Freestanding graphene/VO2 composite films for highly stable aqueous Zn-ion batteries with superior rate performance

Dai, Xianzhe; Wan, Fang; Zhang, Linlin; Cao, Hongmei; Niu, Zhiqiang

doi:10.1016/j.ensm.2018.07.022

Cited by 414 publications

(263 citation statements)

References 63 publications

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“…Recently, VO 2 has been explored as a cathode for ZIBs in combination with various electrolytes. Several reports have proposed that VO 2 is able to reversibly store Zn 2+ when an aqueous Zn(CF 3 SO 3 ) 2 electrolyte is used, based on the pseudocapacitive behavior and ultrafast Zn 2+ kinetics into the unique tunnels of VO 2 (B) . However, when an aqueous ZnSO 4 electrolyte is used, it appears to follow a very different mechanism.…”

Section: Mechanistic Insightsmentioning

confidence: 99%

Mechanistic Insight into the Electrochemical Performance of Zn/VO₂ Batteries with an Aqueous ZnSO₄ Electrolyte

Ganapathy

et al. 2019

Advanced Energy Materials

227

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Zn-H 2 O fuel cells, [8] etc.), rechargeable aqueous Zn-ion batteries (ZIBs) with a mild electrolyte are particularly attractive as zinc is more compatible with water than alkaline metals, Zn-ions are divalent, and the production and recycling of these batteries is relatively simple. [9][10][11][12] A variety of manganese dioxide (MnO 2 ) polymorphs (α-, β-, γ-, δ-, and amorphous) have been investigated as cathodes materials for ZIBs. [10,11,[13][14][15][16][17][18][19] Several studies have demonstrated that the storage capacity of MnO 2 in a neutral or mildly acidic aqueous electrolyte is partly induced by a reversible Zn 2+ insertion/extraction reaction and partly by the reversible H + insertion/extraction. [10,11,19] This process is governed by the reversible phase transition of the MnO 2 polymorphs from a tunneled to layered structure, driven by the electrochemical reaction. During this phase transition, even though the crystalline structure is maintained, Mn 3+ in the tunnel chains are reduced to soluble Mn 2+ leading to a capacity fading, a short cycle life and low Coulombic efficiency of aqueous Zn/MnO 2 batteries. [17,20] To prevent this dissolution of Mn ions, alternative electrolytes were identified, for example, Zhang et al., found that by using a Zn(CF 3 SO 3 ) 2 aqueous electrolyte, Mn-ion dissolution was suppressed and a high capacity retention with a ZnMn 2 O 4 cathode was achieved. [21] Alternatively by using a MnSO 4 additive to a mild ZnSO 4 aqueous electrolyte, Pan et al. reported that the Mn 2+ dissolution in the aqueous Zn/MnO 2 electrolyte was inhibited. [11] Though research into MnO 2 cathodes for aqueous ZIBs has gained momentum, it is of great importance to develop alternative high capacity cathode materials for ZIBs that are stable in an aqueous electrolyte.Very recently, vanadium oxide and its related compounds have been reported as cathodes for ZIBs, showing higher energy densities and better capacity retention compared to MnO 2 cathodes. Senguttuvan et al. reported the reversible Zn 2+ insertion/extraction process in a V 2 O 5 cathode for a nonaqueous ZIBs. [22] Kundu et al. developed a highly stable vanadium bronze (Zn 0.25 V 2 O 5 ·nH 2 O) cathode for aqueous ZIBs, which displayed a high energy density and capacity retention through a reversible Zn 2+ (de)intercalation process. [12] In addition, LiV 3 O 8 , [23] H 2 V 3 O 8 , [24] and V 2 S [25] cathodes exhibit good capacity reversibility and power density for aqueous ZIBs. Although Oberholzer et al. [26] observed a proton intercalation Rechargeable aqueous zinc-ion batteries (ZIBs) are promising for cheap stationary energy storage. Challenges for Zn-ion insertion hosts are the large structural changes of the host structure upon Zn-ion insertion and the divalent Zn-ion transport, challenging cycle life and power density respectively. Here a new mechanism is demonstrated for the VO 2 cathode toward proton insertion accompanied by Zn-ion storage through the reversible deposition of Zn 4 (OH) 6 SO 4 ·5H 2 O on the cathode surface, sup...

