Stable Zinc Anodes Enabled by Zincophilic Cu Nanowire Networks

AbstractZn-based electrochemical energy storage (EES) systems have received tremendous attention in recent years, but their zinc anodes are seriously plagued by the issues of zinc dendrite and side reactions (e.g., corrosion and hydrogen evolution). Herein, we report a novel strategy of employing zincophilic Cu nanowire networks to stabilize zinc anodes from multiple aspects. According to experimental results, COMSOL simulation and density functional theory calculations, the Cu nanowire networks covering on zinc anode surface not only homogenize the surface electric field and Zn2+ concentration field, but also inhibit side reactions through their hydrophobic feature. Meanwhile, facets and edge sites of the Cu nanowires, especially the latter ones, are revealed to be highly zincophilic to induce uniform zinc nucleation/deposition. Consequently, the Cu nanowire networks-protected zinc anodes exhibit an ultralong cycle life of over 2800 h and also can continuously operate for hundreds of hours even at very large charge/discharge currents and areal capacities (e.g., 10 mA cm−2 and 5 mAh cm−2), remarkably superior to bare zinc anodes and most of currently reported zinc anodes, thereby enabling Zn-based EES devices to possess high capacity, 16,000-cycle lifespan and rapid charge/discharge ability. This work provides new thoughts to realize long-life and high-rate zinc anodes.

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Nitrogen-rich covalent organic frameworks with multiple carbonyls for high-performance sodium batteries

Nature Communications ◽

10.1038/s41467-019-13739-5 ◽

2020 ◽

Vol 11 (1) ◽

Cited By ~ 32

Author(s):

Ruijuan Shi ◽

Luojia Liu ◽

Yong Lu ◽

Chenchen Wang ◽

Yixin Li ◽

...

Keyword(s):

High Performance ◽

Density Functional ◽

Specific Capacity ◽

Density Functional Theory Calculations ◽

Rechargeable Batteries ◽

High Rate ◽

Ex Situ ◽

Covalent Organic Frameworks ◽

Rate Performance ◽

Practical Applications

AbstractCovalent organic frameworks with designable periodic skeletons and ordered nanopores have attracted increasing attention as promising cathode materials for rechargeable batteries. However, the reported cathodes are plagued by limited capacity and unsatisfying rate performance. Here we report a honeycomb-like nitrogen-rich covalent organic framework with multiple carbonyls. The sodium storage ability of pyrazines and carbonyls and the up-to twelve sodium-ion redox chemistry mechanism for each repetitive unit have been demonstrated by in/ex-situ Fourier transform infrared spectra and density functional theory calculations. The insoluble electrode exhibits a remarkably high specific capacity of 452.0 mAh g−1, excellent cycling stability (~96% capacity retention after 1000 cycles) and high rate performance (134.3 mAh g−1 at 10.0 A g−1). Furthermore, a pouch-type battery is assembled, displaying the gravimetric and volumetric energy density of 101.1 Wh kg−1cell and 78.5 Wh L−1cell, respectively, indicating potentially practical applications of conjugated polymers in rechargeable batteries.

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Encapsulating Metal-Organic-Foam Derived Nanocages into a Microcapsule for Shuttle Effect-Suppressive Lithium-Sulfur Batteries

Nanomaterials ◽

10.3390/nano12020236 ◽

2022 ◽

Vol 12 (2) ◽

pp. 236

Author(s):

Jinyun Liu ◽

Yajun Zhu ◽

Junfei Cai ◽

Yan Zhong ◽

Tianli Han ◽

...

Keyword(s):

Density Functional ◽

Coulombic Efficiency ◽

Specific Capacity ◽

Density Functional Theory Calculations ◽

Binding Energies ◽

High Rate ◽

Lithium Storage ◽

Shuttle Effect ◽

Metal Organic ◽

High And Low Temperatures

Long-term stable secondary batteries are highly required. Here, we report a unique microcapsule encapsulated with metal organic foams (MOFs)-derived Co3O4 nanocages for a Li-S battery, which displays good lithium-storage properties. ZIF-67 dodecahedra are prepared at room temperature then converted to porous Co3O4 nanocages, which are infilled into microcapsules through a microfluidic technique. After loading sulfur, the Co3O4/S-infilled microcapsules are obtained, which display a specific capacity of 935 mAh g−1 after 200 cycles at 0.5C in Li-S batteries. A Coulombic efficiency of about 100% is achieved. The constructed Li-S battery possesses a high rate-performance during three rounds of cycling. Moreover, stable performance is verified under both high and low temperatures of 50 °C and −10 °C. Density functional theory calculations show that the Co3O4 dodecahedra display large binding energies with polysulfides, which are able to suppress shuttle effect of polysulfides and enable a stable electrochemical performance.

