H3PO4-Induced Nano-Li3PO4 Pre-reduction Layer to Address Instability between the Nb-Doped Li7La3Zr2O12 Electrolyte and Metallic Li Anode

Tang, Jiawen; Niu, Yajun; Zhou, Yongjian; Chen, Shuqing; Yang, Yan; Huang, Xiao; Tian, Bingbing

doi:10.1021/acsami.2c21133

Cited by 13 publications

(4 citation statements)

References 88 publications

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“…After the LiF addition, the ratio of Li 2 CO 3 to C-C peaks obviously decreases. It suggests that the coated LiF layer could efficiently inhibit the reaction of LLZTO with H 2 O and CO 2 in air [41], which is attributed to the LiF's stability in air. The less impurity of Li 2 CO 3 on the LLZTO surface may benefit the CCD performance and improve stability during cycling.…”

Section: Resultsmentioning

confidence: 99%

Constructing electron-blocking grain boundaries in garnet to suppress lithium dendrite growth

Xiang,

Fang,

et al. 2024

Journal of Advanced Ceramics

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Li 7 La 3 Zr 2 O 12 (LLZO) is considered as a promising solid-state electrolyte due to its high ionic conductivity, wide electrochemical window, and excellent electrochemical stability. However, its application in solid-state lithium metal batteries (SSLMBs) is impeded by the growth of lithium dendrites in LLZO due to some reasons such as its high electronic conductivity. In this study, lithium fluoride (LiF) was introduced into Ta-doped LLZO (LLZTO) to modify its grain boundaries to enhance the performance of SSLMBs. A nanoscale LiF layer was uniformly coated on the LLZTO grains, creating a threedimensional continuous electron-blocking network at the grain boundaries. Benefiting from the electronic insulator LiF and the special structure of the modified LLZTO, the symmetric cells based on LLZO achieved a high critical current density (CCD) of 1.1 mA•cm −2 (in capacity-constant mode) and maintained stability over 2000 h at 0.3 mA•cm −2 . Moreover, the full cells combined with a LiFePO 4 (LFP) cathode, demonstrated excellent cycling performance, retaining 97.1% of capacity retention after 500 cycles at 0.5 C. Therefore, this work provides a facile and effective approach for preparing a modified electrolyte suitable for high-performance SSLMBs.

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Section: Resultsmentioning

confidence: 99%

Constructing electron-blocking grain boundaries in garnet to suppress lithium dendrite growth

Xiang,

Fang,

et al. 2024

Journal of Advanced Ceramics

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“…Because the Nb-LLZO is unstable against lithium metal [58][59][60] , the Li|Nb-LLZO|Li cells soon (no more than 50 h) short-circuited at 0.05 mA cm -2 [Supplementary Figure 9]. Therefore, as-produced Li0L2-dry pellets were fabricated into Li|LE (liquid electrolyte) |Nb-LLZO|LE (liquid electrolyte) |Li symmetric cells.…”

Section: Resultsmentioning

confidence: 99%

In-situ Li₂O-atmosphere assisted solvent-free route to produce highly conductive Li₇La₃Zr₂O₁₂ solid electrolyte

Tang,

Zhou,

et al. 2024

Energy Mater

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Solid-state batteries have garnered attention due to their potentiality for increasing energy density and enhanced safety. One of the most promising solid electrolytes is garnet-type Li7La3Zr2O12 (LLZO) ceramic electrolyte because of its high conductivity and ease of manufacture in ambient air. The complex gas-liquid-solid sintering mechanism makes it difficult to prepare LLZO with excellent performance and high consistency. In this study, an in-situ Li2O-atmosphere assisted solvent-free route is developed for producing the LLZO ceramics. First, the lithium-rich additive Li6Zr2O7 (LiZO) is applied to in-situ supply Li2O atmosphere at grain boundaries, where its decomposition products (Li2ZrO3) build the bridge between the grain boundaries. Second, comparisons were studied between the effects of dry and wet routes on the crystallinity, surface contamination, and particle size of calcined powders and sintered ceramics. Third, by analyzing the grain boundary composition and the evolution of ceramic microstructure, the impacts of dry and wet routes and lithium-rich additive LiZO on the ceramic sintering process were studied in detail to elucidate the sintering behavior and mechanism. Lastly, exemplary Nb-doped LLZO pellets with 2 wt% LiZO additives sintered at 1,300 °C × 1 min deliver Li+ conductivities of 8.39 × 10-4 S cm-1 at 25 °C, relative densities of 96.8%, and ultra-high consistency. It is believed that our route sheds light on preparing high-performance LLZO ceramics for solid-state batteries.

