Thin lamellar Li7La3Zr2O12 solid electrolyte with g-C3N4 as grain boundary modifier for high-performance all-solid-state lithium battery

Guo, Zibiao; Ye, Chao; Zhao, Ting; Wu, Wenjia; Kou, Weijie; Zhang, Yafang; Dong, Wenying; Li, Wenpeng; Wang, Jingtao

doi:10.1016/j.jpowsour.2023.232784

Cited by 11 publications

(6 citation statements)

References 53 publications

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“…A semicircle exists in the high- and medium-frequency region, and it is assigned to the contribution of the lithium-ion transport in bulk and grain boundary of LLZT, while a small arc exists in the low-frequency region and is assigned to the contribution of the Li/LLZT surface. The solid line represents the fitting to the experimental data based on the equivalent circuit of R bulk ( R gb //CPE gb ) ( R int //CPE int ), ,, where R is the resistance, CPE is the constant phase element, and the subscripts bulk, gb, and int refer to the bulk, grain boundary, and Li/LLZT interface contribution, respectively. The lithium-ion conductivity of these three types of samples, i.e., 1165 °C × 16 h, 1320 °C × 10 min, and 1320 °C × 2 h, is determined to be 0.78, 0.76, and 0.82 mS cm –1 , respectively, and the Li/LLZT interfacial resistance of the symmetric cells is about 19.74, 20.83, and 29.06 Ω cm –2 , respectively.…”

Section: Resultsmentioning

confidence: 99%

Correlating the Microstructure and Current Density of the Li/Garnet Interface

Ouyang,

Zheng,

Chen

et al. 2023

ACS Appl. Mater. Interfaces

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Solid-state lithium batteries hold great promise for next-generation energy storage systems. However, the formation of lithium filaments within the solid electrolyte remains a critical challenge. In this study, we investigate the crucial role of morphology in determining the resistance of garnet-type electrolytes to lithium filaments. By proposing a new test method, namely, cyclic linear sweep voltammetry, we can effectively evaluate the electrolyte resistance against lithium filaments. Our findings reveal a strong correlation between the microscopic morphology of the solid electrolyte and its resistance to lithium filaments. Samples with reduced pores and multiple grain boundaries demonstrate remarkable performance, achieving a critical current density of up to 3.2 mA cm–2 and excellent long-term cycling stability. Kelvin probe force microscopy and finite element method simulation results shed light on the impact of grain boundaries and electrolyte pores on lithium-ion transport and filament propagation. To inhibit lithium penetration, minimizing pores and achieving a uniform morphology with small grains and plenty of grain boundaries are essential.

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Section: Resultsmentioning

confidence: 99%

Correlating the Microstructure and Current Density of the Li/Garnet Interface

Ouyang,

Zheng,

Chen

et al. 2023

ACS Appl. Mater. Interfaces

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“…This presents two important factors for dendrite formation and propagation: (1) the heterogeneity shows regions of pure polymer amid the LLZO mixture, and (2) wherever there is LLZO present, its effective modulus is lower than pure LLZO, either due to inherently lower modulus at the nanoscale or due to being covered by a thin layer of PEO-LiTFSI. These modulus ranges lower than the Young’s modulus of lithium metal (5–11 GPa) have been observed previously in LLZO nanosheets and composite electrolytes with nanoindentation. , …”

Section: Results and Discussionmentioning

confidence: 45%

“…These modulus ranges lower than the Young's modulus of lithium metal (5−11 GPa) have been observed previously in LLZO nanosheets and composite electrolytes with nanoindentation. 55,56 Figure 5b compares these numbers with those of LLZO and lithium metal reported in the literature at room temperature. 57 Also shown is the shear modulus, estimated from the relationship G = E/(2 × (1 + ν)), where G is the shear modulus, E is the Young's modulus, and ν is the Poisson's ratio, which is around 0.25 for both LLZO and solid polymer electrolytes.…”

Section: Effect Of Fiber Loading On Ce and Ccd Our Resultsmentioning

confidence: 76%

Understanding the Influence of Li₇La₃Zr₂O₁₂ Nanofibers on Critical Current Density and Coulombic Efficiency in Composite Polymer Electrolytes

