Electrolyte Additives Research Articles

Coupling Solvation Structure Regulation and Interface Engineering via Reverse Micelle Strategy Toward Highly Stable Zn Metal Anode

AbstractThe stability of aqueous Z inc (Zn) ion energy storage devices is significantly compromised by the instability at the electrode/electrolyte interface, which can result in the growth of Zn dendrites, self‐corrosion, and various other side reactions. Regulating the Zn‐ion （Zn2+) solvation structure through electrolyte additives has been proved to be effective strategy in stabilizing the Zn anode, but the influence of free water on the solvation structure is often lacking in‐depth exploration. Herein, the piperazine‐N,N‐bis(2‐hydroxypropanesulfonic acid) sodium salt (POPSO‐Na) is presented as a multifunctional electrolyte additive, which enhances the stability of the Zn anode by modulating the deposition and stripping environment of Zn2⁺ and limiting the presence of free water in the electrolyte during cycling. Theoretical calculation and experimental results demonstrate that the POPSO‐Na additive can not only replace the structural water around Zn2+ to destroy the original solvation sheath, but also form reverse micelle interface structure to hinder the proton transition and constrain the free water in the electrolyte. Thus, the Zn||Zn battery utilizing the ZnSO4+POPSO‐Na electrolyte exhibits an impressive cycle life of 1600 h at a current density of 1 mA cm−2, achieving an average Coulomb efficiency (CE) of ≈100%, which is significantly better than that observed with the ZnSO4 electrolyte. Moreover, the Zn||Cu battery with ZnSO4+POPSO‐Na electrolyte achieves high stability even after cycling for over 2000 h.

Underlying Mechanism of Electrolyte Compositional Engineering Based on Additive Solvation-Structure Governing Solid Electrolyte Interphase Formation in Lithium-Ion Batteries.

Substantial efforts are dedicated to optimizing the additive dosage in the electrolyte and studying its effect on solid electrolyte interphase (SEI) formation in Li-ion batteries (LIBs). This study reveals that the decomposition characteristics of the additive based on its lithium-ion solvation nature significantly contribute to controlling SEI formation. During SEI formation, the strong lithium-ion solvating additive spontaneously migrates to the negative electrode due to negative charge accumulation on the surface, and SEI reinforcement is feasible by increasing the additive dosage. In contrast, population-based SEI formation occurs with a weaker solvating additive, so dosage-dependent modification of the SEI is not effective. These findings demonstrate that compositional electrolyte engineering based on the solvation properties of the additive can be more effective than empirical and experimental studies based on trial and error.

The Interaction Between Fluorinated Additives and Imidazolyl Ionic Liquid Electrolytes in Lithium Metal Batteries: A First‐Principles Study

ABSTRACTThis investigation employs first‐principles calculations to explore the interaction between imidazolium ionic liquids (ILs) and fluoride additives on lithium metal surface. Our focus lies in the comprehensive analysis of three distinct categories of fluorinated additives, each differing in their degree of fluorination. The computations reveal that fluorination plays a significant role in determining both the ionic conductivity and the formation of the solid–electrolyte interphase (SEI) film. Specifically, heightened fluorination enhances the oxidative stability of the system but diminishes the strength of solvent binding, resulting in the formation of larger salt/anion clusters and a decrease in ionic conductivity. Conversely, increased fluorination facilitates the interaction between fluorinated additives and the lithium metal surface, thereby aiding in the formation of a stable SEI film characterized by an abundance of inorganic LiF components. This is important as it serves to suppress dendrite growth and mitigate interface side reactions. Considering the combined influences of ionic conductivity and film formation, 1FP is suggested as the optimal candidate for pyridine‐based additive systems, with FEC preferred for cyclic ester‐based additive systems and BC for chain ester‐based additive systems. This study provides theoretical references for the design of ionic liquid‐fluorinated additive electrolyte systems that can protect the lithium metal anode.

Viscoelastic properties of electro-rheological fluids containing ion-conductive polyurethane particles under electric field

Abstract A non-hydrous electro-rheological fluid (ERF) containing polyurethane (PU) particles with electrolytes and automotive dampers utilizing it have been developed. In this study, we investigated the influence of electrolytes and particle properties on ER effect (yield stress) leading to improving the ER effect of non-hydrous ERFs. As a result, yield stress was increased by the inclusion of electrolytes to PU particles and decreased by increasing the glass transition point (Tg) of PU. The inclusion of electrolyte in particles doubled the yield stress of ERF at 5 kV mm−1. The change in Tg of PU particles from −26.3 °C to −15.3 °C resulted in a decrease in yield stress by 0.7 times at 5 kV mm−1. According to a theoretical model for calculating the ER effect and experimental data, the ionic conductivity associated with the electrolyte addition and the Tg change contributed to the dielectric constant of the PU particles, which affected the ER effect. This result provides important knowledge for deriving material compositions that can further improve the ER effect.

