LZC-family SSEs for constructing high performance ASSLBs.

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High-performance solid-state lithium metal batteries achieved by interface modification Lei Zhai, Kai Yang, Fuyi Jiang, Wenbao Liu, Zhenhua Yan, Jianchao Sun 2023, 79(4): 357-364.  DOI: 10.1016/j.jechem.2023.01.022 Abstract ( 5 )   PDF (2389KB) ( 2 )   Garnet-structured ceramic electrolyte Li6.75La3Zr1.75Ta0.25O12 (LLZTO) attracts significant consideration in solid-state Li metal batteries due to its wide electrochemical window and favorable compatibility with Li metal. However, the deployment of LLZTO is severely hampered by poor contact between LLZTO and Li metal anode. In this paper, an ultra-thin Al-Si interface buffer layer (10 nm) is constructed on LLZTO by a magnetron sputtering method, which allows superior wetting of Li onto the LLZTO surface due to the alloying reaction between the Al-Si layer and Li metal. The resulting Li/Al-Si coated LLZTO (ASL)/Li symmetrical cell delivers an interfacial resistance of 15.0 X cm-2, which is much lower than that of 1140.3 X cm-2 for the bare LLZTO symmetrical cell. Moreover, the Li/ASL/Li symmetrical cells exhibit stable plating/striping performance (800 h) with small voltage hysteresis at 1.0 mA cm-2. Besides, the full cell with LiFePO4 cathode reveals a high capacity of 124.1 mA h g-1 after 600 cycles at 0.5C with a low-capacity decay of 0.032% per cycle. We believe this work will facilitate the development of solid-state rechargeable batteries.

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Engineering d-band states of (CuGa)xZn1-2xGa2S4 material for photocatalytic syngas production Peng Liu, Baopeng Yang, Ziyi Xiao, Shengyao Wang, Shimiao Wu, Min Liu, Gen Chen, Xiaohe Liu, Renzhi Ma, Ning Zhang 2023, 79(4): 365-372.  DOI: 10.1016/j.jechem.2023.01.015 Abstract ( 8 )   PDF (2037KB) ( 2 )   The d-band states of catalytic materials participate in adsorbing reactive intermediate species and deter-mine the catalytic behaviors in CO2 reduction reactions. However, surface d-band states relating to the photocatalytic CO2 reduction reactions behaviors are rarely concerned. Herein, a slightly amount of Cd2+ is decorated on the surface of (CuGa)xZn1-2xGa2S4 material (Cd2+/(CuGa)xZn1-2xGa2S4) to tune the sur-face d-band states for improved CO2 reduction reactions. The Cd2+/(CuGa)xZn1-2xGa2S4 is fabricated via the facile ions-exchange method to make that slightly Zn2+ is substituted by Cd2+. The Cd2+/(CuGa)xZn1-2xGa2S4 exhibits much enhanced photocatalytic activity in CO2 reduction reactions to produce CO and water splitting to produce H2. Physical characterizations show that the energy band structure is not changed obviously. Density functional theory reveals that Cd2+/(CuGa)xZn1-2xGa2S4 possesses a closer shift of d-band center to Fermi level than (CuGa)xZn1-2xGa2S4, suggesting easier adsorption of CO2 reduc-tion reactive intermediates after Cd2+ decoration. Further calculations confirm that a relatively reduced adsorption Gibbs energy of reactive intermediates in CO2 reduction reaction is required on Zn atoms in Cd2+/(CuGa)xZn1-2xGa2S4 material, benefiting the photocatalytic CO2 reduction reactions. This work engi-neers surface d-band states by surface Cd2+ decoration, which gives an effective strategy to design highly efficient photocatalysts for syngas production.

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Ultrasmall CoS nanoparticles embedded in heteroatom-doped carbon for sodium-ion batteries and mechanism explorations via synchrotron X-ray techniques Congcong Liu, Qiongqiong Lu, Mikhail V. Gorbunov, Ahmad Omar, Ignacio G. Gonzalez Martinez, Panpan Zhao, Martin Hantusch, Antonius Dimas Chandra Permana, Huanyu He, Nikolai Gaponik, Daria Mikhailova 2023, 79(4): 373-381.  DOI: 10.1016/j.jechem.2023.01.011 Abstract ( 7 )   PDF (2075KB) ( 3 )   Transition metal sulfides have been regarded as promising anode materials for sodium-ion batteries (SIB). However, they face the challenges of poor electronic conductivity and large volume change, which result in capacity fade and low rate capability. In this work, a composite containing ultrasmall CoS (~7 nm) nanoparticles embedded in heteroatom (N, S, and O)-doped carbon was synthesized by an efficient one-step sulfidation process using a Co(Salen) precursor. The ultrasmall CoS nanoparticles are beneficial for mechanical stability and shortening Na — ions diffusion pathways. Furthermore, the N, S, and O — doped defect-rich carbon provides a robust and highly conductive framework enriched with active sites for sodium storage as well as mitigates volume expansion and polysulfide shuttle. As anode for SIB, CoS@HDC exhibits a high initial capacity of 906 mA h g-1 at 100 mA g-1 and a stable long-term cycling life with over 1000 cycles at 500 mA g-1, showing a reversible capacity of 330 mA h g-1. Meanwhile, the CoS@HDC anode is proven to maintain its structural integrity and compositional reversibility during cycling. Furthermore, Na — ion full batteries based on the CoS@HDC anode and Na3V2(PO4)3 cathode demonstrate a stable cycling behavior with a reversible specific capacity of ~ 200 mA h g-1 at least for 100 cycles. Moreover, advanced synchrotron operando X-ray diffraction, ex-situ X-ray absorption spectroscopy, and comprehensive electrochemical tests reveal the structural transformation and the Co coordination chemistry evolution of the CoS@HDC during cycling, providing fundamental insights into the sodium storage mechanism.

