Conductivity Of Polymer Electrolytes Research Articles

Identifying ultrathin dielectric nanosheets induced interface polarization for high-performance solid-state lithium metal batteries

Solid-state lithium metal batteries (SSLMBs) with polymer electrolytes are promising due to enhanced safety and high energy density, but the low ionic conductivity of polymer electrolytes and the unstable interface of lithium metal anode hinder the development of SSLMBs. Herein, we propose a unique strategy to address these challenges by coupling ultrathin high-dielectricity Ca2Nb3O10 (CNO) nanosheets with PEO-based electrolyte. The interfacial polarization originating from the distortion of NbO6 octahedra along the vertical direction of CNO nanosheets is maximized and so the interaction between CNO and LiTFSI, which greatly supports the dissociation of LiTFSI and improves the ionic conductivity (2.0 × 10−4 S cm−1) of the composite polymer electrolyte, compared to that without CNO. The optimized interfacial polarization effect is thoroughly demonstrated by theoretical calculation and experimental results. Moreover, due to a homogeneous, robust and LiF-rich solid electrolyte interphase film with promoted Li+ ion transport being formed at the lithium metal interface, the superior cycling stability (90% capacity retention after 440 cycles at 0.5 C) and rate capability for LFP||Li full batteries are achieved. This design of composite polymer electrolyte with ultrathin dielectric nanosheet fillers demonstrates a new approach to the development of high-performance polymer electrolytes for SSLMBs.

Application of triblock copolymers in lithium-ion batteries based on solid electrolyte

In the future, all-solid Li-ion batteries are expected to gain widespread acceptance in larger markets due to their high safety and excellent electrochemical performance. However, it is important to acknowledge their drawbacks, including the inadequate compatibility between the electrode and electrolyte interface and the low ionic conductivity at room temperature. This paper reviews the specific methods and the latest research progress of triblock copolymers to solve the above problems. Block copolymerization is an effective way to enhance the efficiency and performance of electrolyte. Its advantage is that two or more monomers with different properties can be polymerized into the same structure, which is conducive to the ionic conductivity of polymer electrolyte. In the latest research results, straight-chain block copolymers have been synthesized, which have better physical and chemical properties compared to traditional comb block copolymers. However, the electrochemical properties of the straight-chain block copolymer electrolyte and the stability of the interface between the electrode and the solid electrolyte are rarely reported. Therefore, it is particularly important to systematically study the electrochemical properties and interface properties of block copolymer electrolytes. In the future, more attention should be drawn to not only improving the properties of SPEs but also building a stable interface with low interface resistance.

Ion Transport in Polymer Electrolytes: Building New Bridges between Experiment and Molecular Simulation.

ConspectusPolymer electrolytes constitute a promising type of material for solid-state batteries. However, one of the bottlenecks for their practical implementation lies in the transport properties, often including restricted Li+ self-diffusion and conductivity and low cationic transference numbers. This calls for a molecular understanding of ion transport in polymer electrolytes in which molecular dynamics (MD) simulation can provide both new physical insights and quantitative predictions. Although efforts have been made in this area and qualitative pictures have emerged, direct and quantitative comparisons between experiment and simulation remain challenging because of the lack of a unified theoretical framework to connect them.In our work, we show that by computing the glass transition temperature (Tg) of the model system and using the normalized inverse temperature 1000/(T - Tg + 50), the Li+ self-diffusion coefficient can be compared quantitatively between MD simulations and experiments. This allows us to disentangle the effects of Tg and the polymer dielectric environment on ion conduction in polymer electrolytes, giving rise to the identification of an optimal solvating environment for fast ion conduction.Unlike Li+ self-diffusion coefficients and ionic conductivity, the transference number, which describes the fraction of current carried by Li+ ions, depends on the boundary conditions or the reference frame (RF). This creates a non-negligible gap when comparing experiment and simulation because the fluxes in the experimental measurements and in the linear response theory used in MD simulation are defined in different RFs. We show that by employing the Onsager theory of ion transport and applying a proper RF transformation, a much better agreement between experiment and simulation can be achieved for the PEO-LiTFSI system. This further allows us to derive the theoretical expression for the Bruce-Vincent transference number in terms of the Onsager coefficients and make a direct comparison to experiments. Since the Bruce-Vincent method is widely used to extract transference numbers from experimental data, this opens the door to calibrating MD simulations via reproducing the Bruce-Vincent transference number and using MD simulations to predict the true transference number.In addition, we also address several open questions here such as the time-scale effects on the ion-pairing phenomenon, the consistency check between different types of experiments, the need for more accurate force fields used in MD simulations, and the extension to multicomponent systems. Overall, this Account focuses on building new bridges between experiment and simulation for quantitative comparison, warnings of pitfalls when comparing apples and oranges, and clarifying misconceptions. From a physical chemistry point of view, it connects to concentrated solution theory and provides a unified theoretical framework that can maximize the power of MD simulations. Therefore, this Account will be useful for the electrochemical energy storage community at large and set examples of how to approach experiments from theory and simulation (and vice versa).

