High Anhydrous Proton Conductivity Research Articles

High anhydrous proton conductivity and a smart proton transportation approach of a sulfate coordination polymer.

We successfully synthesized a one-dimensional cobalt sulfate coordinating polymer, whose simple hydrogen bond web structure facilitated the analysis of the proton transfer process. At 175 °C, without humidity, the conductivity is 0.0311 S cm-1, which exceeds those of most of the organic inorganic hybrid materials under anhydrous conditions (world record rank 8). Based on its crystal structure and theoretical calculations, the subversive proton conduction pathway was inferred clearly. We, for the first time, found that the proton smartly chose the path with a lower energy barrier but not the one with short distance to transport avoiding short circuit.

Modulation of defects in metal organic gels to enhance anhydrous proton conduction from subzero to moderate temperature

Exploitation of solid-state proton-conducting materials with high anhydrous proton conductivity from subzero temperature (<273 K) to moderate temperature (>353 K) is a great challenge. Here, Brönsted acid-dopped zirconium-organic xerogels (Zr/BTC-xerogels) are prepared for anhydrous proton conduction from subzero to moderate temperature. Abundant acid sites and strong H-bonding interactions make the CF3SO3H (TMSA)-introduced xerogel gain high proton conductivity from 9.0 × 10-4 S cm−1 (253 K) to 1.40 × 10-2 S cm−1 (363 K) under anhydrous conditions, which are in the leading level. This provides a new possibility to develop wide-operating-temperature conductors.

Solvent-Free Mechanochemical Dense Pore Filling Yields CPO-27/MOF-74 Metal–Organic Frameworks with High Anhydrous and Water-Assisted Proton Conductivity

Proton-conducting solids operating in both anhydrous and humid conditions are of paramount importance for the development of fuel cells. We demonstrate that incorporating formamidinium or methylammonium ions in CPO-27/MOF-74 metal–organic frameworks renders them highly conductive under the two conditions. Highest proton conductivities reach 8 × 10–4 S/cm under anhydrous conditions, exceed 10–3 S/cm already at low relative humidity (30–50% RH) and low temperatures (25–60 °C), and reach 10–2 S/cm at 60 °C and 70% RH. The dense pore filling with the protic cations is enabled by solvent-free mechanochemistry and stoichiometric saturation of open metal sites (Mg, Ni) with thiocyanate ligands. DFT modeling reveals that high anhydrous proton conductivity is associated with the presence of water-free extended networks of hydrogen bonds along the [001] channel and together with electrochemical impedance measurements (EIS) shed light on the mechanism of proton transport.

Developing a Unique Hydrogen-Bond Network in a Uranyl Coordination Framework for Fuel Cell Applications.

Crystalline materials with persistent high anhydrous proton conductivity that can be directly used as a practical electrolyte of the intermediate-temperature proton exchange membrane fuel cells for durable power generation remain a substantial challenge. The present work proposes a unique way of the axial uranyl oxo atoms as hydrogen-bond acceptors to form a dense hydrogen-bonded network within a stable uranyl-based coordination polymer, UO2(H2PO3)2(C3N2H4)2 (HUP-3). It exhibits stable and efficient anhydrous proton conductivity over a super-wide temperature range (-40-170 °C). It was also assembled into a H2/O2 fuel cell as the electrolyte and shows a high electrical power density of 11.8 mW·cm-2 at 170 °C, which is among one of the highest values reported from crystalline solid electrolytes. The cell was tested for over 12 h without notable power loss.

Imidazole encapsulated in core–shell MOF@COFs with a high anhydrous proton conductivity

A novel core–shell imidazole@MOF@COF proton conductor is constructed using UiO-67 and TAPB-DMTP-COFs.

Abundant defects of zirconium-organic xerogels: High anhydrous proton conductivities over a wide temperature range and formic acid impedance sensing

There exists a challenge to develop solid-state proton conductors with high conductivity not only at high working temperatures (>353 K) but at start-up temperature and even at subzero temperature (<273 K) in cold climates or high-altitude drones. Here we present a series of zirconium-organic xerogels (Zr/Fum-xerogels) with porosity and defectivity, supported by N2 sorption, thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS), exhibiting a high anhydrous proton conductivity over the temperature range of 233 to 433 K. The anhydrous conductivity of Zr/Fum-xerogel-0.04 reaches 5.68 × 10−4 (233 K) and 2.5 × 10−2 S cm−1 (433 K), situating in the leading level of all anhydrous conductors reported to date. Further, the defective effects on acidities and conductive mechanisms of xerogels, especially structural changes of water clusters generated by varying temperatures are investigated by ion exchange capacity (IEC), X-ray photoelectron spectroscopy (XPS), temperature programmed desorption of NH3 (NH3-TPD) and in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The zirconium-organic xerogels with outstanding conducting performance is further implemented as impedance sensor towards formic acid.

