Ultrathin δ-MnO2 nanosheets as cathode for aqueous rechargeable zinc ion battery

Guo, Cong; Liu, Huimin; Li, Jingfa; Hou, Zhiguo; Liang, Jianwen; Zhou, Jie; Zhu, Yongchun; Qian, Yitai

doi:10.1016/j.electacta.2019.03.008

Cited by 229 publications

(151 citation statements)

References 40 publications

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“…Based on the total mass of active P‐MnO 2‐ x arrays, the as‐prepared flexible battery device possesses a maximum energy density of 393.6 Wh kg −1 (aqueous) and 369.5 Wh kg −1 (solid state) at a current density of 0.5 A g −1 , and remains 211.6 Wh kg −1 (aqueous) and 143.6 Wh kg −1 (solid state) at 8.0 A g −1 , again confirming the excellent rate performance of P‐MnO 2‐ x @VMG//Zn@VMG battery. These values are higher than those of recently reported cathodes for aqueous ZIBs, like the δ‐MnO 2 //Zn battery (320 Wh kg −1 ), MnO//Zn battery (383.8 Wh kg −1 ), ZnMn 2 O 4 //Zn battery (202 Wh kg −1 ), VS 2 //Zn battery (123 Wh kg −1 ), V 2 O 5 //Zn battery (237.2 Wh kg −1 ), H 2 V 3 O 8 //Zn battery (250 Wh kg −1 ), and MoS 2 //Zn battery (148.2 Wh kg −1 ) . In the meantime, even at 8.0 A g −1 , our P‐MnO 2‐ x @VMG//Zn@VMG battery could deliver a maximum power density of 10.6 kW kg −1 (aqueous) and 8.5 kW kg −1 (solid state), which is superior to MnO 2 //Bi 2 O 3 ASC (3.37 kW kg −1 ), Co 3 O 4 @NiO//Zn battery (3.45 kW kg −1 ), MnO 2 //AG ASC (7.5 kW kg −1 ), and δ‐MNOH//Zn battery (7.7 kW kg −1 ) .…”

Section: Resultsmentioning

confidence: 62%

Introducing Oxygen Defects into Phosphate Ions Intercalated Manganese Dioxide/Vertical Multilayer Graphene Arrays to Boost Flexible Zinc Ion Storage

et al. 2020

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Designed and fabricated flexible high-performance MnO 2 cathode materials are highly desirable for developing advanced rechargeable Zn-MnO 2 batteries. In this work, a facile phosphorization process is reported for introducing oxygen defects into phosphate ions intercalated manganese dioxide/vertical multilayer graphene (VMG) arrays, forming an integrated P-MnO 2-x @VMG cathode. The oxygen defects and phosphate ions intercalation are achieved simultaneously via phosphorization. The former can increase the electrical conductivity of MnO 2 , while the latter is able to expand its interlayer spacing accelerating ion transfer. Furthermore, flexible VMG conductive networks provide excellent peripheral charge transfer and endow the cathode with favorable mechanical strength. Benefiting from these virtues, the obtained P-MnO 2-x @VMG cathode demonstrates high capacity (302.8 mAh g -1 at 0.5 A g -1 ) and long-term cycling stability (>90% capacity retention after 1000 cycles at 2.0 A g -1 ) in aqueous electrolytes. More impressively, the P-MnO 2-x @VMG cathode exhibits a high energy density of 369.5 Wh kg -1 in quasi-solid-state flexible devices (P-MnO 2-x @VMG//Zn@VMG), and thereby shows great prospects for applications in wearable electronics. This work demonstrates a new synergistic way to construct high-performance electrodes for energy storage toward divalent metal ions.

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Section: Resultsmentioning

confidence: 62%

Introducing Oxygen Defects into Phosphate Ions Intercalated Manganese Dioxide/Vertical Multilayer Graphene Arrays to Boost Flexible Zinc Ion Storage

et al. 2020

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“…Taking the N‐MnO 2– x @TiC/C electrode for example, two main reduction peaks at around 1.32 and 1.2 V are noticed due to the intercalation reactions of H + and Zn 2+ into N‐MnO 2– x host . Typically, it is reported that the broad peak at 1.32 V corresponds to the reversible intercalation/deintercalation of H + into/from the interlayer of N‐MnO 2– x host .…”

Section: Resultsmentioning

confidence: 99%

Defect Promoted Capacity and Durability of N‐MnO_2–_x Branch Arrays via Low‐Temperature NH₃ Treatment for Advanced Aqueous Zinc Ion Batteries