Highly Frustrated Poly(ionic liquid) ABC Triblock Terpolymers with Exceptionally High Morphology Factors.

In this work, we report the successful synthesis of 17 unique compositions of a poly(ionic liquid) (PIL) ABC triblock terpolymer, poly(S-b-VBMIm-TFSI-b-HA), where S is styrene, VBMIm-TFSI is vinylbenzyl methylimidazolium bis(trifluoromethanesulfonyl)imide, and HA is hexyl acrylate. Nine distinct morphologies were observed, including two-phase and three-phase disordered microphase separated (D2 and D3), two-phase hexagonally packed cylinders (C2), core-shell hexagonally packed cylinders (CCS), three-phase lamellae (L3), two-phase lamellae (L2), core-shell double gyroid (Q230), spheres-in-lamellae (LSI), and a three-phase hexagonal superlattice of cylinders (CSL). The LSI morphology was unambiguously confirmed using small-angle X-ray scattering and transmission electron microscopy. Morphology type significantly impacted the ion conductivity of the PIL ABC triblock terpolymers, where remarkable changes in morphology factor (normalized ion conductivity) were observed with only small changes in the conducting volume fraction, i.e., PIL block composition. An exceptionally high morphology factor of 2.0 was observed from the PIL ABC triblock terpolymer with a hexagonal superlattice morphology due to the three-dimensional narrow, continuous PIL nanodomains that accelerate ion conduction. Overall, this work demonstrates the first systematic study of highly frustrated single-ion conducting ABC triblock terpolymers with a diverse set of morphologies and exceptionally high morphology factors, enabling the exploration of transport-morphology relationships to guide the future design of highly conductive polymer electrolytes.

Perfluorinated Single-Ion Li+ Conducting Polymer Electrolyte for Lithium-Metal Batteries

Single-ion (Li+) conducting electrolytes with a high Li+ conductivity and transference number (LTN) are promising electrolyte candidates for eliminating the concentration polarization and inhibiting the growth of lithium dendrites in lithium-metal batteries at high power and energy densities. This study presents the synthesis and electrochemical characterization of an AB-type single-ion Li+ conducting polymer consisting of a perfluorinated lithium-salt monomer (A) covalently bonded to a polyethylene glycol monomer (B). An investigation into several plasticizers reveals that ether-based solvents with moderate dielectric constants significantly enhance the Li+ conductivity of single-ion (Li+) conducting gel polymer electrolytes (SIC-GPE) while also maintaining the mechanical integrity of SIC-GPE. The perfluorinated lithium-salt units with weakly coordinating anions provide the advantage of high Li+ conductivity (1.1 × 10–4 S cm–2) and transference number (0.92), while polyethylene glycol units contribute to high flexibility and enhance plasticizer wettability in the SIC-GPE. The interfacial stability and electrochemical performance of SIC-GPE are demonstrated in lithium-metal symmetric cells (maintaining stability for >1300 h at 1 mAh cm–2) and lithium-metal batteries (retaining 98% capacity after 200 cycles).

Lithium Superionic Conductive Nanofiber-Reinforcing High-Performance Polymer Electrolytes for Solid-State Batteries.

Although composite solid-state electrolytes (CSEs) are considered promising ionic conductors for high-energy lithium metal batteries, their unsatisfactory ionic conductivity, low mechanical strength, poor thermal stability, and narrow voltage window limit their practical applications. We have prepared a new lithium superionic conductor (Li-HA-F) with an ultralong nanofiber structure and ultrahigh room-temperature ionic conductivity (12.6 mS cm-1). When it is directly coupled with a typical poly(ethylene oxide)-based solid electrolyte, the Li-HA-F nanofibers endow the resulting CSE with high ionic conductivity (4.0 × 10-4 S cm-1 at 30 °C), large Li+ transference number (0.66), and wide voltage window (5.2 V). Detailed experiments and theoretical calculations reveal that Li-HA-F supplies continuous dual-conductive pathways and results in stable LiF-rich interfaces, leading to its excellent performance. Moreover, the Li-HA-F nanofiber-reinforced CSE exhibits good heat/flame resistance and flexibility, with a high breaking strength (9.66 MPa). As a result, the Li/Li half cells fabricated with the Li-HA-F CSE exhibit good stability over 2000 h with a high critical current density of 1.4 mA cm-2. Furthermore, the LiFePO4/Li-HA-F CSE/Li and LiNi0.8Co0.1Mn0.1O2/Li-HA-F CSE/Li solid-state batteries deliver high reversible capacities over a wide temperature range with a good cycling performance.

