Li6PS5Cl microstructure and influence on dendrite growth in solid-state batteries with lithium metal anode

Singh, Dheeraj K.; Henß, Anja; Mogwitz, Boris; Gautam, Ajay Kumar; Horn, Jonas; Krauskopf, Thorben; Burkhardt, Simon; Sann, Joachim; Richter, Felix H.; Janek, Jürgen

doi:10.1016/j.xcrp.2022.101043

Cited by 65 publications

(86 citation statements)

References 62 publications

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“…For oxide SSEs, due to their relatively high Young's modulus (e.g., E (LLZO) = 175 GPa) and K IC (e.g., K IC LLZO = 1.25 MPa m 1/2 ), the internal stress of the battery may lead to plastic flow of lithium rather than crack growth within the SSE. [96] In this case, micro-short-circuit behavior in oxide SSEs may be dominated by internal lithium nucleation (lithium dendrites propagate through voids and grain boundaries with preferential ion pathways) rather than the electrochemo-mechanical damage/dendrite penetration behavior in sulfide SSEs. [99] Scalable sheet-type electrodes are necessary for the practical application of sulfide-based ASSBs.…”

Section: Inactive Components: Electrochemistry and Mechanicsmentioning

confidence: 99%

“…In general, sulfide SSEs have favorable mechanical properties (lower Pugh's ratio, e.g., LPSCl with a G / B of 0.28, where G and B are shear and bulk modulus, respectively) so that densification of the electrolytes can be achieved at lower external pressures (e.g., 360 MPa) and room temperature. [ 96 ] In comparison to sulfide SSEs, another typical class of inorganic solid‐state electrolytes, oxide SSEs, due to distinctive differences in mechanical properties (e.g., Pugh's ratio of 0.54 for LLZO), require a much higher external pressure (up to hundreds of GPa) and high temperature (up to 1000 °C) to achieve densification. [ 97 ] In addition, the higher hardness ( H ) and elastic modulus (hardness H = 9.2, 9.1, 7.1 GPa, and Young's modulus E = 200, 150, 115 GPa for LLTO, LLZO, and LATP, respectively) of oxide SSEs than sulfide SSEs (detailed in Table 2) make them less prone to elastic deformation.…”

Section: Applicationmentioning

confidence: 99%

“…For sulfide SSEs, their Young's modulus (e.g., E (LPSCl) = 22 GPa) is not much different from that of Li metal (7.8 GPa), and the fracture toughness K IC is lower (e.g., K IC LPSCl = 0.23 MPa m 1/2 ), so the internal stress during battery cycling is likely to lead to a heterogeneous distribution of lithium protrusions, which increases the local K IC of the SSE/Li interface. [ 96 ] The increased local K IC will cause the cracks to occur within the SSE layer, and then the lithium dendrites will grow along the cracks, resulting in the short‐circuit phenomenon. For oxide SSEs, due to their relatively high Young's modulus (e.g., E (LLZO) = 175 GPa) and K IC (e.g., K IC LLZO = 1.25 MPa m 1/2 ), the internal stress of the battery may lead to plastic flow of lithium rather than crack growth within the SSE.…”

Section: Applicationmentioning

confidence: 99%

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Electrochemo‐Mechanical Stresses and Their Measurements in Sulfide‐Based All‐Solid‐State Batteries: A Review

Liang

Shi

et al. 2022

Advanced Energy Materials

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Sulfide‐based all‐solid‐state batteries (ASSBs) are one of the most promising energy storage devices due to their high energy density and good safety. However, due to the volume (stress) changes of the solid active materials during the charging and discharging process, the generation and evolution of electrochemomechanical stresses are becoming serious and unavoidable problems during the operation of all‐solid‐state batteries due to the lack of a liquid electrolyte to partially buffer the stress generated in the electrodes. To understand these electrochemo‐mechanical effects, including the origins and evolution of mechanical or internal stresses, it is necessary to develop some highly sensitive probing techniques to measure them precisely and bridge the relationship between the electrochemical reaction process and internal stress evolution. Herein, recent progress on uncovering the origins of the internal stresses, the working principle and experimental devices for stress measurement, and the application of those stress‐measuring techniques in the study of electrochemical reactions in sulfide‐based ASSBs are briefly summarized and overviewed. The investigation of precise and operando monitoring techniques and strategies for suppressing or relaxing these electrochemomechanical stresses will be an important direction in future solid‐state batteries.

