Nature Communications
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2025
·Vol. 16
·期 1
·1-18
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IF 15.7
Li Rui,Xu Kaiqi,Wen Shenhao,Tang Xiaohan,Lin Zheyu,Guo Xia,Avdeev Maxim,Zhang Zhizhen,Hu Yong-Sheng
Halides are promising solid electrolytes due to their high ionic conductivity and high oxidation potential. Here we report a superionic chloride material, NaTaCl 6 , which exhibits a high ionic conductivity of 3.3 mS cm −1 at 27 °C, being two-orders of magnitude higher than that of NaNbCl 6 (0.01 mS cm −1 ). The considerably higher conductivity exhibited by NaTaCl 6 vs. NaNbCl 6 arises from the more facile rotational/reorientational dynamics of the [TaCl 6 ] polyanions in comparison to the [NbCl 6 ] anions. [TaCl 6 ] polyanion rotation is readily activated while [NbCl 6 ] polyanion reorientation is hindered at room temperature but can be turned on as the temperature increases or under prolonged mechanical milling. The higher degree of structural disorder exhibited by NaTaCl 6 compared to NaNbCl 6 —likely attributed to its greater mechanical and phonon softness—is found to contribute to the more pronounced [TaCl 6 ] anion rotation. Anion rotation is coupled with, and facilitates, macroscopic Na + -ion diffusion. As a result, enhanced rotational dynamics are directly correlated with the higher Na + -ion conductivity observed in NaTaCl 6 . The high ionic conductivity, combined with its electrochemical stability against positive electrode materials, enables good rate capability and long-term cycling performance in solid-state cells. These findings provide insights into ion transport mechanism in the newly emerging halide solid electrolytes.
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JOURNAL OF POWER SOURCES
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2025
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IF 7.9
Jing Zhang,Chenxiao Han,Lu Pan,Mannan Yang,Caiyin You,Yongzheng Zhang,Lujie Jia,Huihua Li,Ke Xu,Jian Su,Hongzhen Lin,Jian Wang
Aqueous zinc metal batteries (AZMBs) are promising for large-scale energy storage due to their intrinsic safety and cost effectiveness. However, the cycling stability of metallic Zn anode under low temperature surroundings is severely hindered by harmful hydrogen evolution reaction (HER) and uncontrollable dendrite growth, which is ascribed to sluggish desolvation kinetics of hydrated [Zn(H 2 O) x ] 2+ and blocked Zn 2+ diffusion kinetics. Herein, the strategy of “adsorption-sieving-catalysis” is initially proposed and the titanium nitride anchored on self-assembly porous reduced graphene oxide (TiN@RGO) as functional modulator is constructed on the surface of Zn anode. The abundant electrocatalytic sites on sieving pores significantly enhance interfacial desolvation, thereby accelerating Zn 2+ diffusion kinetics for dendrite-free plating. Consequently, TiN@RGO modified Zn delivers a long-term stripping/plating lifespan above 2600 h at 0.5 mA cm −2 and maintains reversible stability of 500 h at 2 mA cm −2 even under low temperature of 0 °C. Decreasing to as low as −8 °C, stable overpotential around 130 mV without any short-circuit is achieved. The coupled full cell with MnO 2 presents a high capacity retention of 72 % after 1000 cycles at 1.0 A g −1 at low temperature of 0 °C, providing new insights for the rational design of efficient LT-AZMBs.
