查找使用阿拉丁产品的科研文献

Mechanistic study on photochemical generation of I•/I2•− radicals in coastal atmospheric aqueous aerosol

Xiaoyu Jiao,Rui Zeng,Guangcai Lan,Siyu Zuo,Jun He,Chengjun Wang

The reactive iodine species may exhibit significant impacts on many global atmospheric issues and the I • /I 2 •− radicals play key roles for inducing the formation of these reactive iodine species. However, the current understanding on the formation of I • /I 2 •− radicals in atmospheric aqueous aerosol is still quite limited. The results reported herein suggest that I • /I 2 •− can be produced simultaneously in aqueous aerosol by several sunlight-driven photochemical pathways including direct photo-dissociation of soluble organic iodine (SOI) at rates of 0.10–1.34 × 10 −9 M ns −1 and 0.99–5.68 × 10 −7 M μs −1 , • OH-mediated oxidation of I − at 0.03–1.41 × 10 −8 M ns −1 and 0.05–4.10 × 10 −6 M μs −1 , and 3 DOM ⁎ -induced oxidation of I − at 1.57–1.65 × 10 −9 M ns −1 and 0.99–5.68 × 10 −7 M μs −1 for generation of I • and I 2 •− , respectively. Meanwhile, the pathway of e aq − -initiated stepwise reduction of IO 3 − to I 2( aq ) and further photolyzed into I • plays negligible role in formation of I • /I 2 •− due to the low reaction rates and severe quenching effect of e aq − by dissolved O 2 . Our work presented the new data on mechanism and kinetics for comprehensive elucidation of I • /I 2 •− formation in coastal atmospheric aqueous aerosol and would help to better understand the transformation mechanism of iodine species, pathways of iodine cycling and the associated environmental impacts involving atmospheric reactive iodine radicals.

Boosting Zn||I2 Battery’s Performance by Coating a Zeolite-Based Cation-Exchange Protecting Layer

Shang Wenshuo,Li Qiang,Jiang Fuyi,Huang Bingkun,Song Jisheng,Yun Shan,Liu Xuan,Kimura Hideo,Liu Jianjun,Kang Litao

Highlights High-performance Zn||I 2 batteries were established by coating zeolite protecting layers. The Zn 2+ -conductive layer suppresses I 3 − shuttling, Zn corrosion/dendrite growth. The Zeolite-Zn||I 2 batteries achieve long lifespan (91.92% capacity retention after 5600 cycles), high coulombic efficiencies (99.76% in average) and large capacity (203–196 mAh g −1 at 0.2 A g −1 ) simultaneously. Abstract The intrinsically safe Zn||I 2 battery, one of the leading candidates aiming to replace traditional Pb-acid batteries, is still seriously suffering from short shelf and cycling lifespan, due to the uncontrolled I 3 − -shuttling and dynamic parasitic reactions on Zn anodes. Considering the fact that almost all these detrimental processes terminate on the surfaces of Zn anodes, modifying Zn anodes’ surface with protecting layers should be one of the most straightforward and thorough approaches to restrain these processes. Herein, a facile zeolite-based cation-exchange protecting layer is designed to comprehensively suppress the unfavored parasitic reactions on the Zn anodes. The negatively-charged cavities in the zeolite lattice provide highly accessible migration channels for Zn 2+ , while blocking anions and electrolyte from passing through. This low-cost cation-exchange protecting layer can simultaneously suppress self-discharge, anode corrosion/passivation, and Zn dendrite growth, awarding the Zn||I 2 batteries with ultra-long cycle life (91.92% capacity retention after 5600 cycles at 2 A g −1 ), high coulombic efficiencies (99.76% in average) and large capacity (203–196 mAh g −1 at 0.2 A g −1 ). This work provides a highly affordable approach for the construction of high-performance Zn-I 2 aqueous batteries.

