An ionic liquid- and PEO-based ternary polymer electrolyte for lithium metal batteries: an advanced processing solvent-free approach for solid electrolyte processing.

A processing solvent-free manufacturing process for cross-linked ternary solid polymer electrolytes (TSPEs) is presented. Ternary electrolytes (PEODA, Pyr14TFSI, LiTFSI) with high ionic conductivities of >1 mS cm-1 are obtained. It is shown that an increased LiTFSI content in the formulation (10 wt% to 30 wt%) decreases the risk of short-circuits by HSAL significantly. The practical areal capacity increases by more than a factor of 20 from 0.42 mA h cm-2 to 8.80 mA h cm-2 before a short-circuit occurs. With increasing Pyr14TFSI content, the temperature dependency of the ionic conductivity changes from Vogel-Fulcher-Tammann to Arrhenius behavior, leading to activation energies for the ion conduction of 0.23 eV. In addition, high Coulombic efficiencies of 93% in Cu‖Li cells and limiting current densities of 0.46 mA cm-2 in Li‖Li cells were obtained. Due to a temperature stability of >300 °C the electrolyte guarantees high safety in a broad window of conditions. In LFP‖Li cells, a high discharge capacity of 150 mA h g-1 after 100 cycles at 60 °C was achieved.

A Non-Alkaline Electrolyte for Electrically Rechargeable Zinc-Air Batteries with Long-Term Operation Stability in Ambient Air.

Electrically rechargeable zinc-air batteries attract extensive research interests due to their potentially high energy density and low cost but suffer from chemical instability and poor electrochemical reversibility caused by the corrosive nature of the conventional alkaline electrolyte. Here we demonstrate a non-alkaline zinc acetate electrolyte for electrically rechargeable zinc-air batteries with long-term operation stability (>600 hours) in ambient air without any special cell engineering. The unique battery chemistry with reversible formation/decomposition of zinc hydroxyacetate dihydrate is systematically revealed using diversified electrochemical and analytical techniques. Furthermore, the carbon-based air cathode is modified towards a hydrophilic surface to increase the energy efficiency. This work provides new insight on effective electrolyte design to achieve long-term operation zinc-air batteries.

Opportunities and Limitations of Ionic Liquid- and Organic Carbonate Solvent-Based Electrolytes for Mg-Ion-Based Dual-Ion Batteries.

Dual-ion batteries (DIBs) offer a great alternative to state-of-the-art lithium-ion batteries, based on their high promises due to the absence of transition metals and the use of low-cost materials, which could make them economically favorable targeting stationary energy storage applications. In addition, they are not limited by certain metal cations, and DIBs with a broad variety of utilized ions could be demonstrated over the last years. Herein, a systematic study of different electrolyte approaches for Mg-ion-based DIBs was conducted. A side-by-side comparison of Li- and Mg-ion-based electrolytes using activated carbon as negative electrode revealed the opportunities but also limitations of Mg-ion-based DIBs. Ethylene sulfite was successfully introduced as electrolyte additive and increased the specific discharge capacity significantly up to 93±2 mAh g-1 with coulombic efficiencies over 99 % and an excellent capacity retention of 88 % after 400 cycles. In addition, and for the first time, highly concentrated carbonate-based electrolytes were employed for Mg-ion-based DIBs, showing adequate discharge capacities and high coulombic efficiencies.

Insights into the Solubility of Poly(vinylphenothiazine) in Carbonate-Based Battery Electrolytes.

Organic materials are promising candidates for next-generation battery systems. However, many organic battery materials suffer from high solubility in common battery electrolytes. Such solubility can be overcome by introducing tailored high-molecular-weight polymer structures, for example, by cross-linking, requiring enhanced synthetic efforts. We herein propose a different strategy by optimizing the battery electrolyte to obtain insolubility of non-cross-linked poly(3-vinyl-N-methylphenothiazine) (PVMPT). Successive investigation and theoretical insights into carbonate-based electrolytes and their interplay with PVMPT led to a strong decrease in the solubility of the redox polymer in ethylene carbonate/ethyl methyl carbonate (3:7) with 1 M LiPF6. This allowed accessing its full theoretical specific capacity by changing the charge/discharge mechanism compared to previous reports. Through electrochemical, spectroscopic, and theoretical investigations, we show that changing the constituents of the electrolyte significantly influences the interactions between the electrolyte molecules and the redox polymer PVMPT. Our study demonstrates that choosing the ideal electrolyte composition without chemical modification of the active material is a successful strategy to enhance the performance of organic polymer-based batteries.

