Gel Electrolyte Research Articles

The Modulation of Cross-Linking Density in Gel Polymer Electrolyte for the Inhibition of Lithium Dendrite

The Modulation of Cross-Linking Density in Gel Polymer Electrolyte for the Inhibition of Lithium Dendrite

Poly(ionic) Liquid-Enhanced Ion Dynamics in Cellulose-Derived Gel Polymer Electrolytes.

Gel polymer electrolytes (GPEs) are regarded as a promising alternative to conventional electrolytes, combining the advantages of solid and liquid electrolytes. Leveraging the abundance and eco-friendliness of cellulose-based materials, GPEs were produced using methyl cellulose and incorporating various doping agents, either an ionic liquid (1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [Pyr14][TFSI]), its polymeric ionic liquid analogue (Poly(diallyldimethylammonium bis(trifluoromethylsulfonyl)imide) [PDADMA][TFSI]), or an anionically charged backbone polymeric ionic liquid (lithium poly[(4-styrenesulfonyl)(trifluoromethyl(S-trifluoromethylsulfonylimino) sulfonyl) imide] LiP[STFSI]). The ion dynamics and molecular interactions within the GPEs were thoroughly analyzed using Attenuated Total Reflectance Fourier-Transform Infrared Spectroscopy (ATR-FTIR), Heteronuclear Overhauser Enhancement Spectroscopy (HOESY), and Pulsed-Field Gradient Nuclear Magnetic Resonance Diffusion (PFG-NMR). Li+ transference numbers (tLi+) were successfully calculated. Our study found that by combining slow-diffusing polymeric ionic liquids (PILs) with fast-diffusing lithium salt, we were able to achieve transference numbers comparable to those of liquid electrolytes, especially with the anionic PIL, LiP[STFSI]. This research highlights the influence of the polymer's nature on lithium-ion transport within GPEs. Additionally, micro supercapacitor (MSC) devices assembled with these GPEs exhibited capacitive behavior. These findings suggest that further optimization of GPE composition could significantly improve their performance, thereby positioning them for application in sustainable and efficient energy storage systems.

In Situ Gel Polymer Electrolyte with Rapid Li+ Transport Channels and Anchored Anion Sites for High‐Current‐Density Lithium‐Ion Batteries

AbstractIn situ formed gel polymer electrolytes (GPEs) have advantages in safety and adaptability to current high‐voltage lithium‐ion batteries (LIBs). However, it is challenging for GPEs to achieve stable cycling at high current densities. A flexible framework is proposed for stable in situ GPE, by introducing ─CF3 groups to the polymer network to establish rapid Li+ transport channels, and incorporating secondary amine N─H groups to anchor anion. The obtained GPE exhibits a high ionic conductivity of 2.6 mS cm−1 and a high Li+ transference number of 0.67. The assembled Li||NCM811 cell demonstrates excellent rate performance, with a discharging capacity of 112.3 mAh g⁻¹ at 10C, and capacity retention of 87.6% after 260 cycles at 1C. Furthermore, the assembled graphite||NCM811 cell demonstrates excellent long‐term cycling stability with impressive capacity retention of 73.2% after 300 cycles 3C (1.8 mA cm−2). This work presents a promising approach to enhancing the cycling stability of GPEs for high‐voltage LIBs at high current density.

Transparent Electrode‐Free Light‐Emitting Devices Exploiting Ion Transport‐Controlled Electrochemiluminescence

AbstractTransparent electrode‐free light‐emitting devices are presented that exploit electrochemiluminescence (ECL). These devices feature two side‐by‐side noble metal electrodes connected by an ECL active layer. The significance of bulk ion‐transport characteristics is investigated within the ECL active layer in producing uniform planar emission from the device. These characteristics can be enhanced by simply increasing the ECL active layer thickness or adding an ion gel electrolyte layer on top of the ECL active layer. The use of only electrochemically stable noble metal electrodes results in an operational lifetime exceeding 10 h, which is the longest lifetime reported for ECL‐based light‐emitting devices to date. The device structure based on ECL does not require transparent electrodes, allowing for increased flexibility when designing devices for future light‐emitting device applications.