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Centimeter-sized Cs3Cu2I5 single crystals grown by oleic acid assisted inverse temperature crystallization strategy and their films for high- quality X-ray imaging Tao Chen, Xin Li, Yong Wang, Feng Lin, Ruliang Liu, Wenhua Zhang, Jie Yang, Rongfei Wang, Xiaoming Wen, Bin Meng, Xuhui Xu, Chong Wang 2023, 79(4): 382-389.  DOI: 10.1016/j.jechem.2022.12.016 Abstract ( 4 )   PDF (1883KB) ( 3 )   Low-dimensional halide perovskites have become the most promising candidates for X-ray imaging, yet the issues of the poor chemical stability of hybrid halide perovskite, the high poisonousness of lead halides and the relatively low detectivity of the lead-free halide perovskites which seriously restrain its commercialization. Here, we developed a solution inverse temperature crystal growth (ITCG) method to bring-up high quality Cs3Cu2I5 crystals with large size of centimeter order, in which the oleic acid (OA) is introduced as an antioxidative ligand to inhibit the oxidation of cuprous ions effieiently, as well as to decelerate the crystallization rate remarkalby. Based on these fine crystals, the vapor deposition tech-nique is empolyed to prepare high quality Cs3Cu2I5 films for efficient X-ray imaging. Smooth surface mor-phology, high light yields and short decay time endow the Cs3Cu2I5 films with strong radioluminescence, high resolution (12 lp/mm), low detection limits (53 nGyair/s) and desirable stability. Subsequently, the Cs3Cu2I5 films have been applied to the practical radiography which exhibit superior X-ray imaging per-formance. Our work provides a paradigm to fabricate nonpoisonous and chemically stable inorganic halide perovskite for X-ray imaging.

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Full-chain enhanced ion transport toward stable lithium metal anodes Yuliang Gao, Fahong Qiao, Nan Li, Jingyuan You, Yong Yang, Jun Wang, Chao Shen, Ting Jin, Xi Li, Keyu Xie 2023, 79(4): 390-397.  DOI: 10.1016/j.jechem.2023.01.030 Abstract ( 11 )   PDF (1361KB) ( 3 )   The dendrite growth that results from the slow electrode process kinetics prevents the lithium (Li) metal anode from being used in practical applications. Here, full-chain enhanced ion transport for stabilizing Li metal anodes is proposed. Experimental and theoretical studies confirm that full-chain enhanced ion transport (electrocrystallization, mass transport in the electrolyte and diffusion in solid electrolyte inter-phase) under magnetoelectrochemistry contributes to a homogeneous, dense, and dendrite-free mor-phology. Specifically, the enhanced electrocrystallization behavior promotes the Li nucleation; the enhanced mass transport in the electrolyte alleviates the ion concentration gradient at the electrode sur-face, which helps to inhibit dendrite growth; and the enhanced diffusion in the solid electrolyte inter-phase further homogenizes the Li deposition behavior, obtaining regular and uniform Li particles. Consequently, the Li metal anode has exceptional cycling stability in both symmetric and full cells, and the pouch cell performs long cycles (170 cycles) in practice evaluation. This work advances funda-mental knowledge of the magneto-dendrite effect and offers a new perspective on stabilizing metal anodes.

