Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries

Bouchet, Renaud; Maria, Sébastien; Meziane, R; Aboulaich, Abdelhay; Liénafa, Livie; Bonnet, Jean-Pierre; Phan, Trang N. T.; Bertin, Denis; Gigmès, Didier; Devaux, Didier; Denoyel, Renaud; Armand, Michel

doi:10.1038/nmat3602

Cited by 1,292 publications

(1,186 citation statements)

References 43 publications

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“…The t + value of this electrolyte was about 0.12 (SI Appendix, Fig. S6), consistent with literature reports that t + values for LiTFSI/PEO electrolytes are between 0.1 and 0.3 (31,32). In the future, we will use more rigorous approaches to measure t + (33).…”

Section: Significancesupporting

confidence: 86%

“…Although the relatively low conductivity of PFPE electrolytes may hinder power capacities, the near-unity transference number may mitigate some of these shortcomings: theoretical calculations show that materials with high t + values exhibit better battery performance than those possessing greater conductivity but a lower t + (34). The absence of polarization also reduces the risk of lithium plating and dendrite formation (31,35). The Li-ion transference number of conventional carbonate electrolytes usually ranges between 0.1 and 0.5 (16); concomitant salt concentration gradients across the electrolyte limit battery life and power density.…”

Section: Significancementioning

confidence: 99%

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Nonflammable perfluoropolyether-based electrolytes for lithium batteries

Wong

Thelen

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

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204

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The flammability of conventional alkyl carbonate electrolytes hinders the integration of large-scale lithium-ion batteries in transportation and grid storage applications. In this study, we have prepared a unique nonflammable electrolyte composed of low molecular weight perfluoropolyethers and bis(trifluoromethane)sulfonimide lithium salt. These electrolytes exhibit thermal stability beyond 200°C and a remarkably high transference number of at least 0.91 (more than double that of conventional electrolytes). Li/LiNi 1/3 Co 1/3 Mn 1/3 O 2 cells made with this electrolyte show good performance in galvanostatic cycling, confirming their potential as rechargeable lithium batteries with enhanced safety and longevity.fluorinated polymers | nonflammable electrolytes L arge-scale rechargeable batteries are expected to play a key role in today's emerging sustainable energy landscape (1, 2). State-of-the-art lithium (Li) batteries not only are used to power zero-emission electric vehicles, but they currently are gaining traction as backup power in aircraft and smart grid applications (3, 4). The electrolyte used in these batteries, however, hinders their use in large-scale applications: it contains a flammable mixture of alkyl carbonate solvents that frequently leads to safety issues. Dimethyl carbonate (DMC), an important component in commercial Li-ion battery electrolytes, has an HMIS (Hazardous Materials Identification System) flammability rating of 3 on a scale of 0-4, indicating a high risk of ignition under most operating conditions. The intrinsic instability of carbonate-based solvents worsens at higher temperatures, at which exothermic electrolyte breakdown often leads to thermal runaway (5, 6), resulting in catastrophic failure of the battery. Although this failure rate stands at about one in ten million systems, it is intolerable for large-scale applications in which cost and user safety might be heavily compromised. This necessitates the development of radically new electrolytes with improved safety.Desirable electrolyte properties include a large window of phase stability (no vaporization or crystallization), complete nonflammability, a wide electrochemical stability window, and suitable ionic transport for the targeted application. There are many approaches to synthesizing materials with these properties, e.g., ionic liquids (7, 8), gel-polymer matrices (9, 10), and small molecule additives (11-13). Systems using poly(ethylene oxide) (PEO) also are well studied (14,15). PEO can solvate high concentrations of lithium salts and is considered nonflammable. Unfortunately, practical conductivity often is limited within a high temperature range (14), and it is well known that in these systems, the motion of the Li ion carries only a small fraction of the overall current (also known as the Li-ion transference number, t + ). PEO-based electrolytes typically exhibit t + values between 0.1 and 0.5 (16-20), leading to strong salt concentration gradients across the electrolytes that limit power density. Recently, we repor...

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Section: Significancesupporting

confidence: 86%

Section: Significancementioning

confidence: 99%

Nonflammable perfluoropolyether-based electrolytes for lithium batteries

Wong

Thelen

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

204

214

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“…Single‐ion polymer159 and solid electrolyte160 are also useful strategies to improve ionic conductivity ( Figure 13 ). Besides the very low ionic conductivity, partial delamination of Li foils and the polymer/solid electrolyte layers is also responsible for capacity fade and failure 161.…”

Section: Sei Regulationmentioning

confidence: 99%

A Review of Solid Electrolyte Interphases on Lithium Metal Anode

et al. 2015

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Lithium metal batteries (LMBs) are among the most promising candidates of high‐energy‐density devices for advanced energy storage. However, the growth of dendrites greatly hinders the practical applications of LMBs in portable electronics and electric vehicles. Constructing stable and efficient solid electrolyte interphase (SEI) is among the most effective strategies to inhibit the dendrite growth and thus to achieve a superior cycling performance. In this review, the mechanisms of SEI formation and models of SEI structure are briefly summarized. The analysis methods to probe the surface chemistry, surface morphology, electrochemical property, dynamic characteristics of SEI layer are emphasized. The critical factors affecting the SEI formation, such as electrolyte component, temperature, current density, are comprehensively debated. The efficient methods to modify SEI layer with the introduction of new electrolyte system and additives, ex‐situ‐formed protective layer, as well as electrode design, are summarized. Although these works afford new insights into SEI research, robust and precise routes for SEI modification with well‐designed structure, as well as understanding of the connection between structure and electrochemical performance, is still inadequate. A multidisciplinary approach is highly required to enable the formation of robust SEI for highly efficient energy storage systems.

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“…Among various approaches to overcoming the issues of lithium metal anode, it is recognized that electrolyte selection is one of the most dominant factors for stabilizing the lithium metal surface [14][15][16][17][18][19][20][21][22][23][24][25][26][27] . Although various polymeric and ceramic electrolytes have been demonstrated to suppress lithium dendrite growth [14][15][16][17][18][19][20] , their ionic conductivity, interfacial impedance, mechanical moduli or chemical stability when in contact with metallic lithium were not satisfying and still need further improvement for their implementation.…”

mentioning

confidence: 99%

The synergetic effect of lithium polysulfide and lithium nitrate to prevent lithium dendrite growth

et al. 2015

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Lithium metal has shown great promise as an anode material for high-energy storage systems, owing to its high theoretical specific capacity and low negative electrochemical potential. Unfortunately, uncontrolled dendritic and mossy lithium growth, as well as electrolyte decomposition inherent in lithium metal-based batteries, cause safety issues and low Coulombic efficiency. Here we demonstrate that the growth of lithium dendrites can be suppressed by exploiting the reaction between lithium and lithium polysulfide, which has long been considered as a critical flaw in lithium-sulfur batteries. We show that a stable and uniform solid electrolyte interphase layer is formed due to a synergetic effect of both lithium polysulfide and lithium nitrate as additives in ether-based electrolyte, preventing dendrite growth and minimizing electrolyte decomposition. Our findings allow for re-evaluation of the reactions regarding lithium polysulfide, lithium nitrate and lithium metal, and provide insights into solving the problems associated with lithium metal anodes.

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Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries

Cited by 1,292 publications

References 43 publications

Nonflammable perfluoropolyether-based electrolytes for lithium batteries

Nonflammable perfluoropolyether-based electrolytes for lithium batteries

A Review of Solid Electrolyte Interphases on Lithium Metal Anode

The synergetic effect of lithium polysulfide and lithium nitrate to prevent lithium dendrite growth

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