Fast Li-ion transport pathways via 3D continuous networks in homogeneous garnet-type electrolyte for solid-state lithium batteries

Qin, Zhiwei; Meng, Xianghai; Xie, Yuming; Qian, Delai; Deng, Huankun; Mao, Dongxin; Wan, Long; Huang, Yongxian

doi:10.1016/j.ensm.2021.09.005

Cited by 43 publications

(13 citation statements)

References 72 publications

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“…The appearance of Ta 2 O 5 precipitates indicates that the Ta-doping strategy for LLZTO is challenging to achieve uniform element distribution during sintering. Figure c shows that cubic LLZTO is synthesized, while a lattice fringe of 5.27 Å is assigned to the (21̅1) plane . The corresponding element mappings are exhibited in Figure d–g to investigate its chemical composition, revealing the insufficient reaction between Ta 2 O 5 and La 2 O 3 .…”

Section: Resultsmentioning

confidence: 98%

“…Figure 3c shows that cubic LLZTO is synthesized, while a lattice fringe of 5.27 Å is assigned to the (21̅ 1) plane. 40 The corresponding element mappings are exhibited in Figure 3d−g to investigate its chemical composition, revealing the insufficient reaction between Ta 2 O 5 and La 2 O 3 . It results in the formation of void defects and provides the space for lithium dendrite growth.…”

Section: Microstructural Evolution and Componentmentioning

confidence: 99%

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Grain Boundary Engineering in Ta-Doped Garnet-Type Electrolyte for Lithium Dendrite Suppression

Qin

Xie

Meng

et al. 2022

ACS Appl. Mater. Interfaces

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Solid-state lithium batteries (SSLBs) based on Ta-doped Li6.5La3Zr1.5Ta0.5O12 (LLZTO) suffer from lithium dendrite growth, which hinders their practical application. Herein, first principles simulations indicate that the Ta element prefers to segregate along grain boundaries in the form of Ta2O5 precipitates due to a high energy difference induced by Ta doping. Grain boundary engineering is employed to regulate the distribution of the Ta element and enhance the density of LLZTO by introducing the La2O3 additive. The sufficient La2O3 additive reacts with the Ta2O5 precipitates, while the residual La2O3 nanoparticles fill up void defects, promoting the homogeneous distribution of the Ta element and improving the relative density to ∼98%. Critical current density of the symmetric Li battery reaches 2.12 mA·cm–2 at room temperature with the solid-state electrolyte (LLZTO + 5 wt % La2O3), which increases by 41% compared to pure LLZTO. SSLBs with the LiFePO4 cathode achieve a stable cycling performance with a discharge capacity of 138.6 mA·h·g–1 after 400 cycles at 0.2 C. This work provides theoretical insights into the distribution of Ta-doped LLZTO and inhibits lithium dendrite growth through grain boundary engineering.

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Section: Resultsmentioning

confidence: 98%

Section: Microstructural Evolution and Componentmentioning

confidence: 99%

Grain Boundary Engineering in Ta-Doped Garnet-Type Electrolyte for Lithium Dendrite Suppression

Qin

Xie

Meng

et al. 2022

ACS Appl. Mater. Interfaces

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“…Thus, as a result of the constraint as well as the increase in density of the laser irradiated area, peaks and troughs are formed at the margins and centers of the laser pathways, respectively, causing the shrinkage to take place mostly along the thickness direction. Additionally, the rapid increase of temperature (<1 s to the melting point of LLZTO) also decomposes the Li 2 CO 3 and generates recoil pressure that can accelerate rigid body motion along the thickness direction. , As a result of this anisotropic shrinkage behavior, a 3D wave pattern structure is generated, which could be tuned by changing the laser scanning strategies and parameters. Only slight microstructural differences are observed in the peaks and troughs regions of the laser sintered LLZTO films (Figure b), which could be removed by fine-tuning the hatch spacing.…”