Chitosan as a suitable host for sustainable plasticized nanocomposite sodium ion conducting polymer electrolyte in EDLC applications: Structural, ion transport and electrochemical studies

The challenge in front of EDLC device is their low energy density compared to their battery counter parts. In the current study, a green plasticized nanocomposite sodium ion conducting polymer blend electrolytes (PNSPBE) was developed by incorporating plasticized Chitosan (CS) blended with polyvinyl alcohol (PVA), doped with NaBr salt with various concentration of CaTiO3 nanoparticles. The most optimized PNSPBE film was subsequently utilized in an EDLC device to evaluate its effectiveness both as an electrolyte and a separator. Structural and morphological changes were assessed using XRD and SEM techniques. The PNSPBE film demonstrated a peak ionic conductivity of 9.76×10−5 S/cm, as determined through EIS analysis. The dielectric and AC studies provided further confirmation of structural modifications within the sample. Both TNM and LSV analyses affirmed the suitability of the prepared electrolyte for energy device applications, evidenced by its adequate ion transference number and an electrochemical potential window of 2.86 V. Electrochemical properties were assessed via CV and GCD techniques, confirming non-Faradaic ion storage, indicated by the rectangular CV pattern at low scan rates. The parameters associated with the designed EDLC device including specific capacitance, ESR, power density (1950 W/kg) and energy density (12.3 Wh/kg) were determined over 1000 cycles.

Lithiated Nafion membrane as a single-ion conducting polymer electrolyte in lithium batteries

AbstractSingle lithium-ion conducting polymer electrolytes are promising candidates for next generation safer lithium batteries. In this work, Li+-conducting Nafion membranes have been synthesized by using a novel single-step procedure. The Li-Nafion membranes were characterized by means of small-wide angle X-ray scattering, infrared spectroscopy and thermal analysis, for validating the proposed lithiation method. The obtained membranes were swollen in different organic aprotic solvent mixtures and characterized in terms of ionic conductivity, electrochemical stability window, lithium stripping-deposition ability and their interface properties versus lithium metal. The membrane swollen in ethylene carbonate:propylene carbonate (EC:PC, 1:1 w/w) displays good temperature-activated ionic conductivities (σ ≈ 5.5 × 10–4 S cm−1 at 60 °C) and a more stable Li-electrolyte interface with respect to the other samples. This Li-Nafion membrane was tested in a lithium-metal cell adopting LiFePO4 as cathode material. A specific capacity of 140 mAhg−1, after 50 cycles, was achieved at 30 °C, demonstrating the feasibility of the proposed Li-Nafion membrane.

Impact of Ionic Liquid Functionalized ZrO2 Nanoparticles on Poly (stearyl methacrylate) Grafted Poly (vinylidene fluoride‐co‐hexafluoropropylene) Based Highly Conductive Gel Polymer Electrolytes for Lithium‐Metal Batteries

AbstractIn this study, an organic‐inorganic hybrid polymer membrane is successfully designed and developed by grafting stearyl methacrylate (SMA) side chains onto the backbone of the P(VDF‐HFP) copolymer followed by blending with varying amounts of imidazolium ionic liquids functionalized ZrO2 nanoparticles. Different microporous gel polymer electrolytes (MGPEs) are prepared by immersing the membranes into a LiTFSI salt‐dissolved ionic liquid electrolyte. The membranes′ crystallinity, surface morphology, porosity, and thermal stability are investigated using various characterization techniques. The copolymer membrane blended with 60 wt % functionalized nanoparticles exhibits the highest porosity of 64.5 %, which allows it to achieve a maximum electrolyte uptake of 387 wt %. That enables the corresponding MGPE to achieve the highest room temperature lithium ion conductivity of ~5.34×10−3 S cm−1 with a wide electrochemical stability window and good electrochemical stability against Li metal. Leveraging these advantageous characteristics, the lab‐scale truly solid‐state Li|MGPE|LiFePO4 and Li|MGPE|LiNi0.8Mn0.1Co0.1O2 cells demonstrate excellent rate capability and reversible cycling stability while maintaining high specific capacities (up to 154 and 172 mAh g−1, respectively, at 0.5 C) with >99.0 % coulombic efficiency over 100 cycles. Such exceptional interfacial compatibility with both low‐ and high‐voltage cathodes establishes the applicability of these newly developed MGPEs in next‐generation all‐solid‐state lithium‐metal batteries.