Conjugated Microporous Polymer with C≡C and C-F Bonds: Achieving Remarkable Stability and Super Anhydrous Proton Conductivity.

Introducing nonvolatile liquid acids into porous solids is a promising solution to construct anhydrous proton-conducting electrolytes, but due to weak coordination or covalent bonds building these solids, they often suffer from structural instability in acidic environments. Herein, we report a series of steady conjugated microporous polymers (CMPs) linked by robust alkynyl bonds and functionalized with perfluoroalkyl groups and incorporate them with phosphoric acid. The resulting composite electrolyte exhibits high anhydrous proton conductivity at 30-120 °C (up to 4.39 × 10-3 S cm-1), and the activation energy is less than 0.4 eV. The excellent proton conductivity is attributed to the hydrophobic pores that provide nanospace for continuous proton transport, and the hydrogen bonding between phosphoric acid and perfluoroalkyl chains of CMPs promotes short-distance proton hopping from one side to the other.

Impact of N-Substituent and pKa of Azole Rings on Fuel Cell Performance and Phosphoric Acid Loss.

The influence of N-substituent and pKa of azole rings has been investigated for the performance of high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). Imidazole, benzimidazole, and triazole groups were functionalized on the side chains of poly(phenylene oxide), respectively. Each azole group is categorized by their N-substituent into two types: unsubstituted and methyl-substituted azoles. The membranes with methyl-substituted azoles showed higher phosphoric acid (PA) doping levels with an average increase of 20% compared to those with unsubstituted azoles in the full-doped states. However, unsubstituted azoles more effectively improved the proton conductivity and the membrane with unsubstituted imidazole (IMPPO-H) showed a high anhydrous proton conductivity of 153 mS/cm at 150 °C. In contrast, the membranes with methyl-substituted azoles showed a higher PA retention with an average increase of 81% compared to those with unsubstituted azoles. The higher PA retention of methyl-substituted azoles also led to the higher fuel cell performance with the maximum increase of 95% in the power density. It was also revealed that higher pKa of azoles enhanced the PA retention and the fuel cell performance. Based on the experimental results of PA retention and density functional theory calculations, the PA loss mechanism was also proposed.

Coordination polymer glass from a protic ionic liquid: proton conductivity and mechanical properties as an electrolyte.

High proton conducting electrolytes with mechanical moldability are a key material for energy devices. We propose an approach for creating a coordination polymer (CP) glass from a protic ionic liquid for a solid-state anhydrous proton conductor. A protic ionic liquid (dema)(H2PO4), with components which also act as bridging ligands, was applied to construct a CP glass (dema)0.35[Zn(H2PO4)2.35(H3PO4)0.65]. The structural analysis revealed that large Zn–H2PO4−/H3PO4 coordination networks formed in the CP glass. The network formation results in enhancement of the properties of proton conductivity and viscoelasticity. High anhydrous proton conductivity (σ = 13.3 mS cm−1 at 120 °C) and a high transport number of the proton (0.94) were achieved by the coordination networks. A fuel cell with this CP glass membrane exhibits a high open-circuit voltage and power density (0.15 W cm−2) under dry conditions at 120 °C due to the conducting properties and mechanical properties of the CP glass.

Enhanced proton conduction in zirconium phosphate/ionic liquids materials for high-temperature fuel cells

This work reports the synthesis of high temperature proton conductors based on zirconium phosphate and imidazolium-based ionic liquids. This material is evaluated for high temperature proton exchange membrane fuel cells applications operating at 200 °C. The characterization results show high proton conductivity, enhanced water uptake properties, changes in structure, and exfoliation in zirconium phosphates crystal layers upon the introduction of the ionic liquid. The proton conductivity results demonstrate that there is an optimum amount of ionic liquid that can be introduced into zirconium phosphates to enhance its conductivity beyond which, the conductivity starts to decrease. At the optimum conditions, the addition of ionic liquids enhances the proton conductivity of the zirconium phosphates material by orders of magnitude. The results show a high proton conductivity the order of 10−2 S cm−1 at room temperature and high anhydrous proton conductivity of 10−4 S cm−1 at 200 °C. These findings indicate that the zirconium phosphate-ionic liquid material has a great potential as solid proton conductors for fuel cells applications operating at elevated temperatures.

