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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

A multifunctional nano filler for solid polymer electrolyte toward stable cycling for lithium-metal anodes in lithium–sulfur batteries

XinLong Zhang,HaiYan Zhang,Yuan Geng,ZhangQin Shi,Sheng Zhu,QunJie Xu,YuLin Min

Lithium–sulfur (Li–S) batteries are considered as very promising energy storage systems due to their higher theoretical performance and lower active material cost. However, the notorious shuttle effect and lithium dendrite growth have severely restricted the industrial production of Li–S batteries. In this study, we used polyethylene oxide (PEO) as the matrix and added multifunctional nanofillers (nano In 2 O 3 ) to effectively inhibit the shuttle effect caused by the dissolution of lithium polysulphides (LiPSs) in Li–S batteries. As a multifunctional filler, nano-In 2 O 3 not only improves the ionic conductivity of the PEO electrolyte, but also forms a Li–In alloy layer in situ at the polymer/anode interface, which can cause the rapid diffusion of lithium ions and prevent the side reactions between lithium metal anode and the electrolyte. Achieving the effect of stabilizing the lithium metal anode and suppressing the shuttle effect. Multiple problems in the system are solved by introducing a single component with multiple functions. The symmetrical lithium battery based on the PEO/LiTFSI/In 2 O 3 solid polymer electrolyte (PEO/LiTFSI/In 2 O 3 SPE) has higher cycle stability (over 1200 h) because it is more stable to the lithium metal anode. The Li–S full battery also exhibits excellent electrochemical performance. After 500 cycles at 1C, its capacity can be maintained at 570 mAh g −1 , the capacity decay rate is 0.038%. The coulombic efficiency (CE) during the cycle is also close 100%.

研究领域: 电化学 · 能源材料 · 固态离子学 · 电池技术 · 纳米复合材料
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JOURNAL OF POWER SOURCES · 2022 · IF 9.794

Indium doped sulfide solid electrolyte with tamed lithium dendrite and improved ionic conductivity for all-solid-state battery applications

Yuanyuan Li,Jun Cheng,Jianwei Li,Zhen Zeng,Yixuan Guo,Hongqiang Zhang,Hongbin Liu,Xiao Xu,Yiwei Rao,Deping Li,Lijie Ci

Sulfide solid state electrolytes capture much attention owing to their high conductivity and decent mechanical property. Nevertheless, the moisture instability and poor interfacial compatibility against lithium metal anode remain challenging and hinder the practical application. Herein, we report a novel indium (In) doping strategy based on the hard-soft-acid-base theory to tackle these issues. Optimized Li 7 P 2.9 S 10.9 In 0.1 electrolyte exhibits a high ionic conductivity of 4.1 × 10 −3  S cm −1 and achieves an enhanced interfacial compatibility. Importantly, as In partially replaces the phosphorus (P), the amount of released hydrogen sulfide can be significantly decreased and the air stability is improved. The all-solid-state battery assembled with the Li 7 P 2.9 S 10.9 In 0.1 electrolyte demonstrates a high discharge capacity and a good cycling stability under a high current density of 1.0 C. This work provides a practical and effective method to design sulfide-based solid-state electrolyte with high ionic conductivity and enhanced air stability for all-solid-state battery applications.

研究领域: 材料科学 · 电化学 · 能源存储 · 固态离子学 · 电池技术
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Small · 2018 ·Vol. 14 ·期 34 ·1801798 · IF 9.598

Flexible, Flame-Resistant, and Dendrite-Impermeable Gel-Polymer Electrolyte for Li–O2/Air Batteries Workable Under Hurdle Conditions

Xiaohong Zou,Qian Lu,Yijun Zhong,Kaiming Liao,Wei Zhou,Zongping Shao

Gel-polymer electrolytes are considered as a promising candidate for replacing the liquid electrolytes to address the safety concerns in Li–O 2 /air batteries. In this work, by taking advantage of the hydrogen bond between thermoplastic polyurethane and aerogel SiO 2 in gel polymer, a highly crosslinked quasi-solid electrolyte (FST-GPE) with multifeatures of high ionic conductivity, high mechanical flexibility, favorable flame resistance, and excellent Li dendrite impermeability is developed. The resulting gel-polymer Li–O 2 /air batteries possess high reaction kinetics and stabilities due to the unique electrode–electrolyte interface and fast O 2 diffusion in cathode, which can achieve up to 250 discharge–charge cycles (over 1000 h) in oxygen gas. Under ambient air atmosphere, excellent performances are observed for coin-type cells over 20 days and for prototype cells working under extreme bending conditions. Moreover, the FST-GPE electrolyte also exhibits durability to protect against fire, dendritic Li, and H 2 O attack, demonstrating great potential for the design of practical Li–O 2 /air batteries.