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Electron Transfer to CO2 during Adsorption at the Metal | Solution Interface

10.26434/chemrxiv.8187629.v1 ◽

2019 ◽

Author(s):

Michal Bajdich ◽

Meredith Fields ◽

Leanne D. Chen ◽

Robert B. Sandberg ◽

Karen Chan ◽

...

Keyword(s):

Electron Transfer ◽

Density Functional ◽

Degrees Of Freedom ◽

Adsorption Process ◽

Density Functional Theory Calculations ◽

High Rate ◽

Generalized Gradient ◽

Functional Theory ◽

Generalized Gradient Approximation ◽

Solution Interface

We estimate the rate of electron transfer to CO2 at the Au(211)|water interface during adsorption in an electrochemical environment under negative potentials. Based on density functional theory calculations at the generalized gradient approximation, hybrid, and GW levels of theory, we find electron transfer to adsorbed *CO2 to be very facile. This high rate of transfer is estimated by the energy distribution of the adsorbate-induced density of states as well as from the interaction between diabatic states representing neutral and negatively charged CO2. Up to 0.54 electrons is transferred to CO2, and this charge adiabatically increases with the bending angle to a lower limit of 140°. We conclude that this rate of electron transfer is extremely fast compared to the timescale of the nuclear degrees of freedom, that is, the adsorption process

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Self-Supported Sheets-on-Wire CuO@Ni(OH)2/Zn(OH)2 Nanoarrays for High-Performance Flexible Quasi-Solid-State Supercapacitor

Processes ◽

10.3390/pr9040680 ◽

2021 ◽

Vol 9 (4) ◽

pp. 680

Author(s):

Jianyang Jiang ◽

Xiong Xiong Liu ◽

Jiayu Han ◽

Ke Hu ◽

Jun Song Chen

Keyword(s):

Solid State ◽

Energy Density ◽

Electrode Materials ◽

Red Light ◽

High Capacity ◽

High Energy ◽

High Rate ◽

High Energy Density ◽

Supercapacitor Application ◽

Charge Discharge

Transition metal hydroxides have attracted a lot of attention as the electrode materials for supercapacitors owing to their relatively high theoretical capacity, low cost, and facile preparation methods. However, their low intrinsic conductivity deteriorates their high-rate performance and cycling stability. Here, self-supported sheets-on-wire CuO@Ni(OH)2/Zn(OH)2 (CuO@NiZn) composite nanowire arrays were successfully grown on copper foam. The CuO nanowire backbone provided enhanced structural stability and a highly efficient electron-conducting pathway from the active hydroxide nanosheets to the current collector. The resulting CuO@NiZn as the battery-type electrode for supercapacitor application delivered a high capacity of 306.2 mAh g−1 at a current density of 0.8 A g−1 and a very stable capacity of 195.1 mAh g−1 at 4 A g−1 for 10,000 charge–discharge cycles. Furthermore, a quasi-solid-state hybrid supercapacitor (qss HSC) was assembled with active carbon, exhibiting 125.3 mAh g−1 at 0.8 A g−1 and a capacity of 41.6 mAh g−1 at 4 A g−1 for 5000 charge–discharge cycles. Furthermore, the qss HSC was able to deliver a high energy density of about 116.0 Wh kg−1. Even at the highest power density of 7.8 kW kg−1, an energy density of 20.5 Wh kg−1 could still be obtained. Finally, 14 red light-emitting diodes were lit up by a single qss HSC at different bending states, showing good potential for flexible energy storage applications.

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Facile Electron Transfer to CO2 during Adsorption at the Metal | Solution Interface

10.26434/chemrxiv.8187629 ◽

2019 ◽

Author(s):

Joseph Gauthier ◽

Meredith Fields ◽

Michal Bajdich ◽

Leanne D. Chen ◽

Robert B. Sandberg ◽

...

Keyword(s):

Electron Transfer ◽

Density Functional ◽

Degrees Of Freedom ◽

Adsorption Process ◽

Density Functional Theory Calculations ◽

High Rate ◽

Generalized Gradient ◽

Functional Theory ◽

Generalized Gradient Approximation ◽

Solution Interface

We estimate the rate of electron transfer to CO2 at the Au (211)|water interface during adsorption in an electrochemical environment under reducing potentials. Based on density functional theory calculations at the generalized gradient approximation and hybrid levels of theory, we find electron transfer to adsorbed *CO2 to be very facile. This high rate of transfer is estimated by the energy distribution of the adsorbate-induced density of states as well as from the interaction between diabatic states representing neutral and negatively charged CO2. Up to 0.62 electrons are transferred to CO2, and this charge adiabatically increases with the bending angle to a lower limit of 137°. We conclude that this rate of electron transfer is extremely fast compared to the timescale of the nuclear degrees of freedom, that is, the adsorption process.