Investigating the Reduction of Fluoroethylene Carbonate and Vinylene Carbonate in Lithium‐Ion Cells with Silicon‐Graphite Anodes

AbstractThe electrolyte additives fluoroethylene carbonate (FEC) and vinylene carbonate (VC) improve the lifetime of lithium‐ion batteries with silicon‐containing anodes by their reduction yielding a more stable solid electrolyte interphase (SEI). However, the reductive decomposition mechanism of FEC and VC has not yet been fully clarified. For this purpose, we investigate the electrolyte decomposition in LiNi0.6Co0.2Mn0.2O2 (NCM622)/silicon‐graphite pouch cells containing either 1 M LiPF6 in FEC:dimethyl carbonate (DMC) or 1 M LiPF6 in VC:DMC using high‐performance liquid chromatography, gas chromatography, X‐ray photoelectron spectroscopy, and inductively coupled plasma optical emission spectrometry. Based on the molar consumptions of FEC and VC, and the cumulative irreversible capacities, we show that three electrons are consumed for every reduced FEC molecule, and that one electron is consumed for every reduced VC molecule. Based on the results, reactions of the FEC reduction are proposed yielding LiF, Li2CO3, Li2C2O4, HCO2Li, and a PEO‐type polymer. Furthermore, the reaction of the VC reduction is proposed yielding lithium‐containing, polymerized VC. During formation, the capacity loss of the cells is induced by lithium trapping in LixSiy/LixSiOy under the SEI and by lithium trapping in the SEI. During subsequent cycling, only lithium trapping in the SEI triggers the capacity loss.

Building electrode/electrolyte interphases in aqueous zinc batteries via self-polymerization of electrolyte additives

Abstract Aqueous zinc batteries offer promising prospects for large-scale energy storage, yet their application is limited by undesired side reactions at the electrode-electrolyte interface. Here, we report a universal approach for in situ building an electrode/electrolyte interphase (EEI) layer on both the cathode and anode through the self-polymerization of electrolyte additives. In an exemplified Zn||V2O5·nH2O cell, we reveal that the glutamate additive undergoes radical-initiated electro-polymerization on the cathode and polycondensation on the anode, yielding polyglutamic acid-dominated EEI layers on both electrodes. These EEI layers effectively mitigate undesired interfacial side reactions while enhance reaction kinetics, enabling Zn||V2O5·nH2O cell to achieve a high capacity of 387 mAh g−1 at 0.2 A g−1 and maintain over 96.3% capacity retention after 1500 cycles at 1 A g−1. Moreover, this interphase-forming additive exhibits broad applicability to varied cathode materials, encompassing VS2, VS4, VO2, α-MnO2, β-MnO2, and δ-MnO2. The methodology of utilizing self-polymerizable electrolyte additives to construct robust EEI layers opens a novel pathway of interphase engineering for electrode stabilizing in aqueous batteries.

Engineering in situ heterometallic layer for robust Zn electrochemistry in extreme Zn(BF4)2 electrolyte environment

The performance of zinc metal batteries is critically affected by the electrolyte environment originating from various zinc salt formulations. Zn(BF4)2, in particular, offers a notable cost advantage and its fluoride-containing groups facilitate the formation of a beneficial ZnF2 interfacial layer, thereby making it a promising candidate for application. Nonetheless, the strong acidity of the Zn(BF4)2-based electrolyte exacerbates the dendrite formation and promotes parasitic reactions, leading to rapid battery failure. Herein, M(BF4)n (M: Cu, Sn, In) salts were adopted as additives in Zn(BF4)2 electrolyte to in situ construct the heterometallic layers. Through comparison, the In(BF4)3-derived ZnIn interface demonstrates superior corrosion-resistance capability and the strongest zinc affinity, protecting the anode from acidic erosion and accelerating the Zn2+ transportation kinetics. The symmetric cell with the optimized electrolyte exhibits a long lifespan of 2500 cycles while the full cell involving the polyaniline cathode also presents a high capacity retention of 81.3 % after 1500 cycles, outperforming the cell with the original Zn(BF4)2 electrolyte. The strategy of generating an interface layer within the battery through electrolyte additives can be readily applied to other metal battery technologies.

