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JOURNAL OF MATERIALS CHEMISTRY · 2012 ·Vol. 22 ·期 21 ·10665-10671 · IF 5.968

Epitaxial TiO2/SnO2 core–shell heterostructure by atomic layer deposition

Anmin Nie,Jiabin Liu,Qianqian Li,Yingchun Cheng,Cezhou Dong,Wu Zhou,Peng Wang,Qingxiao Wang,Yang Yang,Yihan Zhu,Yuewu Zeng,Hongtao Wang

Taking TiO2/SnO2 core–shell nanowires (NWs) as a model system, we systematically investigate the structure and the morphological evolution of this heterostructure synthesized by atomic layer deposition/epitaxy (ALD/ALE). All characterizations, by X-ray diffraction, high-resolution transmission electron microscopy, selected area electron diffraction and Raman spectra, reveal that single crystalline rutile TiO2 shells can be epitaxially grown on SnO2 NWs with an atomically sharp interface at low temperature (250 °C). The growth behavior of the TiO2 shells highly depends on the surface orientations and the geometrical shape of the core SnO2 NW cross-section. Atomically smooth surfaces are found for growth on the {110} surface. Rough surfaces develop on {100} surfaces due to (100) − (1 × 3) reconstruction, by introducing steps in the [010] direction as a continuation of {110} facets. Lattice mismatch induces superlattice structures in the TiO2 shell and misfit dislocations along the interface. Conformal epitaxial growth has been observed for SnO2 NW cores with an octagonal cross-section ({100} and {110} surfaces). However, for a rectangular core ({10} and {010} surfaces), the shell also derives an octagonal shape from the epitaxial growth, which was explained by a proposed model based on ALD kinetics. The surface steps and defects induced by the lattice mismatch likely lead to improved photoluminescence (PL) performance for the yellow emission. Compared to the pure SnO2 NWs, the PL spectrum of the core–shell nanostructures exhibits a stronger emission peak, which suggests potential applications in optoelectronics.

CAS / MDL: 7440-31-5
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Journal of Energy Storage · 2024 · IF 8.9

A novel composite solid electrolyte based on chemical bonding and physical reinforcing for all-solid-state lithium metal batteries

Songdong Yuan,Yi Luo,Xiaobo Wang,Chuang Yao,Kai Xia,Jintao Xiao,Xinguang Fang,Guodong Jiang,Jian Xiong,Mingxia Fan

Sulfide electrolytes are a highly promising type of electrolyte due to their intrinsically soft properties and ultrahigh ionic conductivity . However, compatibility issues at the lithium interface have hindered their development in all-solid-state lithium metal batteries . Composite polymer electrolytes can indeed address interface issues, enhancing battery safety. Nonetheless, the incompatibility at the inorganic-organic interface within composite electrolytes can lead to reduced conductivity and diminished mechanical performance. Herein, we demonstrate a composite polymer electrolyte (CPE) composed of the Li 6 PS 5 Cl and polyethylene oxide (PEO) by the chemical bridging effect of (3-chloropropyl) trimethoxysilane (CTMS) on the 3D PET nonwoven framework to resolving the incompatibility between the inorganic and organic components, thereby reinforcing the chemical and mechanical performance of the electrolyte. The CPE shows superior characteristics, including elevated ionic conductivity (7.5 × 10 −4  S cm −1 ), an extended electrochemical stability window (5.3 V versus Li/Li + ), an expanded lithium transference number (t (Li + )  = 0.52), and higher mechanical strength (9.35 MPa). The assembly of a Li/Li symmetric cell, operating steadily for 400 h at a current density of 0.3 mA cm −2 while maintaining a stable and relatively low polarization voltage (70 mV), demonstrates exceptional stability with respect to the lithium electrode. Moreover, the LiFePO 4 /Li cell initially exhibits a discharge-specific capacity of 163.6 mAh g −1 with a coulombic efficiency approaching 100 % after 100 cycles at 0.1C. This endeavor offers a robust, attainable, and scalable methodology for crafting composite electrolytes, thereby paving the path for the practical implementation of all-solid-state lithium metal batteries.

