A fast and low-cost interface modification method to achieve high-performance garnet-based solid-state lithium metal batteries

Zhao, Bing; Ma, Wencheng; Li, Bobo; Hu, Xiongtao; Lu, Shangying; Liu, Xiaoyu; Jiang, Yong; Zhang, Jiujun

doi:10.1016/j.nanoen.2021.106643

Cited by 70 publications

(41 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The third flattened tail was attributed to the polarization of the symmetric cell at low frequencies, where the Li stripping and plating occurred on a time scale of 0.005–1 s. The interface impedance was calculated to be approximately 15 Ω cm 2 . The critical current density performance (Figure b) of the Ta5Li6 production pellet was as high as 1.28 mA cm –2 (0.64 mAh cm –2 ) under a time-fixed testing method, which was comparable to that measured with coating layers in published works. − The internal resistance of the symmetric cell was maintained at approximately 220 Ω cm 2 before the short circuit, indicating there was no soft short circuit inside Ta5Li6 ceramic solid electrolyte . Interestingly, the internal resistance varied from 50 to 150 Ω cm 2 after short circuit, indicating a repeatedly short-recovery procedure inside LLZO ceramics at current densities higher than 1.28 mA cm –2 .…”

Section: Resultssupporting

confidence: 70%

Production of Ta-Doped Li₇La₃Zr₂O₁₂ Solid Electrolyte with High Critical Current Density

Zhou

Yang

et al. 2022

ACS Appl. Energy Mater.

View full text Add to dashboard Cite

Solid-state electrolytes are key materials for developing high-safety solid-state Li-ion batteries. The garnettype Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte is one of the most promising solid electrolytes due to its high conductivity and feasible preparation in ambient air. Among several dopants, Tadoped LLZO (Ta-LLZO) delivers high stability against lithium metal and high conductivity, which attracts lots of researchers. However, production of Ta-LLZO ceramics is less problematic due to the complicated gas−liquid−solid sintering mechanism. This work aims to develop an efficient method to produce Ta-LLZO solid electrolyte ceramic pellets, including providing a stacking sintering method and optimizing the amount of excessive Li source, the wet milling duration, and the sintering temperature. First, a low-cost, efficient "gravel-separator" strategy is provided for multiple sintering of LLZO. Second, the Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (Ta5) samples with different excessive Li levels (2, 4, 6, and 8%) are sintered at various sintering conditions of 1240 °C for 60 min, 1280 °C for 20 min, and 1320 °C for 2 min to search for the optimum excessive amount of Li. Third, Ta5 samples with optimized excessive Li (4, 6%) after milling for longer duration are sintered at 1280 °C for 30 min, 1300 °C for 10 min, 1320 °C for 10 min, 1320 °C for 30 min to finally optimize the preparation craft. After optimization, the Ta5 ceramics with excessive 4 and 6% Li sintered at 1320 °C for 10 min deliver homogeneous and dense crosssectional morphology, high conductivity of over 1 × 10 −3 S cm −1 at room temperature, and relative densities of above 96%. Furthermore, symmetric Li cells assembled with the Ta-LLZO solid electrolyte prepared with the optimized method deliver a critical current density of 1.28 mA cm −2 at 30 °C and over 1000 h of stable cycling at 0.2 mA cm −2 (0.2 mA h cm −2 ) at 30 °C.

show abstract

Section: Resultssupporting

confidence: 70%

Production of Ta-Doped Li₇La₃Zr₂O₁₂ Solid Electrolyte with High Critical Current Density

Zhou

Yang

et al. 2022

ACS Appl. Energy Mater.

View full text Add to dashboard Cite

show abstract

“…The Li/LLZTO*/ Li and Li/LLZTO*/NCA cell exhibits the best performance than all the previously reported ones. [8,9,[11][12][13]27] We propose a mechanism to explain how the interlayer improves battery performance, as illustrated in Figure 7. Surface flaws deteriorate the contact between Li and LLZTO, resulting in dendrites growth at the crack during the cycling (Figure 7a).…”

Section: Resultsmentioning

confidence: 99%

“…As a result, a high critical current density up to 0.5 mA cm −2 and stable galvanostatic cycling for over 1000 h at 0.2 mA cm −2 in the Li symmetric cell were achieved. [12] Lee et al constructed a multifunctional interface layer composed of LiF and LiSn alloy at the Li/LLZTO interface by a conversion reaction of SnF 2 film with Li metal, which achieved a stable galvanostatic cycling for over 1000 h at 0.5 mA cm −2 in the Li symmetric cell and high critical current density up to 2.4 mA cm −2 . [13] Although numerous efforts have been devoted to the improvement of the interface and suppression of Li dendrites, short circuit caused by Li dendrites penetration is still a critical issue for the LLZO based SSLMBs.…”