Machine Learning-Assisted Bayesian Optimization for the Discovery of Effective Additives for Dendrite Suppression in Lithium Metal Batteries.

In the pursuit of enhancing the performance and safety of lithium (Li)-metal batteries, the discovery of effective electrolyte additives to suppress Li dendrites has emerged as a paramount objective. In this study, we employ an inverse design strategy to identify potential additives for dendrite mitigation. Two key mechanisms, namely, the formation of robust solid electrolyte interphase layers and the leveling mechanism, serve as the foundation for our investigation. Our inverse design strategy is guided by molecular properties such as the lowest unoccupied molecular orbital energy and interaction energy upon Li surface adsorption. An active learning process utilizing Bayesian optimization (BO) was utilized to identify potential molecules with ideal properties. Through this screening process, we uncover a collection of 62 molecules with the potential to act as SEI-forming additives, along with 106 molecules for leveling additives, both surpassing the performance of established additives reported in the literature. This work highlights the potential of BO methods in computationally based inverse design of materials for many applications, and the discovered additives could potentially boost the commercialization of Li-metal batteries.

Regulating the Zn electrode/electrolyte interface with lactose additive for high performance Zn anode

The practical utilization of rechargeable aqueous zinc metal batteries (AZMBs) has been constrained by the formation of zinc dendrites and other associated issues. This article introduces lactose, a compound rich in hydroxyl groups, as an electrolyte additive into the aqueous solution of the electrolyte with the objective of suppressing the harmful growth of zinc dendrites. The lactose additive, with its strong zincophilicity, robust intermolecular hydrogen bonding, and a large number of exposed high electronegativity hydroxyl groups, enables lactose to effectively modulate the electrode/electrolyte interface in a dynamic manner, thereby achieving the stability and reversibility of the zinc anode. The findings presented in this work demonstrate the uniform deposition and stripping of zinc in a 2 M ZnSO4 electrolyte with the addition of lactose, thereby enhancing the cycling performance of Zn||Zn batteries. The alteration of the zinc ion environment on the surface of the zinc electrode, in conjunction with the dynamic modulation of the Gouy-Chapman-Stern (GCS) layer by lactose, increases the nucleation overpotential, thereby facilitating to a uniform deposition morphology in lieu of the formation of large-scale dendrites. Furthermore, the formation of hydrogen bonds serves to prevent the occurrence of side reactions. These factors act in concert to enhance the electrochemical performance of AZMBs. The addition of lactose to the electrolyte has resulted in a significant enhancement in the Coulombic efficiency of the card-type Zn||Cu asymmetric battery, reaching 99.7 %. The biodegradability of lactose and the sustainability of its source make this research conducive to the development of environmentally friendly battery electrolyte additives.

Imidazolium-based ionic liquids as proton reservoir for stable polyaniline cathode in zinc-iodine batteries

Aqueous zinc (Zn)-iodine (I2) batteries (ZIBs) are promising large-scale energy storage systems with high safety and low cost. However, the practical application of ZIBs is hindered by the dissolution of I3- ions, which leads to the shuttle effect and the loss of active iodine. Herein, we adopt an electrolyte modification strategy using two imidazolium-based ionic liquids (1-butyl-3-methylimidazolium iodide ([BMIM]I) and 1-ethyl-3-methylimidazolium iodide ([EMIM]I)) as electrolyte additives to restrain the dissolution of I3- ions and enhance the performance of ZIBs. To be specific, the imidazole rings in [BMIM]+ and [EMIM]+ can be used as the proton sources, promoting the conversion of imine to protonated amines –NH+= in the polyaniline and subsequent adsorption of I3- ions. Therefore, the dissolution of I3- ions and shuttle effect are prevented, facilitating the reaction kinetics of cathode. As a proof of concept, the ZIB using [BMIM]I and [EMIM]I as electrolyte additives demonstrates remarkable cycling performance (72.2 % capacity retention after 1000 cycles) at a high current density of 20 mA cm−2

Multifunctional carbonyl-rich compounds for constructing “corrosion-resistant electrodes and electrolyte interface” in high-voltage sodium-metal batteries

