Rechargeable Zn∣ZnSO4∣MnO2-type cells

Yamamoto, Takakazu; Shoji, Takayuki

doi:10.1016/s0020-1693(00)82175-1

Cited by 163 publications

(130 citation statements)

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“…[12][13][14][15][16][17][18][19][20][21][22][23][24] In aw eak acidic aqueous solution containing ZnSO 4 or ZnCl 2 ,t he coulombic efficiency is typicallyc lose to 100 %. For zinc metal, an additional advantage exists in that an aqueous electrolyte can be employedt oa chieveahighly reversible electrodeposition/stripping reactiono nt he negative electrode without dendrite formation.…”

Section: Introductionmentioning

confidence: 99%

“…For zinc metal, an additional advantage exists in that an aqueous electrolyte can be employedt oa chieveahighly reversible electrodeposition/stripping reactiono nt he negative electrode without dendrite formation. [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] The detailed reactionm echanism of these manganese dioxide structures with zinc ions in aqueous solution is still cryptic but wasc onventionally explained by the intercalation of zinc ions into the tunnelstructures. This is certainly advantageous compared to conventional cells employing Zn metal and alkaline electrolytes, which suffer from poor coulombic efficiency and dangerousd endrite formation,a lthough many advances have been made recently.…”

Section: Introductionmentioning

confidence: 99%

“…[25,26] For positive electrodes, manganese dioxide with various tunnel structuresh ave been exploreds o far because they are inexpensive and exhibit reversible reactions with plateau potentials around 1.3 V, delivering discharge capacities of 100-300mAh g À1 .T he manganese dioxide polymorphsw ith various tunnels tructures investigateds of ar span from b-MnO 2 (1 1), a-MnO 2 (2 2), g-MnO 2 and d-MnO 2 (1 1), and l-MnO 2 (1 3) to todorokite (3 3). [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] The detailed reactionm echanism of these manganese dioxide structures with zinc ions in aqueous solution is still cryptic but wasc onventionally explained by the intercalation of zinc ions into the tunnelstructures. [14][15][16][17][18][19][20] This is rather surprising, considering that electrode materials reported to reversibly intercalate aconsiderable amount of multivalent cationsi nto their structures are extremely rare.…”

Section: Introductionmentioning

confidence: 99%

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Critical Role of pH Evolution of Electrolyte in the Reaction Mechanism for Rechargeable Zinc Batteries

et al. 2016

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The reaction mechanism of α-MnO having 2×2 tunnel structure with zinc ions in a zinc rechargeable battery, employing an aqueous zinc sulfate electrolyte, was investigated by in situ monitoring structural changes and water chemistry alterations during the reaction. Contrary to the conventional belief that zinc ions intercalate into the tunnels of α-MnO , we reveal that they actually precipitate in the form of layered zinc hydroxide sulfate (Zn (OH) (SO )⋅5 H O) on the α-MnO surface. This precipitation occurs because unstable trivalent manganese disproportionates and is dissolved in the electrolyte during the discharge process, resulting in a gradual increase in the pH value of the electrolyte. This causes zinc hydroxide sulfate to crystallize from the electrolyte on the electrode surface. During the charge process, the pH value of the electrolyte decreases due to recombination of manganese on the cathode, leading to dissolution of zinc hydroxide sulfate back into the electrolyte. An analogous phenomenon is also observed in todorokite, a manganese dioxide polymorph with 3×3 tunnel structure that is an indication for the critical role of pH changes of the electrolyte in the reaction mechanism of this battery system.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Critical Role of pH Evolution of Electrolyte in the Reaction Mechanism for Rechargeable Zinc Batteries

et al. 2016

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“…Aqueous rechargeable zinc-ion batteries (ZIBs) are developed as a battery system, in which low-cost, non-toxic, and naturally abundant zinc metal is used as an anode and environment-friendly neutral aqueous Zn 2+ -containing solution serves as electrolyte [8]. In recent years, a series of high-performance cathode materials for ZIBs have also been studied such as Prussian blue analog [9][10][11], vanadium oxides [12][13][14][15][16][17][18][19], manganese oxides [20][21][22][23][24][25][26][27][28], and some metal sulfides [29][30][31]. Among these materials, MnO 2 is particularly concerned for its high theoretical specific capacity, low cost, eco-friendliness, and diverse crystallographic polymorphs (e.g., α-MnO 2 , δ-MnO 2 , and γ-MnO 2 ) [27,28,32].…”

Section: Introductionmentioning

confidence: 99%

Novel Insights into Energy Storage Mechanism of Aqueous Rechargeable Zn/MnO2 Batteries with Participation of Mn2+