Dual cation Kgu/PAM Gel polymer electrolyte with high ionic conductivity and mechanical strength for flexible All-Solid-State supercapacitors

Gel polymer electrolytes (GPEs) have attracted much attention due to their excellent flexibility, good interface contact, and high safety in solid-state supercapacitors (SSCs). However, in practical applications, GPEs still face low ionic conductivity and poor mechanical strength. This study delineates a novel dual-cationic Kgu/PAM GPE, the ion diffusion coefficients in which are 1.51 × 10-8 cm2 s−1 (K+) and 4.77 × 10-9 cm2 s−1 (Na+), respectively. Radial distribution function and in-situ Fourier transform infrared spectroscopy have confirmed that the migration mechanism of dual-cations in Kgu/PAM is through the long-range hydration channels, which is depended on the continuous formation of binding water facilitated by movement of Kgu and PAM chain segments. When assembled dual-cationic Kgu/PAM GPE to a flexible solid-state asymmetric supercapacitor, it delivers a high ionic conductivity (86.9 mS cm−1), an excellent energy rate density (86.1 Wh kg−1) and outstanding power density (476 W kg−1). In addition, dual-cationic Kgu/PAM GPE exhibits an excellent strain threshold of 910 % and remarkable mechanical strength of 35 KPa, good flexibility and flame retardant, highlighting the potential for its practical application in various fields. Collectively, these findings herald a novel paradigm in the development of secure and efficacious flexible wearables.

Robust polymer electrolytes with fast ion-transport nanochannels constructed by carbon dots for long lifespan Li metal batteries

As an anode material in energy storage systems, Li metal has exceptional merits, including high specific capacity, low density, and low redox potential. However, challenges such as lithium dendrites and unstable solid electrolyte interphase (SEI) hinder the practical application of lithium metal batteries (LMBs). Solid polymer electrolytes (SPEs), notably PVDF-HFP, are expected to overcome the above problems because of their mechanical merits and safe features, but their limited ion transportation behaviors result in insufficient ionic conductivity at room temperature. Herein, we invent an approach to prepare high performance electrolytes composed by porous PVDF-HFP and functionalized carbon dots (CDs). Such porous PVDF-HFP polymer membranes are created by a subtle phase inversion process, possessing a sponge-like structure, vertical lithium-ion transport channels and CDs decorated surfaces, thus able to uptake the liquid electrolyte (LE) to form gel polymer electrolytes (GPEs). The CDs fillers are produced in large scale with adjustable surface states, which can enhance Li salts disassociation to release free Li ions. As a result, the optimal conductivity of the as-prepared GPEs at room temperature is up to 8.7 mS cm−1 and the lithium transference number reaches 0.64. Our GPEs endow Li symmetric batteries with very stable SEI and long cycling life over 2200 h, and help realize high capacities and retention rates of the LMBs using LiFePO4(LFP) or LiCoO2(LCO) cathodes.

One-pot synthesis of hydroxypropyl methylcellulose-based gel polymer electrolytes for high-performance supercapacitors

The electrolyte is a crucial component that significantly affects the electrochemical performance of supercapacitors. The hydroxypropyl methylcellulose (HPMC)-based gel polymer electrolyte (GPE) with high operating voltage was synthesized via an innovative “one-pot” method in this study, and the impacts of organic solvent/water ratio and LiNO3 concentration on gelation and conductivity of the GPE were investigated systematically. Under the optimal condition with a DMF/water ratio of 10:0 and the incorporation of 7 % LiNO3, the ionic conductivity reached 1.06 S m−1. Integrated into symmetric supercapacitors, the HPMC-based GPE demonstrated an expanded electrochemical window of 2.7 V. It also possessed a specific capacitance of 115.8 F g−1 at 1.0 A g−1, an energy density of 29.31 Wh kg−1, and outstanding cyclic stability, retaining 86 % of its initial capacitance after 2000 cycles. Through cyclic stability tests under pressure conditions, the assembled flexible supercapacitors were able to maintain capacitance retention of 60 % and coulombic efficiency of 97 %. This work offers a streamlined synthesis for HPMC-based GPE with superior electrochemical properties, which exhibits its potential in advancing supercapacitor technology for flexible electronics.

Polymer Electrolytes with High Ionic Conductivities at Freezing Temperature for Aqueous Hybrid Batteries.