In recent years, there has been notable advancement in the development of high-performance materials for sodium-ion batteries, particularly in layered oxide cathodes. However, research on enhancing the interface between electrolytes and cathodes remains nascent. One promising approach involves the addition of electrolyte additives, recognized for their cost-effectiveness and efficiency in bolstering the electrode/electrolyte interface to enhance material stability during high-voltage cycling. In this work, we investigate the use of glutaric anhydride (GA) as an electrolyte additive to improve the cycling stability of NaNi1/3F1/3M1/3O2/Na (NFM/Na) high-voltage sodium-metal batteries. Batteries using GA-containing electrolytes demonstrate impressive capacity retention: 80.51 % after 200 cycles at 4.0 V and 76.01 % after 150 cycles at 4.1 V. The research delves into the mechanistic insights behind GA’s effectiveness in enhancing cyclic stability. Theoretical calculations reveal that GA plays a crucial role in modifying the structure of the first solvation shells, promoting the formation of an elastic cathode-electrolyte interface (CEI) film enriched with OCO groups. This uniform and stable CEI film effectively preserves the material’s crystal structure and mitigates the dissolution of transition metals, thereby prolonging battery lifespan under demanding extremely cycling conditions.

Tuning Reaction Kinetics of Fluorinated Molecules to Construct Robust Solid Electrolyte Interphases on SiOx Anode.

Introducing fluorinated electrolyte additives to construct LiF-rich solid-electrolyte interphase (SEI) on Si-based anodes is proven an effective strategy for coping with its massive volume changes during cycling. However, most current research on fluorine-containing additives focuses on their thermodynamics of decomposition, lacking studies on the correlation between the molecular structure of additives and their decomposition kinetics. Herein, two fluorinated ester additives, diethyl fluoromalonate (F1DEM) and diethyl 2,2-difluoromalonate (F2DEM) were designed and synthesized. Through combining a wealth of characterizations and simulations, it is revealed that despite the similar reduction thermodynamics, the favorable reduction kinetics of single-fluorinated F1DEM facilitate a LiF-rich layer during the early stage of SEI formation, contributing to the formation of a more robust SEI on SiOx anode compared to the difluorinated F2DEM. Consequently, the proposed additive achieves excellent cycling stability (84 % capacity retention after 1000 cycles) for 5 Ah 21700 cylindrical batteries under practical testing conditions. By unveiling the role of reaction kinetics, a long-overlooked aspect for the study of electrolyte additives, this work sheds light on how to construct a stable SEI on Si-based anodes.

Tuning Reaction Kinetics of Fluorinated Molecules to Construct Robust Solid Electrolyte Interphases on SiOx Anode

AbstractIntroducing fluorinated electrolyte additives to construct LiF‐rich solid‐electrolyte interphase (SEI) on Si‐based anodes is proven an effective strategy for coping with its massive volume changes during cycling. However, most current research on fluorine‐containing additives focuses on their thermodynamics of decomposition, lacking studies on the correlation between the molecular structure of additives and their decomposition kinetics. Herein, two fluorinated ester additives, diethyl fluoromalonate (F1DEM) and diethyl 2,2‐difluoromalonate (F2DEM) were designed and synthesized. Through combining a wealth of characterizations and simulations, it is revealed that despite the similar reduction thermodynamics, the favorable reduction kinetics of single‐fluorinated F1DEM facilitate a LiF‐rich layer during the early stage of SEI formation, contributing to the formation of a more robust SEI on SiOx anode compared to the difluorinated F2DEM. Consequently, the proposed additive achieves excellent cycling stability (84 % capacity retention after 1000 cycles) for 5 Ah 21700 cylindrical batteries under practical testing conditions. By unveiling the role of reaction kinetics, a long‐overlooked aspect for the study of electrolyte additives, this work sheds light on how to construct a stable SEI on Si‐based anodes.

Recent Advances in Electrolytes for Magnesium Batteries: Bridging the gap between Chemistry and Electrochemistry.

Rechargeable magnesium batteries (RMBs) have the potential to provide a sustainable and long-term solution for large-scale energy storage due to high theoretical capacity of magnesium (Mg) metal as an anode, its competitive redox potential (Mg/Mg2+:-2.37 V vs. SHE) and high natural abundance. To develop viable magnesium batteries with high energy density, the electrolytes must meet a range of requirements: high ionic conductivity, wide electrochemical potential window, chemical compatibility with electrode materials and other battery components, favourable electrode-electrolyte interfacial properties and cost-effective synthesis. In recent years, significant progress in electrolyte development has been made. Herein, a comprehensive overview of these advancements is presented. Beginning with the early developments, we particularly focus on the chemical aspects of the electrolytes and their correlations with electrochemical properties. We also highlight the design of new anions for practical electrolytes, the use of electrolyte additives to optimize anode-electrolyte interfaces and the progress in polymer electrolytes.