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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

3D printed self-healing, degradable on-skin electronics with liquid metal for multifunctional monitoring

Meiyang Hu,Jiyuan Yu,Wenhao Li,Yong Shuai,Liqiang Ai,Zhaolong Wang

Soft, flexible electronics is boosting the monitoring physiological data and assessing health conditions. However, their further practical utilization is limited due to the lack of intrinsic adhesion interfaces for mechanical deformation, self-healing capability against mechanical damages, and degradable properties for the waste electronic products treatment. Herein, we report the design concepts, materials, fabrication methods, and multifunctional applications of a new type of self-healing and degradable flexible health-detection electronics based on three-dimensional (3D) printable polymers and liquid metals. The 3D printable elastomer processes amazing self-healing efficiency (99.5 %), excellent mechanical properties (tensile strength: 3104 kPa), degradable, intrinsic adhesion, and so on. Polymer elastomers combined with the fluidity of Galinstan (GaInSn) allow the electronic devices to heal from fracture and restore electrical performance. Our polymer elastomers effectively solve the coordination problems between solid-state electronic devices and substrates, greatly improving the integration and functional complexity of the functional devices. The reliable connection between the GaInSn circuit, commercial components and elastomers can easily measure various physiological signals such as electrophysiology, temperature, and body motions. In addition, the commercial components and GaInSn circuits can be well recycled through ethanol to reduce pollution to the environment. The present 3D printed self-healing multifunctional electronics enables new opportunities for promising applications of flexible electronic devices.

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ADVANCED FUNCTIONAL MATERIALS · 2024 · IF 18.5

A Local-Dissociation Solid-State Polymer Electrolyte with Enhanced Li+ Transport for High-Performance Dual-Band Electrochromic Smart Windows

Run Li,Fan Lan,Lian Tang,Ya Huang,Siming Zhao,Baoshun Wang,Ying Han,Di Gao,Qinyuan Jiang,Yanlong Zhao,Zhuojing Zhao,Fei Wang,Rufan Zhang

Windows through heat exchange play a vital role in energy saving for realizing a net-zero carbon emission society. Dual-band electrochromic (EC) smart windows by dynamically regulate visible (VIS) and near-infrared (NIR) light are necessary for improving both building energy efficiency and habitant comfort. However, the rational design of high-performance electrochromic devices (ECDs) suffers sluggish EC response due to the slow ion transport. In this work, a locally dissociated Li + concept is proposed to construct a solid-state polymer electrolyte (SPE) with ultrafast Li + transport. The succinonitrile (SN) is employed to loosen the Li + -anion pair and the crystallographic C─O chain in the poly(ethylene glycol) methyl ether methacrylate (PEGMA) electrolyte by its strong solvation capability. The as-prepared SPE shows a high ionic conductivity of 6.48 mS cm −1 at 30 °C and a high transmittance of >90%. The SPE-based EC smart windows exhibited a fast switching speed (3.0/3.2 s for coloration/bleaching), a high coloration efficiency (CE) of 373.8 cm 2 C −1 , and a high optical modulation in the full solar spectrum (85%, 70%, 43% at 673, 1200, and 1600 nm, respectively). Finally, the SPE-based EC smart windows shows three working modes with a temperature regulation range of 19.1 °C, exhibiting great potential in practical application.

CAS / MDL: 7440-31-5 32171-39-4
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ACS Sustainable Chemistry & Engineering · 2024 · IF 7.1

A Green Method of Synthesizing Battery-Grade Lithium Sulfide: Hydrogen Reduction of Lithium Sulfate

Yujiang Sun,Xin Zhang,Shijie Xu,Shunjin Yang,Xinyu Wang,Xiaorou Cao,Xiao Sun,Yuzhe Zhang,Dehang Ren,Xiaohu Hu,Haoyu Yang,Qiaran Zhang,Zongjing Lu,Xuejing Zhang,Yongan Yang