Rechargeable and flexible aqueous batteries (ABs) have emerged as one of promising energy devices which is primarily due to the safety, environmental friendliness and economic efficiency. However, because of the freezing behavior of aqueous electrolytes, most ABs possess poor performance when the working temperature drops below zero. To solve this problem, a gel polymer electrolyte (GPE) with high ionic conductivity (IC) and frost-resistance is designed for aqueous Zn-Li hybrid batteries by a biomass-based polymers complex consisting of carboxyl modified sodium alginate (SA) and zwitterionic betaine (BA). Introducing iminodiacetic acid to enrich -COOH groups along the SA main chains could improve IC of the prepared GPEs to 41.27 and 20.96 mS cm-1 at 20 and -20 oC, respectively. At -20 oC, the discharge capacity of the resultant cell is two times higher than that of the liquid electrolyte-based cell, and the cell presents a capacity retention of 91.6% after 300 charge/discharge cycles at 1 C. This proposed strategy greatly improve the IC of GPEs at freezing temperature, which is expected to broaden the practical application of GPEs in wide range of temperature.

Chitosan-based gel polymer electrolytes for high performance Li-ion battery

This study explores the use of glutaraldehyde-crosslinked chitosan-based gel polymer electrolytes (GPEs) in lithium-ion batteries (LIBs). GPEs are prepared by solution casting using two different molecular weights of chitosan including 150 kDa as medium and 400 kDa as high molecular weight (MMWCS and HMWCS, respectively) with varying amounts of crosslinker. Degree of crystallinity was 25.9 and 24.1 % for HMWCS and MMWCS, respectively that was decreased to 18.3 and 22.7 % by using 5 % crosslinker and 17.8 and 21.1 % by using 10 % crosslinker, and 17.2 and 17.6 % by using 20 % crosslinker. The obtained ionic conductivity for HMWCS and MMWCS was 3.1 × 10−3 and 2.9 × 10−3 S.cm−1. After crosslinking by 5, 10, and 20 % crosslinker, the ionic conductivity was obtained to 0.9 × 10−3 and 0.3 × 10−3 S.cm−1, 6.3 × 10−3 and 5 × 10−3 S.cm−1, and 1.1 × 10−3 and 0.5 × 10−3 S.cm−1 for high and medium molecular weight, respectively. Lithium-ion transfer number was obtained between 0.34 and 0.83 and the highest t+ value was obtained for the MMWCS-GA10. Electrochemical stability window of the prepared polymer electrolytes was >5 V and samples showed no remarkable dendrite growth after cycling analyses. The symmetric cells demonstrated reliable performance, operating for over 300 h without any short-circuiting, which indicates excellent reversible cycling stability for chitosan-based lithium-ion batteries. Furthermore, the Gr/GPE cell exhibited very low voltage polarization, with the over-potential decreasing from 10 mV initially to 6 mV after 300 h at the same current density. Discharge capacity was obtained higher than 170 mAh/g at 0.2C with CE = 97 % for both HMWCS-GA20 and HMWCS-GA20.

Soft-templating of biomass derivatives into edge-N doped 3D-interconnected hierarchical porous carbon for multi-scenario supercapacitive energy storage

Rational design of the pore structure for carbon materials is of great significance for solving the low specific capacitance and poor rate capability of supercapacitors. A novel soft-templating strategy is proposed by using biomass-derived sodium lignosulphonate as a carbon precursor and sublimable hexamethylenetetramine as a soft template. The hexamethylenetetramine nanoparticles are formed in the confined spaces of the precursor, and then these templates sublime to leave mesopores after the lignosulfonate transformed from linear structure to bulk structure by thermostabilization treatment. A high nitrogen content of 40 wt% in hexamethylenetetramine is also beneficial for the subsequent in-situ N-doping. The as-obtained nitrogen-doped hierarchical porous carbon microspheres possess a high specific surface area of 1416 m2 g−1 with an N-doping content of 4.32 % (86.26 % edge-N). In a two-electrode system, the soft-templating carbon exhibits a decent specific capacitance of 234 F g−1 at 0.1 A g−1, an excellent rate capability of 62.4 % at 50 A g−1, and a high energy density of 8.1 Wh kg−1 at 15.0 kW kg−1 in 6 M KOH aqueous electrolyte. Moreover, advanced additive manufacturing technology of direct ink writing was applied to construct a quasi-solid-state in-plane interdigital microsupercapacitor by using the soft-templating carbon, and it presents a superior areal/volumetric capacitance, rate performance, mechanical stability, and flexibility with PVA/H2SO4 gel electrolyte. This work broadens the pore structure engineering methodology by novel soft-templating biocarbon for multi-functional and multi-scenario energy storage systems.