Section: Introductionmentioning

confidence: 99%

Cryo‐EM Studies of Atomic‐Scale Structures of Interfaces in Garnet‐Type Electrolyte Based Solid‐State Batteries

Dai

Yao

et al. 2022

Adv Funct Materials

View full text Add to dashboard Cite

High interfacial impedance is a major obstacle in the application of solidstate Li metal batteries (SSLMBs). Understanding the atomic-scale structure of the interfaces in SSLMBs is thus critical to their practical implementations. However, due to the beam sensitivity of battery materials, such information is not accessible by conventional electron microscopy (EM). Herein, by using cryogenic-EM (cryo-EM), the atomic-scale structures of interfaces in garnet electrolyte based SSLMBs are revealed. A LiF-rich interlayer exhibiting intimate contacts with both Li and LLZTO is shown, thus rendering uniform Li + transport across the interface in turn inhibiting Li dendrite growth. Consequently, the Li symmetric cell based on the LiF-rich interlayer exhibits a high critical current density of 3.2 mA cm −2 and a long lifespan over 1800 cycles at 1 mA cm −2 . Moreover, a full cell with a LiNi 0.88 Co 0.1 Al 0.02 O 2 cathode at a high mass loading ≈12 mg cm −2 reached over 400 cycles at 1.2 mA cm −2 , which represents a major progress in the performance of the garnet-type SSLMBs. This study provides atomic-scale understanding of interfaces in SSLMBs and an effective strategy to design dendrite-free SSLMBs for practical applications.

show abstract

“…In contrast, the SEM image in Figure S4a presents an obvious gap between the interface of the ex situ PLCSSE10 and Li metal. This poor interfacial contact will bring about a terrible interfacial impedance and therefore will lead to uneven current distribution and dendrite growth during cycling, which will affect the overall cycle life of the cell . As a result, the ex situ PLCSSE10-based Li-metal symmetric cell exhibits a large overpotential and a short cycle life (Figure S5).…”

Section: Resultsmentioning

confidence: 99%

Integrated Design for Regulating the Interface of a Solid-State Lithium–Oxygen Battery with an Improved Electrochemical Performance

Ouyang

Min

et al. 2022

ACS Appl. Mater. Interfaces

Self Cite

View full text Add to dashboard Cite

A composite solid-state electrolyte (SSE) with acceptable safety and durability is considered as a potential candidate for high-performance lithium–oxygen (Li–O2) batteries. Herein, to address the safety issues and improve the electrochemical performance of Li–O2 batteries, a solvent-free composite SSE is prepared based on the thermal initiation of poly(ethylene glycol) diacrylate radical polymerization, and an integrated battery is achieved by injecting an electrolyte precursor between electrodes during the assembly process through a simple heat treatment. The Li-metal symmetric cells based on this composite SSE achieve a critical current density of 0.8 mA cm–2 and a stable cycle life of over 900 h at a current density of 0.2 mA cm–2. This composite SSE effectively inhibits the erosion of O2 on the Li metal anode, optimizes the interface between the electrolyte and cathode, and provides abundant reaction sites for the electrochemical reactions during cycling. The integrated solid-state Li–O2 battery prepared in this work achieves stable long cycling (118 cycles) at a current density of 500 mA g–1 at room temperature, showing the promising future application prospects.

show abstract

A fast and low-cost interface modification method to achieve high-performance garnet-based solid-state lithium metal batteries

Cited by 70 publications

References 38 publications

Production of Ta-Doped Li₇La₃Zr₂O₁₂ Solid Electrolyte with High Critical Current Density

Production of Ta-Doped Li₇La₃Zr₂O₁₂ Solid Electrolyte with High Critical Current Density

Cryo‐EM Studies of Atomic‐Scale Structures of Interfaces in Garnet‐Type Electrolyte Based Solid‐State Batteries

Integrated Design for Regulating the Interface of a Solid-State Lithium–Oxygen Battery with an Improved Electrochemical Performance

Contact Info

Product

Resources

About

A fast and low-cost interface modification method to achieve high-performance garnet-based solid-state lithium metal batteries

Cited by 70 publications

References 38 publications

Production of Ta-Doped Li7La3Zr2O12 Solid Electrolyte with High Critical Current Density

Production of Ta-Doped Li7La3Zr2O12 Solid Electrolyte with High Critical Current Density

Cryo‐EM Studies of Atomic‐Scale Structures of Interfaces in Garnet‐Type Electrolyte Based Solid‐State Batteries

Integrated Design for Regulating the Interface of a Solid-State Lithium–Oxygen Battery with an Improved Electrochemical Performance

Contact Info

Product

Resources

About

Production of Ta-Doped Li₇La₃Zr₂O₁₂ Solid Electrolyte with High Critical Current Density

Production of Ta-Doped Li₇La₃Zr₂O₁₂ Solid Electrolyte with High Critical Current Density