Understanding the Role of Imide-Based Salts and Borate-Based Additives for Safe and High-Performance Glyoxal-Based Electrolytes in Ni-Rich NMC811 Cathodes for Li-Ion Batteries.

Herein, the design of novel and safe electrolyte formulations for high-voltage Ni-rich cathodes is reported. The solvent mixture comprising 1,1,2,2-tetraethoxyethane and propylene carbonate not only displays good transport properties, but also greatly enhances the overall safety of the cell thanks to its low flammability. The influence of the conducting salts, that is, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI), and of the additives lithium bis(oxalato)borate (LiBOB) and lithium difluoro(oxalato)borate (LiDFOB) is examined. Molecular dynamics simulations are carried out to gain insights into the local structure of the different electrolytes and the lithium-ion coordination. Furthermore, special emphasis is placed on the film-forming abilities of the salts to suppress the anodic dissolution of the aluminum  current collector and to create a stable cathode electrolyte interphase (CEI). In this regard, the borate-based additives significantly alleviate the intrinsic challenges associated with the use of LiTFSI and LiFSI salts. It is worth remarking that a superior cathode performance is achieved by using the LiFSI/LiDFOB electrolyte, displaying a high specific capacity of 164 mAh g-1 at 6 C and ca. 95% capacity retention after 100 cycles at 1 C. This is attributed to the rich chemistry of the generated CEI layer, as confirmed by ex situ X-ray photoelectron spectroscopy.

Fluorine-Free Lithium-Ion Capacitor with Enhanced Sustainability and Safety Based on Bio-Based Æ´-Valerolactone and Lithium Bis(Oxalato)Borate Electrolyte.

In this work, the properties of a novel electrolyte based on the combination of bio-based Æ´-valerolactone (GVL) solvent with lithium bis(oxalato)borate (LiBOB) salt and its use for lithium-ion capacitors (LICs) are presented. It is shown that the 1 m LiBOB in GVL electrolyte displays good transport properties, high thermal stability, and the ability to prevent anodic dissolution. Its impact on the performance of both battery-type and capacitive-type electrodes is evaluated. In this regard, special attention is paid to the filming properties associated with LiBOB and GVL decomposition at the electrode surfaces. To the best of the authors' knowledge, the full-cell devices assembled in this study are the first example of a fluorine-free LIC. These devices exhibit a favorable energy-to-power ratio, delivering 80 Wh kg-1 AM at 10 000 W kg-1 AM along with excellent cycling stability, retaining 80% of the initial capacitance after 25 000 cycles. Furthermore, post-mortem analysis of the LIC electrodes is conducted to gain deeper insights into the degradation mechanisms within the device.

The "In situ electrolyte" as a sustainable alternative for the realization of high-power devices.

The "in situ electrolyte" displays a concept for electric double-layer- as well as metal-ion capacitors in which the by-products formed during carbon synthesis serve directly as electrolyte salt to minimize waste. In this work, the concept is applied for lithium- and sodium-based systems realizing EDLCs containing aqueous, "Water in Salt" (up to 1.8 V) as well as organic (2.4 V) electrolytes. Via the mechanochemical synthesis, carbon materials with surface areas up to 2000 m2 g-1 and an optimal amount of remaining by-product are designed from the renewable resource lignin. Different cation-anion combinations are enabled by further modification directly inside the pores creating imide-based salts which are tracked by synchrotron in situ XRD. By the addition of solvents, the EDLCs show good capacitances up to 21 F g-1 combined with excellent rate performances and stabilities. Moreover, the LiTFSI loaded carbon as positive electrode introduces a new tunable lithium alternative for the pre-lithiation of Li-ion capacitors displaying a good rate performance and cyclability.

Improving the performance of an anionic MOF by counter cation replacement as electrode material in a full cell setup of a potassium ion capacitor.

