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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
✓ 已验证 DOI 高影响因子
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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
✓ 已验证 DOI 高影响因子
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Energy Technology · 2019 ·Vol. 7 ·期 4 ·1800981 · IF 3.163

Effects of Charge Cutoff Potential on an Electrolyte Additive for LiNi0.6Co0.2Mn0.2O2–Mesocarbon Microbead Full Cells

Bangwei Deng,Hao Wang,Xiang Li,Yan Ding,Daming Sun,Jun Ma,Mianzhong Chen,Tao Chen,Feng Gao,Meizhen Qu,Gongchang Peng

Tris(trimethylsilyl)phosphite (TMSPi) has been reported to be an excellent electrolyte additive. However, scarce reports exist on the effect of the charge cutoff potential on the cyclic stability using high-performance LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622)–mesocarbon microbead (MCMB) full cells. Herein, a high-loading and repeatable NCM622–MCMB coin-type full cell is successfully prepared, and the role of TMSPi on such a full cell at charge cutoff potentials of 4.25 and 4.45 V is studied. Theoretical calculations and detailed analyses reveal that it is oxidized in the first charging process due to its unsaturated P—O bonds, thus forming a stable P—O—F-rich cathode electrolyte interphase and preventing severe decomposition of the electrolyte over NCM622 during long-term cycling. In addition, the P—O and Si—O bonds of TMSPi both display HF-scavenging ability. Moreover, TMSPi may react directly with the LiPF 6 -based electrolyte to form some intermediate products that can be reduced on the MCMB electrode, thereby modifying the solid electrolyte interphase and improving the stability of MCMB during lithium intercalation.

研究领域: 电化学 · 材料科学 · 能源存储 · 锂离子电池 · 界面化学 · 电极材料
✓ 已验证 DOI 高影响因子
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International Journal of Electrochemical Science · 2023 ·Vol. 8 ·期 1 ·670-677 · IF 1.5

Effect of Sodium Chloride as Electrolyte Additive on the Performance of Mesocarbon Microbeads Electrode

Borong Wu,Yonghuan Ren,Daobin Mu,Cunzhong Zhang,Xiaojiang Liu,Guchang Yang,Feng Wu

A low cost and environment benign salt of sodium chloride (NaCl) was used as an additive in low temperature electrolyte (Lithium hexafluorophosphate(LiPF6) / ethylene carbonate(EC) / propylene carbonate(PC) / ethyl methyl carbonate(EMC) (0.14/0.18/0.68, wt.)) to improve the electrochemical performance of mesocarbon microbeads(MCMB) anode. The initial Li extraction capacity of MCMB electrode was 304.8mAh g -1 in this electrolyte when the content of EC was remarkably reduced for a better conductivity. Whereas, a value of 357.6mAh g -1 was attained in the presence of NaCl additive. The electrochemical performance of MCMB was largely enhanced in the low temperature electrolyte with NaCl. The effect of NaCl additive on the electrode performance was examined by cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS), scanning electron microscopy(SEM) and X-ray photoelectron spectroscopic(XPS).

研究领域: 电化学 · 材料科学 · 能源存储 · 锂离子电池 · 电极材料 · 电解液工程
✓ 已验证 DOI 高影响因子
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IONICS · 2021 ·Vol. 27 ·期 8 ·3339-3346 · IF 2.817

Strippable and flexible solid electrolyte membrane by coupling Li6.4La3Zr1.4Ta0.6O12 and insulating polyvinylidene fluoride for solid state lithium ion battery

Liu Huirong,Li Jianling,Feng Wei,Han Guimei

Commercial lithium-ion batteries have safety risks due to the use of electrolyte-containing flammable organic solvents. The development of all solid-state lithium ion batteries with solid electrolyte is a feasible technical way to improve the safety of batteries. In this work, PVDF-based composite solid-state electrolytes (CSEs) were prepared by coupling Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) and polyvinylidene fluoride (PVDF). The electrochemical performance and interfacial compatibility between composite electrolyte and electrode were improved by the combination of appropriate amount of Li-ion-conducting particles and the insulating polymer. The corresponding solid-state battery of LiFePO 4 |PVDF-LLZTO-CSE| Li is fabricated and delivers initial discharge capacity of 162.4 mAh g -1 , and coulomb efficiency is approximately 98.5%. And the solid-state battery exhibits satisfactory rate capability and cycling stability at room temperature. This study suggests that a combination of the lithium garnet particles and insulating polymer is one of the promising methods to solve the problem of liquid electrolyte.