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confidence: 99%

CO₂ Laser Sintering of Garnet-Type Solid-State Electrolytes

et al. 2022

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The processing of garnet-type solid-state electrolytes remains challenging as densification conventionally requires high sintering temperatures and long processing times, which can result in severe Li loss, the formation of secondary phases, and thus high porosity and low ionic conductivity. Here, we report an ultrafast sintering method based on CO2 laser scanning with the assistance of a heating stage. We demonstrate the rapid densification of low-packing-density Li6.4La3Zr1.4Ta0.6O12 (LLZTO) films, which are difficult to densify by conventional furnace sintering methods. This unique approach has three fingerprint characteristics: (1) mitigation of Li loss through ultrafast sintering (dwelling time ≪1 s); (2) a unique anisotropic shrinkage behavior that greatly reduces film thickness; (3) wave-like surface topology from point scanning strategy that enables 3D interfacial contacts with electrode materials. Herein, highly dense (95.68%) and highly conductive (0.26 mS·cm–1 at 25 °C) LLZTO films are obtained through CO2 laser sintering. This work provides a unique, scalable, and widely applicable ultrarapid laser sintering technique to overcome the difficulties associated with classic methods for the integration of SSEs for practical all-solid-state Li-metal battery applications.

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“…For garnet-type oxide electrolytes, although thermodynamic stability at interfaces is maintained relatively, the physical contact with electrodes limits the practical application, which is much more serious in the cathode side, arising from the rigid particles of cathode composites with a variety of interfaces [17][18][19] . Considerable efforts have been devoted to achieve an intimate electrolyte|cathode contact, such as applying liquid electrolyte or polymer as catholyte 20,21 , co-sintering 22,23 , and maintaining high pressure during cycling 24,25 . Throughout those approaches, adding a tiny bit of liquid electrolyte or polymer buffer layer is the most effective way to decrease the interfacial impedance and achieve long cycling batteries 26 .…”

Section: Introductionmentioning

confidence: 99%

Solvent-free and long-cycling garnet-based lithium-metal batteries

Zhang

et al. 2022

Preprint

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Solid-state batteries using ceramic solid electrolytes promise to deliver enhanced energy density and intrinsic safety. However, the challenge of integrating solid electrolytes with electrode materials limits the electrochemical performances. Herein, we report a solvent-free ceramic-based lithium-metal battery with excellent performances at a wide temperature range of 45 to 100°C, enabled by inorganic ternary salt of extreme-low eutectic point. By using garnet electrolyte with molten salts at the electrolyte|cathode interface, the Li||LiFePO4 cells perform a long cycling stably with capacity retention of 81.4% after 1000 cycles at 1 C. High-voltage LiFe0.4Mn0.6PO4 cathodes also deliver good electrochemical performance. Specifically, commercial electrode pieces with high area capacities can be adopted directly in the quasi-solid-state lithium-metal batteries. These superior performances are ascribable to the low melting point, high ionic conductivity and good thermal/electrochemical stability of the ternary salt system. Our findings provide an effective method on fabrication of solid-state batteries towards practical applications.

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Fast Li-ion transport pathways via 3D continuous networks in homogeneous garnet-type electrolyte for solid-state lithium batteries

Cited by 43 publications

References 72 publications

Grain Boundary Engineering in Ta-Doped Garnet-Type Electrolyte for Lithium Dendrite Suppression

Grain Boundary Engineering in Ta-Doped Garnet-Type Electrolyte for Lithium Dendrite Suppression

CO₂ Laser Sintering of Garnet-Type Solid-State Electrolytes

Solvent-free and long-cycling garnet-based lithium-metal batteries

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Fast Li-ion transport pathways via 3D continuous networks in homogeneous garnet-type electrolyte for solid-state lithium batteries

Cited by 43 publications

References 72 publications

Grain Boundary Engineering in Ta-Doped Garnet-Type Electrolyte for Lithium Dendrite Suppression

Grain Boundary Engineering in Ta-Doped Garnet-Type Electrolyte for Lithium Dendrite Suppression

CO2 Laser Sintering of Garnet-Type Solid-State Electrolytes

Solvent-free and long-cycling garnet-based lithium-metal batteries

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Product

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CO₂ Laser Sintering of Garnet-Type Solid-State Electrolytes