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JOURNAL OF POWER SOURCES · 2020 · IF 8.247

Li2S@NC composite enable high active material loading and high Li2S utilization for all-solid-state lithium sulfur batteries

Donghao Wang,Yuqi Wu,Xuefan Zheng,Shijun Tang,Zhengliang Gong,Yong Yang

All-solid-state Li–S batteries (ASSLSBs) offer an opportunity to realize both high energy density , safety and reliability, via eliminating the polysulfides shuttle effect and flammable liquid electrolyte. However, the sluggish kinetics of S and Li 2 S solid conversion results in low discharge capacity at high active material loading, which is critical for ASSLSBs to implement the high energy density potential. Herein, nitrogen doped-carbon (NC) coated Li 2 S (Li 2 S@NC composite) is developed for ASSLSBs that highly improves electrochemical performance. A thin and uniform nitrogen doped-carbon layer is coated on Li 2 S via pyrolysis deposition approach to prepare Li 2 S@NC. The as obtained Li 2 S@NC composite exhibits greatly enhanced electrochemical performance with high reversible capacity, high coulombic efficiency of ~100%, good rate capability and cycling stability. Particularly, outstanding electrochemical performance with high capacity of 931 mAh g −1 can also be obtained at both high Li 2 S content (43%) and high areal Li 2 S loading (10.4 mg cm −2 ).

研究领域: 材料科学 · 电化学 · 能源存储 · 固态电池 · 纳米材料
✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2016 · IF 6.333

Insights on the fundamental lithium storage behavior of all-solid-state lithium batteries containing the LiNi0.8Co0.15Al0.05O2 cathode and sulfide electrolyte

Gang Peng,Xiayin Yao,Hongli Wan,Bingxin Huang,Jingyun Yin,Fei Ding,Xiaoxiong Xu

An insightful study on the fundamental lithium storage behavior of all-solid-state lithium battery with a structure of LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA)/Li 10 GeP 2 S 12 /Li-In is carried out in this work. The relationship between electrochemical performances and particle size, surface impurities and defects of the NCA positive material is systematically investigated. It is found that a ball-milling technique can decrease the particle size and remove surface impurities of the NCA cathode while also give rise to surface defects which could be recovered by a post-annealing process. The results indicate that the interfacial resistance between the NCA and Li 10 GeP 2 S 12 is obviously decreased during the ball-milling followed by a post-annealing. Consequently, the discharge capacity of NCA in the NCA/Li 10 GeP 2 S 12 /Li-In solid-state battery is significantly enhanced, which exhibits a discharge capacity of 146 mAh g −1 at 25 °C.

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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SOLID STATE IONICS · 2020 · IF 3.107

Enhancing the electrochemical performances of Li7P3S11 electrolyte through P2O5 substitution for all-solid-state lithium battery

Yayu Guo,Huilan Guan,Wenxiu Peng,Xuelei Li,Yue Ma,Dawei Song,Hongzhou Zhang,Chunliang Li,Lianqi Zhang

Li 7 P 3 S 11 (70Li 2 S·30P 2 S 5 ) sulfide is a promising electrolyte candidate for all-solid-state lithium batteries (ASSLBs) owing to its high ionic conducivity and wide electrochemical stability window. However, the sensitivity to moisture and the poor interfacial compatibility with electrodes limit the conventional application of Li 7 P 3 S 11 . Herein, we present a substitution strategy to produce a O-incorporated 70Li 2 S·(30-x)P 2 S 5 ·xP 2 O 5 (mol%) sulfide electrolyte to address above issues. The elaborately designed electrolyte is prepared via wet vibration ball milling technique with P 2 O 5 substitution content of 1, 3 and 5. As a result, the 70Li 2 S·27P 2 S 5 ·3P 2 O 5 electrolyte displays the highest ionic conductivity of 2.61× 10 −3  S cm −1 which outperforms than that of pristine Li 7 P 3 S 11 (ionic conductivity of 1.35 × 10 −3  S cm −1 ) and the assembled LiCoO 2 @LiNbO 3 /70Li 2 S·27P 2 S 5 ·3P 2 O 5 /Li-In ASSLB exhibits the superior capacity retention of 93.2% after 100 cycles at 0.5C. The reason for the developed electrochemical performance lies in the substitution of the non-bridging sulfur atom with bridging oxygen atom, from which the interaction between electrolyte and lithium ions is weakened, thereby the rapid transfer of lithium ions is facilitated. Furthermore, Raman and XRD results indicate that the adverse interfacial reactions are suppressed through P 2 O 5 substitution. This work suggests that P 2 O 5 substitution is an effective strategy for sulfide electrolyte toward high energy all-solid-state lithium batteries.

