Using Li<sup>+</sup> as the electrochemical messenger to fabricate an aqueous rechargeable Zn–Cu battery

Zhang, Hanping; Yang, Tao; Wu, Xin; Zhou, Yisen; Yang, Chao; Zhu, Tiejun; Dong, Rulin

doi:10.1039/c5cc00575b

Cited by 28 publications

(12 citation statements)

References 45 publications

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“…The Li‐ion solid electrolyte LTAP separates the alkaline anode electrolyte and the acidic catholyte and provides ionic channels. LTAP does not serve as a direct Zn 2+ ‐ion conductor, but as a Li + ‐ion “messenger” to achieve the charge balance on both sides of an AZAB . The decoupled OER electrode is carbon‐free and binder‐free, ensuring good mechanical integrity in the high‐voltage oxidizing environment.…”

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confidence: 99%

Long‐Life, High‐Voltage Acidic Zn–Air Batteries

Manthiram

2015

Advanced Energy Materials

101

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electrolyte, which can be operated at room temperature, has rarely been reported. [ 11 ] The rechargeability of ZABs requires bifunctional catalytic activity of the air cathode: ORR and OER. The requirements for the active sites and electrochemical environment for ORR and OER are so different that it is very diffi cult to achieve high activity for both reactions within one material. For example, ORR prefers hydrophobic sites, which form a three-phase (solid catalyst, liquid electrolyte, and air) interface. In contrast, OER prefers hydrophilic sites to maximize the contact between the catalyst and the electrolyte. Recently, a "decoupled" design of bifunctional air electrodes has attracted much attention. [ 12 ] By dividing the ORR and OER functions into two different electrodes, which are optimized for ORR and OER respectively, high cell effi ciency as well as long cycle life could be achieved. However, the decoupled design has mainly been pursued with alkaline metal-air batteries, and no such design has been reported for acidic metal-air batteries.We report here AZABs with decoupled air electrodes, which is promising to eliminate the problems of conventional Zn-air batteries. The prototype AZABs are composed of a Zn-metal anode, an alkaline anode electrolyte, a NASICON-type Li-ion solid electrolyte (LTAP), an acidic phosphate buffer catholyte, and a decoupled IrO 2 thin fi lms grown onto a Ti mesh (IrO 2 @Ti) for OER and a commercial Pt/C catalyst on a gas diffusion layer (GDL) for ORR. The Li-ion solid electrolyte LTAP separates the alkaline anode electrolyte and the acidic catholyte and provides ionic channels. LTAP does not serve as a direct Zn 2+ -ion conductor, but as a Li + -ion "messenger" to achieve the charge balance on both sides of an AZAB. [ 13 ] The decoupled OER electrode is carbon-free and binder-free, ensuring good mechanical integrity in the high-voltage oxidizing environment. The decoupled ORR electrode is isolated during the high-voltage charge process, minimizing the problem of catalyst dissolution and oxidation. [ 14 ] During cell operation, a high discharge voltage close to 2.0 V could be achieved at a low current density. The acidic catholyte also eliminates the persistence problem of CO 2 ingression associated with alkaline electrolytes. In addition, the solid electrolyte provides the possibility of blocking Zn dendrite from reaching the cathode, greatly improving the battery safety. Moreover, although the soluble discharge product zincate will still form on the anode side, the solid electrolyte will keep the zincate in the anode chamber, decreasing the mass transport barrier and facilitating zincate reduction upon charge. The assembled AZABs achieve a high voltaic effi ciency of ≈81% at 0.1 mA cm −2 . The cell could also be cycled for hundreds of hours in the ambient air environment without signifi cant degradation. Figure 1 shows the discharge and charge mechanism of an AZAB based on an alkaline anode electrolyte and an acidic catholyte. During discharge, oxygen (O 2 ) from air diff...

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confidence: 99%

Long‐Life, High‐Voltage Acidic Zn–Air Batteries

Manthiram

2015

Advanced Energy Materials

101

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“…The approach also allows fabrication of batteries with anodes of zinc, magnesium, iron and aluminium, solid ion conductors for which are practically unavailable. [45][46][47][48][49] The first battery with a mediator-ion solid electrolyte was unveiled by Chen et al in 2013: [45] an aqueous ZnÀ KMnO 4 cell with solid Zn as anode, a solution of KMnO 4 as cathode and an Li 1 + x + y Al x Ti 2-x Si y P 3-y O 12 ceramic as solid electrolyte. Other innovations have followed, notably those for ZnÀ air, [47] ZnÀ Br 2 [48] and FeÀ air.…”