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Accelerating net-zero carbon emissions by electrochemical reduction of carbon dioxide Fan He, Sirui Tong, Zhouyang Luo, Haoran Ding, Ziye Cheng, Chenxi Li, Zhifu Qi 2023, 79(4): 398-409.  DOI: 10.1016/j.jechem.2023.01.020 Abstract ( 12 )   PDF (1169KB) ( 5 )   Electroreduction of CO2 shows great potential for global CO2 utilization and uptake when collaborated with renewable electricity. Recent advances have been achieved in fundamental understanding and elec-trocatalyst development for CO2 electroreduction. We think this research area has progressed to the stage where significant efforts can focus on translating the obtained knowledge to the development of large-scale electrolyzers, which have the potential to accelerate the transition of the current energy system into a sustainable and zero-carbon emission energy structure. In this perspective paper, we first critically evaluate the advancement of vapor-feed devices that use CO2 as reactants, from the point of view of industry applications. Then, by carefully comparing their performance to the state-of-the-art water elec-trolyzers which are well-established technology providing realistic performance targets, we looped back and discussed the remaining challenges including electrode catalysts, reaction conditions, mass trans-porting, membrane, device durability, operation mode, and so on. Finally, we provide perspectives on the challenges and suggest opportunities for generating fundamental knowledge and achieving techno-logical progress toward the development of practical CO2 electrolyzers for the goal of building low-carbon or/and net carbon-free economies.

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One dimensional nickel phosphide polymorphic heterostructure as carbon-free functional support loading single-atom iridium for promoted electrocatalytic water oxidation Rashid Mehmood, Guifa Long, Wenjun Fan, Mingrun Li, Lifang Liu, Fuxiang Zhang 2023, 79(4): 410-417.  DOI: 10.1016/j.jechem.2022.12.026 Abstract ( 12 )   PDF (7445KB) ( 3 )   Although conducting materials such as carbon nanotube and carbon fiber paper (CFP) have been exten-sively employed as support of electrocatalytic active sites, most of them are of poor catalytic functionality by themselves and undesirable stability during strong acid/alkaline environments or oxidation process. Here we report a novel one-dimensional (1D) nickel phosphide polymorphic heterostructure (denoted as NPPH) to work as one effective carbon-free functional support for loading of single-atom Ir water oxi-dation electrocatalyst. Specifically, the NPPH composed of both Ni12P5 and Ni2P phases is not only active for robust alkaline water oxidation but also is of good stability and hydrophilicity for favorable loading of single-atom dispersed iridium. The NPPH supported single-atom Ir electrocatalyst (Ir/NPPH) is found to exhibit remarkably superior water oxidation activity with respect to the NPPH itself or CFP supported single-atom Ir catalyst (Ir/CFP), demonstrating the synergetic promotion effect between NPPH and single-atom Ir catalyst. Furthermore, the NPPH supported single-atom Ir catalyst can bear alkaline water oxidation for over 120 h at current density of 50 mA cm-2. The NPPH developed here is expected as func-tional support to composite with other water oxidation catalysts, as may be an alternative strategy of developing highly efficient carbon-free electrocatalysts.

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CO2 utilization in syngas conversion to dimethyl ether and aromatics: Roles and challenges of zeolites-based catalysts Ali A. Al-Qadri, Galal A. Nasser, Haruna Adamu, Oki Muraza, Tawfik A. Saleh 2023, 79(4): 418-449.  DOI: 10.1016/j.jechem.2022.12.037 Abstract ( 57 )   PDF (1860KB) ( 38 )   Several studies have proven a strong correlation between global warming and CO2 emissions. Annually, 38 billion tons of CO2 are approximately emitted into the atmosphere. Utilizing CO2 via chemical con-version to clean fuels and value-added aromatics can substantially contribute to controlling the prob-lem. Considering the thermodynamic and environmental limitations of hydrogenation of CO2 alone to value-added aromatics and fuels, CO2 utilization has currently emerged as a promising and practical approach for the production of fuels and aromatics with simultaneous utilization of both CO and CO2 wastes. As such, the approach is economically preferable. CO2 could be converted directly to fuels by the hydrogenation process or as a part of a syngas mixture. Dimethyl ether (DME) is a clean fuel with a higher energy density, which could be used as a substituent for several fuels such as diesel. In the same vein, value-added aromatics such as benzene, toluene, and xylene (BTX) can be produced from a similar process. Herein, we report a review that collects the most recent studies for the conver-sion of CO2 to DME and aromatics via zeolite-based bifunctional catalysts. We highlighted the main routes for producing DME and aromatics, as well as thoroughly discussed the conducted studies on CO2 hydrogenation and CO2-rich syngas utilized as feedstock for conversion to DME and aromatics. The CO2 hydrogenation mostly occurs through the methanol-mediated reaction route but is most often limited by low selectivity and catalyst deactivation, particularly in the utilization of CO2 alone for the reduction reaction. The review takes an overview of the progress made so far and concluded by iden-tifying the roles and challenges of zeolite-based catalysts for CO2 utilization and conversion to DME and aromatics. Accordingly, despite the incredible growth the field received in the last couple of years, however, many research challenges and opportunities associated with this process are still abounded and required to be addressed. Special attention is required for the development of approaches to block diffusion of H2O through zeolite to suppress the excess formation of CO2 in CO2-rich syngas hydro-genation to DME and aromatics, exceed the product distribution limits, and suppress catalysts deactivation.