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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SOLID STATE IONICS · 2019 · IF 2.886

Conformal, nanoscale γ-Al2O3 coating of garnet conductors for solid-state lithium batteries

Fan Deng,Yongmin Wu,Weiping Tang,Shufeng Song,Zhaoyin Wen,Masashi Kotobuki,Li Lu,Jianyao Yao,Ning Hu,Janina Molenda

The use of garnet-type conductors as electrolytes for safe lithium solid-state batteries is impeded by the lack of critical processing strategy to stabilize and densify the cubic lithium garnets. The synthesis and processing of dense cubic lithium garnets are typically depending on solid state reaction as a result of unintentional Al contamination from the alumina crucibles at temperatures up to 1230 °C. High Al concentration is also believed to induce the sluggish migration of lithium ions . Here, we demonstrate an ultrathin, conformal γ-Al 2 O 3 surface coating on garnet solids by a hybrid microemulsion solid-state method for accomplishing rational and controllable synthesis and processing of dense cubic garnets with low Al concentration. The γ-Al 2 O 3 coating demonstrates fast-ion conducting Al-doped Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 phase with low Al concentration (~0.17 mol per formula unit), low tetragonal-to-cubic phase transformation temperature of 500 °C, and total conductivity of ~4.4 × 10 − 4  S cm − 1 . Specifically, the desired microstructures of the sintered pellets with uniform grains are revealed. As a proof-of-concept, we demonstrate that the nanoscale γ-Al 2 O 3 modification garnet conductor Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 is available to suppress lithium dendrites in symmetric Li/γ-Al 2 O 3 coating Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 /Li cells during lithium plating/stripping at room temperature, with current densities of 0.026 to 0.5 mA cm − 2 . The Li/γ-Al 2 O 3 coating Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 /LiNi 0.5 Co 0.2 Mn 0.3 O 2 cell delivered a high initial discharge capacity of ~164.2 mAh g − 1 , more importantly, an outstanding cycling performance with a capacity retention of 90.16% after 30 cycles at 0.1C and room temperature. This new synthesis route and the utilization of nanoscale γ-Al 2 O 3 surface modification could open up new avenue to lithium garnet conductors with reliable synthesis for all-solid-state lithium batteries application.

研究领域: 材料科学 · 电化学 · 固态离子学 · 能源存储 · 纳米材料 · 电池技术
✓ 已验证 DOI 高影响因子
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Journal of Energy Chemistry · 2020 · IF 7.216

Enabling high-performance all-solid-state lithium batteries with high ionic conductive sulfide-based composite solid electrolyte and ex-situ artificial SEI film

Jingguang Yi,Dan Zhou,Yuhao Liang,Hong Liu,Haifang Ni,Li-Zhen Fan

All-solid-state lithium batteries (ASSLBs) employing sulfide electrolyte and lithium (Li) anode have received increasing attention due to the intrinsic safety and high energy density. However, the thick electrolyte layer and lithium dendrites formed at the electrolyte/Li anode interface hinder the realization of high-performance ASSLBs . Herein, a novel membrane consisting of Li 6 PS 5 Cl (LPSCl), poly(ethylene oxide) (PEO) and Li-salt (LiTFSI) was prepared as sulfide-based composite solid electrolyte (LPSCl-PEO3-LiTFSI) (LPSCl:PEO = 97:3 wt/wt; EO:Li = 8:1 mol/mol), which delivers high ionic conductivity (1.1 × 10 −3 S cm −1 ) and wide electrochemical window (4.9 V vs. Li + /Li) at 25 °C. In addition, an ex-situ artificial solid electrolyte interphase (SEI) film enriched with LiF and Li 3 N was designed as a protective layer on Li anode (Li(SEI)) to suppress the growth of lithium dendrites. Benefiting from the synergy of sulfide-based composite solid electrolyte and ex-situ artificial SEI, cells of S-CNTs/LPSCl-PEO3-LiTFSI/Li(SEI) and Al 2 O 3 @LiNi 0.5 Co 0.3 Mn 0.2 O 2 /LPSCl-PEO3-LiTFSI/Li(SEI) are assembled and both exhibit high initial discharge capacity of 1221.1 mAh g −1 (135.8 mAh g −1 ) and enhanced cycling   stability with 81.6% capacity retention over 200 cycles at 0.05 C (89.2% over 100 cycles at 0.1 C). This work provides a new insight into the synergy of composite solid electrolyte and artificial SEI for achieving high-performance ASSLBs .