研究领域: 材料科学 · 电化学 · 能源存储 · 固态离子学 · 电池技术
✓ 已验证 DOI 高影响因子
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IONICS · 2018 ·Vol. 25 ·期 1 ·241-251 · IF 2.347

A new solid-state electrolyte based on polymeric ionic liquid for high-performance supercapacitor

Wen Xinge,Dong Tao,Liu Ao,Zheng Shuohang,Chen Shimou,Han Yifan,Zhang Suojiang

As a polymer host, one polymeric ionic liquid poly(methyl methacrylate-1-vinyl-3-ethyl-imidazolium bis(trifluoromethylsulfonyl) imide) (abbr. P(MMA-co-VEImTFSI)) was successfully synthesized and characterized. Four poly(vinylidene fluoride-co-hexafluoropropylene) (abbr. PVDF-HFP)-based polymer electrolytes were prepared by blending 0, 5,15, and 25 wt% P(MMA-co-VEImTFSI). The electrochemical performances of the prepared electrolytes were studied carefully. The results revealed that increasing the polymeric ionic liquid content, the ionic conductivity of the polymer electrolytes could be enhanced and it obeyed the Arrhenius rule. The highest ionic conductivity of the polymer electrolytes was up to 2.09 × 10 −3  S cm −1 at room temperature. The polymer with 25 wt% polymeric ionic liquid showed an excellent electrochemical performance for supercapacitor electrolyte. After 2000 cycles, the retention of capacitance in P(MMA-co-VEImTFSI)-based polymer electrolyte was above 80%. It implied that the present P(MMA-co-VEImTFSI) polymeric ionic liquid was a decent component candidate in the high-performance polymer electrolytes.

研究领域: 材料科学 · 电化学 · 高分子化学 · 能源存储 · 功能材料
✓ 已验证 DOI 高影响因子
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2022 ·Vol. 47 ·期 79 ·33861-33871 · IF 7.139

The effect of sintering aids on BaCe0·7Zr0·1Y0.1Yb0.1O3-δ as the electrolyte of proton-conducting solid oxide electrolysis cells

Zhizhong Leng,Zuzhi Huang,Xu Zhou,Bo Zhang,Hu Bai,Juan Zhou,Shaorong Wang

Proton-conducting solid oxide electrolysis cells (H-SOECs) are attracting attentions of researchers due to their unique advantages. The proton-conducting material BaCe 0·7 Zr 0·1 Y 0.1 Yb 0.1 O 3-δ (BZCYYb) has both the advantages of barium ceria-based and barium zirconate-based materials. BZCYYb material usually is synthesized by solid-state reaction (SSR) method, hence the densification of this electrolyte material is the key to restrict the application of H-SOECs. In this paper, effects of adding 1 wt% of different sintering aids (NiO, CuO, ZnO) to BZCYYb on the grain size and the conductivity are investigated. After adding 1 wt% of NiO and CuO sintering aids, BZCYYb electrolyte achieves ideal density. The electrical conductivity of four samples (BZCYYb without adding sintering aid, BZCYYb with 1 wt% NiO, CuO, ZnO, respectively) is tested under different steam concentrations of air, nitrogen, hydrogen, and nitrogen-hydrogen mixture. The conductivity increased after the sintering aid is added. With the increase of steam concentration, the conductivity decreased slightly and then increased due to electron holes under oxygen atmosphere with steam at high temperature. In other atmospheres, the conductivity increases with the steam concentration. In the atmosphere of 20 vol% H 2 O-Air and H 2 , the conductivity of the BZCYYb samples with 1 wt% CuO is about 1.087 × 10 −2  S cm −1 and 9.02 × 10 −3  S cm −1 at 650 °C, and the conductivity of the BZCYYb samples with 1 wt% NiO is 1.277 × 10 −2  S cm −1 and 8.24 × 10 −3  S cm −1 , respectively. However, compared with NiO, CuO has advantages in promoting hydration reaction and proton conduction of BZCYYb electrolyte.

