Research Progresses of Garnet-Type Solid Electrolytes for Developing All-Solid-State Li Batteries

Kim, Abin; Woo, Seungjun; Kang, Min‐Sung; Park, Heetaek; Kang, Byoungwoo

doi:10.3389/fchem.2020.00468

Cited by 48 publications

(35 citation statements)

References 95 publications

(150 reference statements)

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“…Unfortunately, the heat treatment causes irreversible degradation reactions at the electrolyte–electrode interface resulting in increased interfacial resistances. [ 10–12 ] In contrast, thiophosphate‐based SSEs are rather soft and, thus, provide good interfacial contact to CAMs. Furthermore, they exhibit high ionic conductivities of above 20 mS cm −1 at room temperature [ 3,13 ] making them more attractive for applications in ASSBs.…”

Section: Introductionmentioning

confidence: 99%

A Dry‐Processed Al₂O₃/LiAlO₂ Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

Negi

Yusim

Pan

et al. 2021

Adv Materials Inter

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Due to their high theoretical energy densities and superior safety, thiophosphate‐based all‐solid‐state batteries (ASSBs) are considered as promising power source for electric vehicles. However, for large‐scale industrial applications, interfacial degradation between high‐voltage cathode active materials (CAMs) and solid‐state electrolytes (SSEs) needs to be overcome with a simple, cost‐effective solution. Surface coatings, which prevent the direct physical contact between CAM and SSE and in turn stabilize the interface, are considered as promising approach to solve this issue. In this work, an Al2O3/LiAlO2 coating for Li(Ni0.70Co0.15Mn0.15)O2 (NCM) is tested for ASSBs. The coating is obtained from a recently developed dry coating process followed by post‐annealing at 600 °C. Structural characterization reveals that the heat treatment results in the formation of a dense Al2O3/LiAlO2 coating layer. Electrochemical evaluations confirm that the annealing‐induced structural changes are beneficial for ASSB. Cells containing Al2O3/LiAlO2‐coated NCM show a significant improvement of the rate capability and long‐term cycling performance compared to those assembled from Al2O3‐coated and uncoated cathodes. Moreover, electrochemical impedance spectroscopy analysis shows a decreased cell impedance after cycling indicating a reduced interfacial degradation for the Al2O3/LiAlO2‐coated electrode. The results highlight a promising low‐cost and scalable CAM coating process, enabling large‐scale cathode coating for next‐generation ASSBs.

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Section: Introductionmentioning

confidence: 99%

A Dry‐Processed Al₂O₃/LiAlO₂ Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

Negi

Yusim

Pan

et al. 2021

Adv Materials Inter

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“…In contrast, the Li||PEO-SPE||NMC cell is only stable for the first 35 cycles, and it drops fast after the 62 cycles with a capacity retention and coulombic efficiency of 83.5 and 90.8%, respectively. This is because the LLZTO/PEO-CPEs have excellent chemical stability against high-voltage cathode materials (NMC) and high-capacity Li metal, 60 as a result of that LLZTO exhibits a high electrochemical potential window and excellent conduction properties. This proves that our designed composite solid electrolyte is electrochemically stable and can work beyond a potential of 4 V.…”

Section: Resultsmentioning

confidence: 99%

Ultrathin Li_6.75La₃Zr_1.75Ta_0.25O₁₂-Based Composite Solid Electrolytes Laminated on Anode and Cathode Surfaces for Anode-free Lithium Metal Batteries

Zegeye

Fenta

et al. 2020

ACS Appl. Energy Mater.

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The low ionic conductivity, thermal stability and incompatibility of pellet-like solid-state electrolytes lead to low cycling performance in anode-free lithium metal batteries. Herein, we report an effective and feasible composite solid electrolyte-designing approach using the garnet (Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 , LLZTO)−polymer composite electrolyte (LLZTO/ PEO-CPE) laminated on both the anode and cathode surfaces with an ultrathin thickness of 7−10 μm by spin coating method. It is found that the LLZTO/PEO-CPE exhibits a high ionic conductivity of about 4.76 × 10 −4 S/ cm at room temperature, excellent thermal stability, and good compatibility. Moreover, it simplifies the preparation of solid electrolytes and reduces the interfacial and grain boundary resistances for ion transfer. The use of both anode and cathode laminating enables dendrite-free lithium plating on copper with a high average coulombic efficiency and cycling stability of 98.8 and 41.2%, respectively, after the 65 cycles at 0.2 mA/cm 2 and 55 °C in an anodefree battery. This work provides a new design of solid-state electrolytes (SSEs) to achieve safe and dendrite-free anode-free batteries.