研究领域: 材料科学 · 电化学 · 能源存储 · 固态电池 · 界面工程
✓ 已验证 DOI 高影响因子
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SOLID STATE IONICS · 2018 · IF 2.751

Cathode/electrolyte interface engineering via wet coating and hot pressing for all-solid-state lithium battery

Wenping Zha,Yinghui Xu,Fei Chen,Qiang Shen,Lianmeng Zhang

In this work, Li 7 La 3 Zr 2 O 12 (LLZO)-based membrane electrolyte, which has good flexibility and can be easily mass-produced, is proposed to address the intrinsic defects of ceramic electrolytes . The LLZO-based membrane electrolyte is electrochemically stable in the voltage range of 0–5.2 V vs. Li/Li + due to the good oxidative stability of LLZO. We also develop a simple and low-cost approach to fabricate the all-solid-state lithium battery (ASSLB). Wet coating and hot pressing are applied to form a continuous and homogeneous electrolyte layer on a cathode layer. Thanks to the integrated preparation process, there is no obvious interface between the cathode layer and the electrolyte layer, hence reducing the interface resistance. The Li/LiFePO 4 batteries exhibit desirable cycling performance at 60 °C, which deliver a maximum discharge specific capacity of 151.6 mAh·g −1 at 0.1C and maintain 97.8% of the capacity after 50 cycles.

研究领域: 材料科学 · 电化学 · 能源存储 · 固态离子学 · 先进电池技术
✓ 已验证 DOI 高影响因子
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JOURNAL OF ALLOYS AND COMPOUNDS · 2023 · IF 6.2

Inhibition of lithium dendrites by a LiPON interlayer with Li+ conductive and electron non-conductive dynamic properties based on Li7La3Zr2O12 solid electrolyte

Yanhua Zhang,Yuhang Mei,Xinglong Gao,Yumei Xiao,Zijun Tang,Xing Xiang,Jiadong Deng

The lithium dendrite problem of Li 7 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) solid electrolyte restricts the practical application and development of all-solid-state lithium batteries (ASSLBs). Herein, a LiPON interlayer with Li + conductive and electron non-conductive dynamic properties is constructed at the Li/LLZTO interface. Results show that the electronic conductivity of solid electrolyte after LiPON modification decreased by nearly three orders of magnitude, indicating that it has good ability to hinder electron conduction . The interlayer enhances the wettability between the Li metal anode and LLZTO, resulting in a decrease of battery resistance from 3400 Ω to 700 Ω. The critical current density of the ASSLBs increase from 0.1 mA cm −2 to 1.2 mA cm −2 at room temperature, and the battery cycle number increase from 31 h to over 1000 h. XPS deep etching results show that the LiPON/LLZTO interface has good electrochemical stability. The Kelvin probe force microscope displays a sharp increase in potential within the LiPON interlayer, indicating its successful hindrance of electron conduction to the solid electrolyte. The effective inhibition of lithium dendrites growth is due to LiPON can promote the Li + transmission from LLZTO solid electrolyte to Li anode, and also hinder the electron conduction to LLZTO to form lithium dendrites.

研究领域: 材料科学 · 电化学 · 能源存储 · 固态电池 · 界面工程
✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2016 · IF 6.333

One-pot preparation of new copolymer electrolytes with tunable network structure for all-solid-state lithium battery

Bo Chen,Qiang Xu,Zhen Huang,Yanran Zhao,Shaojie Chen,Xiaoxiong Xu

A new class of copolymer electrolytes with tunable network structure is successfully designed and prepared via a facile one-pot reaction. The trimethylolpropane triglycidyl ether (TMPEG) is cross-linked with poly (ethylene glycol) diamine (NPEG) to create well-defined solid network polymer electrolyte (SNPE). The network structure could be tuned by changing the molar ratio of TMPEG and NPEG or the molecular weight of NPEG. The effects of molecular weight of NPEG and molar ratio of EO/Li + on the ionic conductivity are systematically investigated. The optimal electrolyte TMPEG-NPEG4K[2:1]-16:1 presents a maximum conductivity of 1.10 × 10 −4  S cm −1 under 30 °C, and an 18-fold ionic conductivity enhancement in that of PEO-based electrolyte. Furthermore, it also exhibits wide electrochemical window (0–5.4 V), excellent compatibility with metallic Li, and superior mechanical properties. The all-solid-state lithium batteries LiFePO 4 /Li are assembled with TMPEG-NPEG4K[2:1]-16:1 electrolyte, and present good cycling and rate performance under 60 °C. The initial discharge specific capacities of the batteries are 161.7 mAh g −1 at 0.2 C and 132.7 mAh g −1 at 1 C, and the capacity retention ratio can be retained at 90.6% and 90.5% after 100 cycles. This new copolymer electrolyte may become a promising candidate for applications in all-solid-state lithium battery.

