Conventional Organic Electrolytes Research Articles

Insights into the LiMn2O4 Cathode Stability in Aqueous Electrolytes

Insights into the LiMn₂O₄ Cathode Stability in Aqueous Electrolytes

Speciation of the proton in water-in-salt electrolytes.

Water-in-salt (WiS) electrolytes are promising systems for a variety of energy storage devices. Indeed, they represent a great alternative to conventional organic electrolytes thanks to their environmental friendliness, non-flammability, and good electrochemical stability. Understanding the behaviour of such systems and their local organisation is a key direction for their rational design and successful implementation at the industrial scale. In the present paper, we focus our investigation on the 21 m bis(trifluoromethanesulfonyl)imide (LiTFSI) WiS electrolyte, recently reported to have acidic pH values. We explore the speciation of an excess proton in this system and its dependence on the initial local environment using ab initio molecular dynamics simulations. In particular, we observe the formation of HTFSI acid in the WiS system, known to act as a superacid in water. This acid is stabilised in the WiS solution for several picoseconds thanks to the formation of a complex with water molecules and a neighboring TFSI- anion. We further investigate how the excess proton affects the microstructure of WiS, in particular, the recently observed oligomerisation of lithium cations, and we report possible notable perturbations of the lithium nanochain organisation. These two phenomena are particularly important when considering WiS as electrolytes in batteries and supercapacitors, and our results contribute to the comprehension of these systems at the molecular level.

The Nanostructured Future of Electrolytes

Lithium-ion and lithium-metal batteries with cobalt-free high-energy cathodes, as well as the newly emerging batteries employing post-lithium ions as charge carriers, are a few topics tackled in recent years for the development of batteries with higher energy density, lower cost, and improved sustainability. While all of them could (and will) be improved over time, electrolytes are prominent because of their ease of adapting to current technologies. Conventional organic electrolytes are usually flammable, toxic, and harmful to humans and the environment. For these reasons, over the years, several alternatives have been proposed. Ionic Liquids1 are promising from a safety point of view, being non-volatile and non-flammable, but they are usually fluorinated to meet specific performance standards. Another sustainable and cost-efficient approach is represented by the Water-in-salt electrolytes (WiSEs)2,3, given that the used salt is sustainable itself. Finally, the newest approach is to tackle the solubility properties of salts to obtain locally concentrated electrolytes using non-solvating solvents4. For all of the proposed new technologies, their impressive properties seem to emerge from the peculiar structural organizations of the species in the system. Therefore, employing experimental (SAXS and Raman) and computational (MD and DFT) techniques to comprehensively understand how the chemical species interact in such systems, is mandatory to further progress in the research.Figure 1: a) Snapshot of the simulation box of a Locally Concentrated electrolyte. The ionic liquid comprise the worm-like structures, the solvent is only depicted on the left side as a transparent medium. b) coordination numbers as a function of salt concentration in a Water-in-salt electrolyte. c) X-ray scattering patterns for ionic liquid electrolytes and locally concentrated ionic liquid electrolytes at two different temperatures (20 °C top, and -20 °C bottom).References1 J. S. Wilkes, A short history of ionic liquids—from molten salts to neoteric solvents, Green Chemistry, 2002, 4, 73–80.2 L. Suo, F. Han, X. Fan, H. Liu, K. Xu and C. Wang, ‘water-in-Salt’ electrolytes enable green and safe Li-ion batteries for large scale electric energy storage applications, J Mater Chem A Mater, 2016, 4, 6639–6644.3 J. Han, A. Mariani, S. Passerini and A. Varzi, Energy Environ Sci, 2023, https://doi.org/10.1039/D2EE03682G4 X. Liu, A. Mariani, H. Adenusi and S. Passerini, Angewandte Chemie - International Edition, 2023,https://doi.org/10.1002/ange.202219318. Figure 1

Dual Interface Compatibility Enabled via Composite Solid Electrolyte with High Transference Number for Long-Life All-Solid-State Lithium Metal Batteries.