Development of long lifespan high-energy aqueous organic||iodine rechargeable batteries

Zhang Zishuai,Zhu Yilong,Yu Miao,Jiao Yan,Huang Yan

Rechargeable aqueous metal||I 2 electrochemical energy storage systems are a cost-effective alternative to conventional transition-metal-based batteries for grid energy storage. However, the growth of unfavorable metallic deposition and the irreversible formation of electrochemically inactive by-products at the negative electrode during cycling hinder their development. To circumvent these drawbacks, herein we propose 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) as negative electrode active material and a saturated mixed KCl/I 2 aqueous electrolyte solution. The use of these components allows for exploiting two sequential reversible electrochemical reactions in a single cell. Indeed, when they are tested in combination with an active carbon-enveloped I 2 electrode in a glass cell configuration, we report an initial specific discharge capacity of 900 mAh g −1 (electrode mass of iodine only) and an average cell discharge voltage of 1.25 V at 40 A g −1 and 25 \(\pm\) 1 °C. Finally, we also report the assembly and testing of a PTCDI|KCl-I 2 |carbon paper multilayer pouch cell prototype with a discharge capacity retention of about 70% after 900 cycles at 80 mA and 25 \(\pm\) 1 °C.

Realizing four-electron conversion chemistry for all-solid-state Li||I2 batteries at room temperature

Cheng Zhu,Liu Hang,Zhang Menghang,Pan Hui,Sheng Chuanchao,Li Wei,Wagemaker Marnix,He Ping,Zhou Haoshen

Rechargeable Li||I 2 batteries based on liquid organic electrolytes suffer from pronounced polyiodides shuttling and safety concerns, which can be potentially tackled by the use of solid-state electrolytes. However, current all-solid-state Li||I 2 batteries only demonstrate limited capacity based on a two-electron I − /I 2 polyiodides chemistry at elevated temperatures, preventing them from rivaling state-of-the-art lithium-ion batteries. Herein, we report a fast, stable and high-capacity four-electron solid-conversion I − /I 2 /I + chemistry in all-solid-state Li||I 2 batteries at room temperature. Through the strategic use of a highly conductive, chlorine-rich solid electrolyte Li 4.2 InCl 7.2 as the catholyte, we effectively activate the I 2 /I + redox couple. This activation is achieved through a robust I-Cl interhalogen interaction between I 2 and the catholyte, facilitated by an interface-mediated heterogeneous oxidation mechanism. Moreover, apart from serving as Li-ion conduction pathway, the Li 4.2 InCl 7.2 catholyte is demonstrated to show a reversible redox behavior and contribute to the electrode capacity without compromising its conductivity. Based on the I − /I 2 /I + four-electron chemistry, the as-designed all-solid-state Li||I 2 batteries deliver a high specific capacity of 449 mAh g -1 at 44 mA g -1 based on I 2 mass and an impressive cycling stability over 600 cycles with a capacity retention of 91% at 440 mA g -1 and at 25 °C.

An aqueous BiI3-Zn battery with dual mechanisms of Zn2+ (de)intercalation and I−/I2 redox

Qi Deng,Fangzhong Liu,Xiongwei Wu,Changzhu Li,Weibin Zhou,Bei Long

The development of aqueous battery with dual mechanisms is now arousing more and more interest. The dual mechanisms of Zn 2+ (de)intercalation and I − /I 2 redox bring unexpected effects. Herein, differing from previous studies using ZnI 2 additive, this work designs an aqueous BiI 3 -Zn battery with self-supplied I − . Ex situ tests reveal the conversion of BiI 3 into Bi (discharge) and BiOI (charge) at the 1st cycle and the dissolved I − in electrolyte. The active I − species enhances the specific capacity and discharge medium voltage of electrode as well as improves the generation of Zn dendrite and by-product. Furthermore, the porous hard carbon is introduced to enhance the electronic/ionic conductivity and adsorb iodine species, proven by experimental and theoretical studies. Accordingly, the well-designed BiI 3 -Zn battery delivers a high reversible capacity of 182 mA h g −1 at 0.2 A g −1 , an excellent rate capability with 88 mA h g −1 at 10 A g −1 , and an impressive cyclability with 63% capacity retention over 20 K cycles at 10 A g −1 . An excellent electrochemical performance is obtained even at a high mass loading of 6 mg cm −2 . Moreover, a flexible quasi-solid-state BiI 3 -Zn battery exhibits satisfactory battery performances. This work provides a new idea for designing high-performance aqueous battery with dual mechanisms.