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Section: Mechanistic Insightsmentioning

confidence: 99%

Mechanistic Insight into the Electrochemical Performance of Zn/VO₂ Batteries with an Aqueous ZnSO₄ Electrolyte

Ganapathy

et al. 2019

Advanced Energy Materials

227

165

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“…In fact, the GO, rGO, or other C-content materials composite with vanadium oxide lift the performance of the ZIBs significantly which are all attributed to the improvement of electrical conductivity. [9,10,17] Nevertheless, the capacitances of VO-GO and VO-LGO are higher than that of the V-HGO indicating that there should exist another Zn 2+ storage mechanism for the tested high capacity of GO composite. [24] In my opinion, the functional groups on the surface of GO take part in the reaction to promote the performance of the ZIBs, similar to the ORR pathways in the zinc-air battery.…”

Section: Pseudo-zn-air and Zn-ion Intercalation Dual Mechanisms To Rementioning

confidence: 99%

“…Therefore, it is crucial to develop suitable cathode materials which are suitable for Zn 2+ ions insertion/extraction and possess rich oxygen-containing functional groups.Recently, lots of reports indicate that the vanadium oxide and graphene oxide (GO) composite demonstrate the enhanced electrochemical properties in ZIBs owing to the high conductivity of the graphene network, but rarely discussion about the effect of the surface function groups on the battery performances. [9][10][11][12] In addition, the cathode materials with crystal water display a very good performance, especially for bilayered vanadium pentoxide. In the most studies, the researchers attribute the good performance to the stable structure and water molecules between the layers function like a "lubricant" to facilitate fast Zn-ion transport.…”

mentioning

confidence: 99%

Pseudo‐Zn–Air and Zn‐Ion Intercalation Dual Mechanisms to Realize High‐Areal Capacitance and Long‐Life Energy Storage in Aqueous Zn Battery

Wei

Yang

et al. 2019

Advanced Energy Materials

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intrinsically safe and low cost. [3,4] In terms of structure, Zn batteries can be classified into two types. [5] One is the closed system, such as Zn-Ni, Zn-Mn, and Zn-ion batteries (ZIBs) using weak acidic or mild electrolytes. Notably, ZIBs have recently received intensive attention due to the rapid and reversible Zn 2+ ions insertion/ extraction in cathode materials, which contribute to the high-rate and long-life performances. However, the practical application of ZIBs is plagued by the relatively low energy density and the unclear reaction mechanism. The other type is the half-open system, in which the most typical is the Zn-air batteries (ZABs). Since oxygen directly absorbed from the air and the four electrons transfer processes, the energy densities of ZABs are quite high in general. But the sluggish reaction kinetics of the disconnection OO bond in ZABs usually causes a waste of energy in charge and poor cycling stability. As reported, the oxygen reduction reaction (ORR) occurring with the OH groups on surface of the material is much more thermodynamically and kinetically favored than the other three ORR processes. [6][7][8] If the Zn 2+ ions insertion/ extraction and the last pathway in ORR reactions (the reduction from OH to OH-) can be combined in aqueous ZIBs, the high rate, high capacity and long cycling life batteries could be achieved simultaneously. Therefore, it is crucial to develop suitable cathode materials which are suitable for Zn 2+ ions insertion/extraction and possess rich oxygen-containing functional groups.Recently, lots of reports indicate that the vanadium oxide and graphene oxide (GO) composite demonstrate the enhanced electrochemical properties in ZIBs owing to the high conductivity of the graphene network, but rarely discussion about the effect of the surface function groups on the battery performances. [9][10][11][12] In addition, the cathode materials with crystal water display a very good performance, especially for bilayered vanadium pentoxide. In the most studies, the researchers attribute the good performance to the stable structure and water molecules between the layers function like a "lubricant" to facilitate fast Zn-ion transport. [9,13] Herein, we report a bulk composite, which is composed of vanadium oxide (V 5 O 12 ·6H 2 O) and graphene oxide via sol-gel process, as the Aqueous zinc batteries are considered as promising alternatives to lithium ion batteries owing to their low cost and high safety. However, the developments of state-of-the-art zinc-ion batteries (ZIB) and zinc-air batteries (ZAB) are limited by the unsatisfied capacities and poor cycling stabilities, respectively. It is of significance in utilizing the long-cycle life of ZIB and high capacity of ZAB to exploit advanced energy storage systems. Herein, a bulk composite of graphene oxide and vanadium oxide (V 5 O 12 ·6H 2 O) as cathode material for aqueous Zn batteries in a mild electrolyte is employed. The battery performance is demonstrated to arise from a combination of the reversible cations insert...

