From Liquid- to Solid-State Batteries: Ion Transfer Kinetics of Heteroionic Interfaces

Weiß, Morten; Simon, Fabian; Busche, Martin R.; Nakamura, Takashi; Schröder, Daniel; Richter, Felix H.; Janek, Jürgen

doi:10.1007/s41918-020-00062-7

Cited by 126 publications

(110 citation statements)

References 95 publications

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“…Overall the Li 6 PS 5 Cl|Li 3 InCl 6 charge transfer resistance is roughly one order of magnitude smaller than the bulk contribution and is 59 Ω cm 2 compared to 589 Ω cm 2 for the bulk process at 193 K, thus it is negligible at room temperature. This small resistance for Li ion charge transfer at the hetero‐contact Li 6 PS 5 Cl|Li 3 InCl 6 supports the general finding that the interface resistance two inorganic SEs is small, once good contact is achieved [16] …”

Section: Resultssupporting

confidence: 79%

Lithium‐Metal Anode Instability of the Superionic Halide Solid Electrolytes and the Implications for Solid‐State Batteries

et al. 2021

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Owing to high ionic conductivity and good oxidation stability, halide‐based solid electrolytes regain interest for application in solid‐state batteries. While stability at the cathode interface seems to be given, the stability against the lithium metal anode has not been explored yet. Herein, the formation of a reaction layer between Li3InCl6 (Li3YCl6) and lithium is studied by sputter deposition of lithium metal and subsequent in situ X‐ray photoelectron spectroscopy as well as by impedance spectroscopy. The interface is thermodynamically unstable and results in a continuously growing interphase resistance. Additionally, the interface between Li3InCl6 and Li6PS5Cl is characterized by impedance spectroscopy to discern whether a combined use as cathode electrolyte and separator electrolyte, respectively, might enable long‐term stable and low impedance operation. In fact, oxidation stable halide‐based lithium superionic conductors cannot be used against Li, but may be promising candidates as cathode electrolytes.

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Section: Resultssupporting

confidence: 79%

Lithium‐Metal Anode Instability of the Superionic Halide Solid Electrolytes and the Implications for Solid‐State Batteries

et al. 2021

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“…That is to say, the ionic CT resistance ( R LPEI‐CT and R PEI‐CT ) is caused by the desolvation/solvation of Li ions at the LPEI and PEI, while the interphase resistance ( R LPEI and R PEI ) is attributed to the limited conductivity of formed interphase. [ 15b,25,26 ] Besides, the constant phase elements (CPE) are used to describe the electrical double layer at the LPEI (CPE LPEI‐dl ) and the PEI (CPE PEI‐dl ), which is also relevant with the ionic CT process. [ 15b ] As shown in Figure 4b, the values of R SUM gradually reduce from 69.8 Ω (12 h) to 17.1 Ω (90 h) owing to the sustained release of PPC.…”

Section: Resultsmentioning

confidence: 99%

Sustained Release‐Driven Formation of Ultrastable SEI between Li₆PS₅Cl and Lithium Anode for Sulfide‐Based Solid‐State Batteries

Sun

et al. 2020

Advanced Energy Materials

102

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considerable advantages are mainly associated with the cooperation of high theoretical capacity (3860 mAh g −1), low density (0.53 g cm −3), and the lowest reduction potential (−3.04 V vs standard hydrogen electrode) of Li anode and the non-flammability, absence of leakage and vaporization of inorganic solid-state electrolytes (SEs). [1b,2] Nevertheless, the unfavorable conductivity of SEs and the large interfacial resistance between Li anode and SEs make it difficult to realize practical application for SSMLBs. Latterly, the sulfide-type solid electrolytes (SSEs), such as Li 10 GeP 2 S 12 , [3] Li 7 P 3 S 11 , [4] and Li 6 PS 5 Cl [5] have attracted widespread concerns due to their outstanding ionic conductivity (>1.0 mS cm −1 at ambient temperature), which holds the promise for providing the potential application in SSLMBs. [6] Unfortunately, the poor compatibility between SSEs and Li anode has been proven theoretically [7] and experimentally, [8] leading to the increase of interfacial resistance and the formation of Li dendrite through the grain boundary or voids in SSEs. [9] In response to this, several strategies have been carried out in SSLMBs as below: i) The doping of element into SSEs can availably modulate their own surface energy to provide a better protection for Li metal, which is conductive to improving its electrochemical stability. [9b,10] ii) Li-M alloys The sulfide-type solid electrolyte (SSE) is considered a promising candidate for solid-state lithium metal batteries (SSLMBs) owing to its advantages of superior ionic conductivity. Nevertheless, the incompatibility of the sulfide and lithium metal can result in undesirable interface resistance and rapid Li dendrite growth, which seriously hinders its commercial applications. Herein, inspired by the moderation and long duration of sustained release drug carriers when combined with active pharmaceutical ingredients in the biomedical field, poly (propylene carbonate) (PPC) and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) gradually interact with a Li anode with constantly decreased Li/SSE interfacial resistance. In addition to intimate contact, the ultrastable LiF-enriched solid electrolyte interphase (SEI) is in situ formed via a sustained release effect, which suppresses the Li dendrite effectively. As a result, the symmetric cells demonstrate stable cycling performance for 1200 h at a current density of 0.1 mA cm −2 and 300 h at 0.5 mA cm −2. Moreover, LiFePO 4 / Li 6 PS 5 Cl /Li SSLMB delivers a high discharge capacity of over 132.8 mAh g −1 for 900 cycles at 1C with steady Coulombic efficiency. Therefore, this sustained release mechanism and its initially successful application in interfacial modification increase the potential for commercial applications of SSLMBs.