Impact of Electrolyte Additives on the Lifetime of High Voltage NMC Lithium-Ion Pouch Cells

Abstract This work involves improving the lifetime of lithium-ion cells during high voltage cycling using electrolyte additives. Three generations of electrolyte additives were investigated and screened in NMC442/graphite pouch cells using a 24 h voltage-hold protocol at 40°C to accelerate oxidative reactions occurring at 4.4 V. Once promising additives and combinations were identified, they were then tested in cobalt-free NMC640/graphite cells for long-term cycling to upper cutoff voltages of 4.3, 4.4, and 4.5 V at temperatures of 20, 40, and 55°C. Degradation mechanisms were probed using dV/dQ analysis, micro-X-ray fluorescence spectroscopy, and electrochemical impedance spectroscopy. The primary failure mode of cells held at high voltages is due to increase in cell impedance, which is correlated to the dissolution of transition metals, specifically manganese, originating from the positive electrode. We believe this dissolution is presumably due to the formation of a high impedance rock salt surface layer on the NMC positive electrode particles. Such deleterious outcomes can be limited by selecting an appropriate electrolyte additive package. It is hoped that this paper can provide a starting point for developing NMC Li-ion cells that can operate to voltages as high as 4.4 V and still display long lifetimes.

Mechanistic Understanding of Long Duration Fast Charge Aqueous Zinc Batteries Using Physically Adsorbed Oligomers as Interphases.

Polymers have been used as additives in the liquid electrolytes typically used for secondary batteries that utilize metals as anode. Such additives are conventionally argued to improve long-term anode performance by suppressing morphological and hydrodynamic instabilities thought to be responsible for out-of-plane and dendritic metal deposition during battery charging. More recent studies have reported that the polymer additives provide even more fundamental mechanisms for stabilizing metal electrodeposition through their ability to regulate metal electrodeposit crystallography and, thereby, morphology. Few studies explore how polymers carried in a liquid electrolyte achieve these functions, and fewer still provide rules for choosing among the various polymer types, the additive polymer molecular weight (Mw), and concentration in the electrolyte. Here, we investigate how these generally easy-to-control variables influence electrochemical interphase formation inside battery cells and their impact on the morphology and reversibility of Zn electrodes in aqueous electrolytes. We focus on aqueous Zn-iodine electrochemical cells containing linear polyethylene glycol (PEG) chains as additives and find that in electrolytes where the polymer concentration is maintained in the dilute solution regime there is an optimum polymer molecular weight (Mw ≈ 1000 Da), above which beneficial effects of polymers on Zn electrode reversibility and Zn-I2 battery lifetime are progressively lost. By means of optical ellipsometry and theoretical calculations, we show that the optimal Mw is associated with saturation of the thickness of a physiosorbed PEG coating on the Zn metal electrode. Electron microscopy and X-ray photoelectron spectroscopy analysis of Zn electrodeposits formed in such electrolytes reveal that the physiosorbed polymer coating has two primary effects─it regulates the deposit morphology and suppresses parasitic reactions between the electrode and electrolyte components. The parasitic reactions produce species like ZnO, which are known to passivate the Zn electrode and promote nonuniform deposition. Galvanostatic cycling measurements in aqueous Zn-I2 cells containing the PEG additives at the optimal Mw show that the cells maintain very high Coulombic efficiencies (≥99%) at current densities as high as 50 mA/cm2─close to the maximum values permissible across the Celgard separator membranes used in our studies.

Screening of F-containing electrolyte additives and clarifying their decomposition routes for stable Li metal anodes.

