ACS Applied Materials & Interfaces
·
2018
·
IF 8.097
Zhihua Zhang,Shaojie Chen,Jing Yang,Junye Wang,Lili Yao,Xiayin Yao,Ping Cui,Xiaoxiong Xu
An ingenious interface re-engineering strategy was applied to in situ prepare a manipulated LiH2PO4 protective layer on the surface of Li anode for circumventing the intrinsic chemical stability issues of Li10GeP2S12 (LGPS) to Li metal, specifically the migration of mixed ionic-electronic reactants to the inner of LGPS, and the kinetically sluggish reactions in the interface. As consequence, the stability of LGPS with Li metal increased substantially and the cycling of symmetric Li/Li cell showed that the polarization voltage could keep relative stable for over 950 h at 0.1 mA cm–2 within ±0.05 V. The optimized ASSLiB of LiCoO2 (LCO)/LGPS/Li with interface-engineered structure was able to deliver long cycle life and high capacity, i.e., a reversible discharge capacity of 131.1 mAh g–1 at the initial cycle and 113.7 mAh g–1 at the 500th cycle under 0.1 C with a retention of 86.7%. In addition, the factors effected on the interphases formation of the LGPS/Li interface were analyzed, and the mechanism of the stability between LGPS and Li anode with protective layer was further investigated. Moreover, the probable causes of battery degradation were also explored. Above all, this work would give an alternative strategy for the modification of Li anode in high energy density solid-state lithium metal batteries.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
International Journal of Electrochemical Science
·
2023
·
IF 1.5
Hongliang Li,Tong Zhang,Zi Yang,Yueli Shi,Quanchao Zhuang,Yanhua Cui
The electrochemical impedance spectroscopy (EIS) technique has been widely used for analysing lithium battery systems, especially to determine kinetic and transport parameters, understand reaction mechanisms, and study capacity fade mechanisms. In this work, the initial charge-discharge process of LiCoO 2 @LiNbO 3 /Li 10 GeP 2 S 12 /Li (LLCO/LGPS/Li) and LiNi 0.5 Co 0.2 Mn 0.3 O 2 @LiNbO 3 /Li 10 GeP 2 S 12 /Li (LNCM523/LGPS/Li) batteries at different potentials was systematically investigated by EIS. During the lithium-ion insertion-removal process, the Nyquist plots of both LLCO/LGPS/Li and LNCM523/LGPS/Li batteries are composed of three parts, namely, two semicircles and an inclined line, which can be attributed to the interfacial impedance between the solid electrolyte and electrode, the charge transfer process, and the solid-state diffusion of the lithium-ion in the cathode with decreasing frequency, respectively. A proper equivalent circuit is proposed to fit the experimental EIS data and the variations in the interfacial resistance ( R if ) between the solid electrolytes (SEs) and electrode. The charge transfer resistance ( R ct ) along with the increase or decrease in the electrode polarization potential is quantitatively analysed in detail. Based on the experimental results, it has been revealed that, the increase in R if between the solid electrolyte and electrode may cause the capacity fade of all-solid-state batteries during charge-discharge.
研究领域:
电化学
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材料科学
·
能源存储
·
固态离子学
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电池技术
✓ 已验证
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2016
·
IF 4.803
Bo Chen,Zhen Huang,Xiaotian Chen,Yanran Zhao,Qiang Xu,Peng Long,Shaojie Chen,Xiaoxiong Xu
A new solid polymer electrolyte (SPE) PEO-LiTFSI-1%LGPS-10%SN is successfully prepared via a convenient method with low cost. The effect of SN on the ionic conductivity of PEO-based electrolyte is systematically investigated. It presents a maximum conductivity of 9.10 × 10 −5 S·cm −1 at 25 °C, and a 15-fold ion conductivity enhancement in PEO-LiTFSI. It exhibits wide electrochemical window (0–5.5 V) and excellent compatibility with metallic Li. The LiFePO 4 /Li batteries exhibit a good cycling and rate performance under 40 °C, whose maximum discharge specific capacity at 0.1 C is 160.6 mAh·g −1 , and 94.7% can be retained after 60 cycles. At 0.5C, the maximum discharge specific capacity is 138.4 mAh·g −1 , and capacity retention close to 90% even after 100 cycles. The reasons of activation process are discussed. This new SPE with outstanding electrochemical performance is a promising solid electrolyte candidate for applications in all-solid-state lithium battery.