Lithium sulfide (Li2S) is a critical material for two systems of next-generation advanced lithium batteries. However, its practical applications are seriously impeded by its expensive price due to its troublesome storage and problematic production. Herein we report the synthesis of Li2S by thermally reducing lithium sulfate with hydrogen. Compared with the industrial approach of carbothermal reduction, this new method using a gaseous reductant is advantageous because of emitting zero amount of carbon oxides, having no solid byproducts or precursor residuals, generating only one environmentally benign and recyclable byproduct of water, and not requiring postsynthesis purification. Those features make this method cost-effective and easy for material storage. Moreover, the actual synthesis involves many parasitic reactions, which surprisingly do not cause real troubles for producing high-purity Li2S. Furthermore, compared with the commercial Li2S, the as-synthesized Li2S demonstrates superior performance when used as the cathode material in lithium–sulfur batteries and as the precursor to make sulfide solid electrolyte Li6PS5Cl for all-solid-state lithium batteries. Therefore, this green method enables paving the way for practical sustainable applications of Li2S.

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ACS Applied Materials & Interfaces · 2024 · IF 8.3

Thermoelectric Transport Performance in p-Type AgSbTe2-Based Materials through Entropy Engineering

Abdul Basit,Tanveer Hussain,Xin Li,Jiwu Xin,Bin Zhang,Xiaoyuan Zhou,Guoyu Wang,Ji-Yan Dai

Being a major obstacle, Ag2Te has always been restricted in p-type AgSbTe2-based materials to improve their thermoelectric performance. This work reveals a stabilized AgSbTe2 through Sn/Ge alloying as synthesized by melting, annealing, and hot press. Interestingly, addition of Sn/Ge in AgSbTe2 extended the solubility limit up to ∼30% and hence suppressed Ag2Te in Ag(1–x)SnxSb(1–y)GeyTe2 compounds and led to enhanced electrical transport. Moreover, electrical and thermal transport properties of AgSbTe2 have been greatly affected by the phase transition of Ag2Te near 425 K. However, high-entropy Ag0.85Sn0.15Sb0.85Ge0.15Te2 compound results in a stabilized rock-salt structure and presents a high power factor of ∼10.8 μW cm–1 K–2 at 757 K. Besides, density functional theory reveals that available multivalence bands in Sn/Ge-doped AgSbTe2 lead to reduction in energy offsets. Meanwhile, a variety of defects appear in the Ag0.85Sn0.15Sb0.85Ge0.15Te2 sample due to entropy change, and thus lattice thermal conductivity decreases. Ultimately, a high figure of merit of ∼1.5 is attained at 757 K. This work demonstrates a roadmap for other group IV–VI materials so that the high-entropy approach may inhibit the impurity phases with extended solubility limit and result in high thermoelectric performance.

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ACS Nano · 2024 · IF 15.8

Three-Dimensional Metal–Organic Framework@Cellulose Skeleton-Reinforced Composite Polymer Electrolyte for All-Solid-State Lithium Metal Battery

Xin Song,Kang Ma,Jian Wang,Han Wang,Haijiao Xie,Zongmin Zheng,Jianmin Zhang

High-safety and high-energy-density solid-state lithium metal batteries (SSLMBs) attract tremendous interest in both academia and industry. Especially, composite polymer electrolytes (CPEs) can overcome the limitations of single-component solid-state electrolytes. In this work, a strategy of combining a rigid functional skeleton with a soft polymer electrolyte to prepare reinforced CPEs was adopted. The in situ grown zeolitic imidazolate frameworks (ZIFs) with three-dimensional cellulose fiber skeleton (ZIF-67@CF) and succinonitrile (SN) plasticizer into poly(ethylene oxide) (PEO) together form ZIF-67@CF/PEO-SN CPEs. The addition of ZIF-67@CF and SN to PEO synergistically enhanced the physical and electrochemical properties of CPEs. Furthermore, the conduction mechanism of lithium-ion (Li+) in CPEs was studied using density functional theory. It is impressive that the ZIF-67@CF/PEO-SN CPEs at 30 °C exhibit a high ionic conductivity of 1.17 × 10–4 S cm–1, a competitive Li+ transference number of 0.40, a wide electrochemical window of 5.0 V, a notable tensile strength of 18.7 MPa, and superior lithium plating/stripping stability (>550 h at 0.1 mA cm2). Such favorable features endowed LiFePO4/(ZIF-67@CF/PEO-SN)/Li cell at 30 °C with a high discharging capacity (152.5 mA h g–1 at 0.2 C), a long cycling lifespan (>150 cycles with 99% capacity retention), and superior operating safety. This work provides insights and promotes the application of functionalized CPEs for SSLMBs.