研究领域: 材料科学 · 电化学 · 能源材料 · 固态离子学 · 陶瓷材料
✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2021 · IF 9.127

Phenyl TrifluoroMethane sulfonate as a novel electrolyte additive for enhancing performance of LiNi0·6Co0·2Mn0·2O2/Graphite cells working in wide temperature ranges

Jingxiong Gao,Songyi Han,Haiming Hua,Jie Wu,Jing Zeng,Yuanyu Sun,Weiping Tang,Shuling Liu,Jinbao Zhao

To optimize the electrochemical behavior of NCM-based high-energy lithium-ion batteries (LIBs) in wide temperature ranges, Phenyl trifluoromethane sulfonate (PTM) is demonstrated as the novel electrolyte additive to enhance the electrochemical behavior of LiNi 0·6 Co 0·2 Mn 0·2 O 2 /graphite cells at 25 °C, −20 °C and 45 °C. The cells with 1.0 wt% PTM-containing electrolyte deliver 80.6% capacity retention after 350 cycles at 25 °C, 73.4% after 100 cycles at −20 °C, and 82.6% after 300 cycles at 45 °C, which are significantly higher than that in standard electrolyte (STD), corresponding to 36.4% at 25 °C, 40.3% at −20 °C, and failure at 45 °C, respectively. According to density functional theory (DFT) simulations and quantitative calculations, the PTM preferentially reduces on the anode and oxidizes on the cathode to participate in the formation of solid electrolyte interphase (SEI) films. In addition, the scanning electron microscopy (SEM), Transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and other analysis suggest that the formed SEI films are thinner and more stable for the electrolyte containing PTM, and the formed SEI films effectively control the decomposition of carbonate-based electrolytes and greatly decrease the increased resistance during the cycle.

研究领域: 电化学 · 材料科学 · 能源存储 · 锂电池技术 · 界面化学
✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2018 · IF 6.945

High ion conductive Sb2O5-doped β-Li3PS4 with excellent stability against Li for all-solid-state lithium batteries

Dongjiu Xie,Shaojie Chen,Zhihua Zhang,Jie Ren,Lili Yao,Linbin Wu,Xiayin Yao,Xiaoxiong Xu

The combination of high conductivity and good stability against Li is not easy to achieve for solid electrolytes , hindering the development of high energy solid-state batteries . In this study, doped electrolytes of Li 3 P 1- x Sb x S 4-2.5 x O 2.5 x are successfully prepared via the high energy ball milling and subsequent heat treatment . Plenty of techniques like XRD , Raman, SEM, EDS and TEM are utilized to characterize the crystal structures, particle sizes, and morphologies of the glass-ceramic electrolytes. Among them, the Li 3 P 0.98 Sb 0.02 S 3.95 O 0.05 ( x  = 0.02) exhibits the highest ionic conductivity (∼1.08 mS cm −1 ) at room temperature with an excellent stability against lithium. In addition, all-solid-state lithium batteries are assembled with LiCoO 2 as cathode, Li 10 GeP 2 S 12 /Li 3 P 0.98 Sb 0.02 S 3.95 O 0.05 as the bi-layer electrolyte, and lithium as anode. The constructed solid-state batteries delivers a high initial discharge capacity of 133 mAh g −1 at 0.1C in the range of 3.0–4.3 V vs. Li/Li + at room temperature, and shows a capacity retention of 78.6% after 50 cycles. Most importantly, the all-solid-state lithium batteries with the Li 10 GeP 2 S 12 /Li 3 P 0.98 Sb 0.02 S 3.95 O 0.05 electrolyte can be workable even at −10 °C. This study provides a promising electrolyte with the improved conductivity and stability against Li for the application of all-solid-state lithium batteries.

研究领域: 材料科学 · 电化学 · 固态电池 · 能源存储 · 无机非金属材料
✓ 已验证 DOI 高影响因子
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Energy Technology · 2020 ·Vol. 8 ·期 10 ·2000606 · IF 3.404

Low-Cost Raw Materials Synthesized Na2.9375PS3.9375Cl0.0625 Solid Electrolyte

Yu Wang,Nachuan Yang,Yi Shuai,Kanghua Chen

Na 3 PS 4 -based materials, which have relatively high conductivities, make promising Na-ion solid electrolytes for realizing all-solid-state sodium batteries. Herein, Na 2.9375 PS 3.9375 Cl 0.0625 solid electrolytes’ power is prepared by a mechanical ball milling process and subsequent heat treatment process using low-cost Na, NaCl, P 2 S 5 , and S as raw materials. In addition, its electrical conductivity and electrochemical performance by compounding with polyethylene oxide–NaClO 4 are studied. The results show that Na 2.9375 PS 3.9375 Cl 0.0625 solid electrolyte heated at 550 °C with polyethylene oxide–NaClO 4 exhibits Na-ion conductivity of 8.75 × 10 −4 S cm −1 . The pragmatic and cost-effective raw materials grant the solid electrolyte with high-performance and higher practical value.

