Manganese Sequestration and Li-Ion Batteries Durability Enhancement by Polymeric 18-Crown-6 Ethers

Ziv, Baruch; Levy, Naomi; Borgel, Valentina; Li, Zicheng; Levi, Mikhael D.; Aurbach, Doron; Pauric, Allen D.; Goward, Gillian R.; Fuller, Timothy; Balogh, Michael P.; Halalay, Ion C.

doi:10.1149/2.0091409jes

Cited by 38 publications

(41 citation statements)

References 23 publications

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“…Therefore, some research groups focused on TM‐ion‐scavengers in LIBs to extend the lifetime. For this, complexing agents were dissolved as additives in the electrolyte or bound to the separator to scavenge‐dissolved TM ions from the cathode [22–26]. It is well known that complexing agents can strongly influence the preferred oxidation state of the TM.…”

Section: Resultsmentioning

confidence: 99%

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Mn²⁺ or Mn³⁺? Investigating transition metal dissolution of manganese species in lithium ion battery electrolytes by capillary electrophoresis

et al. 2020

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Mn 2+ or Mn 3+ ? Investigating transition metal dissolution of manganese species in lithium ion battery electrolytes by capillary electrophoresisA new CE method with ultraviolet-visible detection was developed in this study to investigate manganese dissolution in lithium ion battery electrolytes. The aqueous running buffer based on diphosphate showed excellent stabilization of labile Mn 3+ , even under electrophoretic conditions. The method was optimized regarding the concentration of diphosphate and modifier to obtain suitable signals for quantification. Additionally, the finally obtained method was applied on carbonate-based electrolytes samples. Dissolution experiments of the cathode material LiNi 0.5 Mn 1.5 O 4 (lithium nickel manganese oxide [LNMO]) in aqueous diphosphate buffer at defined pH were performed to investigate the effect of a transition metal-ion-scavenger on the oxidation state of dissolved manganese. Quantification of both Mn species revealed the formation of mainly Mn 3+ , which can be attributed to a comproportionation reaction of dissolved and complexed Mn 2+ with Mn 4+ at the surface of the LNMO structure. It was also shown that the formation of Mn 3+ increased with lower pH. In contrast, dissolution experiments of LNMO in carbonate-based electrolytes containing LIPF 6 showed only dissolution of Mn 2+ .Abbreviations: LIBs, lithium ion batteries; LMO, lithium manganese oxide; LNMO, lithium nickel manganese oxide; SEI, solid electrolyte interphase; TM, transition metal; XANES, Xray absorption near-edge structure spectroscopy Color online: See the article online to view Figs. 1-5 in color.

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Section: Resultsmentioning

confidence: 99%

“…These effects eventually lead to increased cell impedance, more side reactions, and finally to reduced life [16, 20, 21]. Therefore, it is important to prevent the dissolution of TMs in LIBs, their migration to the anode, or to enhance the tolerance of LIBs regarding the dissolved TMs [22–27].…”

Section: Introductionmentioning

confidence: 99%

Mn²⁺ or Mn³⁺? Investigating transition metal dissolution of manganese species in lithium ion battery electrolytes by capillary electrophoresis

et al. 2020

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“…57 Such results can be readily explained by the well-known propensity of macrocycles to enhance ionic transport in electrolyte solutions. 77 Mere trapping of Mn cations by chelating molecules is not thus enough for enhancing LIBs performance, as one must also prevent the migration of cation-chelate complexes in the internal electric field of a battery.…”

Section: A6316mentioning

confidence: 99%

Review—Multifunctional Materials for Enhanced Li-Ion Batteries Durability: A Brief Review of Practical Options