Potassium-based energy storage devices are attracting increasing attention as an alternative to lithium and sodium systems. In addition, metal-organic frameworks (MOFs) can be considered as promising electrode materials for this type of device due to their advantageous properties. Herein, the anionic MOF JUMP-1 and its analog with pre-loading of potassium cations, namely JUMP-1(K), were synthesized and characterized. The anionic framework of JUMP-1 is found to be extremely stable towards the exchange of the dimethylammonium cations by potassium ions. These MOFs were tested in composite electrodes in combination with conventional organic electrolytes as anode materials in a potassium-based system, including the full cell assembly of a potassium ion capacitor (KIC). The results show the significant improvement in capacity between the pristine JUMP-1 and the potassium-exchanged analog JUMP-1(K) as electrode materials. KICs containing JUMP-1(K) coupled with activated carbon (AC) display a promising stability over 4000 cycles. According to the results from these studies, the composite MOF electrode with the potassium-exchange analog JUMP-1(K) presents a promising approach, for which the electrochemical performance compared to the pristine anionic MOF is significantly enhanced.

Glyoxylic-Acetal-Based Electrolytes for Sodium-Ion Batteries and Sodium-Ion Capacitors.

A comprehensive study on the properties and implementation of glyoxylic-acetals in sodium-ion energy storage systems is presented. Electrolytes containing 1,1,2,2-tetramethoxyethane (tetramethoxyglyoxal, TMG), 1,1,2,2-tetraethoxyethane (tetraethoxyglyoxal, TEG) and a mixture of the latter with propylene carbonate (PC) exhibit increased thermal stabilities and higher flash points compared to classical electrolytes based on carbonates as solvents. Due to its favorable properties, 1 m NaTFSI in TEG/PC (3 : 7), has been selected and used for sodium-ion energy storage systems based on a Prussian Blue (PB) positive electrode and a hard carbon (HC) negative electrode. Compared to conventional electrolyte (based on a 1 : 1 mixture of ethylene carbonate, EC, and dimethyl carbonate, DMC), this glyoxylic-acetal electrolyte provides competitive capacity and prolonged cycle life. Postmortem XPS analysis indicates that the electrode-electrolyte interphases formed in presence of TEG are thicker and presumably more protective, inhibiting typical degradation processes of the electrodes. Furthermore, it is demonstrated that the suitable properties of TEG on the cycling stability can also be exploited for the construction of highly stable sodium-ion capacitors.

γ-Valerolactone as Sustainable and Low-Toxic Solvent for Electrical Double Layer Capacitors.

In this work, γ-valerolactone (GVL), a green solvent based on largely available biomass (carbohydrates), highly biodegradable, and with low eco-toxicological profile, was used as electrolyte component in energy storage devices. This solvent allowed the realization of electrolytes with good transport properties and high thermal stability, which could be successfully applied in electrical double layer capacitors (EDLCs). GVL-based EDLCs could operate at 2.7-2.9 V and displayed good performance in term of capacitance, cycling stability, as well as specific energy and power. The results of this study indicate that the use of solvent obtained from largely available natural sources is a feasible strategy for the realization of sustainable and safe electrolytes for EDLCs.

Enhancing Capacity and Stability of Anionic MOFs as Electrode Material by Cation Exchange.

In this study we report on the characterization and use of the anionic metal-organic framework (MOF) JUMP-1, [(Me2NH2)2[Co3(ntb)2(bdc)]] n , alongside with its alkali-metal ion-exchanged analogs JUMP-1(Li) and JUMP-1(Na), as electrode materials for lithium and sodium batteries. Composite electrodes containing these anionic-MOFs were prepared and tested in 1 M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) in propylene carbonate (PC) and/or 1 M sodium TFSI (NaTFSI) in PC. We showed that the ion-exchanged materials JUMP-1(Li) and JUMP-1(Na) display higher capacities in comparison with the original as-prepared compound JUMP-1 (490 mA∙h∙g-1 vs. 164 mA∙h∙g-1 and 83 mA∙h∙g-1 vs. 73 mA∙h∙g-1 in Li and Na based electrolytes, respectively). Additionally, we showed that the stability of the electrodes containing the ion-exchanged materials is higher than that of JUMP-1, suggesting a form of chemical pre-alkalation works to stabilize them prior to cycling. The results of these studies indicate that the use of designed anionic-MOFs represents a promising strategy for the realization of high performance electrodes suitable for energy storage devices.