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In situ construction of a stable composite solid electrolyte interphase for dendrite-free Zn batteries Yiming Zhao, Huanyan Liu, Yu Huyan, Da Lei, Na Li, Shan Tian, Jian-Gan Wang 2023, 79(4): 450-458.  DOI: 10.1016/j.jechem.2022.12.045 Abstract ( 24 )   PDF (2719KB) ( 8 )   Building a stable solid electrolyte interphase (SEI) has been regarded to be highly effective for mitigating the dendrite growth and parasitic side reactions of Zn anodes. Herein, a robust inorganic composite SEI layer is in situ constructed by introducing an organic cysteine additive to achieve long lifetime Zn metal batteries. The chemisorbed cysteine derivatives are electrochemically reduced to trigger a local alkaline environment for generating a gradient layered zinc hydroxide based multicomponent interphase. Such a unique interphase is of significant advantage as a corrosion inhibitor and Zn2+ modulator to enable rever-sible plating/stripping chemistry with a reduced desolvation energy barrier. Accordingly, the cells with a thin glass fiber separator (260 lm) deliver a prolonged lifespan beyond 2000 h and enhanced Coulombic efficiency of 99.5% over 450 cycles. This work will rationally elaborate in situ construction of a desirable SEI by implanting reductive additives for dendrite-free Zn anodes.

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Innovative discontinuous-SEI constructed in ether-based electrolyte to maximize the capacity of hard carbon anode Fanghong Zeng, Lidan Xing, Wenguang Zhang, Zhangyating Xie, Mingzhu Liu, Xiaoyan Lin, Guangxia Tang, Changyong Mo, Weishan Li 2023, 79(4): 459-467.  DOI: 10.1016/j.jechem.2022.12.044 Abstract ( 15 )   PDF (6740KB) ( 31 )   Compared with graphite, the lower sodiation potential and larger discharge capacity of hard carbon (HC) makes it the most promising anode material for sodium-ion battery. Utilizing ether-based electrolyte rather than conventional carbonate-based electrolyte, HC achieves superior electrochemical perfor-mance. Nevertheless, the mechanism by which ether-based electrolyte improves the properties of HC is still controversial, primarily focusing on whether it forms solid electrolyte interphase (SEI) film. In this work, according to the sodium storage mechanisms in HC at low voltage (<0.1 V), including Na+-diglyme co-interaction into the carbon layer (SEI forbidden) and desolvated Na+ insertion in the irregular carbon holes (SEI required), the NaPF6 concentration in ether-based electrolyte was regulated, so as to construct a discontinuous-SEI on the surface of the HC anode, which significantly enhances the electrochemical performances of HC. Specifically, with 0.2 M NaPF6 ether-based electrolyte, HC deliverers a discharge capacity of 459.7 mA h g-1 at 0.1 C and stays at 357.2 mA h g-1 after 500 cycles at 1 C, which is substan-tially higher than that of higher/lower salt concentration electrolytes.

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Phase-separated bimetal enhanced sodium storage: Dimer-like Sn-Bi@C heterostructures with high capacity and long cycle life Xiaoxiao Hou, Yansong Zhu, Qian Yao, Jinmei Song, Chunsheng Wang, Yanli Zhou, Suyuan Zeng, Jian Yang, Yitai Qian 2023, 79(4): 468-476.  DOI: 10.1016/j.jechem.2022.12.059 Abstract ( 7 )   PDF (4030KB) ( 5 )   Phase boundaries facilitate the charge transportation and alleviate the intrinsic stress upon cycles. Therefore, how to achieve regular phase boundaries is very attractive. Herein, dimer-like Sn-Bi@C nanos-tructures, where is a well-defined phase boundary between Sn and Bi, have been prepared by a two-step process for the first time. The phase boundary not only provides additional and fast transportation for Na+, but also mitigates the structure stress/strain upon cycling. Therefore, Sn-Bi@C exhibits a high capac-ity (472.1 mA h g-1 at 2 A g-1 for 200 cycles), an ultra-long cyclic life (355.6 mA h g-1 at 5 A g-1 for 4500 cycles) and an excellent rate performance (372 mA h g-1 at 10 A g-1) for sodium storage, much higher than those of Sn@C, Bi@C, and Sn@C + Bi@C. Notably, the full cells of Sn-Bi@C//Na3V2(PO4)3/rGO (Sn-Bi@C//NVP/rGO) demonstrate impressive performance (323 mA h g-1 at 2 A g-1 for 300 cycles). The underlying mechanism for such an excellent performance is elucidated by in-situ X-ray diffraction, ex-situ scanning electron microscopy /high-resolution transmission electron microscopy and atomic force microscopy, revealing the good electrode stability and improved mechanical properties of Sn-Bi@C. The synthetic method is extended to dimer-like Sn-Pb@C and Sn-Ag@C heterostructures, which also exhi-bit the good cycle stability for sodium storage.