Banerjee

Shilina

Ziv

et al. 2017

J. Electrochem. Soc.

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Transition metal (TM) ions dissolution from positive electrodes, migration to and deposition on negative electrodes, followed by Mn-catalyzed reactions of solvents and anions, with loss of Li + ions, is a major degradation (DMDCR) mechanism in Li-ion batteries (LIBs) with spinel positive electrode materials. While the details of the DMDCR mechanism are still under debate, it is clear that HF and other acid species' attack is the main cause in solutions with LiPF 6 electrolyte. We first review the work on various mitigation measures for the DMDCR mechanism, now spanning more than two decades. We then discuss recent progress on our understanding of Mn species in electrolyte solutions and the extension of a mitigation measure first proposed by Tarascon and coworkers in 1999, namely chelation of TM cations, to Mn cation trapping, HF scavenging, and alkali metal ions dispensing multi-functional materials. We focus on practicable, drop-in technical solutions, based on placing such materials in the inter-electrode space, with significant benefits for LIBs performance: increased capacity retention during operation at room and above-ambient temperatures as well as robust (both maximally ionically conducting and electronically insulating) solid-electrolyte interfaces, having reduced charge transfer and film resistances at both negative and positive electrodes. We illustrate the multifunctional materials approach with both new and previously published data. We also discuss and offer our evaluation regarding the merits and drawbacks of the various mitigation measures, with an eye for practically relevant technical solutions capable to meet both the performance requirements and cost constraints for commercial LIBs, and end with recommendations for future work. Li-ion batteries (LIBs) dominate the global market for energystorage devices nowadays and are used in a variety of applications, ranging from portable consumer electronics, to electrical grid storage, to load-levelling and electrified vehicles.1 Electrified vehicles are the most demanding among all LIBs applications in terms of both duty cycle and durability, since the batteries are subjected to a wide range of temperatures and charging/discharging rates, while customers expect a 10 years lifetime. Incessant research on various positive and negative active materials resulted in several promising electrode materials with various crystal structures and chemistries being developed over the past decades, such as layered (LiCoO 2 , LiNi 1-x-y Co x Al y O 2 , Ni 1-x-y Co x Mn y O 2 ), spinel (LiMn 2 O 4 , a.k.a. LMO; LNi 0.5 Mn 1.5 O 2 , a.k.a. LNMO), and olivine (LiFePO 4, LiVPO 4 ) for positive, as well as graphite, silicon, silicon-oxide, and lithium titanate for negative electrodes.2 New developments in electrode materials notwithstanding, LIBs for automotive transportation still need considerable improvements in terms of both performance and durability. Among transition metal (TM) oxide cathodes, LiMn 2 O 4 spinel would be most suited for automotive power cells due to i...

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“…[1][2][3][4][5][6][7][8][9][10] Despite of the major advances over the last few decades, gas generation during the formation, operation and storage of the LIBs remains a big challenge, due to the concomitant volume swelling, performance failure and safety concerns. [11][12][13][14] Gas generation in the formation step of the batteries is mainly originated from the electrochemical decomposition of electrolyte solvents during the solid-electrolyte interphase (SEI) layer formation, [15][16][17][18][19][20][21] which requires an extra degassing process, especially for the "soft" pouch cells, and thus increase the production cost and potentially degrade the consistency of cell groups.…”

Section: In-situ Analysis Of Gas Generation In Lithium Ion Batteries mentioning

confidence: 99%

In Situ Analysis of Gas Generation in Lithium-Ion Batteries with Different Carbonate-Based Electrolytes

Teng

Zhan²,

Bai

et al. 2015

ACS Appl. Mater. Interfaces

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Gas generation in lithium-ion batteries is one of the critical issues limiting their safety performance and lifetime. In this work, a set of 900 mAh pouch cells were applied to systematically compare the composition of gases generated from a serial of carbonate-based composite electrolytes, using a self-designed gas analyzing system. Among electrolytes used in this work, the composite γ-butyrolactone/ethyl methyl carbonate (GBL/EMC) exhibited remarkably less gassing because of the electrochemical stability of the GBL, which makes it a promising electrolyte for battery with advanced safety and lifetime.

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Manganese Sequestration and Li-Ion Batteries Durability Enhancement by Polymeric 18-Crown-6 Ethers

Cited by 38 publications

References 23 publications

Mn²⁺ or Mn³⁺? Investigating transition metal dissolution of manganese species in lithium ion battery electrolytes by capillary electrophoresis

Mn²⁺ or Mn³⁺? Investigating transition metal dissolution of manganese species in lithium ion battery electrolytes by capillary electrophoresis

Review—Multifunctional Materials for Enhanced Li-Ion Batteries Durability: A Brief Review of Practical Options

In Situ Analysis of Gas Generation in Lithium-Ion Batteries with Different Carbonate-Based Electrolytes

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Manganese Sequestration and Li-Ion Batteries Durability Enhancement by Polymeric 18-Crown-6 Ethers

Cited by 38 publications

References 23 publications

Mn2+ or Mn3+? Investigating transition metal dissolution of manganese species in lithium ion battery electrolytes by capillary electrophoresis

Mn2+ or Mn3+? Investigating transition metal dissolution of manganese species in lithium ion battery electrolytes by capillary electrophoresis

Review—Multifunctional Materials for Enhanced Li-Ion Batteries Durability: A Brief Review of Practical Options

In Situ Analysis of Gas Generation in Lithium-Ion Batteries with Different Carbonate-Based Electrolytes

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Mn²⁺ or Mn³⁺? Investigating transition metal dissolution of manganese species in lithium ion battery electrolytes by capillary electrophoresis

Mn²⁺ or Mn³⁺? Investigating transition metal dissolution of manganese species in lithium ion battery electrolytes by capillary electrophoresis