Trace cesium iodide for uniform zinc deposition and enhanced cathode kinetics in aqueous Zn-I2 batteries

Yu Deng,Zhengquan Xiao,Dajin Liu,Shilin Wu,Jiahang Zou,Zhipeng Jiang,Yongtao Li

Aqueous zinc-iodine batteries (AZIBs) are considered a very promising way to store energy. However, inherent issues such as cathodic slow I₂/I⁻ redox kinetics and anodic zinc (Zn) dendrite growth, limit the practical application of AZIBs. Here, we used just a trace amount of the electrolyte additive cesium iodide (CsI) for homogeneous deposition of Zn 2+ and enhanced cathode kinetics in AZIBs. The introduction of Cs + produces electrostatic shielding layers that regulate the homogenization of Zn 2+ deposition. Besides, I - promotes cathodic kinetics to achieve the effect of increasing the battery capacity. Electrochemical tests show that by adding 5 mM trace CsI to the Zn-Zn symmetric cell, the cycling time was increased to 650 h, and the Zn-Cu half-cell's cycling time was increased to 3000 cycles under conditions of 5 mA cm −2 . More importantly, Zn-I 2 cells can stably cycle for 10000 cycles at 1 A g −1 and 10 A g −1 . The average capacity increased to 97.54 mAh g −1 after 100 cycles at 1 A g −1 and 74.57 mAh g −1 after 100 cycles at 10 A g −1 . After 100 cycles, the Zn-I 2 full cell's capacity retention rose from 2.41 % to 57.47 % under the conditions of 1 A g −1 and a 5.6 N/P ratio.

I2/H2O2 Mediated Synthesis and Photophysical Properties of Imidazole-Fused Heterocycles via [4+1] Cyclization Approach

Haonan Li,Chenping Gao,Qingjie Liu,Yanchun Guo,Yufen Zhao

Graphical We report here a new I 2 /H 2 O 2 co-catalyzed oxidative [4+1] cyclization of benzaldehyde with 2-(aminomethyl)pyridine or o -phenylenediamine/2-aminothiophenol to provide various substituted imidazo[1,5- a ]pyridines and benzimidazoles/thiazole via C(acyl)−N bond construction. Some of heterocyclic products exhibit blue luminescence properties, as well as large Stokes shifts, eminent fluorescence quantum yields (64 %) and long fluorescence lifetimes. An efficient I 2 (10 mmol %)/H 2 O 2 mediated oxidative formal [4+1] cyclization of 2-pyridinemethylamine or o -phenylenediamine (2-aminobenzenethiol) with benzaldehyde via C−N bond formation has been developed. This strategy provides a straightforward approach to imidazo[1,5- a ]pyridines, iodo-substituted imidazo[1,5- a ]pyridines and benzimidazole (benzothiazole) derivatives in yields ranging from 60 % to 98 %, respectively. Several heterocyclic products exhibit promising blue luminous performance with satisfactory fluorescence quantum yields of up to 64 %, large Stokes shifts, and a longer lifetime (7.35 ns). The band gap energies obtained from DFT are also consistent with the absorption spectra.