et al. 2019

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HIGHLIGHTS• Pourbaix diagram of Mn-Zn-H 2 O system was used to analyze the charge-discharge processes of Zn/MnO 2 batteries.• Electrochemical reactions with the participation of various ions inside Zn/MnO 2 batteries were revealed.• A detailed explanation of phase evolution inside Zn/MnO 2 batteries was provided.ABSTRACT Aqueous rechargeable Zn/MnO 2 zinc-ion batteries (ZIBs) are reviving recently due to their low cost, non-toxicity, and natural abundance.However, their energy storage mechanism remains controversial due to their complicated electrochemical reactions. Meanwhile, to achieve satisfactory cyclic stability and rate performance of the Zn/MnO 2 ZIBs, Mn 2+ is introduced in the electrolyte (e.g., ZnSO 4 solution), which leads to more complicated reactions inside the ZIBs systems. Herein, based on comprehensive analysis methods including electrochemical analysis and Pourbaix diagram, we provide novel insights into the energy storage mechanism of Zn/MnO 2 batteries in the presence of Mn 2+ . A complex series of electrochemical reactions with the coparticipation of Zn 2+ , H + , Mn 2+ , SO 4 2− , and OH − were revealed. During the first discharge process, co-insertion of Zn 2+ and H + promotes the transformation of MnO 2 into Zn x MnO 4 , MnOOH, and Mn 2 O 3 , accompanying with increased electrolyte pH and the formation of ZnSO 4 ·3Zn(OH) 2 ·5H 2 O. During the subsequent charge process, Zn x MnO 4 , MnOOH, and Mn 2 O 3 revert to α-MnO 2 with the extraction of Zn 2+ and H + , while ZnSO 4 ·3Zn(OH) 2 ·5H 2 O reacts with Mn 2+ to form ZnMn 3 O 7 ·3H 2 O. In the following charge/discharge processes, besides aforementioned electrochemical reactions, Zn 2+ reversibly insert into/extract from α-MnO 2 , Zn x MnO 4 , and ZnMn 3 O 7 ·3H 2 O hosts; ZnSO 4 ·3Zn(OH) 2 ·5H 2 O, Zn 2 Mn 3 O 8 , and ZnMn 2 O 4 convert mutually with the participation of Mn 2+ . This work is believed to provide theoretical guidance for further research on high-performance ZIBs.

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“…These inactive dendrites or passivation products block the transfer of ions and slow the ion diffusion process, leading to a pronounced anodic capacity fading. [4][5][6][7][8][9][10] In addition, the dendrites can penetrate into the separator and result in an interior short circuit. In the 1990's, the neutral ZnSO 4 solution has been exploited as a replacement for the alkaline electrolyte with some promising results.…”

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confidence: 99%

Enhancement on Cycle Performance of Zn Anodes by Activated Carbon Modification for Neutral Rechargeable Zinc Ion Batteries

Xu²,

Han

et al. 2015

J. Electrochem. Soc.

193

106

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A novel composite anode is prepared by mixing zinc particles with activated carbon (AC) to improve the cycle performance of the neutral rechargeable zinc ion batteries. Galvanostatic charge/discharge cycling tests indicate that the capacity retention of the cell with adding 12 wt% activated carbon in Zn anode is 85.6% after 80 cycles, which is much higher than that of 56.7% for the cell using unmodified Zn anode. X-ray diffraction analysis indicates that the addition of activated carbon can suppress the formation of inactive basic zinc sulfates (Zn 4 SO 4 (OH) 6 · nH 2 0). Morphology, elemental mapping and N 2 adsorption and desorption measurements indicate that the pores of activated carbon can accommodate the deposition of Zn dendrites and insoluble anodic products. As a result, the cycle stability of the Zn anode has been greatly enhanced by activated carbon modification. Compared with other widely used metal anodes, such as lead, cadmium and rare metal mesh, zinc is a non-toxic, abundant, and low cost resource. Since the middle of 19th century, zinc has been used as an excellent anodic material for Zn/Mn, Zn/Ni and Zn/Ag batteries. 1With features such as low cost, environmental benignity and good specific energy, the Zn/MnO 2 system has traditionally provided one of the most popular primary cells for a great number of applications. These attractive characteristics, combined with the growing need of high-performance batteries, have prompted considerable efforts to change its primary nature into a secondary one.In the early 1980s, a rechargeable alkaline Zn/MnO 2 (RAM) has been developed. [1][2][3][4] Over the past three decades, the improvement of this technology has progressed rapidly. However, even now the rechargeability of batteries based on Zn anode in alkaline media remains a significant challenge. It is well known that the capacity of rechargeable alkaline Zn/MnO 2 batteries using both KOH and LiOH electrolytes will dramatically drop to below 50% or even worse at only 40 cycles, meanwhile the columbic efficiency decreases to below 50%. 2,4 It has been pointed out by Y. Shen and K. Kordesch 4 that the capacity fading and columbic efficiency loss of rechargeable alkaline Zn/MnO 2 batteries are mainly attributed to the formation of dendrites and passivation products in Zn anodes. These inactive dendrites or passivation products block the transfer of ions and slow the ion diffusion process, leading to a pronounced anodic capacity fading. [4][5][6][7][8][9][10] In addition, the dendrites can penetrate into the separator and result in an interior short circuit. In the 1990's, the neutral ZnSO 4 solution has been exploited as a replacement for the alkaline electrolyte with some promising results.11-13 Kim et al. 13 reported that addition of 0.1∼0.5 mol L −1 MnSO 4 to 2 mol L −1 ZnSO 4 electrolyte greatly improved the cycle performance of rechargeable Zn/MnO 2 cells. The batteries with aqueous ZnSO 4 electrolyte can be cycled in the potential range of 1.0-1.9 V, where a two-step, two-electron charge-discharge ...

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Rechargeable Zn∣ZnSO4∣MnO2-type cells

Cited by 163 publications

References 2 publications

Critical Role of pH Evolution of Electrolyte in the Reaction Mechanism for Rechargeable Zinc Batteries

Critical Role of pH Evolution of Electrolyte in the Reaction Mechanism for Rechargeable Zinc Batteries

Novel Insights into Energy Storage Mechanism of Aqueous Rechargeable Zn/MnO2 Batteries with Participation of Mn2+

Enhancement on Cycle Performance of Zn Anodes by Activated Carbon Modification for Neutral Rechargeable Zinc Ion Batteries

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