Dibenzo[a,e]Cyclooctatetraene-Functionalized Polymers as Potential Battery Electrode Materials.

Organic redox polymers are attractive electrode materials for more sustainable rechargeable batteries. To obtain full-organic cells with high operating voltages, redox polymers with low potentials (<2 V versus Li|Li+ ) are required for the negative electrode. Dibenzo[a,e]cyclooctatetraene (DBCOT) is a promising redox-active group in this respect, since it can be reversibly reduced in a two-electron process at potentials below 1 V versus Li|Li+ . Upon reduction, its conformation changes from tub-shaped to planar, rendering DBCOT-based polymers also of interest to molecular actuators. Here, the syntheses of three aliphatic DBCOT-polymers and their electrochemical properties are presented. For this, a viable three-step synthetic route to 2-bromo-functionalized DBCOT as polymer precursor is developed. Cyclic voltammetry (CV) measurements in solution and of thin films of the DBCOT-polymers demonstrate their potential as battery electrode materials. Half-cell measurements in batteries show pseudo capacitive behavior with Faradaic contributions, which demonstrate that electrode composition and fabrication will play an important role in the future to release the full redox activity of the DBCOT polymers.

A rechargeable zinc-air battery based on zinc peroxide chemistry.

Rechargeable alkaline zinc-air batteries promise high energy density and safety but suffer from the sluggish 4 electron (e-)/oxygen (O2) chemistry that requires participation of water and from the electrochemical irreversibility originating from parasitic reactions caused by caustic electrolytes and atmospheric carbon dioxide. Here, we report a zinc-O2/zinc peroxide (ZnO2) chemistry that proceeds through a 2e-/O2 process in nonalkaline aqueous electrolytes, which enables highly reversible redox reactions in zinc-air batteries. This ZnO2 chemistry was made possible by a water-poor and zinc ion (Zn2+)-rich inner Helmholtz layer on the air cathode caused by the hydrophobic trifluoromethanesulfonate anions. The nonalkaline zinc-air battery thus constructed not only tolerates stable operations in ambient air but also exhibits substantially better reversibility than its alkaline counterpart.

Wetting Phenomena and their Effect on the Electrochemical Performance of Surface-Tailored Lithium Metal Electrodes in Contact with Cross-linked Polymeric Electrolytes.

Li metal batteries (LMBs) containing cross-linked polymer electrolytes (PEs) are auspicious candidates for next-generation batteries. However, the wetting behavior of PEs on uneven Li metal surfaces has been neglected in most studies. Herein, it is shown that microscale defect sites with curved edges play an important role in a wettability-dependent electrodeposition. The wettability and the viscoelastic properties of PEs are correlated, and the impact of wettability on the nucleation and diffusion near the Li|PE interface is distinguished. It is found that the curvature of the edges is a key factor for the investigation of wetting phenomena. The appearance of microscale defects and phase separation are identified as main causes for erratic nucleation. It is emphasized that the implementation of stable and consistent long-term cycling performance of LMBs using PEs requires a deeper understanding of the "soft-solid"-solid contact between PEs and inherently rough Li metal surfaces.

Phenothiazine-Functionalized Poly(norbornene)s as High-Rate Cathode Materials for Organic Batteries.

Organic cathode materials are handled as promising candidates for new energy-storage solutions based on their transition-metal-free composition. Phenothiazine-based polymers are attractive owing to their redox potential of 3.5 V vs. Li/Li+ and high cycling stabilities. Herein, three types of poly(norbornene)s were investigated, functionalized with phenothiazine units through either a direct connection or ester linkages, as well as their crosslinked derivatives. The directly linked poly(3-norbornylphenothiazine)s demonstrated excellent rate capability and cycling stability with a capacity retention of 73 % after 10 000 cycles at a C-rate of 100 C for the crosslinked polymer. The polymer network structure of the crosslinked poly(3-norbornylphenothiazine) was beneficial for its rate performance.