Superior gel polymer electrolyte for sodium metal battery with long-term cycling stability at elevated current density

Superior gel polymer electrolyte for sodium metal battery with long-term cycling stability at elevated current density

Microwave-assisted vanadium interpolated cobalt-MOF cathode assembled 3 V high performing asymmetric supercapacitor with ionic liquid gel polymer electrolyte

To ameliorate energy storage and conversion, metal synergy, and structural stability, bimetal-assembled metal–organic frameworks (MOFs) are delved into. Augmented surface area, pseudo capacitance, and the ability to alter the MOF edifice of layered oxide have drawn interest in MOF-based oxide layered structures. Simple microwave and hydrothermal techniques use dimethyl formamide and water as solvents and annealing methods to generate the bimetallic organic framework’s Co3V2O8 and Co3VO4 cathode material. Those customized shapes boost redox sites and reduce ion electron distance. Due to cobalt’s faradaic process and vanadium’s highly layered attributes, supercapacitor electrode response is significant. Co3V2O8 has 1391F/g specific capacitance at 2 mV/s scan rate and 1309F/g at 4 mA/cm2 implemented current value. After 10,000 cycles, the cathode material depicts 89 % capacity retention and 98 % coulombic efficiency. Biowaste-derived activated carbon is combined with a Co3V2O8 cathode for asymmetric supercapacitor storage. That device works on 3 V windows with ionic liquid gel polymer electrolyte. With a maximum specific energy of 329.3 Wh/kg and specific power of 15250 W/kg, the achieved galvanometric capacitance is 263.5F/g and 220 mAh/g at the 9 mA/cm2 current and showed 88.5 % potential stability after 10,000 cycles. These findings corroborate its use as a supercapacitor cathode.

MXene Triggered Free Radical Polymerization in Minutes Toward All‐Printed Zn‐Ion Hybrid Capacitors and Beyond

AbstractAdditive manufacturing of (quasi−) solid‐state (QSS) electrochemical energy storage devices (EES) highlights the significance of gel polymer electrolytes (GPEs) design. Creating well‐bonded electrode‐GPEs interfaces in the electrode percolative network via printing leads to large‐scale production of customized EES with boosted electrochemical performance but has proven to be quite challenging. Herein, we report on a versatile, universal and scalable approach to engineer a controllable, seamless electrode‐GPEs interface via free radical polymerization (FRP) triggered by MXene at room temperature. Importantly, MXene reduces the dissociation enthalpy of persulfate initiators and significantly shortens the induction period accelerated by SO4−, enabling the completion of FRP within minutes. The as‐formed well‐bonded electrode‐GPEs interface homogenizes the electrical and concentration fields (i.e., Zn2+), therefore suppressing the dendrites formation, which translates to long‐term cycling (50,000 times), high energy density (105.5 Wh kg−1) and power density (9231 W kg−1) coupled with excellent stability upon deformation in the zinc‐ion hybrid capacitors (ZHCs). Moreover, the critical switch of the rheological behaviours of the polymer electrolyte (as aqueous inks in still state and become solids once triggered by MXene) perfectly ensures the direct all‐printing of electrodes and GPEs with well‐bonded interface in between, opening vast possibilities for all‐printed QSS EES beyond ZHCs.

MXene Triggered Free Radical Polymerization in Minutes Toward All-Printed Zn-Ion Hybrid Capacitors and Beyond.

Additive manufacturing of (quasi-) solid-state (QSS) electrochemical energy storage devices (EES) highlights the significance of gel polymer electrolytes (GPEs) design. Creating well-bonded electrode-GPEs interfaces in the electrode percolative network via printing leads to large-scale production of customized EES with boosted electrochemical performance but has proven to be quite challenging. Herein, we report on a versatile, universal and scalable approach to engineer a controllable, seamless electrode-GPEs interface via free radical polymerization (FRP) triggered by MXene at room temperature. Importantly, MXene reduces the dissociation enthalpy of persulfate initiators and significantly shortens the induction period accelerated by SO4 -, enabling the completion of FRP within minutes. The as-formed well-bonded electrode-GPEs interface homogenizes the electrical and concentration fields (i.e., Zn2+), therefore suppressing the dendrites formation, which translates to long-term cycling (50,000 times), high energy density (105.5 Wh kg-1) and power density (9231 W kg-1) coupled with excellent stability upon deformation in the zinc-ion hybrid capacitors (ZHCs). Moreover, the critical switch of the rheological behaviours of the polymer electrolyte (as aqueous inks in still state and become solids once triggered by MXene) perfectly ensures the direct all-printing of electrodes and GPEs with well-bonded interface in between, opening vast possibilities for all-printed QSS EES beyond ZHCs.