A novel approach to enhance the ionic conductivity of silver nanoparticles incorporated PVA:NaBr polymer electrolyte films via fast neutron irradiation

This study investigates the unprecedented impact of fast neutron irradiation on the structural, electrical, and morphological properties of solid polymer electrolytes (SPEs). The SPE, a poly (vinylalcohol) (PVA)-sodium bromide (NaBr) based matrix with the incorporation of silver nanoparticles (AgNPs), was prepared via a solution casting method and subjected to various time intervals of fast neutron irradiation. X-ray diffraction (XRD) analysis revealed a distinct trend in the polymer electrolyte sample's amorphous phase, with decreased levels at lower neutron fluence and augmented levels at higher fluences. Fourier transform infrared (FTIR) spectroscopy highlighted plausible interactions leading to chain scission and cross-linking. Optical investgations below 300 nm exhibited increased absorbance and a shifted position of the surface plasmon resonance peak correlated with AgNPs. Validation of structural changes in the Ag-incorporated PVA-NaBr system was supported by reduced bandgap and elevation in Urbach energy, corroborating FTIR findings. Enhanced thermal stability was confirmed using thermogravimetric (TGA) analysis. Morphological modification upon irradiation were evident via Field emission scanning electron microscope (FESEM). Transport properties evaluated by Nyquist plot fitting showcased escalating room temperature conductivity with neutron fluence, and the highest conductivity obtained was 4.38 × 10−3 S/cm, an order higher than the pristine sample. Transference number measurements (TNM) indicated that the primary charge carriers are ions rather than electrons. This novel approach confirms that neutron irradiation can be used as a potential way to obtain highly conductive polymer electrolyte films.

Opportunity for lithium-ion conducting polymer electrolytes beyond polyethers

Lithium-ion conducting solid polymer electrolytes (SPEs) are of particular interest for battery applications. In addition to their relatively easy scalability to industrial scale, the ductility and processability of SPEs allows intimate contact between electrode and electrolyte materials, which ensures low cell resistance and thus better cycling performance. Herein, we focus on the non-polyether-based polymers developed for building lithium-ion conducting SPEs, with the aim of circumventing the dilemmas encountered by classic polyether-based SPEs. This review highlights the recent progresses and advances in the development of several kinds of interesting polymer host matrices, including carbonyl-containing polymers [e.g., polycarbonates, polyesters], ionomers-based polymers [e.g., poly(ionic liquids)], fluorine-based polymers, nitrile-based polymers, and so on. Particular attention is paid to the differences between alternative polymer chemistries and polyether systems, in terms of ion transport behavior [e.g., ionic conductivity, cationic transport number], electrochemical properties [e.g., anodic and cathodic stability], compatibility with electrode materials, etc. Possible solutions to further enhance the performances of non-polyether-type SPEs are also discussed.

Current scenario and future aspect of low viscosity doped polymer electrolyte

This paper deals the overall response of mixing ionic liquid into polymer matrix. Ionic liquid is frequently used as novel electrolyte in various electrochemical devices. Mixing ionic liquid into insulator polymers plays dual role. One side it plays as source of charge carriers while in other side it acts as plasticizer when incorporated in polymer matrix. For device application high conducting polymer electrolyte is necessary which can easily be provided by this ionic liquid when used as dopants. It is also necessary to understand detail conduction mechanism within ionic liquid incorporated polymer electrolyte. Possible reasons of conductivity enhancement are discussed in detail in present work.