In situ7Li-NMR analysis of lithium metal surface deposits with varying electrolyte compositions and concentrations.

A major challenge of lithium metal electrodes, in theory a suitable choice for rechargeable high energy density batteries, comprises non-homogeneous lithium deposition and the growth of reactive high surface area lithium, which eventually yields active material losses and safety risks. While it is hard to fully avoid inhomogeneous deposits, the achievable morphology of the occurring lithium deposits critically determines the long-term cycling behaviour of the cells. In this work, we focus on a combined scanning electron microscopy (SEM) and 7Li nuclear magnetic resonance spectroscopy (7Li-NMR) study to unravel the impact of the choice of conducting salts (LiPF6 and LiTFSI), solvents (EC : DEC, 3 : 7, DME : DOL, 1 : 1), as well as their respective concentrations (1 M, 3 M) on the electrodeposition process, demonstrating that lithium deposition morphologies may be controlled to a large extent by proper choice of cycling conditions and electrolyte constituents. In addition, the applicability of 7Li-NMR spectroscopy to assess the resulting morphology is discussed. It was found, that lithium deposition analysis based on the 7Li chemical shift and intensity should be used carefully, as various morphologies can lead to similar results. Still, our case study reveals that the combination of SEM and NMR data is rather advantageous and offers complementary insights that may provide pathways for the future design of tailored electrolytes.

The Power of Stoichiometry: Conditioning and Speciation of MgCl2/AlCl3 in Tetraethylene Glycol Dimethyl Ether-Based Electrolytes.

In many Mg-based battery systems, the reversibility of Mg deposition and dissolution is lowered by parasitic formation processes of the electrolyte. Therefore, high Coulombic efficiencies of Mg deposition and dissolution are only achieved after several "conditioning" cycles. As this phenomenon is especially reported for AlCl3-containing solutions, this study focuses on the "conditioning" mechanisms of MgCl2/AlCl3 and MgHMDS2/AlCl3 (HMDS = hexamethyldisilazide) in tetraethylene glycol dimethyl ether (TEGDME)-based electrolytes. Electrochemical (cyclic voltammetry) and spectroscopic investigations (27Al nuclear magnetic resonance spectroscopy, Raman spectroscopy, inductively coupled plasma optical emission spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy) reveal that cationic AlCl2+ species in TEGDME-based electrolytes with an AlCl3/MgCl2 ratio higher than 1:1 corrode the Mg metal. According to a cementation reaction mechanism, the corrosion of Mg is accompanied with Al deposition. In effect, the consumption of Mg results in low Coulombic efficiencies of Mg deposition and dissolution during the electrolyte "conditioning". After understanding the mechanism of this process, we demonstrate that a careful adjustment of the stoichiometry in MgCl2/AlCl3 and MgHMDS2/AlCl3 in TEGDME formulations prevents Mg corrosion and results in "conditioning"-free, highly efficient Mg deposition and dissolution.

Counterintuitive trends of the wetting behavior of ionic liquid-based electrolytes on modified lithium electrodes.

The demand for high energy densities has brought rechargeable lithium metal batteries back into the research focus. Ionic liquids (ILs) are considered as suitable electrolyte components for these systems. In this work, the wetting behavior of 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide ([C2MIm]TFSI), 1-butyl-3-methylimidazolium bis-((trifluoromethyl)sulfonyl)imide ([C4MIm]TFSI), 1-hexyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide ([C6MIm]TFSI), and N-butyl-N-methylpyrrolidinium bis((trifluoromethyl)sulfonyl)imide (Pyr14TFSI) on mechanically modified lithium electrodes, with and without lithium bis((trifluoromethyl)sulfonyl)imide (LiTFSI) conducting salt, is investigated and is compared to an organic carbonate-based electrolyte. Three different patterns were chosen for the lithium modification, enabling a surface area increase of 12%, 20%, and 56% for the modified lithium electrodes. Especially for pure ILs, the contact angle on lithium was significantly larger with higher surface areas of the lithium electrodes. Since the addition of LiTFSI remarkably decreased the contact angles of the ILs on the modified lithium surfaces, it could be shown that the effect of LiTFSI can be attributed to a decreased surface tension. This observation could be explained by an interruption of the ordering of ionic liquid cations and anions, which is supported by Raman spectroscopy and molecular dynamics (MD) simulations.