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Journal of the American Chemical Society
·
2025
·
IF 15.6
Zi-Wei Wang,Jin-Da Luo,Zhong-Yuan Huang,Wanxia Li,Hao-Yuan Tan,Xiaobin Cheng,Mei-Yu Zhou,Xu-Dong Hao,Chen-Peng Luo,Chuan Wan,Linjun Wang,Yi-Chen Yin,Shuhong Jiao,Hong-Bin Yao
All-solid-state sodium batteries (ASSSBs) with a working voltage of approximately 3.5 V hold great potential for safe, sustainable, and high-energy-density electrochemical energy storage. However, 3.5 V oxide-type cathodes (e.g., NaNi1/3Fe1/3Mn1/3O2) may suffer from interfacial contact loss with solid electrolytes due to their intrinsic rigidity, resulting in irreversible capacity degradation during cycling. Herein, we report a highly deformable chloride cathode, NaFeCl4, displaying Young’s modulus of only 1.33 GPa and excellent structural reversibility. Benefiting from the soft lattice, the NaFeCl4 cathode maintains a crack-free morphology despite significant changes in structural units between tetrahedra [Fe3+Cl4] and octahedra [Fe2+Cl6] upon repeated Na+ insertion/extraction, achieving a high capacity retention of 84.4% over 500 cycles. Moreover, with only 5.2% of the cost of the NaNi1/3Fe1/3Mn1/3O2 and 3.7% of the cost of Na3V2(PO4)3 cathode, NaFeCl4 can deliver a working voltage of ∼3.45 V vs Na+/Na and energy density of ∼405 Wh kg–1. This chloride cathode offers new insight into solving the mechanical issues in solid-state systems, guiding future developments of low-cost, stable, and high-voltage cathodes for ASSSBs.
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DESALINATION
·
2025
·
IF 9.8
Fei Han,Aocheng Yuan,Zhi Zhang,Qingquan Deng,Jiaoting Li,Shuibo Wu,Mingdong Zhang,Jingli Mu
Radiocobalt (e.g., 58 Co and 60 Co), a critical neutron-activated corrosion product in the nuclear industry, poses great challenges due to high toxicity. Effective removal of radioactive Co 2+ from complex environments is significantly urgent. Metal sulfide ion exchangers (MSIEs) are promising adsorbents; however, limited research has focused on Co 2+ removal, especially from seawater and real-world radioactive waste. Herein, a layered K 2 Cu 2 Sn 2 S 6 (CTS-1) was reported for the efficient capture of Co 2+ . The charge-balancing K + ions are exchangeable, endowing CTS-1 with Co 2+ capture ability via an ion exchange mechanism. This mechanism leads to the releasing K + into solution and concurrently immobilizing Co 2+ , which was confirmed macroscopically and microscopically. CTS-1 exhibited Langmuir maximum adsorption capacities of 33.96 and 20.72 mg/g in deionized water and seawater at 25 °C, respectively; the overall adsorption kinetics were similar in both matrices. CTS-1 displayed excellent pH durability with >99 % removal of Co 2+ at pH 4–8 and high selectivity for Co 2+ in various natural matrices. Impressively, in seawater ( C 0 Co = 5 mg/L), CTS-1 achieved 97.38 % of Co 2+ removal with a distribution coefficient ( K d ) up to 3.817 × 10 4 mL/g, surpassing many existing adsorbents. Furthermore, CTS-1 exhibited radiation resistance; its structure and adsorption performance remained largely unchanged after a gamma radiation dose of 200 kGy. CTS-1 demonstrated the ability to remove nearly 99 % of radiocobalt from real-world radioactive wastewater, while also showing removal efficiency for other radionuclides like 51 Cr and 58 Mn. Overall, this work provides a highly promising material to tackle radiocobalt contamination in radioactive waste, greatly promoting environmental protection and safety for the radioactive industry.
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INTERNATIONAL JOURNAL OF REFRACTORY METALS & HARD MATERIALS
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2025
·
IF 4.6
Xu Xia,Chenyang Ma,Tianen Yang,Zhiyuan Ma,Yu Cao,Jiahuan He,Qiwen Zheng,Huaping Hong,Ji Xiong
This study investigates gradient cemented carbide with a cubic phase-free surface layer (CFL), commonly used as substrates for coated inserts to extend their service life. The tough gradient surface layer effectively prevents crack propagation, minimizing coating delamination and edge chipping. We propose using hexagonal boron nitride (h-BN) as a non-cubic nitrogen source for fabricating gradient cemented carbide with cubic (W,Ti)C, as a replacement for traditional cubic nitrogen sources. By employing powder metallurgy, we successfully created gradient cemented carbide with a CFL derived from h-BN. We also analyze the mechanism of gradient structure formation and characterize the microstructure, elemental distribution, and mechanical properties of the novel materials. The results demonstrate the feasibility of producing gradient cemented carbides with a CFL when h-BN is used as the nitrogen source. The crystal orientations at the gradient boundary are randomly distributed, showing no abrupt interface between the surface layer and the interior. Notably, titanium (Ti) and boron (B) are nearly absent in the surface layer, while cobalt (Co) shows higher concentration compared to the interior. The use of h-BN facilitates a nearly homogeneous titanium distribution in the subsurface zone, contrasting with the clustering seen when traditional cubic TiN is employed as the nitrogen source. Additionally, the thickness of the gradient surface layer can be effectively controlled by adjusting the h-BN levels, increasing with higher h-BN content in the raw materials. However, excessive h-BN addition facilitates abnormal WC phase growth in cemented carbides, and negatively affects transverse rupture strength despite the toughening effects of the cubic phase-free layer. Increased h-BN content also promotes the formation of TiB phases, which enhances the hardness of the cemented carbide.