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“…0.8 V), [8] which severely limits their energy density.F urthermore,u nlike the well-established energystorage mechanisms in lithium/sodium-ion batteries,t he energy-storage mechanisms of vanadium-based aqueous ZIBs are under debate.B esides the traditional Zn 2+ ion insertion/extraction mechanism, an H + insertion/extraction process was also observed in aZ n/NaV 3 O 8 ·1.5 H 2 Os ystem. [9] Despite this difference,these energy-storage mechanisms are based on redox reactions of (vanadium) cations.H owever, until now,a nionic redox reactions,w hich have occurred in some cases of batteries based on organic electrolytes and could enhance the capacity and voltage of the corresponding batteries, [10] have not been observed in aqueous ZIBs.Ifredox reactions of (oxygen) anions could be realized in vanadiumbased aqueous ZIBs,their energy density would be enhanced significantly.…”

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confidence: 99%

Reversible Oxygen Redox Chemistry in Aqueous Zinc‐Ion Batteries

et al. 2019

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Rechargeable aqueous zinc-ion batteries (ZIBs) are promising energy-storage devices owing to their low cost and high safety.H owever,t heir energy-storage mechanisms are complex and not well established. Recent energy-storage mechanisms of ZIBs usually depend on cationic redox processes.A nionic redox processes have not been observed owingt ot he limitations of cathodes and electrolytes.H erein, we describe highly reversible aqueous ZIBs based on layered VOPO 4 cathodes and awater-in-salt electrolyte.Suchbatteries displayr eversible oxygen redoxc hemistry in ah igh-voltage region. The oxygen redoxp rocess not only provides about 27 %a dditional capacity,b ut also increases the average operating voltage to around 1.56 V, thus increasing the energy density by approximately 36 %. Furthermore,t he oxygen redoxprocess promotes the reversible crystal-structure evolution of VOPO 4 during charge/discharge processes,t hus resulting in enhanced rate capability and cycling performance.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Freestanding graphene/VO2 composite films for highly stable aqueous Zn-ion batteries with superior rate performance

Cited by 414 publications

References 63 publications

Mechanistic Insight into the Electrochemical Performance of Zn/VO₂ Batteries with an Aqueous ZnSO₄ Electrolyte

Mechanistic Insight into the Electrochemical Performance of Zn/VO₂ Batteries with an Aqueous ZnSO₄ Electrolyte

Pseudo‐Zn–Air and Zn‐Ion Intercalation Dual Mechanisms to Realize High‐Areal Capacitance and Long‐Life Energy Storage in Aqueous Zn Battery

Reversible Oxygen Redox Chemistry in Aqueous Zinc‐Ion Batteries

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Freestanding graphene/VO2 composite films for highly stable aqueous Zn-ion batteries with superior rate performance

Cited by 414 publications

References 63 publications

Mechanistic Insight into the Electrochemical Performance of Zn/VO2 Batteries with an Aqueous ZnSO4 Electrolyte

Mechanistic Insight into the Electrochemical Performance of Zn/VO2 Batteries with an Aqueous ZnSO4 Electrolyte

Pseudo‐Zn–Air and Zn‐Ion Intercalation Dual Mechanisms to Realize High‐Areal Capacitance and Long‐Life Energy Storage in Aqueous Zn Battery

Reversible Oxygen Redox Chemistry in Aqueous Zinc‐Ion Batteries

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Mechanistic Insight into the Electrochemical Performance of Zn/VO₂ Batteries with an Aqueous ZnSO₄ Electrolyte

Mechanistic Insight into the Electrochemical Performance of Zn/VO₂ Batteries with an Aqueous ZnSO₄ Electrolyte