Influence of cations in lithium and magnesium polysulphide solutions: dependence of the solvent chemistry.

In order to gain a deeper understanding of Li and Mg polysulphides in Li/S and Mg/S batteries, respectively, this work investigates the impact of the two different cations as well as the influence of the electrolyte solvents' relative dielectric permittivity and Gutmann's donor number on the solubility and relative stability of different Li and Mg polysulphide species. Therefore, the disproportionation and dissociation equilibria of chemically prepared "Li2S8" and "MgS8" solutions in DMSO, DMF, ACN, THF, DME, TEGDME, and Pyr14TFSI are characterized by UV/Vis spectroscopy. Varying the cation and the solvent reveals their mutual interplay in stabilizing different polysulphide species. To our knowledge, this is the first time that chemically synthesized Mg polysulphides in solutions are studied. The results of this work provide essential knowledge for further development of the economically, ecologically, and also in terms of energy density and safety, attractive Mg/S batteries.

Synthesis of High-Purity Imidazolium Tetrafluoroborates and Bis(oxalato)borates.

The synthesis and purification of imidazolium-based ionic liquids (ILs) with boron-containing anions is reported. The scope was the optimization of the meta thesis reaction and on the purification of the synthesized ILs. It was possible to reduce the reaction and purification times, to avoid the use of acetonitrile as processing solvent, and to increase the yield compared to the known procedure for [BOB]- anion-containing ILs. Furthermore, to the best of our knowledge the flashpoints of the ILs could be determined for the first time by the continuously closed-cup flashpoint (CCCFP) method.

Decomposition of Imidazolium-Based Ionic Liquids in Contact with Lithium Metal.

Ionic liquids (ILs) are considered to be suitable electrolyte components for lithium-metal batteries. Imidazolium cation based ILs were previously found to be applicable for battery systems with a lithium-metal negative electrode. However, herein it is shown that, in contrast to the well-known IL N-butyl-N-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide ([Pyr14 ][TFSI]), 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C2MIm][TFSI]) and 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C4MIm][TFSI]) are chemically unstable versus metallic lithium. A lithium-metal sheet was immersed in pure imidazolium-based IL samples and aged at 60 °C for 28 days. Afterwards, the aged IL samples were investigated to deduce possible decomposition products of the imidazolium cation. The chemical instability of the ILs in contact with lithium metal and a possible decomposition starting point are shown for the first time. Furthermore, the investigated imidazolium-based ILs can be utilized for lithium-metal batteries through the addition of the solid-electrolyte interphase (SEI) film-forming additive fluoroethylene carbonate.

Thianthrene-functionalized polynorbornenes as high-voltage materials for organic cathode-based dual-ion batteries.

Thianthrene-functionalized polynorbornenes were investigated as high-voltage organic cathode materials for dual-ion cells. The polymers show reversible oxidation reactions in solution and as a solid in composite electrodes. Constant current investigations displayed a capacity of up to 66 mA h g(-1) at a high potential of 4.1 V vs. Li/Li(+).

Electrochemical in situ investigations of SEI and dendrite formation on the lithium metal anode.

This comparative work studies the self-enforcing heterogeneity of lithium deposition and dissolution as the cause for dendrite formation on the lithium metal anode in various liquid organic solvent based electrolytes. In addition, the ongoing lithium corrosion, its rate and thus the passivating quality of the SEI are investigated in self-discharge measurements. The behavior of the lithium anode is characterized in two carbonate-based standard electrolytes, 1 M LiPF6 in EC/DEC (3 : 7) and 1 M LiPF6 in EC/DMC (1 : 1), and in two alternative electrolytes 1 M LiPF6 in TEGDME and 1 M LiTFSI in DMSO, which have been proposed in the literature as promising electrolytes for lithium metal batteries, more specifically for lithium/air batteries. As a result, electrolyte decomposition, SEI and dendrite formation at the lithium electrode as well as their mutual influences are understood in the development of overpotentials, surface resistances and lithium electrode surface morphologies in subsequent lithium deposition and dissolution processes. A general model of different stages of these processes could be elaborated.