Counihan,

Powers,

Barai

et al. 2023

ACS Appl. Mater. Interfaces

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Composite polymer electrolytes (CPEs) are attractive materials for solid-state lithium metal batteries, owing to their high ionic conductivity from ceramic ionic conductors and flexibility from polymer components. As with all lithium metal batteries, however, CPEs face the challenge of dendrite formation and propagation. Not only does this lower the critical current density (CCD) before cell shorting, but the uncontrolled growth of lithium deposits may limit Coulombic efficiency (CE) by creating dead lithium. Here, we present a fundamental study on how the ceramic components of CPEs influence these characteristics. CPE membranes based on poly(ethylene oxide) and lithium bis(trifluoromethanesulfonyl)imide (PEO-LiTFSI) with Li7La3Zr2O12 (LLZO) nanofibers were fabricated with industrially relevant roll-to-roll manufacturing techniques. Galvanostatic cycling with lithium symmetric cells shows that the CCD can be tripled by including 50 wt % LLZO, but half-cell cycling reveals that this comes at the cost of CE. Varying the LLZO loading shows that even a small amount of LLZO drastically lowers the CE, from 88% at 0 wt % LLZO to 77% at just 2 wt % LLZO. Mesoscale modeling reveals that the increase in CCD cannot be explained by an increase in the macroscopic or microscopic stiffness of the electrolyte; only the microstructure of the LLZO nanofibers in the PEO-LiTFSI matrix slows dendrite growth by presenting physical barriers that the dendrites must push or grow around. This tortuous lithium growth mechanism around the LLZO is corroborated with mass spectrometry imaging. This work highlights important elements to consider in the design of CPEs for high-efficiency lithium metal batteries.

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“…[21] Researchers modify the PEO-based solid electrolytes with a variety of methods. For example, inorganic fillers, such as LTPO, [22] Al 2 O 3 , [23] TiO 2 , [24] LSO, [25] and g-C 3 N 4 , [26] are added to the polymer electrolytes or a 3D framework is built, such as 3D LLZAO, [27] PAN, [28] LLZTO, [29][30][31] and 3D glass fiber, [32] to improve the ionic conductivity and mechanical strength. Forming a stable solid electrolyte film (SEI) by introducing an intermediate layer, such as Li[(CF 3 ) 3 COBF 3 ], between PEO and lithium meta, can also prevent the decomposition of the electrolyte surface.…”

Section: Introductionmentioning

confidence: 99%

Excellent Stable Cycle Performance of Polyethylene Oxide‐Based 3D Solid Dual‐Salt Composite Electrolyte with Porous Polyimide Thin Films Host

An,

Li,

Pei

et al. 2024

Adv Materials Technologies

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Polyethylene oxide composite electrolytes are widely used in lithium‐ion batteries because of their excellent moldability, good flexibility, and favorable chemical compatibility. However, they still suffer from low ionic conductivity and weak mechanical strength. Herein, a 3D nanofiber‐reinforced dual‐salt composite solid electrolyte (PI@PCB) is synthesized. Benefiting from the support of the porous polyimide films and the addition of lithium bis(oxalate)borate, the obtained PI@PCB electrolyte exhibits high mechanical strength, good thermal stability, excellent electrochemical stability, and a high lithium ion transference number (0.70). In addition, the assembled Li/PI@PCB/Li cell shows the lowest overpotential of 200 mV at the initial cycling stage and increases to 246 mV slightly after 1500 h. The capacity retention rate of Li/PI@PCB/LFP battery is about 88.3% after 500 cycles at 60 °C.

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Thin lamellar Li7La3Zr2O12 solid electrolyte with g-C3N4 as grain boundary modifier for high-performance all-solid-state lithium battery

Cited by 11 publications

References 53 publications

Correlating the Microstructure and Current Density of the Li/Garnet Interface

Correlating the Microstructure and Current Density of the Li/Garnet Interface

Understanding the Influence of Li₇La₃Zr₂O₁₂ Nanofibers on Critical Current Density and Coulombic Efficiency in Composite Polymer Electrolytes

Excellent Stable Cycle Performance of Polyethylene Oxide‐Based 3D Solid Dual‐Salt Composite Electrolyte with Porous Polyimide Thin Films Host

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Thin lamellar Li7La3Zr2O12 solid electrolyte with g-C3N4 as grain boundary modifier for high-performance all-solid-state lithium battery

Cited by 11 publications

References 53 publications

Correlating the Microstructure and Current Density of the Li/Garnet Interface

Correlating the Microstructure and Current Density of the Li/Garnet Interface

Understanding the Influence of Li7La3Zr2O12 Nanofibers on Critical Current Density and Coulombic Efficiency in Composite Polymer Electrolytes

Excellent Stable Cycle Performance of Polyethylene Oxide‐Based 3D Solid Dual‐Salt Composite Electrolyte with Porous Polyimide Thin Films Host

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Understanding the Influence of Li₇La₃Zr₂O₁₂ Nanofibers on Critical Current Density and Coulombic Efficiency in Composite Polymer Electrolytes