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JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY · 2024 · IF 11.2

Ti3C2Tx MXene enhanced PEO/SN-based solid electrolyte for high-performance Li metal battery

Hao Xu,Shuai Liu,Zhiang Li,Fan Ding,Ting Wang,Ting Liu,Weimin Wang,Kaikai Song,Jie Liu,Lina Hu

Succinonitrile has shown significant promise for application in polymer electrolytes for solid-state lithium metal batteries due to its high ionic conductivity at low-temperature. However, the use of Succinonitrile is limited due to its corrosion of Li metal. Herein, we report a solid polymer electrolyte with high ionic conductivity (2.17 × 10 −3 S cm −1 , 35 °C) enhanced by Ti 3 C 2 T x . Corrosion of the Li anode is prevented due to the Succinonitrile molecules being efficiently anchored by Ti 3 C 2 T x . Meanwhile, the coordination environment of Li + is weakened due to the introduction of competitive coordination induction effects into the polymer electrolyte, resulting in efficient Li + conduction. Furthermore, the mechanical properties of the electrolyte are enhanced by modulating the ratio of Ti 3 C 2 T x to suppress the growth of Li dendrites. Therefore, Li||Li symmetric batteries deliver stable cycling up to 8000 h at 28 °C. LiFePO 4 ||Li full batteries exhibit excellent cycling stability of 151.7 mAh g −1 with a capacity retention of 99.3% after 300 cycles. This work not only presents a new idea to suppress the corrosion of the Li anode by Succinonitrile but also provides a simple, feasible, and scalable strategy for high-performance Li metal batteries.

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Nanomaterials · 2024 ·Vol. 14 ·期 5 ·437 · IF 4.4

Polymer Lewis Base for Improving the Charge Transfer in Tin–Lead Mixed Perovskite Solar Cells

Yanjun Xing,Zhiqiang Deng,Qiuxiang Wang,Jiaxing Xiong,Xiaohui Liu,Like Huang,Yuejin Zhu,Jing Zhang

The poor film stability of Sn-Pb mixed perovskite film and the mismatched interface energy levels pose significant challenges in enhancing the efficiency of tin–lead (Sn-Pb) mixed perovskite solar cells. In this study, polyvinylpyrrolidone (PVP) is introduced into the PVK perovskite precursor solution, effectively enhancing the overall stability of the film. This improvement is achieved through the formation of robust coordination bonds between the carbonyl (C=O) in the pyrrole ring and the undercoordinated SnIIand PbII, thereby facilitating the passivation of defects. Furthermore, the introduction of PVP inhibits the oxidation of tin (Sn), thereby enhancing the n-type characteristics of the perovskite film. This adjustment in the energy level of the PVK perovskite film proves instrumental in reducing interface energy loss, subsequently improving interface charge transfer and mitigating device recombination. Consequently, perovskite solar cells incorporating PVP achieve an outstanding champion power conversion efficiency (PCE) of 21.31%.

