Designer Anion Enabling Solid-State Lithium-Sulfur Batteries

Zhang, Heng; Oteo, Uxue; Judez, Xabier; Eshetu, Gebrekidan Gebresilassie; Martínez‐Ibáñez, Maria; Carrasco, Javier; Li, Chunmei; Armand, Michel

doi:10.1016/j.joule.2019.05.003

Cited by 125 publications

(139 citation statements)

References 52 publications

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“…This result is consistent with the simulations that Li 2 O would be generated at Li/PEO interface and partially supports the prediction of the distribution of various Li compounds inside interfacial structure. [29,43] Particularly, we demonstrate that the crystalline Li particles are also incorporated in the interface apart from Li compound crystals.…”

Section: The Application Of Solid Polymer Electrolytes (Spes) Is Stilmentioning

confidence: 72%

“…The atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary-ion mass spectrometry (TOF-SIMS), and Auger electron spectroscopy (AES) have been demonstrated to image the phases distribution or reveal the chemical composition. [43][44][45][46][47][48] However, to atomically visualize such chemically sensitive interfaces and correspondingly employing the underlying promotion strategy, is still in a blank. Recently, cryo-transmission electron microscopy (cryo-TEM) has enabled the atomic observation of sensitive Li metal and its interfacial structure in liquid electrolytes.…”

Section: Doi: 101002/adma202000223mentioning

confidence: 99%

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In Situ Construction of a LiF‐Enriched Interface for Stable All‐Solid‐State Batteries and its Origin Revealed by Cryo‐TEM

et al. 2020

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The application of solid polymer electrolytes (SPEs) is still inherently limited by the unstable lithium (Li)/electrolyte interface, despite the advantages of security, flexibility, and workability of SPEs. Herein, the Li/electrolyte interface is modified by introducing Li2S additive to harvest stable all‐solid‐state lithium metal batteries (LMBs). Cryo‐transmission electron microscopy (cryo‐TEM) results demonstrate a mosaic interface between poly(ethylene oxide) (PEO) electrolytes and Li metal anodes, in which abundant crystalline grains of Li, Li2O, LiOH, and Li2CO3 are randomly distributed. Besides, cryo‐TEM visualization, combined with molecular dynamics simulations, reveals that the introduction of Li2S accelerates the decomposition of N(CF3SO2)2− and consequently promotes the formation of abundant LiF nanocrystals in the Li/PEO interface. The generated LiF is further verified to inhibit the breakage of CO bonds in the polymer chains and prevents the continuous interface reaction between Li and PEO. Therefore, the all‐solid‐state LMBs with the LiF‐enriched interface exhibit improved cycling capability and stability in a cell configuration with an ultralong lifespan over 1800 h. This work is believed to open up a new avenue for rational design of high‐performance all‐solid‐state LMBs.

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Section: The Application Of Solid Polymer Electrolytes (Spes) Is Stilmentioning

confidence: 72%

Section: Doi: 101002/adma202000223mentioning

confidence: 99%

In Situ Construction of a LiF‐Enriched Interface for Stable All‐Solid‐State Batteries and its Origin Revealed by Cryo‐TEM

et al. 2020

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“…The experimental details are available in the previous work. [ 34 ] In brief, the naphthalene radical was prepared by reacting Li° with naphthalene in ultra‐pure and dry THF. Afterward, LiFSI or LiPSTFSI was added to the naphthalene radical soution and the color change was followed.…”

Section: Methodsmentioning

confidence: 99%

Unprecedented Improvement of Single Li‐Ion Conductive Solid Polymer Electrolyte Through Salt Additive

Martínez‐Ibáñez

Sánchez-Díez

Qiao

et al. 2020

Adv Funct Materials

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Solid-state lithium metal (Li°) batteries (SSLMBs) are believed to be the most promising technologies to tackle the safety concerns and the insufficient energy density encountered in conventional Li-ion batteries. Solid polymer electrolytes (SPEs) inherently own good processability and flexibility, enabling large-scale preparation of SSLMBs. To minimize the growth of Li° dendrites and cell polarization in SPE-based SSLMBs, an additive-containing single Li-ion conductive SPE is reported. The characterization results show that a small dose of electrolyte additive (2 wt%) substantially increases the ionic conductivity of single Li-ion conductive SPEs as well as the interfacial compatibility between electrode and SPE, allowing the cycling of SPE-based cells with good electrochemical performance. This work may provide a paradigm shift on the design of highly cationic conductive electrolytes, which are essential for developing safe and high-performance rechargeable batteries.wind, solar). [4] The widely used LIBs comprise a graphitized material and a lithium transition metal oxide as the respective negative and positive electrodes, and a carbonate-based liquid solution as electrolyte. [5] On one side, the high volatility and flammability of carbonate solvents causes severe safety issues when LIBs are under abusive conditions, as noted by the increasing incidents of smartphones, EVs, and stationary batteries. [6] On the other side, the pursuit of higher energy density in battery technologies, due to the demanding requirements in newly emerging applications, has spurred considerable interest in replacing carbonaceous materials with higher capacity Li metal (Li°) electrode (e.g., 3860 mAh g -1 (Li°) vs 372 mAh g -1 (graphite)). Yet, the practical implementation of rechargeable Li°-based batteries using liquid electrolytes is handicapped by the notorious Li° dendrite formation, which results in not only low energy efficiency but also possible internal short-circuit and subsequent thermal runaway. [7] To mitigate aforementioned safety concerns and break the ceiling of energy density in LIB technologies, solid polymer electrolyte (SPE)-based solid-state Li° batteries (SSLMBs) have garnered great attention from both academic and industrial sectors. [8] Since the first perceptive proposal on using SPEs as safe electrolytes for rechargeable batteries by Armand and Duclot in 1978, [9] significant progresses and advances have been achieved in the field. [10] SPE-based batteries have been proven to be technologically feasible by the expanding applications of lithium metal polymer batteries developed by Bolloré group in EV cars and buses, as well as other energy storage scenarios. [11] However, the commonly employed conducting salt lithium bis(trifluoromethanesulfonyl)imide {Li[N(SO 2 CF 3 ) 2 ], LiTFSI} possesses a high anionic mobility (i.e., low Li-ion transference number, <0.3 [12] ) in poly(ethylene oxide) (PEO), engendering pronounced cell polarization and rapid Li° dendrite growth upon cycling of SSLMBs, particularly when...