✓ 已验证
DOI
高影响因子
JOURNAL OF THE AMERICAN CERAMIC SOCIETY
·
2015
·Vol. 98
·期 12
·3831-3835
·
IF 2.61
Kun Yang,Jianying Dong,Long Zhang,Yueming Li,Limin Wang
Multiple doping is widely used to improve the performance of a material, including its electrical transport, mechanical, and photovoltaic properties. In this paper, Sn–Se dual-doped Li 10 GeP 2 S 12 (LGPS, thio-LISICON II analogue) electrolytes were synthesized via ball milling and sintering and compared with those Sn or Se single-doped. Successful Sn and/or Se substitution expanded the unit cell and formed units, which were verified by X-ray powder diffraction, energy-dispersive X-ray spectroscopy, and Raman spectroscopy. In contrast to the limited benefits of Se single doping and the negative effects of Sn single doping, Sn–Se dual doping demonstrated up to 53% enhancement in ionic conductivity. More importantly, Sn–Se dual-doped LGPS showed an extremely low activation energy of 16 kJ/mol, which is one of the lowest known values for lithium ion conductors; as well as one of the widest electrochemical windows of 8 V. Sn–Se dual-doped LGPS is a promising electrolyte for advanced all-solid-state batteries.
研究领域:
材料科学
·
电化学
·
储能
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全固态电池
·
离子导体
✓ 已验证
DOI
高影响因子
SOLID STATE IONICS
·
2017
·
IF 2.354
Yan Sun,Wenning Yan,Li An,Bingbin Wu,Kaifu Zhong,Ruizhi Yang
A super solid electrolyte of Ba-substituted Li 10 GeP 2 S 12 is designed and fabricated to achieve high electrochemical stability. Among the Ba-substituted Li 10 GeP 2 S 12 solid electrolytes, the composition of Li 9.4 Ba 0.3 GeP 2 S 12 exhibits the highest ionic conductivity of 7.04 × 10 − 4 S cm − 1 with an activation energy of 28.27 kJ mol − 1 at 25 °C. The electrochemical window of Li 9.4 Ba 0.3 GeP 2 S 12 is between 0 and 6 V (vs. Li), which is higher than the typical 5 V window of Li 10 GeP 2 S 12 . As compared with Li 10 GeP 2 S 12 , Li 9.4 Ba 0.3 GeP 2 S 12 demonstrates a significantly reduced polarization and a better cycle stability though its ionic conductivity is slightly lower than that of the former. The electrochemical stability of Ba-substituted Li 10 GeP 2 S 12 can be attributed to the structural stability resulting from the stable interaction between Ba 2 + and S 2 − in the structure.
研究领域:
材料科学
·
固态离子学
·
电化学
·
能源材料
·
无机固体化学
✓ 已验证
DOI
高影响因子
ADVANCED MATERIALS
·
2024
·Vol. 36
·期 36
·2408903
·
IF 27.4
Nini Zhang,Qinsheng He,Lu Zhang,Jing Zhang,Liangfeng Huang,Xiayin Yao
The unique structure and exceptionally high lithium ion conductivity over 10 mS cm −1 of Li 10 GeP 2 S 12 have gained extensive attention in all-solid-state lithium batteries. However, its poor resistivity to moisture and chemical/electrochemical incompatibility with lithium metal severely impede its practical application. Herein, a fluorine functionalized Li 10 GeP 2 S 12 is synthesized by stannous fluoride doping and employed as a monolayer solid electrolyte to realize stable all-solid-state lithium batteries. The atomic-scale mechanism underlying the impact of fluorine doping on both moisture and electrochemical stability of Li 10 GeP 2 S 12 is revealed by density functional theory calculations. Fluorine surface doping significantly reduces surface hydrophilicity by electronic regulation, thereby retarding the hydrolysis reaction of Li 10 GeP 2 S 12 . After exposed to a relative humidity of 35%–40% for 20 min, the ionic conductivity of Li 9.98 Ge 0.99 Sn 0.01 P 2 S 11.98 F 0.02 maintains as high as 2.21 mS cm −1 , nearly one order of magnitude higher than that of Li 10 GeP 2 S 12 with 0.31 mS cm −1 . Meanwhile, bulk doping of highly electronegative fluorine promotes the formation of lithium vacancies in the Li 10 GeP 2 S 12 system, thus allowing stable lithium plating/stripping in Li | Li symmetric batteries, boosting a critical current density reaching 2.1 mA cm −2 . The LiCoO 2 | lithium all-solid-state batteries display improved cycling stability and rate capability, showing 80.1% retention after 600 cycles at 1C.