研究领域: 材料科学 · 电化学 · 能源存储 · 固体离子学 · 无机非金属材料
✓ 已验证 DOI 高影响因子
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Energy & Environmental Materials · 2022 ·Vol. 6 ·期 3 ·e12351 · IF 13.443

Molecular Reactivity and Interface Stability Modification in In-Situ Gel Electrolyte for High Performance Quasi-Solid-State Lithium Metal Batteries

Qiyu Wang,Xiangqun Xu,Bo Hong,Maohui Bai,Jie Li,Zhian Zhang,Yanqing Lai

Quasi-solid-state lithium metal battery is a promising candidate for next generation high energy density and high safety power supply. Despite intensive efforts on electrolytes, uncontrolled interfacial reactions on lithium with electrolyte and patchy interfacial contacts still hinder its practical process. Herein, we bring in rationally designed F contained groups into polymer skeleton via in-situ gelation for the first time to establish quasi-solid-state battery. This method achieves a capacity retention of 90% after 1000 cycles at 0.5C with LiFePO 4 cathodes. The interface constructed by polymer skeleton and reaction with –CF 3 lead to the predicted solid electrolyte interface species with high stability. Furthermore, we optimize molecular reactivity and interface stability with regulating F contained end groups in the polymer. Comparisons on different structures reveal that high performance solid stable lithium metal batteries rely on chemical modification as well as stable polymer skeleton, which is more critical to construct robust and steady SEI with uniform lithium deposition. New approach with functional groups regulation proposes a more stable cycling process with a capacity retention of 94.2% at 0.5C and 87.6% at 1C after 1000 cycles with LiFePO 4 cathodes, providing new insights for the practical development of quasi-solid-state lithium metal battery.

研究领域: 电化学 · 材料科学 · 能源存储 · 界面化学 · 高分子化学
✓ 已验证 DOI 高影响因子
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Journal of Materiomics · 2022 ·Vol. 9 ·期 3 ·568-576 · IF 8.589

Synergistically enabling the interface stability of lithium metal batteries with soft ionic gel and garnet-type Li6.4La3Zr1.4Ta0.6O12 ceramic filler

Qiujun Wang,Weiqi Zhu,Ya Su,Di Zhang,Zhaojin Li,Huan Wang,Huilan Sun,Bo Wang,Dan Zhou,Li-Zhen Fan

Lithium metal batteries based on solid electrolytes are considered as promising candidates with high energy density and safety. However, the weak solid-solid contact between electrolyte and electrode can easily lead to interface instability and lithium ions discontinuous migration, which seriously reduces the electrochemical performance of the battery. Herein, we construct a soft gel interfacial layer to improve the stability of the solid-solid interface between electrolyte and electrode by means of polyester-based monomers and imidazole-based ionic liquids. Based on this, garnet-type Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) particles as inorganic ceramic filler were introduced in the layer to obtain composite electrolytes with high ionic conductivity (up to 1.1 × 10 −3  S/cm at 25 °C). As a result, the assembled lithium symmetric battery of Li|THCE-15%LLZTO|Li suggests excellent cycling stability with 700 h at 0.1 mA/cm 2 at 50 °C, and the lithium metal batteries of LFP|THCE-15%LLZTO|Li delivers high initial discharge capacity of 128.2 mA ·h/g with capacity retain of 75.48% after 150 cycles at 2 C. This work paves a new route to build safe and stable lithium metal batteries with synergistic introduction of composite electrolytes between electrolyte and electrode using soft gel interfacial layer and inorganic filler.

研究领域: 电化学 · 材料科学 · 能源存储 · 固体离子学 · 界面工程
✓ 已验证 DOI 高影响因子
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