The development of solid-state electrolytes (SSEs) effectively solves the safety problem derived from dendrite growth and volume change of lithium during cycling. In the meantime, the SSEs possess non-flammability compared to conventional organic liquid electrolytes. Replacing liquid electrolytes with SSEs to assemble all-solid-state lithium metal batteries (ASSLMBs) has garnered significant attention as a promising energy storage/conversion technology for the future. Herein, a composite solid electrolyte containing two inorganic components (Li6.25Al0.25La3Zr2O12, Al2O3) and an organic polyvinylidene difluoride matrix is designed rationally. X-ray photoelectron spectroscopy and density functional theory calculation results demonstrate the synergistic effect among the components, which results in enhanced ionic conductivity, high lithium-ion transference number, extended electrochemical window, and outstanding dual interface compatibility. As a result, Li||Li symmetric battery maintains a stable cycle for over 2500h. Moreover, all-solid-state lithium metal battery assembled with LiNi0.6Co0.2Mn0.2O2 cathode delivers a high discharge capacity of 168mAhg-1 after 360 cycles at 0.1C at 25°C, and all-solid-state lithium-sulfur battery also exhibits a high initial discharge capacity of 912mAhg-1 at 0.1C. This work demonstrates a long-life flexible composite solid electrolyte with excellent interface compatibility, providing an innovative way for the rational construction of next-generation high-energy-density ASSLMBs.

Physical and Electrochemical Analysis of N-Alkylpyrrolidinium-Substituted Boronium Ionic Liquids.

In this work, a series of novel boronium-bis(trifluoromethylsulfonyl)imide [TFSI-] ionic liquids (IL) are introduced and investigated. The boronium cations were designed with specific structural motifs that delivered improved electrochemical and physical properties, as evaluated through cyclic voltammetry, broadband dielectric spectroscopy, densitometry, thermogravimetric analysis, and differential scanning calorimetry. Boronium cations, which were appended with N-alkylpyrrolidinium substituents, exhibited superior physicochemical properties, including high conductivity, low viscosity, and electrochemical windows surpassing 6 V. Remarkably, the boronium ionic liquid functionalized with both an ethyl-substituted pyrrolidinium and trimethylamine, [(1-e-pyrr)N111BH2][TFSI], exhibited a 6.3 V window, surpassing previously published boronium-, pyrrolidinium-, and imidazolium-based IL electrolytes. Favorable physical properties and straightforward tunability make boronium ionic liquids promising candidates to replace conventional organic electrolytes for electrochemical applications requiring high voltages.

Investigating Dry Room Compatibility of Chloride Solid-State Electrolytes for Scalable Manufacturing

Solid-state electrolytes (SSEs) are receiving growing attention as they can replace conventional organic liquid electrolytes to alleviate flammability issues. The low Young’s modulus, decent ionic conductivity, and good oxidation stability make chloride SSEs promising candidates to be used as catholytes in all-solid-state batteries. To assess the scalability of chloride SSEs, their chemical stability in air and dry room environments needs to be evaluated. In this study, threechloride SSEs are investigated for their chemical stability under ambient air and dry room conditions: Li2ZrCl6 (LZC), Li3YCl6 (LYC), and Li3InCl6 (LIC). LZC undergo an irreversible hydrolysis reaction during air exposure and cannot be recovered by heat treatment. LYC decomposes into its hydrated precursors when exposed to ambient air, and further hydrolyzed during heat treatment and was thus not recoverable. LIC forms a stable hydrate and can be easily recovered by heating at 260 °C under vacuum. Finally, the electrochemical performance of dry room exposed chloride SSEs is evaluated where capacity loss was observed due to the lower SSE ionic conductivity due to the irreversible reactions.

An eco-friendly approach of designing arecanut husk ash into high performance Li ion battery anodes

Designing a facile synthesis approach for large scale production of Si based anode materials that would resist the huge volume expansion and subsequent pulverization during cycling is a major challenge that hinders their commercialization. The present paper uses a green approach for the synthesis of a Si based composite electrode material sourced from arecanut husk ash. In addition, the conventional organic electrolytes are replaced with Room Temperature Ionic liquid based solvents to improve the safety as well as stability. It was found that the anode materials exhibit an exceptional stability of 85.3 % at the end of 100 cycles when used in half cells.