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International Journal of Analytical Chemistry
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2020
·
IF 1.678
Lina Huang,Hanke Li,Yuhang Li,Peng Ren,Lezhou Yi,Yang Chen,Tongmei Ma
Background. Organic tin compounds (OTCs), a group of high-risk hazardous substances, are highly concerned in safety regulation of consumer products especially for toys because they can cause serious damage to organs after prolonged or repeated exposure. Gastric juice migration is nowadays widely implemented to assess organic tin intake from toys or food-contact materials; however, the followed up detection method using sodium tetraethylborate [NaB(Et4)] as a derivatization agent may directly lead to false positive of monomethyltins (MMT). Objective. In order to avoid the phenomena of false positive of MMT in the course of laboratory testing of toys, it is necessary and important to perform relative experimental and theoretical studies to reveal the cause of false positive of MMT. Method. With metal tin powder as a representative of inorganic tin which existed in real samples, it was treated with artificial gastric juice (0.07 mol/L·HCl), followed by ethyl derivatization using sodium tetraethylborate [NaB(Et)4] and then analyzed by gas chromatography-mass spectrometry (GC-MS) according to the procedure specified in the standard of EN 71-3:2013+A3:2018 issued by the European Committee for Standardization (CEN). Results. Without any OTCs in the starting materials, MMT false positive can be reproduced by detecting 0.56 mg/L of triethylmethyltin (TEMT) together with approximately 1000 mg/L of tetraethyltin (TeET), which is similar to real samples. Further, it is demonstrated that the detected amount of TEMT is linearly related with the added amount of NaB(Et)4, and that the formation of TEMT (methyl derivative) is easier than TeET (ethyl derivative) even though the ethyl group is present in a larger amount than the methyl group. Conclusions. The phenomena of MMT false positive which occurred in the laboratory testing of toys is mainly because that TEMT is highly likely to be obtained from the reaction of inorganic tin and trace level of methylation agent impurities contained in the derivatization reagent—NaB(Et)4. To avoid MMT false positive, it is concluded that the maximum acceptable mole ratio of methylation agent impurities contained in NaB(Et)4 is approximately 0.028%. This research is helpful to be aware of methylation impurities and is favorable to avoid false judgment caused by MMT false positive in routine analysis of toys.
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ACS Nano
·
2025
·
IF 16
Kai Chen,Anjun Hu,Guo-Rui Zhu,Yuanjian Li,Jingyun Jiang,Borui Yang,Ting Li,Kun Li,Jingze Chen,Wang Xu,Zhen Wang,Ruize Xu,Wei Yang,Jian Wang,Gang Wu,Jianping Long,Zhi Wei Seh
The practical application of semisolid lithium metal batteries is impeded by inadequate ionic conductivity, suboptimal oxidation/reduction stability, and safety concerns of the electrolyte. Herein, a versatile molecular engineering strategy is proposed to construct a robust polymer framework for semisolid electrolytes, which creates highly compatible cross-linked networks by the in situ gelation of concentrated succinonitrile-based plastic crystal electrolytes and multifunctional nitrogen- and fluorine-rich monomers. This strategy allows the electrolyte to promote rapid Li-ion transpsort through weak coordination with the polymer segments. Meanwhile, the strong interactions between the polymer matrix and succinonitrile enhance their mutual solubility, reduce the crystallinity of succinonitrile, and establish fast ion-conductive pathways. The resultant electrolyte induces the formation of LiF/Li3N-rich solid electrolyte interphases and achieves uniform lithium deposition behaviors. Moreover, it mitigates fire risks by cothermally decomposing to produce fire-extinguishing gases (CO2 and NH3) and leveraging the nonflammability of succinonitrile. Significant improvements in electrochemical performance have been observed in Li symmetric, Li||LiFePO4, and Li||LiNi0.8Co0.1Mn0.1O2 cells both at room temperature and high temperature (60 °C). As a demonstration model, this molecular engineering strategy has been successfully applied to enhance thermal stability and safety in Li||LiNi0.8Co0.1Mn0.1O2 pouch cells, offering a promising solution for semisolid lithium metal batteries under extreme conditions.