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Advances in self-powered sports monitoring sensors based on triboelectric nanogenerators Fengxin Sun, Yongsheng Zhu, Changjun Jia, Tianming Zhao, Liang Chu, Yupeng Mao 2023, 79(4): 477-488.  DOI: 10.1016/j.jechem.2022.12.024 Abstract ( 9 )   PDF (1627KB) ( 7 )   The new era of the internet of things brings great opportunities to the field of intelligent sports. The col-lection and analysis of sports data are becoming more intelligent driven by the widely-distributed sens-ing network system. Triboelectric nanogenerators (TENGs) can collect and convert energy as self-powered sensors, overcoming the limitations of external power supply, frequent power replacement and high-cost maintenance. Herein, we introduce the working modes and principles of TENGs, and then summarize the recent advances in self-powered sports monitoring sensors driven by TENGs in sports equipment facilities, wearable equipment and competitive sports specialities. We discuss the existing issues, i.e., device stability, material sustainability, device design rationality, textile TENG cleanability, sports sensors safety, kinds and manufacturing of sports sensors, and data collection comprehensiveness, and finally, propose the countermeasures. This work has practical significance to the current TENG appli-cations in sports monitoring, and TENG-based sensing technology will have a broad prospect in the field of intelligent sports in the future.

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The mechanism of external pressure suppressing dendrites growth in Li metal batteries Genming Lai, Yunxing Zuo, Junyu Jiao, Chi Fang, Qinghua Liu, Fan Zhang, Yao Jiang, Liyuan Sheng, Bo Xu, Chuying Ouyang, Jiaxin Zheng 2023, 79(4): 489-494.  DOI: 10.1016/j.jechem.2023.01.003 Abstract ( 13 )   PDF (1624KB) ( 7 )   Li metal is considered an ideal anode material for application in the next-generation secondary batteries. However, the commercial application of Li metal batteries has not yet been achieved due to the safety concern caused by Li dendrites growth. Despite the fact that many recent experimental studies found that external pressure suppresses the Li dendrites growth, the mechanism of the external pressure effect on Li dendrites remains poorly understood on the atomic scale. Herein, the large-scale molecular dynamics simulations of Li dendrites growth under different external pressure were performed with a machine learning potential, which has the quantum-mechanical accuracy. The simulation results reveal that the external pressure promotes the process of Li self-healing. With the increase of external pressure, the hole defects and Li dendrites would gradually fuse and disappear. This work provides a new perspective for understanding the mechanism for the impact of external pressure on Li dendrites.

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Bifunctional electrolyte regulation towards low-temperature and high-stability Zn-ion hybrid capacitor Shuo Yang, Kui Xue, Haiyang Liao, Yuning Guo, Liujiang Zhou, Yongqi Zhang 2023, 79(4): 495-504.  DOI: 10.1016/j.jechem.2023.01.025 Abstract ( 4 )   PDF (3402KB) ( 4 )   Aqueous Zinc-based energy storage devices are considered as one of the potential candidates in future power technologies. Nevertheless, poor low temperature performance and uncontrollable Zn dendrite growth lead to the limited energy storage capability. Herein, an anti-hydrolysis, cold-resistant, econom-ical, safe, and environmentally friendly electrolyte is developed by utilizing water, ethylene glycol (EG), and ZnCl2 with high ionic conductivity (7.9 mS cm-1 in glass fiber membrane at 20 °C). The spectra data and DFT calculations show the competitive coordination of EG and Cl- to induce a unique solvation con-figuration of Zn2+, conducive to effectively inhibiting the hydrolysis of Zn2+, suppressing the dendrite growth, and broadening the working voltage range and temperature range of ZnCl2 electrolyte. The iso-tope tracing data confirm that Cl- could effectively destroy the ZnO passivation film, promoting the for-mation of Zn nuclei and improving its reaction activity. Compared to the corresponding ZnSO4 electrolyte, the Cu/Zn half-cell with the ZnCl2 electrolyte exhibits a stable cycle life of more than 1600 h at 20 °C, even at the current density of 5 mA cm-2. The assembled Zn-ion hybrid capacitor possesses an average capacity of 42.68 mA h g-1 under —20 °C at a current density of 5 A g-1, 3.5 times than that of the mod-ified ZnSO4 electrolyte. Our work proposes a new approach for optimizing aqueous electrolytes to meet low temperature energy storage applications.

