Ionic Transport in Microhole Fluidic Diodes Based on Asymmetric Ionomer Film Deposits

Mathwig, Klaus; Aaronson, Barak D. B.; Marken, Frank

doi:10.1002/celc.201700464

Cited by 35 publications

(41 citation statements)

References 32 publications

(45 reference statements)

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“…The asymmetry has been realized by patterning of cylindrical capillaries [14,15,24], chemical modification on walls of holes [16,17], selection of materials of pores [6,[18][19][20], specific voltage control [21], and a nanopipette coated with surfactants [25][26][27][28]. A macroscopic concept of the rectification is composed of (i) geometric obstacle of the ion transport through the hole in the closed state and (ii) the localized accumulation of electrolyte owing to ion-exchange membrane in the open state [19,29,30]. A concept from the microscopic viewpoints is a gate linked to the potential distribution in the double-layer or on pore walls [31][32][33][34][35][36][37] as well as molecular instability in a hydrodynamic vortex [38,39].…”

Section: Introductionmentioning

confidence: 99%

Electric Migration of Hydrogen Ion in Pore-Voltammetry Suppressed by Nafion Film

Liu

Aoki²,

Chen

2020

Electrochem

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Micro-hole voltammetry exhibiting rectified current-voltage curves was performed in hydrochloric acid by varying the lengths and the diameters of the micro-holes on one end of which a Nafion film was mounted. Some voltammetric properties were compared with those in NaCl solution. The voltammograms were composed of two line-segments, the slope of one segment being larger than the other. They were controlled by electric migration partly because of the linearity of the voltammograms and partly the independence of the scan rates. Since the low conductance which appeared in the current from the hole to the Nafion film was proportional to the cross section area of the hole and the inverse of the length of the hole, it should be controlled by the geometry of the hole. The conductance of the hydrogen ion in the Nafion film was observed to be smaller than that in the bulk, because the transport rate of hydrogen ion by the Grotthuss mechanism was hindered by the destruction of hydrogen bonds in the film. In contrast, the conductance for the current from the Nafion to the hole, enhancing by up to 30 times in magnitude from the opposite current, was controlled by the cell geometry rather than the hole geometry except for very small holes. A reason for the enhancement is a supply of hydrogen ions from the Nafion to increase the concentration in the hole. The concentration of the hydrogen ion was five times smaller than that of sodium ion because of the blocking of transport of the hydrogen ion in the Nafion film. However, the rectification ratio of H+ was twice as large as that of Na+.

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Section: Introductionmentioning

confidence: 99%

Electric Migration of Hydrogen Ion in Pore-Voltammetry Suppressed by Nafion Film

Liu

Aoki²,

Chen

2020

Electrochem

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“…Ionic diode phenomena (or ion flux rectification phenomena) have been observed first with asymmetrically deposited ionomers such as Nafion [24] or cellulose [25]. The heterojunction approach reported here is governed mainly by the Nafion cation conductor (see Figure 2A) Figure 1B with the main mechanistic feature indicated as salt depletion ("closed") and salt accumulation ("open") [43]. Data in Figure 2A show currents with rectifier characteristics with positive potential applied (the diode is "open").…”

Section: Pim-ea-tb | Nafion Heterojunction Deposits I: Characterisatmentioning

confidence: 66%

“…The magnitude of the current in this state is affected by the electrolyte concentration. Based on recent studies [24,43] this is likely to be mainly a reflection of Na + conductivity within the Nafion deposit in the open state of the diode.…”

Section: Pim-ea-tb | Nafion Heterojunction Deposits I: Characterisatmentioning

confidence: 98%

“…In the open state of the diode, K + is conducted through the Nafion into the opposite compartment with NaClO4 solution. Under these conditions, the K + -enrichment of the interfacial region in the microhole is anticipated [43]. In order to investigate the effects of K + precipitating with ClO4under these conditions, the concentration of NaClO4 is fixed at 100 mM in the external electrolyte solution.…”

Section: Pim-ea-tb | Nafion Heterojunction Deposits Ii: "Inverted" Cmentioning

confidence: 99%

“…We have recently demonstrated that a Nafion film deposited asymmetrically onto a microhole (in PET) is sufficient to trigger ionic diode phenomena [43] and that a PIM-EA-TB deposit opposite to the Nafion can help improving ionic diode perfomance as well as defining a PIM-EA-TB | Nafion interface [4]. The PIM-EA-TB | Nafion heterojunction interface ( Figure 1A) is employed here in a new way.…”

Section: Introductionmentioning

confidence: 99%

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Potassium cation induced ionic diode blocking for a polymer of intrinsic microporosity | nafion “heterojunction” on a microhole substrate

Putra

Carta

Malpass‐Evans

et al. 2017

Electrochimica Acta

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Heterojunction" ionic diodes based on a Nafion cation conductor and a polymer of intrinsic microporosity (PIM) interfaced at a 6 m thickness polyethylene-terephthalate (PET) film with 20 m diameter microhole exhibit rectification effects in cation (K +) flux. When combined with the precipitation reaction of potassium cations with perchlorate anions to give insoluble KClO4 (solubility product ca. 1.05 × 10-2 M 2 at 25 o C) at the PIM | Nafion interface, inversion of the rectification/diode effect occurs and the formerly "open" state changes into a "closed" state due to blocking of ion flow. The localised interfacial precipitation reaction is due to up to three orders of magnitude accumulation of K + at the PIM | Nafion interface and shown to be fast and reversible. The effects of K + /ClO4concentration and of Na + interference are considered. The blocking process within the heterojunction ionic diode is suggested to be dynamic/fast and potentially useful as a diode sensor mechanism based on solubility product dependent precipitation.

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Flexible Ionic Diodes with High Rectifying Ratio and Wide Temperature Tolerance

Guo

Wang

Shao

et al. 2022

Adv Funct Materials

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Soft iontronics expand the toolbox of bio‐integrated or bio‐interfaced devices, owing to their natural resemblance with living systems; however, the development for analogous integrated ionic circuits is immature due to the difficulty of fabricating fundamental ionic logic elements. Among these, ionic diodes have motivated great endeavors for their unique ionic current rectifying characteristics. Nonetheless, it is still challenging to achieve high‐performance ionic diodes; also, most reported aqueous solution‐based ionic diodes fail to work at extreme temperatures, seriously hindering their practical uses. This work reports a highly rectifying, temperature‐tolerant, and flexible hydrogel ionic diode enabled by an ethylene glycol/water binary solvent system. The ionic diodes exhibit outstanding dehydration resistance to high temperatures (100 °C) and anti‐freezing performance at low temperatures (−20 °C). Rectification ratios as high as 1201 (with 0% ethylene glycol content) and 566 (with 40% EG content) are achieved, which are distinctly advantageous over most previous reports. A flexible four‐diode bridge full‐wave rectifier circuit is then fabricated, and its integration with the triboelectric nanogenerator for effective biomechanical energy harvesting is demonstrated. This work is believed to open up new insights for the development of future bio‐interfaced applications.

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Ionic Transport in Microhole Fluidic Diodes Based on Asymmetric Ionomer Film Deposits

Cited by 35 publications

References 32 publications

Electric Migration of Hydrogen Ion in Pore-Voltammetry Suppressed by Nafion Film

Electric Migration of Hydrogen Ion in Pore-Voltammetry Suppressed by Nafion Film

Potassium cation induced ionic diode blocking for a polymer of intrinsic microporosity | nafion “heterojunction” on a microhole substrate

Flexible Ionic Diodes with High Rectifying Ratio and Wide Temperature Tolerance

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