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Materials · 2024 ·Vol. 17 ·期 19 ·4809 · IF 3.1

Preparation and Electrothermal Transport Behavior of Sn8[(Ga2Te3)34(SnTe)66]92 Bulk Glass

Yaqi Zhang,Feng Guo,Huan Zhang,Mingming Zhang,Jianxiu Su,Zhengxin Li

High-conductivity tellurium-based glasses were anticipated to be the attractive candidates in chalcogenide glass systems on account of their distinctive characteristics and extensive application prospects. In this paper, the high-density (>96%) Sn8[(Ga2Te3)34(SnTe)66]92bulk glass with the density of 5.5917 g/cm3was successfully prepared by spark plasma sintering (SPS) technology at 460 K, using a 5 min dwell time and 450 MPa pressure. The room-temperature thermal conductivity of Sn8 bulk materials significantly decreased from 1.476 W m−1∙K−1in the crystalline sample to 0.179 W m−1∙K−1in the glass, and the Seebeck coefficient obviously increased from 35 μV∙K−1in to 286 μV∙K−1, indicating that the glass transition of tellurium-based semiconductors could optimize the thermal conductivity and Seebeck coefficient of the materials. Compared to the conventional tellurium-based glassy systems, the fabricated Sn8 bulk glass presented a high room-temperature conductivity (σ =6.2 S∙m−1) and a large glass transition temperature (Tg=488 K), which was expected to be a promising thermoelectric material.

CAS / MDL: 7440-31-5 12040-02-7
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CRYSTENGCOMM · 2024 ·Vol. 26 ·期 10 ·1418-1429 · IF 2.6

Preparation and growth mechanism of centimeter-scale (AgxCu1−x)2ZnSnS4 single crystals via a molten salt method

Jun Liao,Sihao Ye,Xupeng Zhu,Wenfeng Fu,Shuwen Xue,Jing Qi,Jun Zhang

Kesterite Cu2ZnSnS4 (CZTS) is considered as one of the most promising thin-film solar cell and photocatalytic materials; however, its efficiency in practical photoelectric applications is often seriously limited by the presence of large numbers of Cu–Zn antisite defects. Alloying with Ag to fabricate Ag-alloyed CZTS ((AgxCu1−x)2ZnSnS4, ACZTS) can reduce the Cu–Zn antisite defects in CZTS, but few research studies have been able to separately clarify the effect of Ag content and growth temperature on large-sized (AgxCu1−x)2ZnSnS4 single crystals. In this study, centimeter-scale high-quality ACZTS single crystals were synthesized via an Ag-alloying strategy by a molten salt method for the first time. The results showed that the synthesized ACZTS have a high-quality single-crystal structure. A series of experiments was performed using various characterization techniques and it was found that Ag content and growth temperature were crucial in determining the size of ACZTS single crystals obtained through a molten salt method and that the associated CZTS base generated at high temperature was beneficial for further ACZTS single-crystal growth in this high-temperature environment. The experimental results showed that the growth mechanism of ACZTS crystals prepared using a molten salt method could be attributed to a type of epitaxial growth process. Our study provides a promising approach for growing large-sized ACZTS single crystals with high quality that can provide a potential single-crystal platform for the study of light-emitting diodes, photocatalytic hydrogen production, etc.

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APPLIED CATALYSIS B-ENVIRONMENTAL · 2024 · IF 20.2

Revealing the nontrivial topological surface states of catalysts for effective photochemical carbon dioxide conversion

Kangwang Wang,Longfu Li,Peifeng Yu,Nannan Tang,Lingyong Zeng,Kuan Li,Chao Zhang,Rui Chen,Zaichen Xiang,Huichao Wang,Yongqing Cai,Kai Yan,Huixia Luo

Topological semimetals with protected surface states mark a new paradigm of research beyond the early landmarks of band-structure engineering, allowing fabrication of efficient catalyst to harness the rich metallic surface states to activate specific chemical processes. Herein, we demonstrate a facile solid-phase method for in-situ doping of Ir at the Os sites in the Os 3 Sn 7 , an alloy with topological states, which significantly improves the photocatalytic performance for the reduction of CO 2 to CO and CH 4 . Experimental evidence combined with theoretical calculations reveal that the nontrivial topological surface states greatly accelerate charge-separation/electron-enrichment and adsorption/activation of CO 2 molecules, rendering highly efficient reaction channels to stimulate the formation of *COOH and *CO, as well CHO*. This work shows the promise of achieving high photocatalytic performances with synthesizing topological catalysts and provides hints on the design of novel topological catalysts with superior photoactivity towards the CO 2 reduction reaction.

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