Experimental Investigations on Highly Conducting Solid Bio‐Polymer Electrolytes Based on Latex of Calotropis gigantea Plant

AbstractThe study has prepared highly conducting polymer electrolyte films using solution cast technique with poly(vinylidene fluoride‐co‐hexafluoropropylene) PVDF‐HFP, mixture of ethylene carbonate (EC), and propylene carbonate (PC) as plasticizer and latex of Calotropis gigantea (CGL) as an ionic source. In this study, four films are prepared using PVDF‐HFP:CGL in ratio 1:1 with the increasing concentration of EC+PC as 1, 2, 3, and 4 M named as 1:1:1, 1:1:2, 1:1:3, 1:1:4. The prepared polymer electrolyte is examined by polarized optical microscopy (POM), elemental dispersive X‐ray technique (EDX), and complex impedance spectroscopy. EDX and POM are studied for the surface morphology of all prepared samples and to investigate the porous nature of films. The enhancement in ionic conductivity occurs due to CGL and increasing amount of EC‐PC. Conductivity of highest composition (1:1:4) polymer electrolyte film is found to be ≈10−3 S cm−1. The optimized polymer electrolyte film is considered as a promising candidate for application in supercapacitors.

Structure Optimization of Some Single-Ion Conducting Polymer Electrolytes with Increased Conductivity Used in "Beyond Lithium-Ion" Batteries.

Simulation techniques implemented with the HFSS program were used for structure optimization from the point of view of increasing the conductivity of the batteries' electrolytes. Our analysis was focused on reliable "beyond lithium-ion" batteries, using single-ion conducting polymer electrolytes, in a gel variant. Their conductivity can be increased by tuning and correlating the internal parameters of the structure. Materials in the battery system were modeled at the nanoscale with HFSS: electrodes-electrolyte-moving ions. Some new materials reported in the literature were studied, like poly(ethylene glycol) dimethacrylate-x-styrene sulfonate (PEGDMA-SS) or PU-TFMSI for the electrolyte; p-dopable polytriphenyl amine for cathodes in Na-ion batteries or sulfur cathodes in Mg-ion or Al-ion batteries. The coarse-grained molecular dynamics model combined with the atomistic model were both considered for structural simulation at the molecular level. Issues like interaction forces at the nanoscopic scale, charge carrier mobility, conductivity in the cell, and energy density of the electrodes were implied in the analysis. The results were compared to the reported experimental data, to confirm the method and for error analysis. For the real structures of gel polymer electrolytes, this method can indicate that their conductivity increases up to 15%, and even up to 26% in the resonant cases, via parameter correlation. The tuning and control of material properties becomes a problem of structure optimization, solved with non-invasive simulation methods, in agreement with the experiment.

Solid hybrid electrolytes based on conductive oxides and polymer electrolytes for all-solid-lithium batteries

This article provides an overview of solid hybrid electrolytes based on Li+-conductive oxide and polymer electrolyte for all-solid-state lithium batteries and discusses their composition, conduction mechanism, progress, and perspectives.

Impact of Ammonium Perchlorate Content on Electrically Controlled Gel Polymer Electrolyte Monopropellants

A group of five electrically controlled monopropellants were developed, and their fundamental rheological, electrochemical, thermal, and combustion properties were characterized. A baseline monopropellant was composed of lithium perchlorate complexed with polyethylene glycol to form an ionically conductive gel polymer electrolyte. Subsequent candidates were supplemented with varying amounts of ammonium perchlorate at a fixed polymer-to-oxidizer ratio to determine the effects of shifting oxidizer content on the fundamental properties. The ignition of the gel monopropellants using an applied DC voltage potential at atmospheric conditions was observed and determined to be primarily the result of an electrolytic reaction. Time-resolved infrared thermography confirmed initial heating and initiation of the gels at the cathode once temperatures had reached the decomposition temperature of the polymer. Fourier transform infrared analysis of collected residue from experiments halted before ignition revealed lithium deposition on the cathode, supporting electrochemical activity. It was found that the electrolytic ignition delay time was affected by the oxidizer content, the magnitude of the applied voltage, and the distance between the electrodes supplying the voltage.

Improving the ionic conductivity of polymer electrolytes induced by ceramic nanowire fillers with abundant lithium vacancies.

The addition of ceramic fillers is regarded as an effective strategy for enhancing the ionic conductivity of polymer electrolytes. However, particulate fillers typically fail to provide continuous conductive pathways and effective reinforcement. Herein, we report a ceramic nanowire filler with long-range interfacial conductivity and abundant lithium vacancies for a poly(ethylene oxide) (PEO)-based all-solid-state polymer electrolyte. LLZO nanowires (LLZO NWs) with a high aspect ratio are synthesized by combining sol-gel electrospinning and the multi-step process involving pre-oxidation, pre-sintering, and secondary sintering, resulting in a high tensile strength of the composite electrolyte (6.87 MPa). Notably, tantalum-aluminum co-substituted LLZO NWs (TALLZO NWs) release abundant lithium vacancies, further enhancing the Lewis acid-base properties, leading to a rapid ion migration speed (Li+ transfer number = 0.79) and significantly high ionic conductivity (3.80 × 10-4 S cm-1). Due to the synergistic effect of nanostructure modification and heteroatom co-doping, the assembled all-solid-state lithium-sulfur battery exhibits a high initial discharge capacity (776 mA h g-1 at 25 °C), remarkable rate capability, and excellent cycling performance (81% capacity retention after 200 cycles at 0.1C).