Investigations on the lithium-ion and sodium-ion insertion behavior of amorphous sodium iron carbonophosphate using N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide based ionic liquid electrolyte

In this article, we investigate the electrochemical performance of the amorphous sodium iron carbonophosphate upon transitioning from organic electrolytes (lithium hexafluorophosphate (LiPF6) –ethylene carbonate (EC): diethyl carbonate (DEC) based) to ionic-liquid (N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide; PMP-FSI) based electrolytes. The amorphous sodium iron carbonophosphate is synthesized using microwave-assisted hydrothermal process to obtain the desired phase and microstructure. The nanoparticle morphology, along with the amorphous structure, results in excellent electrochemical properties when tested as cathode for lithium-ion and sodium-ion batteries with organic and ionic-liquid based electrolytes. It is observed that the room-temperature and high-temperature (∼60 °C) cycling performance is superior when ionic-liquids are used instead of organic electrolytes, resulting in nearly fade-free electrochemical cells. Specific capacity retention of ∼97% is reported after 500 cycles with 3 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)/PMP-FSI ionic-liquid at a specific current density of 400 mAg−1 (room temperature), in comparison to ∼70% after 500 cycles for 1 M LiPF6 in EC: DEC = 1:1. At high temperatures (∼60 °C), ionic-liquids outperform the conventional organic electrolytes in terms of capacity retention and rate capability. Post-mortem analysis of the electrodes indicates that a dense and ionically conductive protective film, composed of anion-reduced moieties, is responsible for the superior high-temperature performance of amorphous sodium iron carbonophosphate with the ionic-liquids.

Nanotomography Investigation of 3D Printed Batteries with a Water-in-Salt Gel Polymer Electrolyte

3D printing, also known as additive manufacturing, has emerged as a promising strategy to design and fabricate future energy storage devices. Although significant progress has been reported, current 3D printed battery designs are still limited by the choice of the electrolyte, such as ceramic or conventional toxic organic electrolytes. Here, we incorporated the latest developments in aqueous batteries into a novel 3D printable battery that can be fabricated directly in an ambient environment that is also more environmentally friendly. Specifically, a gel polymer electrolyte with a water-in-salt concept was introduced in our 3D-printed batteries. Combining their advantages, the resulting 3D printable batteries show promise for much simplified processing conditions. The structural, (electro-)chemical, and morphological evolution batteries are being investigated by synchrotron X-ray nanotomography and electrochemical analysis. Overall, our research explores the possibility of an easier and more environmentally friendly way to build 3D printable, customizable batteries for future technologies.

"Water-in-Deep Eutectic Solvent" Gel Electrolytes Synergistically Controlled by Solvation Regulation and Gelation Strategies for Flexible Electronic Devices.

Recent developments in flexible electronics have heightened the need for electrolytes with high safety, ionic conductivity, and electrochemical stability. However, neither conventional organic electrolytes nor aqueous electrolytes can meet the above requirements simultaneously. Herein, a novel "water-in-deep eutectic solvent" gel (WIDG) electrolyte synergistically controlled by the solvation regulation and gelation strategies is reported. The water molecules introduced into deep eutectic solvent (DES) participate in the solvation structure regulation of Li+, thus endowing the WIDG electrolyte with high safety, thermal stability, and outstanding electrochemical performance, including high ionic conductivity (∼1.23 mS cm-1) and a wide electrochemical window (∼5.4 V). Besides, the polymer in the gel interacts with DES and H2O, further optimizing the electrolyte with excellent mechanical strength and higher operating voltage. Benefiting from these advantages, the lithium-ion capacitor constructed by WIDG electrolyte presents a high areal capacitance of 246 mF cm-2 with an energy density of 87.3 μWh cm-2. The use of the gel enhances the electrode structure stability, resulting in desirable cycling stability (>90% capacity retention after 1400 cycles). Moreover, the WIDG-assembled sensor exhibits high sensitivity and rapid real-time detection of motion. This work will provide guidelines for designing high-safety and high-operating-voltage electrolytes for flexible electronics.

Polyethylene glycol modified tetrathiafulvalene for high energy density non-aqueous catholyte of hybrid redox flow batteries

Redox flow batteries (RFBs) are highly promising electrochemical systems for large-scale energy storage. To develop high energy density non-aqueous catholyte for RFBs, herein, two polar and bulky polyethylene glycol tails have been attached to the tetrathiafulvalene (TTF) core by ester exchange reactions. Such modification turns scarcely soluble TTF particles into viscous oils, which are totally miscible with the conventional organic electrolytes. The 4,4′(5′)-bis(2-(2-methoxyethoxy)ethyl)carboxylate -tetrathiafulvalene (TTF-BMEEC) with a mass-based specific capacity of 107.84 mAh g−1 is systematically evaluated in a hybrid RFB. When paired with a Li foil electrode and a permselective separator, the catholyte consisting of 1.0 M of TTF-BMEEC delivers two high discharge voltage plateaus of 3.55 and 3.88 V, a large volumetric capacity of 49.6 Ah L−1, an outstanding energy density of 178.0 Wh L−1, and a high cycling capacity retention of 91.5% after 100 cycles at the current density of 10 mA cm−2. The excellent electrochemical stability of TTF-BMEEC is confirmed by UV–vis and 1H NMR investigations and supported by density functional theory (DFT) calculations. These results demonstrate that molecular engineering has great potential for the development of high performance organic redox-active materials for RFBs.