A Wide‐Temperature Adaptive Electrochromic Device Based on a Poly(vinyl alcohol)/Poly(acrylic acid) Gel Electrolyte

AbstractAs a promising energy‐saving technology, electrochromic technology has been widely investigated for practical applications. However, there is relatively few research about the applications under certain extreme climatic conditions since gel electrolytes often occur freezing and volatilizing. In this work, a poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) gel electrolyte with good anti‐freezing and heat‐resistance performance is developed. Utilizing hydrated tungsten oxide (WO3·xH2O) and polyaniline (PANI) as electrochromic materials and the PVA/PAA gel as electrolyte, a WO3·xH2O/PVA/PAA‐ethylene glycol (EG)‐H2O/PANI electrochromic device (WO3·xH2O/PAEH/PANI ECD) is obtained, which can work efficiently at wide operating temperatures from −20 to 60 °C. The device has multiple reversible color changes, a large optical modulation of 66.2% at 600 nm, high coloration efficiency of 386.0 cm2 C−1, fast responses (with coloration/bleaching times of 1.3/1.1 s), as well as excellent cyclic stability (82.0% of the initial optical modulation is still retained after 2100 cycles). This work reveals the potential application prospects of PAEH gel electrolyte in practical extreme operating conditions.

Glyoxylic‐Acetal‐Based Gel‐Polymer Electrolytes for Lithium‐Ion Batteries

AbstractThis work focuses on the combination of two strategies to improve the safety of lithium‐ion batteries: The use of a glyoxylic‐acetal, 1,1,2,2‐tetraethoxyethane, in the solvent blend to reduce the flammability of the liquid electrolyte and further its confinement inside of a methacrylate‐based polymer matrix, to prevent electrolyte leakage from the battery cells. Physicochemical characterizations of this novel gel‐polymer electrolyte (GPE) confirm its improved thermal properties and suitable ionic conductivity, as well as electrochemical stability window. Tests in LFP and hard carbon half‐cells vs. lithium metal show that the combination of glyoxylic‐acetal‐based electrolyte and the methacrylate‐based polymer matrix can promote lithium‐ion intercalation and deintercalation with stable capacity values. The application in lithium‐ion battery full cells furthermore shows that the GPE can promote a similar performance compared to the respective liquid electrolyte and can therefore make possible the realization of energy storage devices with improved safety characteristics.

3D-Printed Flexible Polyacrylamide/Alginate Gel Polymer Electrolyte for Zinc-Ion Batteries

Flexible and wearable electronics are increasingly popular and utilized in various forms. Batteries have become essential as an energy source for wearable electronics. To meet demands of such electronics, these batteries must remain flexible, lightweight, possess good electrochemical performance, customizable shape, and ensure safety. Zinc-ion batteries (ZIBs) have emerged as a promising energy source for these applications. However, ZIBs encounter challenges due to the lack of flexible electrolytes. Polyacrylamide (PAM) is a polymer widely used as gel polymer electrolytes (GPEs) owing to its versatile electrical conductivity and excellent flexibility. However, PAM alone lacks the mechanical strength required to support flexible and wearable electronics adequately. To address this limitation, alginate (Alg), a polysaccharide with good compatibility with PAM, is incorporated in varying concentrations (0-3 %wt.) to form interpenetrating networks (IPN) hydrogels, with a chemical network of PAM and a physical network of alginate to enhance the overall mechanical properties. Following this, the 3D-printed PAM/Alg hydrogels are immerged in a 2M ZnSO4 electrolyte to create PAM/Alg gel polymer electrolytes (PAM/Alg-GPEs). This process significantly improves the mechanical properties of PAM/Alg-GPEs. Subsequently, the ionic conductivity of these 3D-printed PAM/Alg-GPEs is evaluated using electrochemical impedance spectroscopy (EIS). The results demonstrate that PAM/Alg-GPEs exhibit the desired flexibility along with sufficient electrochemical performance, making them promising candidates for use as wearable electrolytes in zinc-ion batteries.