研究领域:
材料科学
·
能源存储技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Energy Storage Materials
·
2018
·
IF 0
Gaozhan Liu,Dongjiu Xie,Xuelong Wang,Xiayin Yao,Shaojie Chen,Ruijuan Xiao,Hong Li,Xiaoxiong Xu
A series of new solid electrolytes of Li 3+3 x P 1- x Zn x S 4- x O x ( x = 0.01, 0.02, 0.03, 0.04, 0.05, 0.06) are synthesized successfully via Zn, O co-doping the Li 3 PS 4 glass-ceramic for the first time. The result shows that Li 3 PS 4 aliovalent substitution of 2 mol% ZnO (Li 3.06 P 0.98 Zn 0.02 S 3.98 O 0.02 ) presents the highest conductivity of 1.12×10 −3 S cm −1 at room temperature, which is twice that of the pristine Li 3 PS 4 . Besides, Li 3.06 P 0.98 Zn 0.02 S 3.98 O 0.02 exhibits excellent stability against humid air , lithium metal and chlorobenzene solvent. The mechanisms of the enhancement of conductivity and air-stability are well understood by conducting first-principles density functional theory (DFT) calculation and Bond-Valence (BV) analysis, and the results well demonstrate that the conductivity and air-stability of Li 3 PS 4 could be improved via Zn, O dual-doping, in which partial P 5+ could be substituted by Zn 2+ , and a part of S 2- could be replaced by O 2- . Finally, the all-solid-state lithium battery (ASSLB) with bi-layer electrolytes of LiCoO 2 /Li 10 GeP 2 S 12 /Li 3.06 P 0.98 Zn 0.02 S 3.98 O 0.02 /Li is assembled, and it delivers an initial discharge capacity of 139.1 mAh g −1 at 0.1 C and a capacity retention of 81.0% after 100 cycles at room temperature. This work combines systematical experimental characterizations and sufficient theoretical calculations to develop a new promising sulfide electrolyte with superior lithium ion conductivity and high air-stability for ASSLBs application.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
CHEMISTRY OF MATERIALS
·
2015
·
IF 8.354
Xinmiao Liang,Liying Wang,Yangming Jiang,Jian Wang,Huan Luo,Chaoyang Liu,Jiwen Feng
Li10GeP2S12 (LGPS) is a new solid electrolyte of the highest Li ionic conductivity reported as of now. An anisotropic 3D Li ionic transport network consisting of an ultrafast Li 1D diffusion tunnel and fast in-plane 2D pathways was previously predicted by molecular dynamics simulations. In this paper, we have studied in detail the Li ion dynamics in LGPS by multiple solid-state NMR methods. Two different Li motion processes, characterized by apparently different activation energies of 0.16 eV and 0.26 eV, were unambiguously probed by both 7Li and 31P solid-state NMR and assigned to Li ion diffusions in the 1D tunnel and in the 2D plane, respectively. 31P spin-locking relaxation measurement further reveals that interstitial position Li(4) is active for in-plane Li migration.
研究领域:
材料科学
·
物理化学
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2015
·
IF 6.217
Yanran Zhao,Chuan Wu,Gang Peng,Xiaotian Chen,Xiayin Yao,Ying Bai,Feng Wu,Shaojie Chen,Xiaoxiong Xu
Li 10 GeP 2 S 12 (LGPS) is incorporated into polyethylene oxide (PEO) matrix to fabricate composite solid polymer electrolyte (SPE) membranes. The lithium ion conductivities of as-prepared composite membranes are evaluated, and the optimal composite membrane exhibits a maximum ionic conductivity of 1.21 × 10 −3 S cm −1 at 80 °C and an electrochemical window of 0–5.7 V. The phase transition behaviors for electrolytes are characterized by DSC , and the possible reasons for their enhanced ionic conductivities are discussed. The LGPS microparticles , acting as active fillers incorporation into the PEO matrix, have a positive effect on the ionic conductivity, lithium ion transference number and electrochemical stabilities. In addition, two kinds of all-solid-state lithium batteries (LiFeO 4 /SPE/Li and LiCoO 2 /SPE/Li) are fabricated to demonstrate the good compatibility between this new SPE membrane and different electrodes. And the LiFePO 4 /Li battery exhibits fascinating electrochemical performance with high capacity retention (92.5% after 50 cycles at 60 °C) and attractive capacities of 158, 148, 138 and 99 mAh g −1 at current rates of 0.1 C, 0.2 C, 0.5 C and 1 C at 60 °C, respectively. It is demonstrated that this new composite SPE should be a promising electrolyte applied in solid state batteries based on lithium metal electrode.