Hybrid Polyethylene Glycol/Sodium Metaphosphate Composites Prepared via Coacervation.

We report on the fabrication and characterization of homogeneous, monophasic sodium metaphosphate and polyethylene glycol hybrid composites achieved via coacervation in aqueous solution. After separation and drying, an amorphous plastic solid is formed, composed mostly of hydrated sodium phosphate moieties amalgamated with polyethylene glycol chains. These composites are largely X-ray amorphous and can contain up to 8 weight percent of polymer. Impedance spectroscopic measurements reveal DC conductivity values of 12 µS/m at room temperature, an enhancement of three orders of magnitude when compared to glassy sodium metaphosphate, and the presence of the polyethylene glycol is reflected in the equivalent circuit and ionic hopping analyses.

New Diglyme-based Gel Polymer Electrolytes for Na-based Energy Storage Devices.

This work presents for the first time a new diglyme-based gel polymer (DOBn-GPE) suitable for Na-based energy storage devices. The DOBn-GPE, which contains a methacrylate-based polymer, exhibited an excellent high ionic conductivity (2.3 mS cm-1 at 20 °C), broad electrochemical stability (>5.0 V), and high mechanical stability. DOBn-GPE could be successfully used for the realization of Na-ion capacitors, sodium-metal batteries, and sodium-ion batteries, displaying performance comparable with those of systems containing liquid electrolytes at room temperature and at 60 °C. The results of these investigation indicated that the development of diglyme-based gel polymer electrolytes represents a promising strategy for the realization of advanced Na-based energy storage devices.

Water in Protic Ionic Liquid Electrolytes: From Solvent Separated Ion Pairs to Water Clusters.

The large electrochemical and cycling stability of "water-in-salt" systems have rendered promising prospective electrolytes for batteries. The impact of addition of water on the properties of ionic liquids has already been addressed in several publications. In this contribution, we focus on the changes in the state of water. Therefore, we investigated the protic ionic liquid N-butyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide with varying water content at different temperatures with the aid of molecular dynamics simulations. It is revealed that at very low concentrations, the water is well dispersed and best characterized as shared solvent molecules. At higher concentrations, the water forms larger aggregates and is increasingly approaching a bulk-like state. While the librational and rotational dynamics of the water molecules become faster with increasing concentration, the translational dynamics are found to become slower. Further, all dynamics are found to be faster if the temperature increases. The trends of these findings are well in line with the experimental measured conductivities.

Emulsion Polymerizations for a Sustainable Preparation of Efficient TEMPO-based Electrodes.

Organic polymer-based batteries represent a promising alternative to present-day metal-based systems and a valuable step toward printable and customizable energy storage devices. However, most scientific work is focussed on the development of new redox-active organic materials, while straightforward manufacturing and sustainable materials and production will be a necessary key for the transformation to mass market applications. Here, a new synthetic approach for 2,2,6,6-tetramethyl-4-piperinidyl-N-oxyl (TEMPO)-based polymer particles by emulsion polymerization and their electrochemical investigation are reported. The developed emulsion polymerization protocol based on an aqueous reaction medium allowed the sustainable synthesis of a redox-active electrode material, combined with simple variation of the polymer particle size, which enabled the preparation of nanoparticles from 35 to 138 nm. Their application in cell experiments revealed a significant effect of the size of the active-polymer particles on the performance of poly(2,2,6,6-tetramethyl-4-piperinidyl-N-oxyl methacrylate) (PTMA)-based electrodes. In particular rate capabilities were found to be reduced with larger diameters. Nevertheless, all cells based on the different particles revealed the ability to recover from temporary capacity loss due to application of very high charge/discharge rates.

Silica based ionogels: interface effects with aprotic and protic ionic liquids with lithium.