Hierarchically Structured Conductive Lanthanide Metal Organic Framework Nanorods for Ultrastable Flexible Magnesium Ion Capacitors

AbstractAqueous multivalent metal ion capacitors are very attractive owing to their high capacitance, low cost, environmental benignity, and safety. Herein, hierarchically structured, conductive lanthanide metal‐organic frameworks (MOFs) assembled by nanorods for ultrastable flexible magnesium ion capacitors (MICs) is designed. Three MOFs, consisting of lanthanide metals (La, Ho, and Yb) and 2,3,6,7,10,11‐hexahydroxytriphenylene (HHTP), are structurally stabilized through the covalent bonds and electronically conductive due to π‐d conjugation. Among 3 MOFs, Ho‐HHTP electrodes in a full‐cell system achieved long‐term cyclic stability with a high capacitance retention of 65.0% after 12 000 cycles and a high Coulombic efficiency of 96.9%. Furthermore, flexible pouch cells are fabricated using Ho‐HHTP as anode, reduced graphene oxide as cathode, and poly(vinyl alcohol) (PVA)/Mg(ClO4)2 as gel electrolyte, demonstrating a low capacitance decay rate of 0.00444% per cycle during 10 000 cycles owing to the hierarchical structure and intrinsic electronic conductivity. As indicated by density functional theory and spectroscopic characterizations, Mg2+ ions are faradaically stored in the catechol part of the ligand, and Mg2+ inserted into the vacant Ho sites contributes to structural stability. Furthermore, operando 2D correlation Raman spectroscopy identified how Mg2+ ions interact with the ligand of Ho‐HHTP and demonstrated the sequential change of peak change.

Construction of Ordered and Fast Lithium Ion Channels in Gel Electrolytes for Li-SPAN Batteries.

As one of the most promising battery systems, the lithium sulfur battery is expected to be widely used in fields of high energy density demands. Owing to the unique solid-solid conversion mechanism, there is no shuttle effect for the Li-SPAN (sulfurized polyacrylonitrile) battery. However, the compatibility between Li anode and carbonate electrolyte has not been resolved, which prevents the SPAN from practical applications. Herein, an organic-inorganic gel carbonate electrolyte is proposed to stabilize interphases and structures of both the anode and cathode, where polyimide (PI) is used for electrolyte gelation, which can assist in the uniform distribution of inorganic components at the electrolyte interface. Furthermore, ZnS nanodots loaded on two-dimensional MoS2 flakes provide abundant Li-ion diffusion paths, improve the transfer kinetic of Li ions, and induce uniform nucleation and deposition of Li. This gel electrolyte ensures Li symmetric cells a long-term cycle life of more than 900 h under the condition of deep lithium plating/stripping at 5 mAh cm-1. Li∥Cu cells exhibit a prolonged lifespan of 800 h with a CE of 98.3%. Furthermore, the Li-SPAN battery shows stability of more than 850 cycles, with the capacity retention of 85.1%. This work provides an approach for high-energy Li-SPAN batteries with carbonate-based electrolytes.

Novel integrated reference-counter electrode for electrochemical measurements of HOMO and LUMO levels in small-molecule thin-film semiconductors for OLEDs

Organic light-emitting diodes (OLEDs) are a prominent display technology, yet the accurate characterization of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels in their constituent materials remains challenging. This study introduces a novel integrated reference-counter electrode (IRCE) assembly, leveraging a gel polymer electrolyte with an embedded silver quasi-reference electrode, facilitating the electrochemical measurement of HOMO and LUMO levels in small molecular thin-film semiconductors. Calibration of the IRCE against ferrocene enables the establishment of an absolute energy scale. Comparative stability tests against a standard Ag/AgNO3 reference electrode confirm the IRCE's reliability. Electrochemical characterization using cyclic voltammetry was performed on prototypical OLED materials, including NPB, TCTA, PO-T2T neat films, and an NPB:PO-T2T exciplex film. While NPB and PO-T2T exhibited stable voltammograms, TCTA showed signs of electropolymerization. Additionally, the HOMO level of the NPB:PO-T2T exciplex was slightly shifted compared to that of NPB, suggesting interactions within the exciplex. The results demonstrated the IRCE's capability to accurately determine frontier energy levels in thin films, paving the way for better device modeling and a better understanding of underlying electronic processes in organic semiconductors.