Investigation on the properties of PVDF matrix composite porous gel polymer electrolyte doped with lithium silicon gel

Gel polymer electrolytes are safer because they do not contain liquid phase components. On this basis, the introduction of inorganic fillers effectively overcame the problem of low ionic conductivity of polymer electrolyte at room temperature, and the constructed composite polymer electrolyte (CPEs) combined the advantages of inorganic fillers and polymer segments. In this paper, lithium silicon gel SiO2(Li+) was prepared by in-situ polymerization and sol-gel method, and doped in PVDF composite porous gel polymer electrolyte film prepared by immersion precipitation method. The electrochemical properties and surface topography of lithium iron phosphate were investigated by mounting a bonded lithium iron phosphate quasisolid lithium-ion battery. The experimental results show that the solid electrolyte film modified by SiO2(Li+) has good electrochemical and a certain reference value.

Polycarbonate-Based Solid-Polymer Electrolytes for Solid-State Sodium Batteries.

Solid-polymer electrolytes comprised of polypropylene carbonate (PPC) and varied sodium bis(fluorosulfonyl)imide (NaFSI) salt concentrations are investigated for implementation as a conductive solid polymer electrolyte into solid-state cathode composites utilizing a sodium-layered oxide active material. The ionic conductivity generally increases with NaFSI salt content, reaching ≈1mScm-1 at 80°C at the highest salt concentration (PPC:NaFSI = 0.5:1). Through an all-in-one slurry casting method, Na2/3 Ni1/3 Mn2/3 O2 cathode composites are fabricated in which the dispersed PPC electrolyte acts as the primary binder. Enabled by a bilayer polymer electrolyte system, cycling performance with the PPC cathode electrolyte is optimized with respect to salt concentration and anode material. The best cyclability is achieved with a moderate salt concentration electrolyte (PPC:NaFSI = 5:1), showcasing an initial capacity of 83mAhg-1 with a remarkable 80% capacity retention after 150 cycles at C/5 rate and 60°C. The superior performance of the lower salt concentration electrolyte is attributed to better electrochemical stability, as confirmed by linear sweep voltammetry and online electrochemical mass spectrometry measurements. These results underscore the potential of carbonate-based polymer electrolytes and the importance of balancing electrolyte conductivity and stability in cell design.

(Invited) Anode and Cathode Self-Adhesive Ionomers for Durable Alkaline Water Electrolysis

Low-temperature water electrolysis using anion conductive polymer electrolytes has several potential advantages over acid-based polymer electrolyzers. However, the formation of durable, high surface area electrodes remains a challenge. The adhesion and connectivity of high surface area, particulate catalysts to the porous transport layer is critically important to the long-term cell lifetime. The water-fed, oxygen-evolving anode and dry hydrogen-evolving cathode has their own unique challenges in terms of catalyst adhesion, water uptake and ionic conductivity.In this study, a family of covalently bonded, self-adherent, hydroxide conducting ionomers has been synthesized and tested under alkaline electrolysis conditions. The ionomers are based on hydroxide conducting poly(norbornene) terpolymers used in fuel cell and electrolyzers. Ionomers used in electrolysis electrodes must provide adhesion between the catalyst particles, porous transport layer and solid polymer membrane. Adhesion is especially important at the oxygen producing anode because of the intra-electrode forces created during the volumetric expansion of the liquid water into oxygen gas. However, the need for high ion conductivity is eased due to the supporting electrolyte in the water feed. The hydrogen-evolving cathode does not experience the same liquid-to-gas forces, but requires higher water uptake and ion conductivity because it is run without liquid or gas feed.The terpolymer and tetrapolymer ionomers used in this work have been functionalized to provide cites for chemical bonding to the ionomer, catalyst, and porous transport layer. The resulting electrodes show excellent adhesion of the catalyst particles to the porous transport layer, as determined by adhesion and electrolyzer durability measurements. The anode and cathode ionomers have been customized for each electrode.