Advanced Nonflammable Organic Electrolyte Promises Safer Li-Metal Batteries: From Solvation Structure Perspectives.

Batteries with a Li-metal anode have recently attracted extensive attention from the battery communities owing to their high energy density. However, severe dendrite growth hinders their practical applications. More seriously, when Li dendrites pierce the separators and trigger short circuit in a highly flammable organic electrolyte, the results would be catastrophic. Although the issues of growth of Li dendrites have been almost addressed by various methods, the highly flammable nature of conventional organic liquid electrolytes is still a lingering fear facing high-energy-density Li-metal batteries given the possibility of thermal runaway of the high-voltage cathode. Recently, various kinds of nonflammable liquid- or solid-state electrolytes have shown great potential toward safer Li-metal batteries with minimal detrimental effect on the battery performance or even enhanced electrochemical performance. In this review, recent advances in developing nonflammable electrolyte for high-energy-density Li-metal batteries including high-concentration electrolyte, localized high-concentration electrolyte, fluorinated electrolyte, ionic liquid electrolyte, and polymer electrolyte are summarized. Then, the solvation structure of different kinds of nonflammable liquid and polymer electrolytes are analyzed to provide insight into the mechanism for dendrite suppression and fire extinguishing. Finally, guidelines for future design of nonflammable electrolyte for safer Li-metal batteries are provided.

Self-curing solid-state electrolytes based on transamination bond exchange for reliable lithium batteries

BTC acts as a tri-topic center for three-dimensional cross-linking with Jeffamine ED-2003 through the Schiff-base reaction, forming a dynamic network structure with reversible imine bonds.

Zwitterionic surfactant–stabilized ionogel electrolytes with high ionic conductivity for lithium secondary batteries

Considering the safety risks posed by the liquid organic electrolytes of conventional lithium-ion batteries, considerable attention has been drawn to the development of safer solid-state alternatives such as ionic liquid (IL)-containing ionogels. Although photocurable ionogels can entrap ILs without altering their primary properties and do not suffer from liquid outflow, the lithium salts dissolved in ILs form ion pairs rather than dissociate into free ions, which results in poor ion-transport properties. To address this problem, we herein immobilize a zwitterionic surfactant on the surface of a polymeric matrix to afford stabilized ionogels with the surfactant dipole structure oriented toward the IL-based electrolyte. The enhanced lithium-ion conductivity of these ionogels positively influences lithium plating/stripping behavior and performance in lithium iron phosphate half-cell tests, with the best rate capability (116.8 mAh g−1 at 1 C) and cycling performance (initial discharge capacity = 148.9 mAh g−1, capacity fading rate = 0.069% per cycle) obtained at a surfactant loading of only 2 wt%. Thus, this study paves the way to the design of high-performance zwitterion-containing ionogel electrolytes as less flammable and leakage-prone alternatives to conventional liquid organic electrolytes for lithium secondary batteries.

High rate and long-term cycling of silicon anodes with phosphonium-based ionic liquids as electrolytes for lithium-ion batteries

This paper describes the effects of the length of the phosphonium alkyl chain in FSI-based ionic liquids (ILs) used as an electrolyte solvent with Si electrodes in a Li/Si half-cell. The electrochemical performance of Si nanoparticles at a high rate in the synthesized triethyl-n-butylphosphonium bis(fluorosulfonyl)imide) [P2224][FSI] and triethyl-n-octylphosphonium bis(fluorosulfonyl)imide) [P2228][FSI] ILs, which also contain 1 M LiFSI, is compared with that of a common organic electrolyte using either polyacrylic acid (PAA) or polyacrylonitrile (PAN) as a binder. For the three electrolytes, the highest performance was obtained with the PAN binder, while both electrodes in ILs exhibited superior performance compared to the conventional organic electrolyte. For the Si/PAN composite electrode, after 1000 cycles at 1 A.g−1, the delithiation capacities were 1344, 550 and 136 mAh.g−1 for [P2224][FSI] in 1 M LiFSI, [P2228][FSI] in 1 M LiFSI and the commercial organic electrolyte, which corresponded to capacity retentions of 61%, 50% and 5%, respectively. Our results indicate that the chemical structure of the phosphonium cation enabled the tuning of transport properties and significantly influences the electrochemical behavior of the Si anode in the presence of LiFSI/IL as an electrolyte.