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“…Considering the variety of experimental data on that topic already acquired, we recently published a review on the existing data, as well studying the impact of the solid electrolyte, the solvent, and the conducting salt on the growth and magnitude of the SLEI's resistance. [ 86 ]…”

Section: Discussionmentioning

confidence: 99%

The Formation of the Solid/Liquid Electrolyte Interphase (SLEI) on NASICON‐Type Glass Ceramics and LiPON

Busche

Weiß

Leichtweiß

et al. 2020

Adv Materials Inter

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to the high bulk conductivity and because LEs easily wet and fill the porous electrodes. These features enable fast bulk and interface kinetics of Li-ion exchange required for high rate capability. Otherwise, in any LE-based battery system, secondary reactions are taking place apart from the desired Li +-ion exchange that can be detrimental for cycle life and rate capability. This is especially the case if active material dissolves and diffuses from the cathode to the anode, creating a chemical short circuit or cross-talk, most particularly known as the polysulfide shuttle effect taking place in LE-based lithium-sulfur secondary batteries (LSSB). [1-7] Shuttle and active mass migration effects occur as well in LIBs [8] and redox catalyzed Li-O 2 cells. [9,10] Recent investigations prove that the migration of electrolyte decomposition products in high-voltage LIBs leads to strong capacity fading. [8] Main approaches to cure the parasitic shuttle shown forbut not limited to-LLSBs are as follows: 1) in situ established solid electrolyte interphase (SEI) formed via reaction of lithium and electrolyte compounds or additives (e.g., LiNO 3) [11] or 2) ex situ formed passivation layer (artificial SEI), using purely ion-conducting polymers [12] or inorganic coatings [13,14] are applied for anode protection. 3) The polysulfide diffusion out of the cathode is delayed by a cathode nanoscale architecture or sealing measures. [2,15-19] 4) "Solidification" of the Li-S 8 cell exclusively using polymers [20-23] or solid electrolytes [24,25] (SEs) circumvents the dissolution of polysulfides but suffers from slow transport kinetics of Li-ions inside solid lithium-ion conductors and across the interfaces. Especially the low rate capability of such systems limits their practical application as it is-beyond the energy density-the second crucial LIB property to enable energy storage for the electrification. Most recent approaches refer to hybrid cells (anode/LE a /SE/ LE c /cathode), comprising an LE in contact to the electrodes and an SE as a lithium-ion-selective barrier. The SE is separating anolyte (LE a) and catholyte (LE c) to suppress the chemical shortcircuit as well as to reduce the danger of dendrite growth and electronic short-circuit. [26-39] Hybrid cells can be tailored to 1) allow fast kinetics of the LE/porous electrode interfaces as well as 2) apply thin solid electrolyte membranes to limit the Li-ion path length through the solid phase with lower conductivity. Most electrochemical energy storages (battery cells) consist of solid electrodes separated by a liquid electrolyte. If electrode materials are-at least partially-soluble in the electrolyte, detrimental mass transport between both electrodes (electrode cross-talk) occurs. The shuttle mechanism in lithium-sulfur batteries and leaching of Mn in high voltage cathode materials are important examples. Implementing a solid electrolyte (SE) membrane between the electrodes is a comprehensible approach to suppress undesired mass transport but additional resistances arise d...

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From Liquid- to Solid-State Batteries: Ion Transfer Kinetics of Heteroionic Interfaces

Cited by 126 publications

References 95 publications

Lithium‐Metal Anode Instability of the Superionic Halide Solid Electrolytes and the Implications for Solid‐State Batteries

Lithium‐Metal Anode Instability of the Superionic Halide Solid Electrolytes and the Implications for Solid‐State Batteries

Sustained Release‐Driven Formation of Ultrastable SEI between Li₆PS₅Cl and Lithium Anode for Sulfide‐Based Solid‐State Batteries

The Formation of the Solid/Liquid Electrolyte Interphase (SLEI) on NASICON‐Type Glass Ceramics and LiPON

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From Liquid- to Solid-State Batteries: Ion Transfer Kinetics of Heteroionic Interfaces

Cited by 126 publications

References 95 publications

Lithium‐Metal Anode Instability of the Superionic Halide Solid Electrolytes and the Implications for Solid‐State Batteries

Lithium‐Metal Anode Instability of the Superionic Halide Solid Electrolytes and the Implications for Solid‐State Batteries

Sustained Release‐Driven Formation of Ultrastable SEI between Li6PS5Cl and Lithium Anode for Sulfide‐Based Solid‐State Batteries

The Formation of the Solid/Liquid Electrolyte Interphase (SLEI) on NASICON‐Type Glass Ceramics and LiPON

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Product

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Sustained Release‐Driven Formation of Ultrastable SEI between Li₆PS₅Cl and Lithium Anode for Sulfide‐Based Solid‐State Batteries