XPS and SIMS Analysis of Solid Electrolyte Interphases on Lithium Formed by Ether-Based Electrolytes

Fiedler, Carsten; Luerßen, Bjoern; Rohnke, Marcus; Sann, Joachim; Janek, Jürgen

doi:10.1149/2.0851714jes

Cited by 60 publications

(80 citation statements)

References 34 publications

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“…All these components are well known to build up the SEI on metallic lithium anodes. [11,69,65,74] The additional line at 289.4 eV represents the (CF 3 ) group in LiTFSI [66] and is visible on all samples, presumably originating either from conducting salt residuals or LiTFSI decomposition. For all SEs analyzed in this study, the highest contribution of organic lithium salts is found in the binary mixture, while it is rather low for the single solvents.…”

Section: (6 Of 14)mentioning

confidence: 95%

“…It may originate from SE surface degradation due to unavoidable water traces in the LE. [65] Via complementary analysis of reference material it can be shown that the − CHO 2 fragment assigned to formate and − CHO 2,P , as a fragment of poly-DOL, are indeed distinguishable. [65] Compared to DME, we detect a significantly higher signal intensity for − CHO 2,P in the second region of the depth profile and assume that poly-DOL is a major constituent of the SLEI in DOL.…”

Section: (6 Of 14)mentioning

confidence: 99%

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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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Section: (6 Of 14)mentioning

confidence: 95%

Section: (6 Of 14)mentioning

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

Self Cite

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“…Identify the composition of the Li surface; Identify the composition of SEI in two different kind of electrolyte solvents;…”

Section: Characterization Of Li−metal Anodesmentioning

confidence: 99%

“…performed SIMS on Li−O 2 batteries cathode to confirm the reversible formation of Li 2 O 2 , Figure a . In addition, SIMS has another advantage of depth analysis, Figure b . Janek et al.…”

Section: Characterization Of Li−metal Anodesmentioning

confidence: 99%

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Safe Lithium‐Metal Anodes for Li−O₂ Batteries: From Fundamental Chemistry to Advanced Characterization and Effective Protection

Hong

Zhao

Xiao

et al. 2019

Batteries & Supercaps

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Rechargeable LiÀ O 2 batteries play an increasing important role as energy storage devices, which have both, a high capacity anode and a cathode using an inexhaustible resource. As a key component in LiÀ O 2 batteries, the Li-metal anode suffers from major drawbacks related to Li dendrite formation and SEI layer growth, which are also major issues for Li-metal rechargeable batteries. This review presents an overview on the scientific challenges, fundamental mechanisms and modification strategies of Li-metal anodes for LiÀ O 2 batteries. Firstly, basic principles and challenges on Li-metal anodes are briefly retrospected. We further summarize and categorize the prevailing characterization techniques based on Li dendrite morphology characterization and SEI composition analysis. The up-to-date development of in-situ and operando characterization is also included. Following the obtained insights, effective protection/modification strategies towards practical application for LiÀ O 2 batteries are presented. Furthermore, we highlight the significance of advanced characterization techniques in interrogating the buried keys for solving practical hindrances for LiÀ O 2 batteries. The comprehensive characterization and analysis of Li anodes, cathodes, and electrolytes by various methods together with the development of novel techniques are expected to be indispensable to gain a thorough understanding of the battery operation and for offering guidelines for their practical development.

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Stabilizing Polymer–Lithium Interface in a Rechargeable Solid Battery

Yan

Liang

Zuo

et al. 2019

Adv Funct Materials

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Solid polymer electrolytes (SPEs) are promising candidates for developing highenergy-density Li metal batteries due to their flexible processability. However, the low mechanical strength as well as the inferior interfacial regulation of ions between SPEs and Li metal anode limit the suppress ion of Li dendrites and destabilize the Li anode. To meet these challenges, interfacial engineering aiming to homogenize the distribution of Li + /electron accompanied with enhanced mechanical strength by Mg 3 N 2 layer decorating polyethylene oxide is demonstrated. The intermediary Mg 3 N 2 in situ transforms to a mixed ion/ electron conducting interlayer consisting of a fast ionic conductor Li 3 N and a benign electronic conductor Mg metal, which can buffer the Li + concentration gradient and level the nonuniform electric current distribution during cycling, as demonstrated by a COMSOL Multiphysics simulation. These characteristics endow the solid full cell with a dendrite-free Li anode and enhanced cycling stability and kinetics. The innovative interface design will accelerate the commercial application of high-energy-density solid batteries.as well as low cost. [4] Nevertheless, the relatively low ionic conductivity of SPEs leads sluggish Li + transfer kinetics, limiting the full play of cell's capacity, while the low transference number hinds the efficient regulation of Li + as well as its low mechanical strength results in the limited capability to suppress Li dendrites (Figure 1a,b). [5] Great effort has been dedicated to modifying SPEs via combining rigid skeletons or layers in order to increase the ionic conductivities and improve mechanical strength. [6] However, the effect of interface regulation always wears off after long cycles because of the intrinsic relatively low transference number of SPEs. [7] In this premise, nanosized inorganic fillers are introduced to SPEs to increase the transference number and immobilize the anions. [8] Note that the large portion of ceramic impedes the pursue of high-energy-density Li metal batteries. Therefore, a facile interfacial modification between SPEs and Li anode, buffering the Li + concentration gradient and leveling the nonuniform current distribution without sacrificing low cost and high energy density, is of urgent demanding. [9] Herein, an in situ formed mixed ion/electron conducting interlayer (MIECI) by an intermediary Mg 3 N 2 layer decorated on polyethylene oxide (PEO) (noted as PEO-Mg 3 N 2 ) to manipulate ion and electron distributions was achieved (Figure 1c-e) in the solid system. The PEO membrane has a compact contact with cathode accelerating the Li + transport, while the Mg 3 N 2 layer converses to Li 3 N and magnesium metal ( Figure S1, Supporting Information) during cycling via in situ electrochemical reaction with Li anode. Li 3 N is well known as a fast Li + conductor of ≈10 −3 S cm −1 at room temperature and has superior stability against Li metal, conducting to realize rapid Li + transfer and mitigate the Li + concentration gradient. [10] Moreover...

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XPS and SIMS Analysis of Solid Electrolyte Interphases on Lithium Formed by Ether-Based Electrolytes

Cited by 60 publications

References 34 publications

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

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

Safe Lithium‐Metal Anodes for Li−O₂ Batteries: From Fundamental Chemistry to Advanced Characterization and Effective Protection

Stabilizing Polymer–Lithium Interface in a Rechargeable Solid Battery

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XPS and SIMS Analysis of Solid Electrolyte Interphases on Lithium Formed by Ether-Based Electrolytes

Cited by 60 publications

References 34 publications

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

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

Safe Lithium‐Metal Anodes for Li−O2 Batteries: From Fundamental Chemistry to Advanced Characterization and Effective Protection

Stabilizing Polymer–Lithium Interface in a Rechargeable Solid Battery

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Product

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Safe Lithium‐Metal Anodes for Li−O₂ Batteries: From Fundamental Chemistry to Advanced Characterization and Effective Protection