Progress in Gel Polymer Electrolytes for Sodium‐Ion Batteries

Sodium‐ion battery is a potential application system for large‐scale energy storage due to the advantage of higher nature abundance and lower production cost of sodium‐based materials. However, there exist inevitably the safety problems such as flammability due to the use of the same type of organic liquid electrolyte with lithium‐ion battery. Gel polymer electrolytes are being considered as an effective solution to replace conventional organic liquid electrolytes for building safer sodium‐ion batteries. In this review paper, the authors present a comprehensive overview of the research progress in electrochemical and physical properties of the gel polymer electrolyte‐based sodium batteries. The gel polymer electrolytes based on different polymer hosts namely poly(ethylene oxide), poly(acrylonitrile), poly(methyl methacrylate), poly(vinylidene fluoride), poly(vinylidene fluoride‐hexafluoro propylene), and other new polymer networks are summarized. The ionic conductivity, ion transference number, electrochemical window, thermal stability, mechanical property, and interfacial issue with electrodes of gel polymer electrolytes, and the corresponding influence factors are described in detail. Furthermore, the ion transport pathway and ion conduction mechanism are analyzed and discussed. In addition, the advanced gel polymer electrolyte systems including flame‐retardant polymer electrolytes, composite gel polymer electrolytes, copolymerization, single‐ion conducting polymer electrolytes, etc. with more superior and functional performance are classified and summarized. Finally, the application prospects, development opportunities, remaining challenges, and possible solutions are discussed.

Electrochemical Characteristics of Composite Solid Polymer Electrolytes Containing 1-Dimensional Active Ceramic Filler for All-Solid-State Lithium-Ion Batteries

Recently, the battery market for electric vehicle (EV) and energy storage system (ESS) is expanding. In addition, attempts and studies to implement a high energy density by applying a lithium metal anode to a Li-ion battery (LIB) system are in progress. However, the conventional organic liquid electrolytes have safety problems, such as a short circuit due to lithium dendrite growth, and a risk of ignition and explosion due to electrolyte leakage. To address the issues, all-solid-state batteries (ASSBs) using stable solid electrolytes have attracted much attention as new-generation batteries. Among solid electrolytes, composite solid polymer electrolyte (CSPE) has excellent merits over existing liquid electrolytes such as no electrolyte leakage, non-flammability, and a wide electrochemical potential window. In addition, various types of inorganic fillers may be introduced to improve electrochemical properties of CSPEs. In this study, the CSPEs were fabricated by incorporating 1D or OD Li0.33La0.557Ti0.99Al0.01O3 (A-LLTO) perovskite solid electrolyte fillers in a PVDF-HFP polymer matrix and their electrochemical properties were investigated. The optimized 1D A-LLTO containing CSPE (1D A-LLTO CSPE) exhibited a high ionic conductivity of 0.21 mS cm-1, a good potential stability of up to 4.87 V for Li/Li+, and a lithium ion transport number of 0.499 at 50 °C. In addition, 1D A-LLTO CSPE showed better thermal stability and electrochemical properties compared with 0D A-LLTO CSPE. The 1D A-LLTO CSPE exhibited a reduced overpotential of about 45 mV for 1000 h in contact with lithium metal at 50 °C. Furthermore, the Li/1D A-LLTO CSPE/NCM622 full cell exhibited satisfactory rate capability, cycling stability with a discharge capacity of 159.95 mAh g-1 and a coulombic efficiency of 97.6% over 100 cycles at a rate of 0.2 C, and performed stable long-term cycling performance at the rate of 0.5 C over 400 cycles at 50 ℃. These results demonstrate that the 1D A-LLTO CSPE is expected to become one of the hopeful candidates for ASSBs.

Understanding the Nanostructures in the Electrolytes By Small-Angle X-Ray Scattering

The solution solvation structure of the liquid electrolyte directly affects transport properties, which ultimately determines the performance of batteries. It has been predicted that the nanoscale aggregates in the liquid electrolytes, especially as the salt concentrations increase. However, little is known about these structures due to the limitation of the traditional methods. Herein, we demonstrate that small-angle X-ray scattering-wide angle X-ray scattering (SAXS-WAXS), even ultra-small-angle X-ray scattering (USAXS) could be applied to capture these larger aggregates in the electrolytes, including conventional organic electrolytes, high concentration electrolytes, water-in-slat electrolytes, and redox-active electrolytes. Raman, neutron scattering, IR, and molecular dynamics (MD) simulations further support the proposed structures. This work highlights the fundamental structure analysis in nanoscale, which will prompt better electrolytes in the future.