研究领域: 电化学能源 · 材料科学 · 纳米复合材料 · 先进电池技术 · 固态离子学
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ELECTROCHIMICA ACTA · 2020 · IF 6.215

A dendrite-suppressed flexible polymer-in-ceramic electrolyte membrane for advanced lithium batteries

Shi Wang,Qingyuan Li,Minglei Bai,Jixin He,Chongyang Liu,Zengxi Li,Xiangfeng Liu,Wen-yong Lai,Liaoyun Zhang

Lithium-ion batteries (LIBs) using solid-state electrolytes (SSEs) can improve safety and energy density comparable with the liquid electrolytes (LE)-based counterparts. Especially, employing garnet-type SSEs to prepare solid-state LIBs are promising to achieve high-energy cells. However, the unbending and brittle issues of the inorganic SSE films are not suitable to fabricate flexible and stretchable energy storage devices. Here, We find that introducing specific polymer (30 wt%) into Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 (LLZTO) can strongly increase the strength of the composite polymer-in-inorganic electrolyte (CIE) film. Both in-situ and ex-situ characterizations demonstrate that CIE delivers an excellent ability to suppress the growth of Li dendrites due to the close packing of LLZTO and effective filled grain boundaries and voids inside the CIE film by the polymer. The CIE inherits impressive electrochemical performance from LLZTO. As a result, the assembled LiFePO 4 (LFP)/CIE/Li cell delivers better cell performance than LFP/LE-separator/Li cell at ambient temperature (AT). The assembled high-voltage cathode (Li 1.2 Mn 0.6 Ni 0.2 O 2 , 4.8 V)/CIE/Li cell also displays an excellent cell performance at AT. The present study offers new insights into exploring of flexible polymer-in-ceramic electrolytes for high-voltage LIBs with improved safety and energy density .

研究领域: 材料科学 · 电化学 · 能源存储 · 固态电池 · 纳米复合材料 · 界面工程
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Nano Energy · 2020 · IF 16.602

Electrolyte with boron nitride nanosheets as leveling agent towards dendrite-free lithium metal anodes

Jingyi Wu,Xiongwei Li,Zhixiang Rao,Xiaoning Xu,Zexiao Cheng,Yaqi Liao,Lixia Yuan,Xiaolin Xie,Zhen Li,Yunhui Huang

Lithium metal is a promising anode material for rechargeable batteries with high energy density . However, the uncontrollable dendrite growth severely hinders the commercialization of Li metal anode . Inspired by the “leveling” mechanism in traditional electroplating, we demonstrate that boron nitride nanosheets (BNNSs) as a liquid electrolyte additive can level out Li protrusions and enable dendrite-free Li metal anodes. 2D BNNSs can automatically and continuously flatten Li deposits and accommodate volume changes during Li plating/stripping. B atoms in BNNS as Lewis acid sites interact with Lewis basic anions in electrolyte, reducing Li + concentration gradient and unifying Li deposition. The collect effects of BNNS additive give rise to dendrite-free Li anodes over 400 h and deep plating/stripping up to 35 mAh cm −2 , as well as potential application in sub-zero temperature batteries (−20 °C). Li–S full cells using BNNS electrolyte also exhibit improved performance. This simple and effective strategy is applicable to develop dendrite-free Li or other metal anodes in high-performance energy storage devices.

研究领域: 材料科学 · 电化学 · 能源存储 · 纳米材料 · 电池技术
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Journal of Materials Chemistry A · 2016 ·Vol. 4 ·期 25 ·9816-9821 · IF 8.262

Hierarchical forest-like photoelectrodes with ZnO nanoleaves on a metal dendrite array

Li Cheng,Qing Chang,Yu Chang,Nannan Zhang,Changyuan Tao,Zhaona Wang,Xing Fan

Hierarchical forest-like photoelectrodes were prepared by assembling nano-ZnO on an array of micro-metal dendrites, aiming to demonstrate the idea of highly efficient photon-harvesting inside a biomimetic dendrite structure. Via a facile aqueous electrochemical deposition process, the metal dendrites were deposited on both flat and wire substrates with different alignments, showing wide adaptability. A strong, broadband anti-reflection effect was observed, owing to the diffuse reflection inside the microdendrites. By increasing the dendrite height, the overall reflectivity of the metal electrode can be reduced from 75% to 45%, which could be further reduced to 12% after combining with acicular-leaf-like ZnO nanoarrays. Its applications in light-driven water splitting were successfully demonstrated. Taking advantage of the forest-like photoelectrode, we have artificially constructed an efficient photo-electrochemical system similar to plants in a forest, with photons harvested by the crown-like photoanodes in the sunshine, and synthetic reactions driven by the root-like electrode in the shadow.