Loading Acid–Base Pairs into Periodic Mesoporous Organosilica for High Anhydrous Proton Conductivity over a Wide Operating Temperature Window

The design and fabrication of high proton conductors over a wide working temperature range are significant for the development of proton exchange membrane (PEM) fuel cells, as fuel cell vehicle technology requires solid electrolytes that should have the ability of conductivity at both high and subzero temperatures. Here, we demonstrated that biphenylene-bridged periodic-mesoporous-organosilica (PMO) and its sulfonated derivatives (s-PMO) are good hosts to load proton carrier imidazole for such sophisticated proton-conducting materials. With the acid–base pairs, the resulting material Im@s-PMO shows efficient proton conductivity over the temperature range from −40 °C (1.12 × 10–6 S/cm) to 180 °C (7.11 × 10–3 S/cm) under anhydrous conditions; the maximum value is significantly higher than that of Im@PMO (2.30 × 10–4 S/cm, 180 °C). The interaction between imidazole and the sulfonate group obviously affects the conductivity, which was confirmed by thermogravimetric analysis, MALDI-TOF mass spectrum, Fourier t...

Unique Proton Transportation Pathway in a Robust Inorganic Coordination Polymer Leading to Intrinsically High and Sustainable Anhydrous Proton Conductivity.

Although comprehensive progress has been made in the area of coordination polymer (CP)/metal-organic framework (MOF)-based proton-conducting materials over the past decade, searching for a CP/MOF with stable, intrinsic, high anhydrous proton conductivity that can be directly used as a practical electrolyte in an intermediate-temperature proton-exchange membrane fuel cell assembly for durable power generation remains a substantial challenge. Here, we introduce a new proton-conducting CP, (NH4)3[Zr(H2/3PO4)3] (ZrP), which consists of one-dimensional zirconium phosphate anionic chains and fully ordered charge-balancing NH4+ cations. X-ray crystallography, neutron powder diffraction, and variable-temperature solid-state NMR spectroscopy suggest that protons are disordered within an inherent hydrogen-bonded infinite chain of acid-base pairs (N-H···O-P), leading to a stable anhydrous proton conductivity of 1.45 × 10-3 S·cm-1 at 180 °C, one of the highest values among reported intermediate-temperature proton-conducting materials. First-principles and quantum molecular dynamics simulations were used to directly visualize the unique proton transport pathway involving very efficient proton exchange between NH4+ and phosphate pairs, which is distinct from the common guest encapsulation/dehydration/superprotonic transition mechanisms. ZrP as the electrolyte was further assembled into a H2/O2 fuel cell, which showed a record-high electrical power density of 12 mW·cm-2 at 180 °C among reported cells assembled from crystalline solid electrolytes, as well as a direct methanol fuel cell for the first time to demonstrate real applications. These cells were tested for over 15 h without notable power loss.

Metal–organic frameworks with a large breathing effect to host hydroxyl compounds for high anhydrous proton conductivity over a wide temperature range from subzero to 125 °C

Flexible MOFs with a large breathing effect to host hydroxyl compounds for high anhydrous proton conductivity over a wide temperature range.

Robust Crystalline Hybrid Solid with Multiple Channels Showing High Anhydrous Proton Conductivity and a Wide Performance Temperature Range.

A proton conductor displaying high anhydrous proton conductivity (≈10(-2) S cm(-1)) and good performance over a broad temperature range is presented. This hybrid material is produced via doping HCl into open-framework chalcogenide(C2N2H10)(C2N2H9)2 Cu8 Sn3S12, and has cubopolyhedral cavities and multiple channels.

Polyelectrolyte microcapsules as ionic liquid reservoirs within ionomer membrane to confer high anhydrous proton conductivity

Herein, novel composite membranes are prepared by embedding methacrylic acid polyelectrolyte microcapsules (PMCs) into sulfonated poly(ether ether ketone) (SPEEK) matrix, followed by impregnating imidazole-type ionic liquids (ILs). Within the composite membrane, the lumens of PMCs act as IL reservoirs, which provide large space for IL storage and thus significantly elevate the IL uptake. The IL leaching measurement suggests that the cross-linked shells of PMCs manipulate the IL release, endowing the composite membrane with high IL retention. Moreover, the high IL retention renders the composite membrane more anhydrous hopping sites (e.g., the imidazole groups on IL and the acid-base pairs between imidazole and sulfonic acid groups), imparting a facilitated proton conduction via Grotthuss mechanism. In particular, the composite membrane containing 12% PMCs achieves a high anhydrous proton conductivity of 33.7 mS cm−1 at 150 °C. The same membrane also exhibits a surprising steady-state IL retention of 36.9% after leaching in liquid water.

High anhydrous proton conductivity of imidazole-loaded mesoporous polyimides over a wide range from subzero to moderate temperature.