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Isolated diatomic Zn-Co metal-nitrogen/oxygen sites with synergistic effect on fast catalytic kinetics of sulfur species in Li-S battery Chun-Lei Song, Qiao-Tong He, Zhongyi Zeng, Jing-Yan Chen, Tian Wen, Yu-Xiao Huang, Liu-Chun Zhuang, Wei Yi, Yue-Peng Cai, Xu-Jia Hong 2023, 79(4): 505-514.  DOI: 10.1016/j.jechem.2022.12.050 Abstract ( 13 )   PDF (3035KB) ( 10 )   Lithium-sulfur batteries are severely restricted by low electronic conductivity of sulfur and Li2S, shuttle effect, and slow conversion reaction of lithium polysulfides (LiPSs). Herein, we report a facile and high-yield strategy for synthesizing dual-core single-atom catalyst (ZnCoN4O2/CN) with atomically dispersed nitrogen/oxygen-coordinated Zn-Co sites on carbon nanosheets. Based on density functional theory (DFT) calculations and LiPSs conversion catalytic ability, ZnCoN4O2/CN provides dual-atom sites of Zn and Co, which could facilitate Li+ transport and Li2S diffusion, and catalyze LiPSs conversion more effectively than homonuclear bimetallic single-atom catalysts or their simple mixture and previously reported single-atom catalysts. Li-S cell with ZnCoN4O2/CN modified separator showed excellent rate performance (789.4 mA h g-1 at 5 C) and stable long cycle performance (0.05% capacity decay rate at 6C with 1000 cycles, outperforming currently reported single atomic catalysts for LiPSs conversion. This work high-lights the important role of metal active centers and provides a strategy for producing multifunctional dual-core single atom catalysts for high-performance Li-S cells.

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Dual metal atom catalysts: Advantages in electrocatalytic reactions Kaihua Liu, Jing Li, Yuanyuan Liu, Meiri Wang, Hongtao Cui 2023, 79(4): 515-534.  DOI: 10.1016/j.jechem.2023.01.021 Abstract ( 6 )   PDF (5966KB) ( 4 )   The dual-metal-atom catalysts (DACs) have aroused much attention as they possess the advantages of single-atom and metal alloy catalysts. And the DACs have exhibited enhanced performance in various electrocatalytic reactions, such as hydrogen/oxygen evolution and oxygen/carbon dioxide/nitrogen reduction. In this review, we mainly overview the latest understanding of the advantages of DACs for these reactions. This review will start with the familiar characterization methods for DACs, then the pri-mary synthesis strategies for DACs will be discussed. Emphasis is given to the advantages of DACs in cat-alytic reactions, including the adsorption and activation, electronic structure regulation, breaking scaling relations, reducing energy barriers, cascading and coupling, synergy effect, and providing mechanism research platforms. Finally, personal perspectives and challenges for the further development of DACs are briefly discussed.

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Cooperative catalysis of Co single atoms and nanoparticles enables selective CAr—OCH3 cleavage for sustainable production of lignin-based cyclohexanols Baoyu Wang, Peng Zhou, Ximing Yan, Hu Li, Hongguo Wu, Zehui Zhang 2023, 79(4): 535-549.  DOI: 10.1016/j.jechem.2022.12.020 Abstract ( 6 )   PDF (3779KB) ( 6 )   In this work, a dual-size MOF-derived Co catalyst (0.2Co1-NPs@NC) composed of single atoms (Co1) and highly dispersed nanoparticles (Co NPs) was prepared by in-situ Zn evaporation for the high-performance conversion of lignin-derived o-methoxyphenols (lignin oil) to cyclohexanols (up to 97% yield) via cascade demethoxylation and dearomatization. Theoretical calculations elaborated that the dual-size Co catalyst exhibited a cooperative effect in the selective demethoxylation process, in which the Co NPs could initially dissociate hydrogen at lower energies while Co1 remarkably facilitated the cleavage of the CAr — OCH3 bond. Moreover, the intramolecular hydrogen bonds formed in the o-methoxy-containing phenols were found to result in a decrease in the bond energy of the CAr — OCH3 bond, which was more prone to be activated by the dual-size Co sites. Notably, the pre-hydrogenated intermediate (e.g., 2-methoxycyclohexanol from guaiacol) is difficult to undergo demethoxylation, indi-cating that the selective CAr — OCH3 bond cleavage is a prerequisite for the synthesis of cyclohexanols. The 0.2Co1-NPs@NC catalyst was highly recyclable with a neglect decline in activity during five consecu-tive cycles. This cooperative catalytic strategy based on the metal size effect opens new avenues for bio-mass upgrading via enhanced C — O bond cleavage of high selectivity.