研究领域: 材料科学 · 纳米科技 · 光电化学 · 可再生能源 · 仿生学
✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2023 · IF 9.2

In-situ electrochemical optical techniques in the investigation of lithium interfacial phenomena with a liquid and a solid-state electrolyte

Tianyao Ding,Dong Zheng,Huainan Qu,Weixiao Ji,Xiaoxiao Zhang,Dongping Lu,Gongwei Wang,Deyang Qu

An in-situ electrochemical optical diagnosis is the key to the investigation of electrode interface during a redox reaction . Because the morphology changes particularly, dendrite formation, dendrite shapes, solid electrolyte interface formation and gas generation can be revealed visually. The challenge of ensuring uniform current density on a flat Li anode in a liquid electrolyte is addressed and uniform Li plating is demonstrated. The dendrite shape change under different reduction current density is discussed. The Li dendrite shape change and the performance of Li anodes with a surface lamination of graphite and red phosphate are used as examples to demonstrate the capability of the in-situ optical cell. An in-situ electrochemical optical cell used in the investigation of the increasingly popular solid-state Li batteries has its own challenges. Due to the untransparent nature of a solid-state electrolyte, an optical investigation on a solid-state electrolyte Li battery needs to be done by exposing the cross-section of the cell. In addition, it is very difficult to assemble an optical cell with a brittle and fragile solid-state electrolyte in a glove box. A set of formation and transfer dies, and an optical cell are introduced. The Li dendrite growth at the interface can be observed in a solid-state Li cell.

研究领域: 电化学 · 材料科学 · 能源存储 · 固态电池 · 界面科学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2021 · IF 8.128

Enhanced ionic conductivity and lithium dendrite suppression of polymer solid electrolytes by alumina nanorods and interfacial graphite modification

Xin-yu Hu,Mao-xiang Jing,Hua Yang,Quan-yao Liu,Fei Chen,Wei-yong Yuan,Le Kang,Dong-hong Li,Xiang-qian Shen

Poor room-temperature ionic conductivity and lithium dendrite formation are the main issues of solid electrolytes. In this work, rod-shaped alumina incorporation and graphite coating were simultaneously applied to poly (propylene carbonate) (PPC)-based polymer solid electrolytes (Wang et al., 2018). The obtained alumina modified solid electrolyte membrane (Al-SE) achieves a high ionic conductivity of 3.48 × 10 −4 S/cm at room temperature with a wide electrochemical window of 4.6 V. The assembled NCM622/Al-SE/Li solid-state battery exhibits initial discharge capacities of 198.2 mAh/g and 177.5 mAh/g at the current density of 0.1 C and 0.5 C, with the remaining capacities of 165.8 mAh/g and 161.3 mAh/g after 100 cycles respectively. The rod-shaped structure of Al 2 O 3 provides fast transport channels for lithium ions and its Lewis acidity promotes the dissociation of lithium salts and release of free lithium ions. The lithiophilic Al 2 O 3 and Graphite form intimate contact with metallic Li and create fast Li + conductive layers of Li-Al-O layer and LiC 6 layer, thus facilitating the uniform deposition of Li and inhibiting Li dendrite formation during long-term cycling. This kind of composite Al-SE is expected to provide a promising alternative for practical application in solid electrolytes.

研究领域: 材料科学 · 电化学 · 能源存储 · 固态离子学 · 纳米复合材料 · 锂金属电池
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JOURNAL OF ALLOYS AND COMPOUNDS · 2023 · IF 6.2

Regulating the anion disorder and synthesizing the low-cost and high-performance Li6−xPS5−xCl1+x solid electrolytes

Chengyu Mo,Yutao Yang,Zhenyu Wang,Yanpeng Lv,Rongzheng Tian,Zixiang Zhao,Hongzhou Zhang,Chunliang Li,Lianqi Zhang,Yongan Yang,Dawei Song