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Small
·
2025
·
IF 12.1
Ming Li,Xiongwei Gong,Yilong Hu,Yi Shuai,Yunong Zhou,Mingliang Wu,Xiaoyi Huangyang,Jinqi Huang,Yingpeng Wu
Due to the abundant availability of Na resources, Na batteries garner significant attention. Anode-free Na batteries, devoid of active negative materials, are deemed promising candidates for the next generation of high-energy-density Na batteries. The cyclic stability of anode-free Na batteries primarily hinges on the stability of the limited Na supplied by the cathode, and the design of the anode substrate plays a pivotal role. In this study, a cost-effective aluminum–tin eutectic alloy substrate is developed using a straightforward melting process. In eutectic alloy, tin element is present in its metallic form, which facilitates the disruption of the compactness of the Passivation film (Al 2 O 3 ). Besides, tin metal and tin dioxide on the surface of the eutectic alloy show a strong Na affinity (strong binding energy with Na atom and lower Na nucleation barrier), thereby promoting the uniform nucleation of sodium. This eutectic alloy substrate enables highly reversible Na plating/stripping with an average coulombic efficiency of 99.97%, and the cycle life exceeds 4000 cycles. Coupling with Na 3 V 2 (PO 4 ) 3 , the AlSn-2%-NVP full cell exhibits a capacity retention of up to 81% after 100 cycles, significantly outperforming coated carbon aluminum foils and aluminum foils. This study introduces an efficient approach to the anode-free Na battery.
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Micromachines
·
2025
·Vol. 17
·期 1
·
IF 3
Xiaofei Liu,Tianren Liu,Kaixin Su,Jingxin Lei,Yuanfu Chen,Yuan Chen,Dongxu Yang
As metal-containing resists attract increasing research interest in high-resolution lithography, gaining insights into the photochemical mechanisms, particularly in relation to the ligand functionality, is actively demanded. In this work, a controlled pair of organotin carboxylates with analogous structures but different functional groups has been designed and synthesized as deep-ultraviolet (DUV) resists. Both resists demonstrate 90 nm half-pitch resolution and the capability of pattern transfer on carbon-based hard-mask layers. Through various characterizations and comparison of the controlled pair, we propose two competitive reaction paths for the organotin system with olefin groups, which regulate the lithographic sensitivity and dissolution contrast. Our findings highlight the structural adjustability of organotin carboxylates and their potential application as high-resolution and etch-durable DUV resists.
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Cell Reports Physical Science
·
2025
·
IF 7.3
Run Li,Fan Lan,Aike Xi,Di Gao,Yunrui Li,Ya Huang,Siming Zhao,Yilin Ding,Yanlong Zhao,Rufan Zhang
As an energy-efficient technology, electrochromic devices (ECDs) represent a promising solution for smart windows in buildings and vehicles. However, conventional all-solid-state ECDs suffer from sluggish ion diffusion. Here, we propose a high-performance all-solid-state ECD enabled by a rapid H + transfer pathway. A solid-state polyaniline (PANI) interface serves as an efficient H + reservoir, replacing Li + ions to drive electrochromism in Prussian blue (PB). By integrating a sodium-ion-conducting solid polymer electrolyte (SPE) above PANI, H + ions are selectively pumped into PB via an ion exchange mechanism. The PANI network also stabilizes PB’s framework by preventing anion/solvent intercalation. The optimized ECDs exhibit exceptional performance: fast switching speeds (1.2 s coloration, 3.0 s bleaching), high optical modulation (72.5% at 600 nm), and robust cycling stability (>5,000 cycles with <10% decay). Furthermore, large-area flexible ECDs (20 × 30 cm 2 , ∼0.4 mm thickness) are demonstrated, highlighting their potential as replaceable smart films for energy-efficient buildings and vehicles.