Two-dimensional Cd3-based metal–organic frameworks with halogen bonding sites for the uptake of I2

Zhi-Hao Zhang,Jia-Lu Ge,Yan Li,Qing Li,Pin-Pin Ma,Xiao-Yan Tang,Wen-Hua Zhang,David J. Young

Developing porous materials for the efficient capture of I2 is relevant to the sequestration and storage of radioactive iodine towards clean nuclear energy. In this work, three topologically identical two-dimensional (2D) metal–organic frameworks (MOFs) [Cd3(BTB)2(Pz)4]·xSol. (2), [Cd3(BTB)2(3-PyCN)2(H2O)2]·xSol. (3), and [Cd3(BTB)2(4-PyCN)4]·xSol. (4) have been prepared by ligand exchange with [Cd3(BTB)2(DEF)4]·2(DEF)0.5 (1) via single-crystal to single-crystal transformations (H3BTB = benzene-1,3,5-tribenzoic acid; DEF = diethylformamide; Pz = pyrazine; 3-PyCN = 3-cyanopyridine; 4-PyCN = 4-cyanopyridine; xSol. = guest solvates). MOFs 1–4 feature linear Cd3 cluster secondary building units (SBUs) interconnected by BTB ligands, with each Cd3 unit also associated with four terminally bonded ligands bearing halogen bonding sites, viz. N(DEF) for 1, N(Pz) for 2, –CN(3-PyCN) for 3, and –CN(4-PyCN) for 4. MOFs 1–4 adsorbed I2 in the sequence 2 > 3 > 4 > 1 with a maximum uptake of 54.1 mg g−1 for 2.

A cascade reaction pathway enabled by sub-micron bismuth-decorated cathode for aqueous Zn-I2 batteries

Zhuoran Ao,Huixin Ren,Yuxi Guo,Lijing Yan,Zhan Lin

Sub-micron Bi chemically anchors polyiodides via Bi-I bonds to suppress shuttling. • S-Bi acts as both an iodine host and an electroactive capacity contributor. • A cascade reaction involving I 0 /I − and Bi 3+ /Bi redox couples is realized. • The Zn–I₂ battery delivers 245 mAh g −1 and cycles 20,000 times with 77.7% retention. • A pouch cell achieves 5.26 mAh cm −2 under 22 mg cm −2 mass loading. Polyiodide shuttling is the primary obstacle to impede the practical application of aqueous zinc–iodine batteries (AZIBs). Although various host materials have been developed to suppress the shuttle effect, most of them are electrochemically inactive and inevitably reduce the overall energy density of the cathode. Herein, sub-micron bismuth (S-Bi) powder as a multifunctional redox-active iodophilic additive was introduced into the iodine electrode to simultaneously regulate iodine conversion chemistry and contribute additional electrochemical capacity. Experiment results showed that S-Bi powder with high electronic conductivity and mesopore structure can chemically anchor polyiodide by forming Bi-I bonds, which benefits suppressing polyiodide shuttling and enhancing reaction kinetics. More importantly, a cascade reaction process containing I 0 /I − and Bi 3+ /Bi redox couples is realized, significantly boosting battery capacity. In-situ XRD characterization revealed the conversion route of bismuth species (BiOI ↔ Bi 2 O 3 ↔ Bi) during the reaction, providing the direct evidence for the bismuth-involved cascade reaction mechanism. As a result, the assembled AZIBs based on S-Bi powder deliver a high discharge specific capacity of 245.19 mAh g −1 at 0.5 A g −1 and operate stably for 20,000 cycles at 3 A g −1 with a capacity retention of 77.7%. Encouragingly, the pouch battery achieves an areal capacity of 5.26 mAh cm −2 under a high active material mass loading of 22 mg cm −2 , demonstrating practical application potential. This work paves the way for designing materials with iodine affinity and redox activity to simultaneously suppress polyiodide shuttling and contribute extra capacity for AZIBs. Submicron mesoporous bismuth as a functional additive in I₂/KB cathode establishes a cascade reaction mechanism and inhibits polyiodide shuttling by forming Bi-I bonding, enabling 20,000-cycle stability. Download: Download high-res image (105KB) Download: Download full-size image