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Nanometer-size Na cluster formation in micropore of hard carbon as origin of higher-capacity Na-ion battery

npj Computational Materials ◽

10.1038/s41524-021-00515-7 ◽

2021 ◽

Vol 7 (1) ◽

Author(s):

Yong Youn ◽

Bo Gao ◽

Azusa Kamiyama ◽

Kei Kubota ◽

Shinichi Komaba ◽

...

Keyword(s):

Density Functional ◽

Cluster Formation ◽

High Capacity ◽

Density Functional Theory Calculations ◽

High Energy ◽

High Energy Density ◽

Hard Carbon ◽

Functional Theory ◽

Nanometer Size ◽

Li Ion

AbstractDevelopment of high-energy-density anode is crucial for practical application of Na-ion battery as a post Li-ion battery. Hard carbon (HC), though a promising anode candidate, still has bottlenecks of insufficient capacity and unclear microscopic picture. Usage of the micropore has been recently discussed, however, the underlying sodiation mechanism is still controversial. Herein we examined the origin for the high-capacity sodiation of HC, based on density functional theory calculations. We demonstrated that nanometer-size Na cluster with 3–6 layers is energetically stable between two sheets of graphene, a model micropore, in addition to the adsorption and intercalation mechanisms. The finding well explains the extended capacity over typical 300 mAhg−1, up to 478 mAhg−1 recently found in the MgO-templated HC. We also clarified that the MgO-template can produce suitable nanometer-size micropores with slightly defective graphitic domains in HC. The present study considerably promotes the atomistic theory of sodiation mechanism and complicated HC science.

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Bismuth germanate (Bi4Ge3O12), a promising high-capacity lithium-ion battery anode

Chemical Communications ◽

10.1039/c8cc05861j ◽

2018 ◽

Vol 54 (81) ◽

pp. 11483-11486 ◽

Cited By ~ 5

Author(s):

Jassiel R. Rodriguez ◽

Carlos Belman-Rodriguez ◽

Sergio A. Aguila ◽

Yanning Zhang ◽

Hongxian Liu ◽

...

Keyword(s):

Density Functional ◽

High Capacity ◽

Lithium Ion ◽

Density Functional Theory Calculations ◽

Reversible Capacity ◽

Functional Theory ◽

Tap Density ◽

Micron Size ◽

A Current ◽

Battery Anode

Cubic Bi4Ge3O12 lithiation-host electrode material with micron size, low surface area (3 m2 g−1) and high tap density yielded a reversible capacity of 586 mA h g−1 at a current density of 200 mA g−1 after 500 charge–discharge cycles. Density functional theory calculations detected distorted [BiO6]9− octahedra with two types of Bi–O bonds.

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Hydrogen Bond-Assisted Ultra-Stable and Fast Aqueous NH4+ Storage

Nano-Micro Letters ◽

10.1007/s40820-021-00671-x ◽

2021 ◽

Vol 13 (1) ◽

Author(s):

Xikun Zhang ◽

Maoting Xia ◽

Haoxiang Yu ◽

Junwei Zhang ◽

Zhengwei Yang ◽

...

Keyword(s):

Energy Storage ◽

Density Functional ◽

Sustainable Energy ◽

Diffusion Mechanism ◽

High Capacity ◽

Density Functional Theory Calculations ◽

Superior Performance ◽

Ammonium Ion ◽

Copper Hexacyanoferrate ◽

Continuous Formation

AbstractAqueous ammonium ion batteries are regarded as eco-friendly and sustainable energy storage systems. And applicable host for NH4+ in aqueous solution is always in the process of development. On the basis of density functional theory calculations, the excellent performance of NH4+ insertion in Prussian blue analogues (PBAs) is proposed, especially for copper hexacyanoferrate (CuHCF). In this work, we prove the outstanding cycling and rate performance of CuHCF via electrochemical analyses, delivering no capacity fading during ultra-long cycles of 3000 times and high capacity retention of 93.6% at 50 C. One of main contributions to superior performance from highly reversible redox reaction and structural change is verified during the ammoniation/de-ammoniation progresses. More importantly, we propose the NH4+ diffusion mechanism in CuHCF based on continuous formation and fracture of hydrogen bonds from a joint theoretical and experimental study, which is another essential reason for rapid charge transfer and superior NH4+ storage. Lastly, a full cell by coupling CuHCF cathode and polyaniline anode is constructed to explore the practical application of CuHCF. In brief, the outstanding aqueous NH4+ storage in cubic PBAs creates a blueprint for fast and sustainable energy storage.