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“…This approach has been demonstrated to improve the lithiophilicity of LLZO via converting the surface contaminants to Li 3 PO 4 . 35,36 The significant improvement in the stability of HPO-LLZO with DMA is demonstrated by a ∼ 7-fold decrease in the R int of sulfur symmetric cells from 300 to 40 Ω cm 2 (Figure 4a,b). However, R int of HPO-LLZO increases on storage and it remains below that of HCl-LLZO (300 Ω cm 2 ).…”

Section: −mentioning

confidence: 99%

Surface Chemistry of LLZO Garnet Electrolytes with Sulfur in Electron Pair Donor Solvents

Shyamsunder,

Palmer,

Kochetkov

et al. 2023

ACS Appl. Mater. Interfaces

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Conventional Li−S batteries rely on liquid electrolytes based on LiNO 3 /DOL/DME mixtures that produce a quasistable interface with the lithium anode. Electron pair donor (EPD) solvents, also known as high donor number solvents, provide much higher polysulfide solubility and close-to-ideal sulfur utilization, making them solvents of choice for lean electrolyte Li− S cells. However, their instability to reduction requires incorporation of an ion-conductive membrane that is stable with Li−such as garnet LLZO and also stable with sulfur/polysulfides. We report that even trace amounts of LiOH on a LLTZO surface trigger a complex reaction with sulfur dissolved in typical EPD solvents (i.e., N,N-dimethylacetamide, DMA) to produce a highly resistive impedance layer that quickly grows with time from 1000 to 10,000 Ω cm 2 over a few hours, thus impeding Li + transport across the interface. Decorating the LLZO with protective phosphate groups to produce a modified surface provides a very low charge-transfer resistance of 40 Ω cm 2 that is maintained over time and inhibits the reaction of LiOH and dissolved sulfur. Hybrid liquid−solid electrolyte cells constructed on this concept result in a high sulfur utilization of 1400 mAh g −1 which is 85% of theoretical and remains constant over cycling even with conventional, unoptimized carbon/sulfur cathodes.

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H₃PO₄-Induced Nano-Li₃PO₄ Pre-reduction Layer to Address Instability between the Nb-Doped Li₇La₃Zr₂O₁₂ Electrolyte and Metallic Li Anode

Cited by 13 publications

References 88 publications

Constructing electron-blocking grain boundaries in garnet to suppress lithium dendrite growth

Constructing electron-blocking grain boundaries in garnet to suppress lithium dendrite growth

In-situ Li₂O-atmosphere assisted solvent-free route to produce highly conductive Li₇La₃Zr₂O₁₂ solid electrolyte

Surface Chemistry of LLZO Garnet Electrolytes with Sulfur in Electron Pair Donor Solvents

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H3PO4-Induced Nano-Li3PO4 Pre-reduction Layer to Address Instability between the Nb-Doped Li7La3Zr2O12 Electrolyte and Metallic Li Anode

Cited by 13 publications

References 88 publications

Constructing electron-blocking grain boundaries in garnet to suppress lithium dendrite growth

Constructing electron-blocking grain boundaries in garnet to suppress lithium dendrite growth

In-situ Li2O-atmosphere assisted solvent-free route to produce highly conductive Li7La3Zr2O12 solid electrolyte

Surface Chemistry of LLZO Garnet Electrolytes with Sulfur in Electron Pair Donor Solvents

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H₃PO₄-Induced Nano-Li₃PO₄ Pre-reduction Layer to Address Instability between the Nb-Doped Li₇La₃Zr₂O₁₂ Electrolyte and Metallic Li Anode

In-situ Li₂O-atmosphere assisted solvent-free route to produce highly conductive Li₇La₃Zr₂O₁₂ solid electrolyte