Zhang

Deng

Luo

et al. 2019

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184

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Defect engineering (doping and vacancy) has emerged as a positive strategy to boost the intrinsic electrochemical reactivity and structural stability of MnO2‐based cathodes of rechargeable aqueous zinc ion batteries (RAZIBs). Currently, there is no report on the nonmetal element doped MnO2 cathode with concomitant oxygen vacancies, because of its low thermal stability with easy phase transformation from MnO2 to Mn3O4 (≥300 °C). Herein, for the first time, novel N‐doped MnO2–x (N‐MnO2–x) branch arrays with abundant oxygen vacancies fabricated by a facile low‐temperature (200 °C) NH3 treatment technology are reported. Meanwhile, to further enhance the high‐rate capability, highly conductive TiC/C nanorods are used as the core support for a N‐MnO2–x branch, forming high‐quality N‐MnO2–x@TiC/C core/branch arrays. The introduced N dopants and oxygen vacancies in MnO2 are demonstrated by synchrotron radiation technology. By virtue of an integrated conductive framework, enhanced electron density, and increased surface capacitive contribution, the designed N‐MnO2–x@TiC/C arrays are endowed with faster reaction kinetics, higher capacity (285 mAh g−1 at 0.2 A g−1) and better long‐term cycles (85.7% retention after 1000 cycles at 1 A g−1) than other MnO2‐based counterparts (55.6%). The low‐temperature defect engineering sheds light on construction of advanced cathodes for aqueous RAZIBs.

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“…Then, the fast capacity fading occurred after 20 cycles, because the dissolved Mn 2+ ions migrate to the anode along with Zn 2+ together during the charge process, and thereby, less Mn 2+ ions stay in the cathode to be oxidized. [ 6,34,35 ] This also proves the poor reversibility of the MnO 2 /Mn 2+ reaction. In the case of the EMS3 cathode, the EMS can adsorb the Mn 2+ , thereby reducing the concentration polarization near the cathode and enhancing the reversibility of the MnO 2 /Mn 2+ reaction.…”

Section: Resultsmentioning

confidence: 87%

Mn²⁺ Ions Confined by Electrode Microskin for Aqueous Battery beyond Intercalation Capacity

Liu

Zhi

Sedighi

et al. 2020

Advanced Energy Materials

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In aqueous rechargeable zinc–manganese dioxide batteries (ZMBs), some irreversible side reactions, such as Mn2+ dissolution, often lead to capacity fading over cycling. These side reactions play a crucial role in the capacity and cycle performance of the battery. The implementation of a bionic electrode microskin (EMS) composed of collagen hydrolysate to convert the irreversible side reactions into reversible reactions is reported. The proposed EMS effectively adsorbs and confines the Mn2+ ions around the cathode through van der Waals forces, hydrogen bonds, and/or ionic interactions, which makes the MnO2/Mn2+ reactions reversible during the charge/discharge process. Such Mn2+ dissolution reactions, with an ultrahigh theoretical capacity (617 mAh g‐1), contribute a large amount of capacity, ≈44% of the total specific capacity at a low scan rate. Based on these fundamental findings, the assembled ZMBs with an EMS display an unprecedented discharge capacity of 415 mAh g‐1 at 20 mA g‐1, which overcomes the theoretical capacity (308 mAh g‐1) limitation of the Zn2+ intercalation mechanism. More significantly, the EMS on all α‐, β‐, and γ‐MnO2 cathodes exhibits similar high capacity beyond the theoretical capacity of Zn intercalation and capacity retention enhancement after 3000 cycles.

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Ultrathin δ-MnO2 nanosheets as cathode for aqueous rechargeable zinc ion battery

Cited by 229 publications

References 40 publications

Introducing Oxygen Defects into Phosphate Ions Intercalated Manganese Dioxide/Vertical Multilayer Graphene Arrays to Boost Flexible Zinc Ion Storage

Introducing Oxygen Defects into Phosphate Ions Intercalated Manganese Dioxide/Vertical Multilayer Graphene Arrays to Boost Flexible Zinc Ion Storage

Defect Promoted Capacity and Durability of N‐MnO_2–_x Branch Arrays via Low‐Temperature NH₃ Treatment for Advanced Aqueous Zinc Ion Batteries

Mn²⁺ Ions Confined by Electrode Microskin for Aqueous Battery beyond Intercalation Capacity

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Ultrathin δ-MnO2 nanosheets as cathode for aqueous rechargeable zinc ion battery

Cited by 229 publications

References 40 publications

Introducing Oxygen Defects into Phosphate Ions Intercalated Manganese Dioxide/Vertical Multilayer Graphene Arrays to Boost Flexible Zinc Ion Storage

Introducing Oxygen Defects into Phosphate Ions Intercalated Manganese Dioxide/Vertical Multilayer Graphene Arrays to Boost Flexible Zinc Ion Storage

Defect Promoted Capacity and Durability of N‐MnO2–x Branch Arrays via Low‐Temperature NH3 Treatment for Advanced Aqueous Zinc Ion Batteries

Mn2+ Ions Confined by Electrode Microskin for Aqueous Battery beyond Intercalation Capacity

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Product

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Defect Promoted Capacity and Durability of N‐MnO_2–_x Branch Arrays via Low‐Temperature NH₃ Treatment for Advanced Aqueous Zinc Ion Batteries

Mn²⁺ Ions Confined by Electrode Microskin for Aqueous Battery beyond Intercalation Capacity