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“…The nature of salt anions in electrolytes plays a critical role in dictating the electrochemical behavior and performance of batteries. [11,12] Different anion species may strongly affect the ion association properties in solution, possible side reactions, and even redox reactions in electrode materials. [13][14][15] Recently, an electrolyte-dependent reaction mechanism has been identified for the high-rate δ-MnO 2 cathode, where the bulky anion bis(trifluoromethane)sulfonimide (TFSI − ) in aqueous electrolytes leads to a joint nondiffusion-controlled Zn 2+ intercalation and H + conversion reaction.…”

Section: Introductionmentioning

confidence: 99%

Toward a Reversible Mn⁴⁺/Mn²⁺ Redox Reaction and Dendrite‐Free Zn Anode in Near‐Neutral Aqueous Zn/MnO₂ Batteries via Salt Anion Chemistry

Zeng

Liu

Mao

et al. 2020

Advanced Energy Materials

247

185

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Rechargeable aqueous Zn/MnO2 batteries are very attractive large‐scale energy storage technologies, but still suffer from limited cycle life and low capacity. Here the novel adoption of a near‐neutral acetate‐based electrolyte (pH ≈ 6) is presented to promote the two‐electron Mn4+/Mn2+ redox reaction and simultaneously enable a stable Zn anode. The acetate anion triggers a highly reversible MnO2/Mn2+ reaction, which ensures high capacity and avoids the issue of structural collapse of MnO2. Meanwhile, the anode‐friendly electrolyte enables a dendrite‐free Zn anode with outstanding stability and high plating/stripping Coulombic efficiency (99.8%). Hence, a high capacity of 556 mA h g−1, a lifetime of 4000 cycles without decay, and excellent rate capability up to 70 mA cm−2 are demonstated in this new near‐neutral aqueous Zn/MnO2 battery by simply manipulating the salt anion in the electrolyte. The acetate anion not only modifies the surface properties of MnO2 cathode but also creates a highly compatible environment for the Zn anode. This work provides a new opportunity for developing high‐performance Zn/MnO2 and other aqueous batteries based on the salt anion chemistry.

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Designer Anion Enabling Solid-State Lithium-Sulfur Batteries

Cited by 125 publications

References 52 publications

In Situ Construction of a LiF‐Enriched Interface for Stable All‐Solid‐State Batteries and its Origin Revealed by Cryo‐TEM

In Situ Construction of a LiF‐Enriched Interface for Stable All‐Solid‐State Batteries and its Origin Revealed by Cryo‐TEM

Unprecedented Improvement of Single Li‐Ion Conductive Solid Polymer Electrolyte Through Salt Additive

Toward a Reversible Mn⁴⁺/Mn²⁺ Redox Reaction and Dendrite‐Free Zn Anode in Near‐Neutral Aqueous Zn/MnO₂ Batteries via Salt Anion Chemistry

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Designer Anion Enabling Solid-State Lithium-Sulfur Batteries

Cited by 125 publications

References 52 publications

In Situ Construction of a LiF‐Enriched Interface for Stable All‐Solid‐State Batteries and its Origin Revealed by Cryo‐TEM

In Situ Construction of a LiF‐Enriched Interface for Stable All‐Solid‐State Batteries and its Origin Revealed by Cryo‐TEM

Unprecedented Improvement of Single Li‐Ion Conductive Solid Polymer Electrolyte Through Salt Additive

Toward a Reversible Mn4+/Mn2+ Redox Reaction and Dendrite‐Free Zn Anode in Near‐Neutral Aqueous Zn/MnO2 Batteries via Salt Anion Chemistry

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Toward a Reversible Mn⁴⁺/Mn²⁺ Redox Reaction and Dendrite‐Free Zn Anode in Near‐Neutral Aqueous Zn/MnO₂ Batteries via Salt Anion Chemistry