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Section: Inactive Components: Electrochemistry and Mechanicsmentioning

confidence: 99%

Section: Applicationmentioning

confidence: 99%

Section: Applicationmentioning

confidence: 99%

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Electrochemo‐Mechanical Stresses and Their Measurements in Sulfide‐Based All‐Solid‐State Batteries: A Review

Liang

Shi

et al. 2022

Advanced Energy Materials

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“…[22] High pressures would lead to extensive interfacial fracture within these ISEs, and the resulting cracks would serve as favorable pathways for dendrite growth through the bulk microstructure. [23][24][25][26] In effect, this lowers the critical current density (CCD), i.e., the maximum current density before shorting. [27] Since ceramics in general do not exhibit fatigue, [28] these interfacial fractured zones are expected to significantly affect the long-term cyclability.…”

Section: Introductionmentioning

confidence: 99%

Overcoming Anode Instability in Solid‐State Batteries through Control of the Lithium Metal Microstructure

Singh

Fuchs

Krempaszky

et al. 2022

Adv Funct Materials

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Enabling the lithium metal anode (LMA) in solid‐state batteries (SSBs) is the key to developing high energy density battery technologies. However, maintaining a stable electrode–electrolyte interface presents a critical challenge to high cycling rate and prolonged cycle life. One such issue is the interfacial pore formation in LMA during stripping. To overcome this, either higher stack pressure or binary lithium alloy anodes are used. Herein, it is shown that fine‐grained (d = 20 µm) polycrystalline LMA can avoid pore formation by exploiting the microstructural dependence of the creep rates. In a symmetric cell set‐up, i.e., LiǀLi6.25Al0.25La3Zr2O12(LLZO)ǀLi, fine‐grained LMA achieves > 11.0 mAh cm−2 compared to ≈ 3.6 mAh cm−2 for coarse‐grained LMA (d = 295 µm) at 0.1 mA cm−2 and at moderate stress of 2.0 MPa. Smaller diffusion lengths (≈ 20 µm) and higher diffusivity pathway along dislocations (Dd ≈ 10−7 cm2 s−1), generated during cell fabrication, result in enhanced viscoplastic deformation in fine‐grained polycrystalline LMA. The electrochemical performances corroborate well with estimated creep rates. Thus, microstructural control of LMA can significantly reduce the required stack pressure during stripping. These results are particularly relevant for “anode‐free” SSBs wherein both the microstructure and the mechanical state of the lithium are critical parameters.

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“…Singh et al carried out a study which also used variation of particle size to produce cold-pressed Li 6 PS 5 Cl pellets (referred to in the study as 'small-grain' and 'large-grain' samples) demonstrating the same trend in CCD [41]. Their work showed the samples made from larger particles to have a higher surface roughness, which was used to explain their worse resistance to lithium filament growth [41]. Firstly, the current focusing will be enhanced in the case of increased surface roughness, as is demonstrated in figure 3 showing finite element analysis of the current density distribution at the interfaces between small-and large-grained samples with the lithium metal anode [41].…”

Section: The Effect Of Grain Size On Ccdmentioning

confidence: 99%

The role of grain boundaries in solid-state Li-metal batteries

Milan

Pasta

2022

Mater. Futures

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Despite the potential advantages promised by solid-state batteries, the success of solid-state electrolytes has not yet been fully realised. This is due in part to the lower ionic conductivity of solid electrolytes. In many solid superionic conductors, grain boundaries are found to be ionically resistive and hence contribute to this lower ionic conductivity. Additionally, in spite of the hope that solid electrolytes would inhibit lithium filaments, in most scenarios their growth is still observed, and in some polycrystalline systems this is suggested to occur along grain boundaries. It is apparent that grain boundaries affect the performance of solid-state electrolytes, however a deeper understanding is lacking. In this perspective, the current theories relating to grain boundaries in solid-state electrolytes are explored, as well as addressing some of the challenges which arise when trying to investigate their role. Glasses are presented as a possible solution to reduce the effect of grain boundaries in electrolytes. Future research directions are suggested which will aid in both understanding the role of grain boundaries, and diminishing their contribution in cases where they are detrimental.

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Li6PS5Cl microstructure and influence on dendrite growth in solid-state batteries with lithium metal anode

Cited by 65 publications

References 62 publications

Electrochemo‐Mechanical Stresses and Their Measurements in Sulfide‐Based All‐Solid‐State Batteries: A Review

Electrochemo‐Mechanical Stresses and Their Measurements in Sulfide‐Based All‐Solid‐State Batteries: A Review

Overcoming Anode Instability in Solid‐State Batteries through Control of the Lithium Metal Microstructure

The role of grain boundaries in solid-state Li-metal batteries

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