Sulfide solid electrolytes have attracted wide attention due to their high ionic conductivity . Li 6 PS 5 Cl is one of the most promising electrolytes for all-solid-state lithium batteries with high-energy-density. It is reported that the disordered arrangement of Cl - in the aragonite structure has a significant effect on the conductivity of Li 6 PS 5 Cl. In this work, the disorder of anion sites is modestly regulated by adjusting the ratio of S and Cl in Li 6−x PS 5−x Cl 1+x electrolyte. In addition, to verify the commonality of this strategy, Li 5.6 PS 4.6 Cl 1.4 is prepared using self-made Li 2 S, and similar results are obtained. On this basis, the density of Li 5.6 PS 4.6 Cl 1.4 electrolyte sheet is improved by hot-pressing, which can successfully inhibit the growth of lithium dendrites . As expected, the ionic conductivity of the sulfide electrolyte and the electrochemical performance of the ASSLBs are greatly improved. A highest ionic conductivity of 8.2 × 10 −3 S cm −1 of Li 5.6 PS 4.6 Cl 1.4 is obtained at room temperature. A high capacity retention of 99.99 % is maintained for NCM811 @Li 2 O//Li 5.6 PS 4.6 Cl 1.4 //Li-In system after 400 cycles at 1 C with ultra-high cathode loading of 35.6 mg cm −2 . Besides, the cost of sulfide electrolytes can be reduced as the decreased usage of Li 2 S. This work proposes a novel synthesis method of low-cost and high-performance Li 6−x PS 5−x Cl 1+x electrolytes.

研究领域: 材料科学 · 电化学 · 能源存储 · 固态离子学 · 电池技术
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Journal of Nanomaterials · 2018 ·Vol. 2018 ·期 1 ·1465760 · IF 2.207

Synthesis of Platinum Nanocrystals within Iodine Ions Mediated

Jiamao Li,Jingwei Hou,Yu Gong,Chengjian Xiao,Lei Yue,Linjie Zhao,Huan Ma,Heyi Wang,Shuming Peng,Chao Chen,Hongli Chen

A liquid-phase reducing method of synthesizing Pt nanocrystals was demonstrated, and dendrite-, cube-, and cuboctahedron-shaped Pt nanocrystals (NCs) with well-defined monomorphic were successfully synthesized through iodine ions mediated with the CTAB agent. When the KI concentration was increased to thirty times of K 2 PtCl 4 at the nucleation stage, the high-quality Pt nanodendrites could be obtained. However, no matter how many KI were added at the growth age, only cube- and cuboctahedron-shaped Pt nanocrystals formed. The results of high-resolution TEM, EDX, and XRD indicated that the size and shape of Pt NCs could be turned by changing the concentration and time of KI. In the nucleation stage, it might be due to that some iodine ions adsorb on the surfaces of Pt NCs, which probably cause the rapid growth process resulting in the formation of Pt nanodendrites. In the growth stage, although high concentrations of I − ions could contribute to the shape control and generate bigger particles of Pt NCs, small Pt particles do not grow into dendrites. The insight into the role of I − ions in synthesis of Pt NCs reported here provided a viewpoint for clearly understanding the formation mechanism of anisotropic platinum nanostructures.

研究领域: 纳米材料科学 · 物理化学 · 无机合成 · 催化化学 · 材料表征技术
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CHEMICAL ENGINEERING JOURNAL · 2020 · IF 10.652

Organic-inorganic multi-scale enhanced interfacial engineering of sulfide solid electrolyte in Li-S battery

Yang Bai,Yanbiao Zhao,Weidong Li,Linghui Meng,Yongping Bai,Guorong Chen

The developing sulfide solid electrolyte is a promising way to overcome shuttle effect of polysulfide in the traditional liquid Li-S battery. However, an air stable sulfide solid electrolyte and competitive solid–solid interface structure must be constructed firstly. Herein, we have designed an organic–inorganic multi-scale composite electrolytes to overcome the interfacial issues of solid state Li-S batteries (SSLSBs). The organic–inorganic composite electrolyte consists of a gel polymer electrolyte (GPE) and an oxygen doped inorganic sulfide solid electrolyte. The O doped sulfide solid electrolyte improves its chemical stability and suppresses the lithium dendrites. A thin GPE film protects the crystal structural stability during cycles and greatly enhances the performance of O doped sulfide solid electrolyte due to the GPE not only constructs soft interface contact between S cathode and solid electrolyte, but also builds lithium ion transport paths by ionic liquid between them. Those SSLSBs display a very good cycling performance with the specific capacity of 1023 mAh/g after 50 cycles at 60 °C and 541 mAh/g after 150 cycles at 30 °C under same rate of 0.1 C. This study demonstrates that the development of advanced solid-state Li-S battery needs to fully integrate a number of technical advantages.

研究领域: 电化学 · 材料科学 · 固态电池 · 能源存储 · 界面化学 · 纳米材料 · 电极材料
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