✓ 已验证
DOI
高影响因子
Journal of Energy Chemistry
·
2019
·
IF 5.162
Xuelei Li,Liubing Jin,Dawei Song,Hongzhou Zhang,Xixi Shi,Zhenyu Wang,Lianqi Zhang,Lingyun Zhu
In order to obtain high power density, energy density and safe energy storage lithium ion batteries (LIB) to meet growing demand for electronic products, oxide cathodes have been widely explored in all-solid-state lithium batteries (ASSLB) using sulfide solid electrolyte. However, the electrochemical performances are still not satisfactory, due to the high interfacial resistance caused by severe interfacial instability between sulfide solid electrolyte and oxide cathode, especially Ni-rich oxide cathodes, in charge-discharge process. Ni-rich LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) material at present is one of the most key cathode candidates to achieve the high energy density up to 300 Wh kg −1 in liquid LIB, but rarely investigated in ASSLB using sulfide electrolyte. To design the stable interface between NCM811 and sulfide electrolyte should be extremely necessary. In this work, in view of our previous work, LiNbO 3 coating with about 1 wt% content is adopted to improve the interfacial stability and the electrochemical performances of NCM811 cathode in ASSLB using Li 10 GeP 2 S 12 solid electrolyte. Consequently, LiNbO 3 -coated NCM811 cathode displays the higher discharge capacity and rate performance than the reported oxide electrodes in ASSLB using sulfide solid electrolyte to our knowledge.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2019
·
IF 8.355
Yi Cao,Shuaifeng Lou,Zhen Sun,Weiping Tang,Yulin Ma,Pengjian Zuo,Jiajun Wang,Chunyu Du,Yunzhi Gao,Geping Yin
Solid-state lithium batteries (SSLBs) exhibit numerous advantages including high safety, high energy density and power density, etc., and therefore become the most promising candidate for next-generation batteries. However, constructing an intimate contact within the composite electrode and the electrode/electrolyte interface via simple mixing and cold-pressing processes is still challenging. Herein, a novel fabrication process for homogeneous composite electrodes used in SSLBs is successfully demonstrated. An in-situ liquid-phase approach employing the [Li(triglyme)] + [TFSI] - (LiG3) solvent-salt complex with excellent stability to modify the sulfide-based solid-state electrolyte interfaces, is introduced into the SSLBs system, which enables SSLBs to work efficiently at lower external pressures. The quasi-solid-state prototype cells with Li 4 Ti 5 O 12 (LTO) active material deliver excellent room-temperature performance, generating a super high capacity of 160 mA h g −1 and high capacity retention of 91.4% for 1500 cycles under 0.25 C. This work gives new insight into the interface engineering, processing and more positive impact on the industrial production of SSLBs.
研究领域:
材料科学
·
电化学
·
固态离子学
·
能源存储
·
界面工程
·
先进电池技术
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2020
·
IF 8.758
Xinmiao Liang,Yangming Jiang,Wuyao Cai,Shuaishuai Wu,Liying Wang,Zhenyu Lei,Junfei Chen,Youyi Lei,Li Yang,Jiwen Feng
The fast Li-ion pathways in crystals contribute to superionic conductivity—extraordinarily high ionic conductivity—of the Li10GeP2S12 (LGPS) structure. Composition tuning is expected to improve the conductivity. The phase behavior, microstructure, and ion dynamics of a series of solid solutions of xLi4GeS4–yLi3PS4 (4/1 ≥ x/y ≥ 1/2) were studied by multiple 7Li and 31P solid-state NMR methods. Li10GeP2S12 (Ge/P = x/y = 1/2) is the smallest x/y of the disordered LGPS structure. When the Ge/P ratio increases, the room-temperature Li ionic conductivity first increases to a maximum around x/y = 1/1.2 and then decreases. Meanwhile, a disordered LGPS structure transforms into an ordered LGPS′ structure synchronously with conductivity reduction. The Li4GeS4–Li3PS4 phase diagram with the order–disorder structure transition was reconstructed accordingly. Both ordered LGPS′ and disordered LGPS exhibit similar two-dimensional (2D) and one-dimensional (1D) Li diffusion paths. But the disordered LGPS structure is conducive to fast ionic conductivity, rooted in its fast 2D Li+ diffusion in the ab-plane rather than 1D diffusion along the c-axis. Two high-temperature relaxation processes are observed in the LGPS′ structure, suggesting heterogeneous 2D jumps of rapid and slow rates, whereas only a single homogeneous 2D jump process was found in the LGPS structure. Our findings provide insight into understanding the relationship between structure order (or disorder) and ionic conductivity of superionic materials, offering guidelines for optimizing ionic conductivity for extensive solid electrolyte materials rather than LGPS materials.
研究领域:
材料科学
·
固态化学
·
能源材料
·
核磁共振（NMR）
·
离子导体与电解质
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）