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“…2 The superior conductivity (~10 -4 S.cm -1 ) and excellent stability of the oxide garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) solid-state electrolyte has ignited significant interest for its utilization in solid-state battery technology. 3 The highest lithiumion conductivity is found with the cubic phase (space group Ia3̅ d) of the Li 7 La 3 Zr 2 O 12 garnet. 4 However, at room temperature, a lowenergy reordering of Li-ions into the 16f, 32g (octahedral) and 8a…”

Section: Introductionmentioning

confidence: 99%

First-principles study on structural, mechanical and electronic properties of Li7La3Zr2O12 solid electrolyte

Maphoto

Masedi

Ngoepe

et al. 2022

SATNT

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The oxide garnet Li7La3Zr2O12 (LLZO) is a promising solid electrolyte for Li-based batteries due to its high Li-ion conductivity and chemical stability with respect to Li metal anode. However, at room temperature, it crystallizes into a poorly Li-ion conductive tetragonal phase. To this end, supervalent cation doping has been an effective way to stabilize the highly conductive cubic phase and enhance the ionic conductivity of the tetragonal phase at room temperature, through the creation of lithium vacancies. Yet, the fundamental aspects regarding this supervalent substitution remain poorly understood. In this study, we have employed the first-principle calculations to offer a better understanding of the stabilization of tetragonal Li7La3Zr2O12 phases by determining the structural, mechanical, and electronic properties for high-conductivity LLZO composition. We find that the structural properties calculated are in good agreement which is within a 2% error of the experimentally measured results. The negative energy of formation for t-LLZO shows that the material is thermodynamically stable. The calculated Young’s modulus is in good agreement with the experimental observations, which indicates that the material is mechanically stable. Owing to its wide electrochemical stability, the calculated band structure of t-LLZO shows that the material is a wide and indirect magnetic separator with a g-symmetry point band gap which is in good agreement with the experimental observations. Therefore, the structural, mechanical, and electronic stability of t-LLZO provides better insight about the stability of the material and this capacitates further investigations associated with ionic conductivity of the pure and supervalently doped LLZO.The oxide garnet Li7La3Zr2O12(LLZO) is a promising solid electrolyte for Li-based batteries due to its high Li-ion conductivity and chemical stability with respect to Li metal anode. However, at room temperature, it crystallizes into a poorly Li-ion conductive tetragonal phase. To this end, supervalent cation doping has been an effective way to stabilize the highly conductive cubic phase and enhance the ionic conductivity of the tetragonal phase at room temperature, through the creation of lithium vacancies. Yet, the fundamental aspects regarding this supervalent substitution remain poorly understood. In this study, we have employed the first-principle calculations to offer a better understanding of the stabilization of tetragonal Li7La3Zr2O12 phases by determining the structural, mechanical, and electronic properties for high-conductivity LLZO composition. We find that the structural properties calculated are in good agreement which is within a 2% error of the experimentally measured results. The negative energy of formation for t-LLZO shows that the material is thermodynamically stable. The calculated Young’s modulus is in good agreement with the experimental observations, which indicates that the material is mechanically stable. Owing to its wide electrochemical stability, the calculated band structure of t-LLZO shows that the material is a wide and indirect magnetic separator with a g-symmetry point band gap which is in good agreement with the experimental observations. Therefore, the structural, mechanical, and electronic stability of t LLZO provides better insight about the stability of the material and this capacitates further investigations associated with ionic conductivity of the pure and supervalently doped LLZO.

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Research Progresses of Garnet-Type Solid Electrolytes for Developing All-Solid-State Li Batteries

Cited by 48 publications

References 95 publications

A Dry‐Processed Al₂O₃/LiAlO₂ Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

A Dry‐Processed Al₂O₃/LiAlO₂ Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

Ultrathin Li_6.75La₃Zr_1.75Ta_0.25O₁₂-Based Composite Solid Electrolytes Laminated on Anode and Cathode Surfaces for Anode-free Lithium Metal Batteries

First-principles study on structural, mechanical and electronic properties of Li7La3Zr2O12 solid electrolyte

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Research Progresses of Garnet-Type Solid Electrolytes for Developing All-Solid-State Li Batteries

Cited by 48 publications

References 95 publications

A Dry‐Processed Al2O3/LiAlO2 Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

A Dry‐Processed Al2O3/LiAlO2 Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

Ultrathin Li6.75La3Zr1.75Ta0.25O12-Based Composite Solid Electrolytes Laminated on Anode and Cathode Surfaces for Anode-free Lithium Metal Batteries

First-principles study on structural, mechanical and electronic properties of Li7La3Zr2O12 solid electrolyte

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A Dry‐Processed Al₂O₃/LiAlO₂ Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

A Dry‐Processed Al₂O₃/LiAlO₂ Coating for Stabilizing the Cathode/Electrolyte Interface in High‐Ni NCM‐Based All‐Solid‐State Batteries

Ultrathin Li_6.75La₃Zr_1.75Ta_0.25O₁₂-Based Composite Solid Electrolytes Laminated on Anode and Cathode Surfaces for Anode-free Lithium Metal Batteries