On-board fuel cell technology requires proton conducting materials with high conductivity not only at intermediate temperatures for work but also at room temperature and even at subzero temperature for startup when exposed to the colder climate. To develop such materials is still challenging because many promising candidates for the proton transport on the basis of extended microstructures of water molecules suffer from significant damage by heat at temperatures above 80 °C or by freeze below -5 °C. Here we show imidazole loaded tetrahedral polyimides with mesopores and good stability (Im@Td-PNDI 1 and Im@Td-PPI 2) exhibiting a high anhydrous proton conductivity over a wide temperature range from -40 to 90 °C. Among all anhydrous proton conductors, the conductivity of 2 is the highest at temperatures below 40 °C and comparable with the best materials, His@[Al(OH)(1,4-ndc)]n and [Zn3(H2PO4)6(H2O)3](Hbim), above 40 °C.

Phosphoric acid‐doped imidazolium ionomers with enhanced stability for anhydrous proton‐exchange membrane applications

ABSTRACTPhosphoric acid‐doped crosslinked proton‐conducting membranes with high anhydrous proton conductivity, and good chemical stability in phosphoric acid were synthesized and characterized. The synthetic procedure of the acid‐doped composite membranes mainly involves the in situ crosslinking of polymerizable monomer oils (styrene and acrylonitrile) and vinylimidazole, and followed by the sulfonation of pendant imidazole groups with butanesultone, and further doped with phosphoric acid. The resultant phosphoric acid‐doped composite electrolyte membranes are flexible and show high thermal stability and high‐proton conductivity up to the order of 10−2 S cm−1 at 160 °C under anhydrous conditions. The phosphoric acid uptake, swelling degree, and proton conductivity of the composite membranes increase with the vinylimidazole content. The resultant composite membranes also show good oxidative stability in Fenton's reagent (at 70 °C), and quite good chemical stability in phosphoric acid (at 160 °C). The properties of the prepared electrolyte membranes indicate their promising prospects in anhydrous proton‐exchange membrane applications. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013, 51, 1311–1317

Characterization of mechanochemically synthesized MHSO4–H4SiW12O40 composites (M = K, NH4, Cs)

Anhydrous proton conductive MHSO4–H4SiW12O40 (MHS–STA) composites were successfully synthesized using mechanochemical treatment. 80MHS·20STA (mol%) composite, for example, showed very high anhydrous proton conductivity above 10−3Scm−1 in a temperature range from 160 to 60°C under ambient pressure. From the X-ray diffraction study, it was confirmed that the mechanochemical treatment induced chemical interactions via ion-exchange between M+ ion in MHS and H+ ion in STA. Furthermore, phase-transition of raw substances, such as melting, dehydration and superprotic phase-transition, was suppressed in mechanochemically synthesized MHS–STA composites, indicating that improvement of anhydrous proton conductivity for MHS–STA composites is caused by the changes in protic conduction behavior.

Anhydrous proton conductivity of KHSO 4–H 3PW 12O 40 composites and the correlation with hydrogen bonding distance under ambient pressure

Anhydrous proton conductive KHSO 4–H 3PW 12O 40 (KHS–WPA) composites were successfully synthesized using mechanochemical treatment. 95KHS·5WPA (mol%) composite, for example, showed very high anhydrous proton conductivity of 1.3 × 10 −2 to 2.4 × 10 −3 S cm −1 in a temperature range from 160 °C to 80 °C under ambient pressure. Chemical interactions via ion-exchange and hydrogen bond between KHS and WPA were confirmed from structural studies. Furthermore, the anhydrous proton conductivity of the KHS–WPA composites was well correlated with their estimated hydrogen bonding distance, indicating that reduction of the hydrogen bonding distance in the KHS–WPA composites is significant in the proton hopping to achieve anhydrous high proton conductivity.

Heteropolyacid-Encapsulated Self-Assembled Materials for Anhydrous Proton-Conducting Electrolytes

The composite material of heteropolyacid (12-phosphotungstic acid; PWA) and polystyrene sulfonic acid (PSS) construct the PWA-encapsulated material by the self-assembly of -SO3H onto the PWA surface; as a result, the fast proton transfer occurred at the interface between the PWA and -SO3H, and the encapsulated material indicated the high anhydrous proton conductivity of 1 x 10(-2) S cm(-1) at 180 degrees C. These anhydrous proton-conducting materials without the existence of water molecules are quite different from customary ion-exchange membrane, such as Nafion, and may have advantages as an electrolyte membrane for polymer electrolyte membrane fuel cells operating at intermediate temperatures under anhydrous conditions but also for electrochemical devices including electrochromic displays, chemical sensors, and others.