A Thermodynamically Consistent, Phase-Field Electro-Chemo-Mechanical Theory with Account for Damage in Solids: Application to Metal Filament Growth in Solid-State Batteries

Solid-state batteries (SSBs) present a promising technology and have attracted significant research attention owing to their superior properties including increased energy density (3860 mAh), wider electrochemical window (0-5V) and safer electrolyte design. From a safety standpoint, SSBs are particularly appealing in that replacement of flammable conventional organic electrolytes with highly conductive, mechanically stiff inorganic solid-state electrolytes (SSEs) can alleviate failure due to short circuit or ignition. However, operation of SSBs is hampered by numerous chemo-mechanical challenges [1 - 4], the most critical one associated with metal filament growth across the SSE.Filament protrusions can initiate at perturbations of the interface or microstructural heterogeneities and subsequently grow through the SSE, causing the battery to short-circuit. It is critical to understand from both an experimental and modeling perspective the interplay of various mechanisms including morphology of the SSE microstructure, elastic-viscoplastic behavior of Li-metal, critical current density and stack pressure on the morphology of filamentary protrusions across the SSE. While much has been done to understand the interplay of aforementioned mechanisms from an experimental standpoint [5,6], theoretical frameworks on modeling of filaments growth in SSBs are still at their infancy and typically simplify dendrites as pressurized cracks under a linear-elastic fracture mechanics (LEFM) approach [7-8]. In this work, we propose a thermodynamically consistent phase-field reaction-diffusion-damage theory to investigate the morphology of filament growth across the SSE under varying chemo-mechanical operational conditions. The theory is fully coupled with electrodeposition at the Li metal-SSE interface impacting mechanical deformation, stress generation and subsequent fracture of the SSE. Conversely, electrodeposition kinetics are affected by mechanical stresses through a thermodynamically consistent, physically motivated driving force that distinguishes the role of various chemical, electrical and mechanical contributions. Concurrently, the theory captures the interplay between crack propagation and electrodeposition phenomena by tracking the damage and reaction field using separate phase-field variables such that metal growth is preceded by and confined to damaged regions within the SSE accessible by Li-metal. This is a critical feature of the theory and confirms experimental observations that the crack front propagates ahead of Li. We specialize the theory and study the role of variations of chemo-mechanical properties (i.e. applied electric potential, SSE fracture energy) on the morphology of metal filament growth and map operational conditions to distinguish between domains of i) stable vs. unstable growth ii) intergranular vs. transgranular growth mode. In doing so, the proposed framework provides a quantitative understanding on mechanisms dictating metal filament growth in SSEs and identifies mitigation strategies to employ in future SSB designs for successful operation.

Enabling High-Stability of Aqueous-Processed Nickel-Rich Positive Electrodes in Lithium Metal Batteries.

Lithium batteries occupy the large-scale electric mobility market raising concerns about the environmental impact of cell production, especially regarding the use of poly(vinylidene difluoride) (teratogenic) and N-methyl-2-pyrrolidone (NMP, harmful). To avoid their use, an aqueous electrode processing route is utilized in which a water-soluble hybrid acrylic-fluoropolymer together with sodium carboxymethyl cellulose is used as binder, and a thin phosphate coating layer is in situ formed on the surface of the nickel-rich cathode during electrode processing. The resulting electrodes achieve a comparable performance to that of NMP-based electrodes in conventional organic carbonate-based electrolyte (LP30). Subsequently, an ionic liquid electrolyte (ILE) is employed to replace the organic electrolyte, building stable electrode/electrolyte interphases on the surface of the nickel-rich positive electrode (cathode) and metallic lithium negative electrode (anode). In such ILE, the aqueously processed electrodes achieve high cycling stability with a capacity retention of 91% after 1000 cycles (20 °C). In addition, a high capacity of more than 2.5 mAh cm-2 is achieved for high loading electrodes (≈15mg cm-2 ) by using a modified ILE with 5% vinylene carbonate additive. A path to achieve environmentally friendly electrode manufacturing while maintaining their outstanding performance and structural integrity is demonstrated.