研究领域: 材料科学 · 高分子化学 · 电化学 · 能源存储 · 固态离子学 · 锂离子电池
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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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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2019 ·Vol. 31 ·期 1 ·542-547 · IF 2.195

Study on preparation of LSTP thin film electrolyte by RF magnetron sputtering and electrical properties

Zhang Xiuyun,Zhao Yunyun,Ling Qia,Zhu Guisheng,Zhou Xiujuan,Deng Jianqiu,Yan Dongliang,Liu Laijun,Xu Huarui,Yu Aibing

Amorphous Li–Si–Ti–P–O (LSTP) thin film electrolyte was successfully prepared by radio frequency magnetron sputtering using Li 1.4 Si 0.4 Ti 1.6 (PO 4 ) 3 powder targets and stainless steel sheet as substrate. The effects of sputtering power on the structure, morphology, ionic conductivity, and electronic conductivity of the LSTP thin film electrolyte were investigated. The results showed that the LSTP thin film electrolyte obtained with sputtering power kept at 160 W, displayed uniform particles compacted in arrangement, proper stoichiometric ratio to the powder target as well as sufficient Li-ion for diffusion. Hence, it held a considerable ionic conductivity of 4.12 × 10 −6 S cm −1 and a high σ ion / σ ele ratio about 8 magnitudes, indicating that it can be used as film electrolyte in all-solid-state lithium batteries.

研究领域: 材料科学 · 电化学 · 固态离子学 · 薄膜技术 · 能源材料
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PARTICLE & PARTICLE SYSTEMS CHARACTERIZATION · 2020 ·Vol. 37 ·期 8 ·2000164 · IF 3.099

Sub-10 nm V2O5 Crystals on Carbon Nanosheets for Advanced All-Solid-State Lithium Metal Batteries

Liwei Su,Linhui Liu,Jinpei Hei,Huan Chen,Lianbang Wang,Yuanhao Wang,Manman Ren

V 2 O 5 , as a lithium-free cathode material, has inherent defects such as sluggish kinetics and volume change and, at the same time, requires a lithium metal anode that tends to form dendrites in liquid electrolytes. Both the lithium dendrite and the flammable electrolyte solvent bring longtime safety issues. This work introduces nonflammable inorganic–organic composite solid electrolyte to inhibit the growth of the lithium dendrite and suppress the instability caused by V 2 O 5 nanometerization. However, the long-term cycling and rate performances are still insufficient even when reducing V 2 O 5 size to about 50 nm. As an improvement, sub-10 nm V 2 O 5 /C nanosheets are designed and prepared using corn stalks as precursors through simple impregnation and calcination process. The V 2 O 5 /C offers a much better electrode/electrolyte contact and interface stability than bulk V 2 O 5 and commercial V 2 O 5 in the inorganic–organic composite solid electrolyte. The discharge capacity is 228 mAh g −1 at 0.1 C after 50 cycles and ≈110 mAh g −1 at 2.0 C.

研究领域: 材料科学 · 电化学 · 纳米能源 · 固态电池 · 电极材料设计
✓ 已验证 DOI 高影响因子
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Science China-Materials · 2021 ·Vol. 64 ·期 6 ·1378-1385 · IF 8.273

Interplay between Li3YX6 (X = Cl or Br) solid electrolytes and the Li metal anode

Fu Yuanyuan,Ma Cheng

The interplay between solid electrolytes and electrodes is of vital importance to the performance of all-solid-state Li batteries. Recently, halide superionic conductors have emerged as a new family of high-performance solid electrolytes, but their compatibility with Li metal, i.e., the anode with the highest theoretical capacity, has not been systematically studied. Here, we investigate the interaction between Li metal and two representative halide solid electrolytes: Li 3 YCl 6 and Li 3 YBr 6 . Both materials are found to form interphases with Li, similar to most solid electrolytes. However, the interphases observed here contain electronic conducting components, which are detrimental to their compatibility with Li. By elucidating this phenomenon, the present study provides guiding principles for improving the Li compatibility of halide solid electrolytes.

研究领域: 材料科学 · 电化学 · 固态离子学 · 能源存储 · 电池技术
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