In the frame of the development of solid ionogel electrolytes with enhanced ion transport properties, this paper investigates ionogel systems constituted by ∼80 wt% of ionic liquids (ILs) confined in meso-/macroporous silica monolith materials. The anion-cation coordination for two closely related ILs, either aprotic (AIL) butylmethylpyrrolidinium or protic (PIL) butylpyrrolidinium, both with bis(trifluoromethylsulfonyl)imide (TFSI) anions, with and without lithium cations, is studied in depth. The ILs are confined within silica with well-defined mesoporosities (8 to 16 nm). The effects of this confinement, onto melting points, onto conductivity followed by impedance spectroscopy, and onto lithium-TFSI coordination followed by Raman spectroscopy, are presented. Opposite effects have been observed on the melting temperature: it increased for the AIL (+2 °C) upon confinement, while it decreased for the PIL (-2 °C). With lithium, the confinement led to an increase of the melting temperature (+1 °C) for the PIL and AIL. Regarding ionic conductivities, a relative maximum was observed at 40 °C for a mesopore diameter of 10 nm for the AIL with 0.5 M lithium, while it was not clearly visible for the PIL. These differences are discussed in view of the charge balance at the interface between silanols and ILs: the presence of a PIL, contrary to an AIL, is expected to modify the acidity of the silica. Raman data showed that the coordination number of lithium by TFSI is reduced upon AIL confinement, although this was not observed for PILs. At last, this work highlights the impact of the acidity of a PIL on the chemistry occurring at the interface of the host network within ionogels.

Polyimide@Ketjenblack Composite: A Porous Organic Cathode for Fast Rechargeable Potassium-Ion Batteries.

Potassium-ion batteries (PIBs) configurated by organic electrodes have been identified as a promising alternative to lithium-ion batteries. Here, a porous organic Polyimide@Ketjenblack is demonstrated in PIBs as a cathode, which exhibits excellent performance with a large reversible capacity (143 mAh g-1 at 100 mA g-1 ), high rate capability (125 and 105 mAh g-1 at 1000 and 5000 mA g-1 ), and long cycling stability (76% capacity retention at 2000 mA g-1 over 1000 cycles). The domination of fast capacitive-like reaction kinetics is verified, which benefits from the porous structure synthesized using in situ polymerization. Moreover, a renewable and low-cost full cell is demonstrated with superior rate behavior (106 mAh g-1 at 3200 mA g-1 ). This work proposes a strategy to design polymer electrodes for high-performance organic PIBs.

A Comparative Review of Electrolytes for Organic-Material-Based Energy-Storage Devices Employing Solid Electrodes and Redox Fluids.

Electrolyte chemistry is critical for any energy-storage device. Low-cost and sustainable rechargeable batteries based on organic redox-active materials are of great interest to tackle resource and performance limitations of current batteries with metal-based active materials. Organic active materials can be used not only as solid electrodes in the classic lithium-ion battery (LIB) setup, but also as redox fluids in redox-flow batteries (RFBs). Accordingly, they have suitability for mobile and stationary applications, respectively. Herein, different types of electrolytes, recent advances for designing better performing electrolytes, and remaining scientific challenges are discussed and summarized. Due to different configurations and requirements between LIBs and RFBs, the similarities and differences for choosing suitable electrolytes are discussed. Both general and specific strategies for promoting the utilization of organic active materials are covered.

Water in Protic Ionic Liquids: Properties and Use of a New Class of Electrolytes for Energy-Storage Devices.

In this work, the properties of "water-in-PIL" (PIL=protic ionic liquid) electrolytes are reported based on 1-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PyrH4 TFSI). Taking advantage of experimental and theoretical investigations, it is shown that the amount of water inside the electrolyte has a dramatic effect on the viscosity, conductivity, density, cation-anion interplay, and electrochemical stability of PyrH4 TFSI. The impact of water on the properties of this ionic liquid also affects its use as an electrolyte for electrochemical double-layer capacitors (EDLCs). It is shown that the presence of water improves the transport properties of PyrH4 TFSI, with a beneficial effect on the capacitance retention of the devices in which these electrolytes are used. However, at the same time, water reduces the operative voltage of EDLCs containing this PIL as the electrolyte and, furthermore, it has a strong impact on the inactive components of these systems. To suppress this latter problem, and to realize EDLCs with high stability, the use of inactive components stable in aqueous environment appears necessary.