Constructing a LiF-rich solid electrolyte interphase (SEI) is a feasible strategy for inhibiting lithium (Li) dendrites of Li metal anodes (LMAs). However, selecting appropriate F-containing additives with efficient LiF contribution is still under active research. Herein, a series of fluorinated additives with diverse F/C molar ratios are investigated, and we demonstrate that the hexafluoroglutaric anhydride (F6-0) holds the best capability to derive the LiF-rich SEI in regular carbonate electrolytes (RCEs). To ameliorate the decomposition kinetics of the F6-0, LiNO3 (LNO) as an adjuvant is further introduced in the system. As a result, the reduction efficiency of F6-0 is increased to 91% under the F6-0/LNO synergistic effect, enabling the LMA with a uniform LiF-rich SEI in the RCE with merely 4 vol. % F6-0/LNO (F6L) addition. The LiNi0.8Co0.1Mn0.1O2||Li-20μm full-cell with the F6L also showcases better cycling and rate performances than the cases with other F-containing additives.

Dual Strategies of Na+ Electrolyte Additives and Dendrites Protective Ti3C2TX‐MXene/Zn Anode with 2D MXene Nanosheet Encased Niobium Pyrophosphate (NbP2O7) Composite Binder‐Free Cathode for Stable Zinc‐Ion Storage

AbstractZinc‐ion capacitors (ZICs) are promising next‐generation energy storage systems (ESS) owing to high safety, material abundance, environmental friendliness, and low cost; however, the energy density of ZICs must be improved to compete with lithium‐ion batteries (LIBs). Here, the study implements three strategies to enhance the electrochemical performance and manage dendritic growth on Zn anodes, including crafting a highly efficient redox electroactive niobium pyrophosphate (NbP2O7)/Ti3C2TX‐MXene binder‐free cathode, incorporating a NaClO4 additive electrolyte, and applying a protective Ti3C2TX‐MXene layer on Zn anode. The cathode facilitates rapid Zn2+ ion diffusion and a stable host structure. An electrostatic protection layer formed in additive electrolyte and MXene layers regulates the uniform distribution of the electric fields and supports the equalization of nucleation sites. These results are supported by density functional theory (DFT) calculations. The ZICs display an excellent specific capacitance (113.3 F g−1 at 1.5 A g−1) in aqueous additive electrolytes. The flexible solid‐state ZICs exhibits a volumetric capacitance of 865.05 mF cm−3, and an energy density of 0.347 mWh cm−3 at 2.29 mW cm−3 along with capacitance retention of >100% over 38 000 charge‐discharge cycles.

AI-Driven Electrolyte Additive Selection to Boost Aqueous Zn-Ion Batteries Stability.

In tackling the stability challenge of aqueous Zn-ion batteries (AZIBs) for large-scale energy storage, the adoption of electrolyte additive emerges as a practical solution. Unlike current trial-and-error methods for selecting electrolyte additives, a data-driven strategy is proposed using theoretically computed surface free energy as a stability descriptor, benchmarked against experimental results. Numerous additives are calculated from existing literature, forming a database for machine learning (ML) training. Importantly, this ML model relies solely on experimental values, effectively addressing the challenge of large solvent molecule models that are difficult to handle with quantum chemistry computation. The interpretable linear regression algorithm identifies the number of heavy atoms in the additive molecule and the liquid surface tension as key factors. Artificial intelligence (AI) clustering categorizes additive molecules, identifying regions with the most significant impact on enhancing battery stability. Experimental verification successfully confirms the exceptional performance of 1,2,3-butanetriol and acetone in the optimal region. This integrated methodology, combining theoretical models, data-driven ML, and experimental validation, provides insights into the rational design of battery electrolyte additives.

The combined effects of electrolyte addition and mechanical shearing on cellulose nanocrystal alignment

AbstractThis research explored the impact of four different electrolytes on the orientation of cellulose nanocrystals (CNCs) in shear-cast films prepared from aqueous CNC gels. Changes in the aqueous CNC gels’ rheological properties with electrolyte addition were correlated to the orientation and optical properties of dried CNC films. Film alignment was qualitatively assessed using cross-polarized optical microscopy and quantified by order parameters computed by UV–Vis transmission spectroscopy. Electrolyte addition resulted in an increased alignment in dried CNC films. For pure CNCs, the film order parameters remained constant at approximately 0.3 for shear rates from 20 s−1 to 100 s−1. However, higher order parameters were achieved in the presence of electrolytes. Notably, an order parameter of 0.88 was achieved at a shear rate of only 20 s−1. In addition, films produced from dispersions containing electrolytes exhibited improved clarity and haze. The results of this work highlight that electrolyte addition can enable higher order parameters at lower shear rates and facilitate the development of aligned CNC films for applications such as polarizers, clear coatings, and piezoelectric materials. Graphical abstract