Section: Solid State Batteriesmentioning

confidence: 99%

“…The physical decoupling of the anode and cathode avoids problems of undesirable chemical reactions due to crossover between the anode and cathode sides, internal gas diffusion and dendritic shorting. The approach also allows fabrication of batteries with anodes of zinc, magnesium, iron and aluminium, solid ion conductors for which are practically unavailable [45–49] . The first battery with a mediator‐ion solid electrolyte was unveiled by Chen et al .…”

Section: Introductionmentioning

confidence: 99%

Electrochemistry: Retrospect and Prospects

Shukla

Kumar

2020

Israel Journal of Chemistry

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Since the beginning of modern civilization, static electricity and later current electricity have been used to get to grips with many situations. The publication of Gilbert's De magnete in 1600 triggered a series of inventions such as Leyden jar (1745: von Kleist; van Musschenbrock) and torsion balance (1784: Charles Coulomb). Current electricity was discovered at the end of the eighteenth century. Humphry Davy's remarkable prescience that electricity could overcome the normal ‘chemical affinity’ that holds elements together was a gamechanger, ushering in an explosion of electrochemical science. Today, electrochemistry has transformed human life in ways unimaginable only decades ago. This article is an effort to reflect upon the role of electrochemistry in our search for solutions to everyday problems and its continuing forays into areas spanning the mundane to outer space.

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“…Given the above situation, a unique battery-development strategy has recently been pursued since 2013 by employing a mediator-ion solid-electrolyte separator. [43][44][45][46][47][48][49] Over the last few years, a few aqueous battery systems have been successfully demonstrated with liquid or gaseous electrode materials. [43][44][45][46][47][48][49] Herein, we introduce first the ''mediator-ion'' battery concept, followed by the history, progress, and future prospects of this novel development strategy.…”

Section: Context and Scalementioning

confidence: 99%

“…The Li + -ion in these studies was termed an ''electrochemical messenger,'' since it conducts ionic species (Li + -ion) rather than reacts with the two electrodes during battery operation. 44,45 Since 2016, our group has demonstrated two aqueous battery systems (zinc-air and zinc-bromine batteries) based on an Li + -ion conductive solid electrolyte (LATP) and have termed this unique battery-development approach the mediator-ion strategy. 46,47 By strategically separating an alkaline zinc anode and an acidic air cathode by an LATP solid-electrolyte separator as schematically illustrated in Figure 2C (the cell is annotated as Zn(LiOH) k Li-SSE k air (H 3 PO 4 /LiH 2 PO 4 )), the Zn-air battery we developed exhibited a higher cell voltage than conventional alkaline Zn-air batteries due to the higher potential of oxygen reduction reaction under acidic condition relative to that under alkaline condition.…”

Section: Mediator-ion Batteries With Lithium-ion Solid Electrolytesmentioning

confidence: 99%

Electrochemical Energy Storage with Mediator-Ion Solid Electrolytes

Manthiram

2017

Joule

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This perspective presents a new battery concept with a ''mediator-ion'' solidstate electrolyte for the development of next-generation battery technologies to meet the growing needs of large-scale electrical energy storage. The uniqueness of this mediator-ion strategy is that the redox reactions at the anode and the cathode are sustained by a shuttling of a mediator ion between the anolyte and the catholyte through the solid-state electrolyte. The active anode and cathode materials can be in the form of solid, liquid, or gas. Use of a solid-electrolyte separator eliminates the common problem of chemical crossover between the anode and cathode, overcomes the dendrite problem when employing metal anodes, and offers the possibility of employing different liquid electrolytes at the anode and cathode. Based on these unique features, the mediator-ion battery concept offers a versatile approach for the development of a broad range of new battery systems.

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Using Li⁺ as the electrochemical messenger to fabricate an aqueous rechargeable Zn–Cu battery

Cited by 28 publications

References 45 publications

Long‐Life, High‐Voltage Acidic Zn–Air Batteries

Long‐Life, High‐Voltage Acidic Zn–Air Batteries

Electrochemistry: Retrospect and Prospects

Electrochemical Energy Storage with Mediator-Ion Solid Electrolytes

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Using Li+ as the electrochemical messenger to fabricate an aqueous rechargeable Zn–Cu battery

Cited by 28 publications

References 45 publications

Long‐Life, High‐Voltage Acidic Zn–Air Batteries

Long‐Life, High‐Voltage Acidic Zn–Air Batteries

Electrochemistry: Retrospect and Prospects

Electrochemical Energy Storage with Mediator-Ion Solid Electrolytes

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Product

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Using Li⁺ as the electrochemical messenger to fabricate an aqueous rechargeable Zn–Cu battery