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Robust wrinkled MoS2/N-C bifunctional electrocatalysts interfaced with single Fe atoms for wearable zinc-air batteries

Proceedings of the National Academy of Sciences ◽

10.1073/pnas.2110036118 ◽

2021 ◽

Vol 118 (40) ◽

pp. e2110036118

Author(s):

Yan Yan ◽

Shuang Liang ◽

Xiang Wang ◽

Mingyue Zhang ◽

Shu-Meng Hao ◽

...

Keyword(s):

High Performance ◽

Density Functional ◽

High Capacity ◽

Density Functional Theory Calculations ◽

Catalytic Performance ◽

Cycling Stability ◽

Single Atom ◽

Core Shell ◽

Bifunctional Electrocatalysts ◽

Zinc Air Batteries

The ability to create highly efficient and stable bifunctional electrocatalysts, capable of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in the same electrolyte, represents an important endeavor toward high-performance zinc-air batteries (ZABs). Herein, we report a facile strategy for crafting wrinkled MoS2/N-doped carbon core/shell nanospheres interfaced with single Fe atoms (denoted MoS2@Fe-N-C) as superior ORR/OER bifunctional electrocatalysts for robust wearable ZABs with a high capacity and outstanding cycling stability. Specifically, the highly crumpled MoS2 nanosphere core is wrapped with a layer of single-Fe-atom-impregnated, N-doped carbon shell (i.e., Fe-N-C shell with well-dispersed FeN4 sites). Intriguingly, MoS2@Fe-N-C nanospheres manifest an ORR half-wave potential of 0.84 V and an OER overpotential of 360 mV at 10 mA⋅cm−2. More importantly, density functional theory calculations reveal the lowered energy barriers for both ORR and OER, accounting for marked enhanced catalytic performance of MoS2@Fe-N-C nanospheres. Remarkably, wearable ZABs assembled by capitalizing on MoS2@Fe-N-C nanospheres as an air electrode with an ultralow area loading (i.e., 0.25 mg⋅cm−2) display excellent stability against deformation, high special capacity (i.e., 442 mAh⋅g−1Zn), excellent power density (i.e., 78 mW⋅cm−2) and attractive cycling stability (e.g., 50 cycles at current density of 5 mA⋅cm−2). This study provides a platform to rationally design single-atom-interfaced core/shell bifunctional electrocatalysts for efficient metal-air batteries.

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Horizontally Arranged Zinc Platelet Electrodeposits Modulated by Fluorinated Covalent Organic Framework Film for High-Rate and Durable Aqueous Zinc Ion Batteries

10.21203/rs.3.rs-494431/v1 ◽

2021 ◽

Author(s):

Zaiping Guo ◽

Zedong Zhao ◽

Rong Wang ◽

Chengxin Peng ◽

Wuji Chen ◽

...

Keyword(s):

Coulombic Efficiency ◽

Protective Layer ◽

Lithium Ion ◽

Zinc Ion ◽

High Rate ◽

High Mass ◽

Side Reactions ◽

Zinc Anode ◽

Covalent Organic Framework ◽

Organic Framework

Abstract Rechargeable aqueous zinc-ion batteries (RZIBs) provide a promising complementarity to the existing lithium-ion batteries due to their low cost, non-toxicity and intrinsic safety. However, Zn anodes suffer from zinc dendrite growth and continuous unfavorable side reactions, resulting in low Coulombic efficiency (CE) and severe capacity decay. Here, we develop an ultrathin, fluorinated two-dimensional porous covalent organic framework (FCOF) film as a protective layer on the Zn surface to address these issues. The strong interaction between fluorine (F) in FCOF and Zn reduces the surface energy of the Zn (002) crystal plane and regulates planar growth of zinc anode materials. As a result, Zn deposits underneath FCOF films show parallel platelet morphology with (002) planar orientations preferred. Furthermore, F-containing nanochannels facilitate the de-solvation of hydrated Zn ions and prevent electrolyte penetration, thus retarding corrosion of Zn. Such unique FCOF films prolonged the Zn symmetric cell lifespan to over 1700 h, which is 13 times longer than the cells without protection (125 h). The assembled full cells demonstrate a cycle life of over 250 cycles at 3 mAcm-2 under practical conditions, including lean electrolyte (12 μLmAh-1), limited Zn excess (only 1×excess), and a high mass loading of MnO2 cathode (16 mgcm-2). This work provides a new perspective for the realization of planar deposition of zinc metal anodes for developing high performance Zn-based batteries.

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