The impact of carbonate solvents on the self-discharge, thermal stability and performance retention of high voltage electrochemical double layer capacitors.

Advanced electrolytes for supercapacitors with high electrochemical stability are necessary to improve the suitability of supercapacitors for many applications. In this work we investigated electrolytes based on the solvent propylene carbonate (PC) and butylene carbonate (BC). A comparison of different solvent-salt combinations shows that 1 M N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI) in BC is superior to conventionally used PC-based electrolytes examined in this work in terms of voltage window and capacitance. In order to gain a better understanding of the influence of the ions and the solvent on the formation of the electrochemical double layer, the self-discharge mechanism and its temperature dependence have been investigated in detail. By coupling thermogravimetry (TGA), infrared spectroscopy (IR), gas chromatography and mass spectrometry (GC-MS), also decomposition and temperature stability have been assessed.

Molecular Dynamics Simulations of Lithium-Doped Ionic-Liquid Electrolytes.

Lithium bis(trifluoromethanesulfonyl)imide (LiNTf2) doped ionic liquids (ILs) are investigated herein, as potential electrolytes for lithium-ion batteries, via scaled-charge molecular dynamics simulations. Four model ILs based on the [NTf2]- anion and heterocyclic ammonium cations were studied with varying concentrations, ranging from 0 to 1 M solutions, of the dissolved lithium salt. The pyrrolidinium ([pyrHH]+), piperidinium ([pipHH]+), N-butyl-pyrrolidinium ([pyrH4]+), and N-butyl- N-methyl-pyrrolidinium ([pyr14]+) cations were considered to evaluate the combined effects of increased ring size, as well as the introduction of apolar groups on the nitrogen atom of the cations, on the liquid structure properties of the electrolytes. Among the investigated ILs, [pyr14][NTf2] is the only aprotic IL allowing for a comparison of protic and aprotic ILs. The lithium coordination shell is seen to be quite different in the various IL-based systems; networks of lithium ions bridged by [NTf2]- ions have interesting consequences on the solvation shells and coordination numbers. Aggregate existence and velocity autocorrelation functions are finally evaluated in order to characterize the caging effect of [NTf2]- ions around lithium ions. In conclusion, we find that the lithium mobility and transport are directly proportional to the strength of the interionic interactions within the liquids, whereas the ease of solvation shows opposite trends.

Preface to Special Issue of ChemSusChem on Interfacing Experiment and Theory in the Development of Energy Storage and Devices.

This Editorial discusses the importance of scientists currently working in separate fields-experimental characterization of novel materials and theoretical investigations of electrochemical processes-joining forces to advance the field of energy-storage materials and devices. Some of these efforts are published in this Special Issue by ChemSusChem.

Glyoxal-Based Solvents for Electrochemical Energy-Storage Devices.

In this work an investigation about the use of the solvents 1,1,2,2-tetramethoxyethane, also called tetramethoxy glyoxal (TMG), and 1,1,2,2-tetraethoxyethane [also called tetraethoxy glyoxal (TEG)], which belong to the chemical family of carbonyl derivatives, as electrolyte components for electrical double layer capacitors (EDLCs) and lithium-ion batteries (LIBs) is reported for the first time. TEG and TMG are commercial solvents displaying a good set of properties, a low toxicity, and a low price. Although for EDLCs the use of these solvents does appear particularly appealing, their use in LIBs is certainly interesting. The preliminary results reported in this study indicate that the performance of lithium iron phosphate electrodes in LIBs using electrolytes based on TEG and TMG is promising in terms of capacity, capacity retention at high C rates, and cycling stability.