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Self-catalytic induced interstitial C-doping of Pd nanoalloys for highly selective electrocatalytic dehydrogenation of formic acid Jun Li, Liying Cai, Xiaosi Liang, Shuke Huang, Xiaosha Wang, Yongshuai Kang, Yongjian Zhao, Lei Zhang, Chenyang Zhao 2023, 79(4): 550-558.  DOI: 10.1016/j.jechem.2023.01.026 Abstract ( 6 )   PDF (1556KB) ( 1 )   Light-metalloid-atom-doped Pd interstitial nanoalloy is promising candidate for electrocatalysis because of the favorable electronic effect. Herein, an innovative method was developed to synthesize C-doped Pd interstitial nanoalloy using palladium acetate both as metal precursor and C dopant. Elaborate character-izations demonstrated that C atoms were successfully doped into the Pd lattice via self-catalytic decom-position of acetate ions. The as-synthesized C-doped Pd catalysts showed excellent activity and durable stability for formic acid electrooxidation. The mass activity and specific activity at 0.6 V of C-doped Pd were approximately 2.59 A/mg and 3.50 mA cm-2, i.e., 2.4 and 2.6 times of Pd, respectively. DFT calcu-lations revealed that interstitial doping with C atoms induced differentiation of Pd sites. The strong non-covalent interaction between the Pd sites and the key intermediates endowed Pd with high-selectivity to direct routes and enhanced CO tolerance. This work presents a sites-differentiation strategy for metallic catalysts to improve the electrocatalysis.

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Bio-inspired tetracarbene compounds as a new family of energy saving catalysts Bo Zhang, Fritz E. Kühn 2023, 79(4): 559-561.  DOI: 10.1016/j.jechem.2023.01.019 Abstract ( 5 )   PDF (165KB) ( 2 )

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Mechanical densification synthesis of single-crystalline Ni-rich cathode for high-energy lithium-ion batteries Gwonsik Nam, Jaeseong Hwang, Donghun Kang, Sieon Oh, Sujong Chae, Moonsu Yoon, Minseong Ko 2023, 79(4): 562-568.  DOI: 10.1016/j.jechem.2022.12.057 Abstract ( 12 )   PDF (2369KB) ( 14 )   The intergranular microcracking in polycrystalline Ni-rich cathode particle is led by anisotropic volume change and stress corrosion along grain boundary, accelerating battery performance decay. Herein, we have suggested a simple but advanced solid-state method that ensures both uniform transition metal dis-tribution and single-crystalline morphology for Ni-rich cathode synthesis without sophisticated co-precipitation. Pelletization-assisted mechanical densification (PAMD) process on solid-state precursor mixture enables the dynamic mass transfer through the increased solid-solid contact area which facili-tates the grain growth during sintering process, readily forming micro-sized single-crystalline particle. Furthermore, the improved chemical reactivity by a combination of capillary effect and vacancy-assisted diffusion provides homogeneous element distribution within each primary particle. As a result, single-crystalline Ni-rich cathode with PAMD process has eliminated a potential evolution of intergran-ular cracking, thus achieving superior energy retention capability of 85% over 150 cycles compared to polycrystalline Ni-rich particle even after high-pressure calendering process (corresponding to electrode density of ~3.6 g cm-3) and high cut-off voltage cycling. This work provides a concrete perspective on developing facile synthetic route of micron-sized single-crystalline Ni-rich cathode materials for high energy density lithium-ion batteries (LIBs).

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Unveiling the redox electrochemistry of 1D, urchin-like vanadium sulfide electrodes for high-performance hybrid supercapacitors K. Karuppasamy, Dhanasekaran Vikraman, Sajjad Hussain, Balamurugan Thirumalraj, P. Santhoshkumar, Hemalatha Parangusan, Hyun-Chang Park, Jongwan Jung, Hyun-Seok Kim 2023, 79(4): 569-580.  DOI: 10.1016/j.jechem.2023.01.005 Abstract ( 9 )   PDF (3630KB) ( 1 )   Exploring novel versatile electrode materials with outstanding electrochemical performance is the key to the development of advanced energy conversion and storage devices. In this work, we aim to construct new-fangled one-dimensional (1D) quasi-layered patronite vanadium tetrasulfide (VS4) nanostructures by using different sulfur sources, namely thiourea, thioacetamide, and L-cysteine through an ethyleneaminetetraacetic-acid (EDTA)-mediated solvothermal process. The as-prepared VS4 exhibits sev-eral unique morphologies such as urchin, fluffy nanoflower, and polyhedron with appropriate surface areas. Among the prepared nanostructures, the VS4-1@NF nanostructure exhibited excellent electro-chemical properties in 6 M KOH solution, and we explored its redox electrochemistry in detail. The as-prepared VS4-1@NF electrode exhibited battery-type redox characteristics with the highest capacity of 280 C g-1 in a three-electrode assembly. Moreover, it offered a capacity of 123 F g-1 in a hybrid two-electrode set-up at 1 A g-1 with the highest specific energy and specific power of 38.5 W h kg-1 and 750 W kg-1, respectively. Furthermore, to ensure the practical applicability and real-world performance of the prepared hybrid AC@NF//VS4-1@NF cell, we performed a cycling stability test with more than 5,000 galvanostatic charge-discharge cycles at 2 A g-1, and the cell retained around 84.7% of its capacitance even after 5,000 cycles with a CE of 96.1%.

