Solid-to-liquid transition of polycarbonate solid electrolytes in Li-metal batteries

Commarieu, Basile; Paolella, Andrea; Collin-Martin, Steve; Gagnon, Catherine; Vijh, Ashok K.; Guerfi, Abdelbast; Zaghib, Karim

doi:10.1016/j.jpowsour.2019.226852

Cited by 66 publications

(63 citation statements)

References 19 publications

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“…Increasing water absorption has been shown to lower T g ( Donoso et al., 1995 ). Lower T g values are expected to result in the polymer electrolyte becoming more mobile over a larger temperature range contributing to increased ionic conductivity ( MacFarlane et al., 1998 ; Commarieu et al., 2019 ). In addition to changes in T g , the melting point (T m ), where the crystalline regions of the polymer transition into a disordered melt, is lowered with increasing water content.…”

Section: Impact Of Water Absorption On the Properties Of Polymer Elecmentioning

confidence: 99%

“…Water and other solvents have been found to have a plasticizing effect on PEO and other commonly used polymers, resulting in lower T g values for amorphous polymer fractions, decreased crystallinity, and increased side chain mobility ( Harris and Rukavina, 1995 ; Zhang et al., 2018 ). Overall, the impact of ppm-level amounts of adsorbed solvent on solid polymer electrolytes has been shown to be significant ( Commarieu et al., 2019 ).…”

Section: Introductionmentioning

confidence: 99%

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The Impact of Absorbed Solvent on the Performance of Solid Polymer Electrolytes for Use in Solid-State Lithium Batteries

et al. 2020

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Summary The effects of solvent absorption on the electrochemical and mechanical properties of polymer electrolytes for use in solid-state batteries have been measured by researchers since the 1980s. These studies have shown that small amounts of absorbed solvent may increase ion mobility and decrease crystallinity in these materials. Even though many polymers and lithium salts are hygroscopic, the solvent content of these materials is rarely reported. As ppm-level solvent content may have important consequences for the lithium conductivity and crystallinity of these electrolytes, more widespread reporting is recommended. Here we illustrate that ppm-level solvent content can significantly increase ion mobility, and therefore the reported performance, in solid polymer electrolytes. Additionally, the impact of absorbed solvents on other battery components has not been widely investigated in all-solid-state battery systems. Therefore, comparisons will be made with systems that use liquid electrolytes to better understand the consequences of absorbed solvents on electrode performance.

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Section: Impact Of Water Absorption On the Properties Of Polymer Elecmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Impact of Absorbed Solvent on the Performance of Solid Polymer Electrolytes for Use in Solid-State Lithium Batteries

et al. 2020

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“…The local temperature can increase as a result of exothermic reactions, such as SEI decomposition, electrolyte decomposition, or lithium reaction with the electrolyte 30 or due to an increase in the resistance of the area. Commarieu et al 31 investigation on polycarbonate solid electrolytes also shows the decomposition of this SPE in lithium metal batteries. Further studies need to be focused on decomposition of other polymers.…”

Section: Resultsmentioning

confidence: 86%

In situ observation of solid electrolyte interphase evolution in a lithium metal battery

et al. 2019

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Lithium metal is a favorable anode material in all-solid Li-polymer batteries because of its high energy density. However, dendrite formation on lithium metal causes safety concerns. Here we obtain images of the Li-metal anode surface during cycling using in situ scanning electron microscopy. Constructing videos from the images enables us to monitor the failure mechanism of the battery. Our results show the formation of dendrites on the edge of the anode and isles of decomposed lithium bis(trifluoromethanesulfonyl)imide on the grain boundaries. Cycling at high rates results in the opening of the grain boundaries and depletion of lithium in the vicinity of the isles. We also observe changes in the surface morphology of the polymer close to the anode edge. Extrusion of lithium from these regions could be evidence of polymer reduction due to a local increase in temperature and thermal runaway assisting in dendrite formation.

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“…Origin of High Conductivity.-The origin of the completely amorphous polymer structure and abnormally high conductivity of PEO:LiTFSI films was initially unknown. Inspired by literature examples of strong interactions between LiTFSI and solvents 29 such as acetonitrile which could result in residual solvent in electrolytes 30 and can provide a plasticizing affect, we sought to explore if a similar phenomenon was occurring in these films. To investigate this, we performed TGA with off-gas analysis by mass spectrometry and FTIR.…”

Section: Conductivity Of Peo:litfsi Films-blockingmentioning

confidence: 99%

“…Hence, it indicates that the presence of solvents such as NMP and acetonitrile are not readily reacted at Li metal in a catastrophic way. 29,30 This is likely due to strong ion-solvent interactions which prevent the solvent from reacting too rapidly with Li metal. After an additional 100 cycles at 0.1 mAh/cm 2 the interfacial ASR increased to 1.02 kohm cm 2 .…”

Section: Llzo/li Interfacial Modification-symmetricmentioning

confidence: 99%

Modification of Lithium Metal Anode and Solid-State Electrolyte Interface with a Gel Electrolyte

Renna¹,

Blanc²,

Giordani³

2020

Preprint

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Solid-state electrolytes are continually being explored for Li-ion batteries due to their enhanced safety and their enabling of high energy density active materials, particularly Li metal anodes. However, the interface between solid-state electrolytes and Li metal anodes are prone to high impedance due to poor contact, limiting their applicability. Introducing a thin gel polymer electrolyte interlayer to conformally coat solid electrolytes can improve the interfacial contact of Li metal anode and thus reduce the interfacial resistance. Here we used a plasticized poly(ethylene oxide)-based electrolyte with high concentrations of bis(trifluoromethane)sulfonamide lithium (LiTFSI) that show 100% amorphous character. These electrolytes show Li+ conductivity as high as σ = 2.9×10-4 S/cm at room temperature. We discovered by thermogravimetric analysis (TGA) with off-gas analysis in conjunction with nuclear magnetic resonance (NMR) spectroscopy that the electrolyte films had absorbed N-methyl-2-pyrrolidone (NMP) vapors to form a gel electrolyte. We incorporated the gel electrolyte as an interfacial modification layer between LLZO and Li metal electrodes and found a 58 times reduction in the area specific resistance (ASR) at room temperature.

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Solid-to-liquid transition of polycarbonate solid electrolytes in Li-metal batteries

Cited by 66 publications

References 19 publications

The Impact of Absorbed Solvent on the Performance of Solid Polymer Electrolytes for Use in Solid-State Lithium Batteries

The Impact of Absorbed Solvent on the Performance of Solid Polymer Electrolytes for Use in Solid-State Lithium Batteries

In situ observation of solid electrolyte interphase evolution in a lithium metal battery

Modification of Lithium Metal Anode and Solid-State Electrolyte Interface with a Gel Electrolyte

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