Zn2+-crosslinking enhanced natural gelatinizer binders for low self-discharge and long-life Zn-I2 batteries

Yunming Li,Xiaojing Wu,Xinle Sun,Jianuo Wang,Xiangyu Liu,Lingyu Du,Litao Kang

A series of natural gelatinizers is evaluated as alternative binders to replace the conventional PVDF binder. • The waterborne binders can improve both cycling stability and anti-self-discharge performance. • The optimized binder slows the 200 h self-discharge rate from 37% down to 16%, while prolonging the lifetime by ∼ 2.6 times. Aqueous zinc-iodine (Zn-I 2 ) batteries have been identified as one kind of promising energy storage device, but still suffer from self-discharge and short lifetime problems due to polyiodide shuttling. To improve the polyiodide confining ability of the I 2 cathodes, a series of natural gelatinizers, including carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), polyanionic cellulose (PAC), xanthan gum (XG), and sodium alginate (SA), are evaluated as alternative binders to replace the conventional polyvinylidene fluoride (PVDF). Experimental results suggest that all these water-borne binders can improve the cycling stability of the electrodes by forming a flexible hydrogel skeleton. In addition, the abundant heteroatoms in the binders can effectively adsorb polyiodide and suppress the shuttle effect. As a result, the adoption of these water-borne binders can significantly slow down the self-discharge rate of the resulting Zn-I 2 batteries, compared to the traditional PVDF binder (capacity loss: 16–21% vs. 37%, after 200 h). Among these binders, SA endows the cathodes with the best anti-self-discharging performance (capacity loss: 23.7% vs. 49.3% after 500 h, compared with the PVDF-binder battery). This strategy opens a new avenue to enhance the anti-self-discharge performance of Zn-I 2 batteries with natural polymers. Download: Download high-res image (149KB) Download: Download full-size image

Molecular Weaving-Inspired Dual-Cross-Linked Natural-Polymer Hydrogel Electrolyte for Stable Aqueous Zn–I2 Battery

Xunzhen Sun,Xiao Zhang,Hui Gu,Jiayi Li,Fei Lu,Long Su,Xinpei Gao

Aqueous zinc–iodine (Zn–I2) batteries are promising for sustainable energy storage owing to their intrinsic safety, environmental benignity, and the highly reversible redox chemistry of iodine. However, water-induced side reactions at the Zn anode and the shuttling effect of polyiodides trigger severe self-discharge and interfacial instability. Herein, a molecular-weaving–inspired strategy was developed, in which topological chain entanglements cooperate with dynamic ionic/coordination junctions to build a dual-cross-linked hydrogel electrolyte. In such weaving-inspired entangled networks, Zn2+-activated junction dynamics dissipate energy and prevent stress localization, while the enduring entanglement preserves network integrity. Simultaneously, the introduction of abundant coordination sites along the polymer backbone reconfigures the local Zn2+ solvation environment and mitigates Zn anode side reactions and dendrite growth. Moreover, these coordinated Zn2+ nodes effectively suppress the polyiodide shuttle without compromising ionic conductivity. Benefiting from these synergistic effects, the designed hydrogel electrolyte enables highly stable Zn plating/stripping, achieving an average Coulombic efficiency of 99.46% in Zn//Cu cells. The assembled Zn//I2 full cells deliver excellent durability with a high capacity retention of 87.8% after 9000 cycles at 5.0 A g–1. This work establishes a viable weaving-inspired design strategy for natural polymer-based hydrogel electrolytes toward durable aqueous Zn–I2 batteries and beyond.

Synthesis of (E)-β-iodovinyl sulfones via DTBP/I2 promoted difunctionalization of alkynes with sodium benzenesulfinates

Wenzhu Bi,Chunyan Ren,Linguo Jia,Xiaoyi Xia,Xi Chen,Xiaolan Chen,Yufen Zhao