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Designing high-efficiency light-to-thermal conversion materials for solar desalination and photothermal catalysis Hanjin Jiang, Xinghang Liu, Dewen Wang, Zhenan Qiao, Dong Wang, Fei Huang, Hongyan Peng, Chaoquan Hu 2023, 79(4): 581-600.  DOI: 10.1016/j.jechem.2023.01.009 Abstract ( 5 )   PDF (3671KB) ( 3 )   Light-to-thermal conversion materials (LTCMs) have been of great interest to researchers due to their impressive energy conversion capacity and wide range of applications in biomedical, desalination, and synergistic catalysis. Given the limited advances in existing materials (metals, semiconductors, p-conjugates), researchers generally adopt the method of constructing complex systems and hybrid struc-tures to optimize performance and achieve multifunctional integration. However, the development of LTCMs is still in its infancy as the physical mechanism of light-to-thermal conversion is unclear. In this review, we proposed design strategies for efficient LTCMs by analyzing the physical process of light-to-thermal conversion. First, we analyze the nature of light absorption and heat generation to reveal the physical processes of light-to-thermal conversion. Then, we explain the light-to-thermal conversion mechanisms of metallic, semiconducting and p-conjugated LCTMs, and propose new material design strategies and performance improvement methods. Finally, we summarize the challenges and prospects of LTCMs in emerging applications such as solar water evaporation and photothermal catalysis.

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Selectively converting CO2 to HCOOH on Cu-alloys integrated in hematite-driven artificial photosynthetic cells Jiwu Zhao, Liang Huang, Lan Xue, Zhenjie Niu, Zizhong Zhang, Zhengxin Ding, Rusheng Yuan, Xu Lu, Jinlin Long 2023, 79(4): 601-610.  DOI: 10.1016/j.jechem.2022.12.062 Abstract ( 9 )   PDF (2496KB) ( 12 )   The integration of electrochemical CO2 reduction (CO2RR) and photoelectrochemical water oxidation offers a sustainable access to valuable chemicals and fuels. Here, we develop a rapidly annealed hematite photoanode with a photocurrent density of 2.83 mA cm-2 at 1.7 VRHE to drive the full-reaction. We also present Cu-alloys electrocatalysis extended from CuInSnS4, which are superior in both activity and selec-tivity for CO2RR. Specifically, the screened CuInSn achieves a CO2 to HCOOH Faradaic efficiency of 93% at a cell voltage of 2.0 V by assembling into artificial photosynthesis cell. The stability test of IT exhibits less than 3% degradation over 24 h. Furthermore, in-situ Raman spectroscopy reveals that both CO2-3 and CO2 are involved in CO2RR as reactants. The preferential affinity of C for H in the *HCO2 intermediate enables an improved HCOOH-selectivity, highlighting the role of multifunctional Cu in reducing the cell voltage and enhancing the photocurrent density.

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Strengths, weaknesses, opportunities, and threats (SWOT) analysis of supercapacitors: A review Pragati A. Shinde, Qaisar Abbas, Nilesh R. Chodankar, Katsuhiko Ariga, Mohammad Ali Abdelkareem, Abdul Ghani Olabi 2023, 79(4): 611-638.  DOI: 10.1016/j.jechem.2022.12.030 Abstract ( 17 )   PDF (6079KB) ( 3 )   The development of clean and sustainable energy sources has received widespread interest in the past few decades due to the rolling energy demands while extenuating the rising tiers of greenhouse gases and environmental pollution. Due to their intermittent nature, these green and sustainable sources require appropriate energy storage systems. Amongst different energy storage technologies, electro-chemical energy storage devices, particularly supercapacitors (SCs), have fascinated global attention for their utilization in electric vehicles, power supports, portable electronics, and many others application requiring electric energy devices for their operation. Thus, the growth of SCs in the commercial market has squeezed requirements, and further developments are obligatory for their effective industrialization. In the meantime, SCs also face technical complications and contests for their introduction in industrial settings because of their low energy density and high Levelized cost. The present study combines core strengths, weaknesses, opportunities, and threats (SWOT) analysis of SCs with new perspectives and recent ideas. The challenges and the future progressive prospects of SCs are also presented in detail. This review will afford consistent direction and new superhighways for the further development of SCs as standalone and complementary energy storage systems.