Calcium-doping effects on structure and electric performances of garnet-type Li6.6La3Zr1.6Sb0.4O12 solid-state electrolytes

Luo, Yi; Zhang, Qixi; Shen, Ao; Shen, Muyi; Xie, Dianchen; Yan, Yan

doi:10.1016/j.ssi.2021.115812

Cited by 17 publications

(4 citation statements)

References 46 publications

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“…The microstructures of 0La-LLZTO and 5La-LLZTO samples after cycling are shown in Figure a,b. In 0La-LLZTO, the existence of Ta 2 O 5 precipitates along grain boundaries and the void defects lead to a low relative density, which results in lithium dendrite growth due to the high electronic conductivity at grain boundaries. , The corresponding element mappings verify the lithium dendrite growth inside 0La-LLZTO (Figure c). Compared to the 0La-LLZTO electrolyte, the dense 5La-LLZTO electrolyte is obtained by introducing sufficient La 2 O 3 additives, which react with the Ta 2 O 5 precipitates and fill the void defects for achieving a high relative density (Figure d).…”

Section: Resultsmentioning

confidence: 77%

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: 77%

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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“…However, the performance of the CCPE electrolyte at higher C-rates delivers less discharge capacity, which needs to be further enhanced with synergetic structural modification in Ca(OH) 2 by utilizing lithium ion. 48 The charge/discharge performance clearly shows that the cross-linking structure and the incorporation of Ca(OH) 2 exhibit good electrochemical performance compared to NCCPE and pristine electrolytes. Figure 9c shows the Coulombic efficiency performance at 60 °C.…”

Section: Resultsmentioning

confidence: 99%

“…It is important to note that the polarization keeps increasing due to the poor interface between the electrodes and electrolyte during charging/discharging. However, the performance of the CCPE electrolyte at higher C-rates delivers less discharge capacity, which needs to be further enhanced with synergetic structural modification in Ca(OH) 2 by utilizing lithium ion . The charge/discharge performance clearly shows that the cross-linking structure and the incorporation of Ca(OH) 2 exhibit good electrochemical performance compared to NCCPE and pristine electrolytes.…”

Section: Resultsmentioning

confidence: 99%

Cross-Linked Polymer Composite Electrolyte Incorporated with Waste Seashell Based Nanofiller for Lithium Metal Batteries

et al. 2023

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The next-generation electric vehicle requires superior safety and high-energy-density batteries for better performance. Currently, solid polymer electrolytes provide better safety, high mechanical stability, and a desirable electrode-toelectrolyte interface in lithium-ion batteries compared to those in conventional battery systems. However, the ionic conductivity of solid-state electrolytes remains challenging at room and low operating temperatures. Herein, we report that incorporating a greener calcium hydroxide (CH) based nanofiller derived from natural waste seashells with polymer electrolyte gives a tremendously increased lithium-ion conductivity of 4.12 × 10 −5 S cm −1 at 25 °C. The cross-linked composite polymer electrolyte (CCPE) was prepared with PEO, LiClO 4 salt, greener nanofiller, and cross-linking monomers via the facile ultraviolet (UV) polymerization technique. The photosensitive vinyl groups of diacrylate and the thio groups of the tetrathiol monomer undergo a thiol−ene click reaction to form a highly cross-linked network with homogeneously distributed LiClO 4 and CH nanofiller. The incorporation of 15 wt % of CH greener nanofiller significantly improved the amorphous phase of the composite electrolyte and showed a wide electrochemical window of 5 V. The fine porous structure of CH greener nanofiller incorporated in the solid-state cross-linked network electrolyte channelizes for smooth lithium-ion mobility. The fabricated full cell exhibits good discharge capacity, of 160 mAh g −1 to 150 mAh g −1 at 0.1 C over 50 cycles with a high Coulombic efficiency of 95 % at 60 °C. Naturally derived, cost-effective greener nanofiller from waste seashells acts as a prominent additive to prepare solid-state electrolytes with high stability in lithium metal batteries.

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“…In contrast, in the cubic phase LLZO (Figure 1b), Li atoms occupy only two types of crystal sites (tetrahedral Li1 sites (24d) and twisted octahedral Li2 sites (96h)) which have shorter inter‐Li atoms distances, and Li + sites and vacancies are arranged in a disordered distribution. [ 17 ] Theoretical calculation results show that the structural framework with body‐centered‐cubic (bcc) anion packing yields the flattest energy landscape with the lowest Li + migration barrier, whereas nonbcc structural frameworks such as face‐centered‐cubic or hexagonal‐close‐packed exhibit significantly higher‐energy barriers (Figure 1c). [ 18 ] So the cubic‐phase LLZO has higher ion conductivity, which is applied in ASSLBs as an ionic conductor, and the ionic conductivity between the two differs by 2–3 orders of magnitude.…”

Section: Li+ Transport Mechanism At the Composite Cathodesmentioning

confidence: 99%

Constructing Low‐Impedance Li₇La₃Zr₂O₁₂‐Based Composite Cathode Interface for All‐Solid‐State Lithium Batteries

et al. 2022

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Garnet‐type solid‐state electrolytes (SEs) represented by Li7La3Zr2O12 (LLZO) are considered ideal ion‐conducting materials for oxide all‐solid‐state lithium batteries (ASSLBs) due to their high ionic conductivity and wide electrochemical window. However, there are still many problems at the interface of the composite cathode side with LLZO‐based SEs as ion conductors as LLZO has poor interfacial contact with other particles and shows air instability when exposed to air because of the spontaneous reaction with water and CO2. Among them, the high impedance at the interface is a key issue that severely limits the actual energy density and cycle life of ASSLBs. With the optimized modification of LLZO‐based SEs and the in‐depth study of the interfacial mechanism, some breakthroughs have been made in the electrochemical performance of LLZO‐based ASSLBs. Hence, this review first describes the factors causing high interfacial impedance inside LLZO‐based composite cathode, such as poor interparticle contact, stress disruption and elemental diffusion at the interface, and discontinuous ion/electron percolation paths and then summarizes the solution strategies, for example, microstructure design, component optimization, and internal interface modification. Finally, the development prospect of LLZO‐based ASSLBs composite cathode is prospected to provide a useful reference for exploring the practical application of LLZO‐based ASSLBs.

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Calcium-doping effects on structure and electric performances of garnet-type Li6.6La3Zr1.6Sb0.4O12 solid-state electrolytes

Cited by 17 publications

References 46 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

Cross-Linked Polymer Composite Electrolyte Incorporated with Waste Seashell Based Nanofiller for Lithium Metal Batteries

Constructing Low‐Impedance Li₇La₃Zr₂O₁₂‐Based Composite Cathode Interface for All‐Solid‐State Lithium Batteries

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Calcium-doping effects on structure and electric performances of garnet-type Li6.6La3Zr1.6Sb0.4O12 solid-state electrolytes

Cited by 17 publications

References 46 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

Cross-Linked Polymer Composite Electrolyte Incorporated with Waste Seashell Based Nanofiller for Lithium Metal Batteries

Constructing Low‐Impedance Li7La3Zr2O12‐Based Composite Cathode Interface for All‐Solid‐State Lithium Batteries

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Constructing Low‐Impedance Li₇La₃Zr₂O₁₂‐Based Composite Cathode Interface for All‐Solid‐State Lithium Batteries