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JOURNAL OF ALLOYS AND COMPOUNDS
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2025
·
IF 6.3
Jiawei Lu,Liyuan Chai,Xiaobo Min,Yong Ke,Yun Li,Yunyan Wang,Xin Wang,Yiming Liu,Cong Peng
The synergistic and enhanced bath smelting of primary ores with secondary resources is a key strategy to address the paradox of resource scarcity and recycling of secondary resources in zinc metallurgy. However, due to the high melting temperature of high zinc slags (Zn > 25 %), bath smelting below 1250 °C has not yet been practically implemented. This study proposes a new approach for reducing the melting temperature of high zinc slags by tailoring slag composition and co-smelting secondary resources to promote synergistic melting. The melting properties and regulation mechanisms of high zinc slags were systematically investigated through FactSage thermodynamic calculations, in-situ observation using an ash fusion temperatures auto detecting system, and quenching experiments. The results reveal that CaO/SiO₂ and FeO/SiO₂ mass ratio are the primary factors influencing the melting temperature. Excessively high or low CaO/SiO₂ and FeO/SiO₂ promote the formation of high melting point phases such as zincite, spinel, willemite and melilite, thereby increasing the melting temperature. Components from secondary resources, such as B₂O₃, Na₂O and Cu₂O, can significantly reduce the content of high melting point phase in the melting process, and reduce the melting temperature, while MgO, Cr₂O₃, etc., have the opposite effect. The melting temperature of co-smelting high zinc slag with 15 % sludge and 4 % borax was reduced over 125 °C. In industrial pilot-scale trial exceeding 20 tons, the flow temperature of high zinc slag containing 27.08 % zinc was 1118 °C. This study establishes technical foundations for low-energy and clean co-smelting of secondary resources with primary ores.
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Journal of Materials Research and Technology-JMR&T
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2025
·
IF 6.6
Bingqin Wang,Yadi Zhao,Ruichao Yan,Liangan Liu,Xuequn Cheng,Luntao Wang,Zhong Li,Chao Liu,Dawei Zhang,Xiaogang Li
In this study, 45 steel was taken as the research object, and a tin-iron alloy layer was prepared on its surface via a thermal diffusion tinning process. Combined with a series of characterization methods, the microstructure and element distribution of the thermal diffusion layer were systematically analyzed. Additionally, through cyclic immersion tests, electrochemical measurements, and outdoor exposure tests in marine atmosphere, the effects of thermal diffusion temperature and tin content in the diffusion agent on the structure and corrosion resistance of the thermal diffusion layer were systematically investigated. The results show that thermal diffusion tinning can form an alloy layer dominated by FeSn2 on the surface of 45 steel. Moreover, the higher the thermal diffusion temperature and the greater the tin content in the diffusion agent, the larger the thickness (up to 15 μm) and the better the compactness of the alloy layer. The corrosion resistance of the tinned steel is significantly better than that of 45 steel, and it is further improved with the increase of thermal diffusion temperature, tin content, and extension of thermal diffusion time. Among them, the tinned steel prepared under the thermal diffusion process of 80%-280°C-4h exhibits a corrosion current density of 4.027 μA · cm -2 , which is only 1/400 of that of 45 steel (12.095 μA · cm -2 ), and demonstrates the latest corrosion initiation and slowest development rate in marine atmospheric exposure. The key factors contributing to the improved corrosion resistance are the stable structure of FeSn 2 intermetallic compounds in the thermal diffusion layer, the physical barrier effect of the dense alloy layer, and the protective rust layer formed during the corrosion process.
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