Dendrite-free Zn anode with dual channel 3D porous frameworks for rechargeable Zn batteries

Guo, Wenbin; Cong, Zifeng; Guo, Zihao; Chang, Caiyun; Liang, Xiaoqiang; Liu, Yadi; Hu, Weiguo; Pu, Xiong

doi:10.1016/j.ensm.2020.04.038

Cited by 264 publications

(215 citation statements)

References 62 publications

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“…In addition, the powdery state of Zn@C implies that substantial organic binders are needed for fabricating the Zn@C electrode as the Zn battery, which further decrease the content of Zn in the final Zn@C electrode. [ 64 ]…”

Section: Resultsmentioning

confidence: 99%

Electrochemical Fixation of Carbon Dioxide in Molten Salts on Liquid Zinc Cathode to Zinc@Graphitic Carbon Spheres for Enhanced Energy Storage

Xiao

Weng

et al. 2020

Advanced Energy Materials

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to epoxides is realized in ionic liquids by Sun and co-workers. [14,15] Fixation and utilization of CO 2 is also elaborately explored via designing the metal-CO 2 batteries by Ding and co-workers. [16] Fixation of CO 2 into functional carbonaceous materials by capture and electrochemical reduction of CO 2 in molten salts has many advantages. [6,17-19] CO 2 shows a high solubility in molten salts, guaranteeing a highflux uptake rate for a direct and deep removal of CO 2 from atmosphere and industrial flue gas. [6] The wide electrochemical window of molten salt electrolytes promises a high current efficiency of the electrochemical reduction of CO 2 in molten salts. [6,20-24] The high-temperature environment of inorganic molten salts brings about enhanced mass transfer and facilitated reaction kinetics, enabling an appealing conversion rate of CO 2 free of any precious catalysts. [6,14,15] Molten salts possess a high heat capacity, which means the heat required by the molten salt fixation of CO 2 can be supplied by solar-thermal systems. [17] The decomposition voltage of CO 2-capture-generated CO 3 2− in molten salts is lower than 2.0 V (1.3 V for Li 2 CO 3 , 1.6 V for Na 2 CO 3 , and 1.8 V for K 2 CO 3 at 500 °C), therefore the electricity for the conversion of CO 2 in molten salts can be supplied by solar photovoltaic systems. [17] Finally, oxygen in CO 2 can simultaneously be released as anodic O 2 , which is of prime implications on future colony on Mars. [6] One of the major challenges for the electrochemical fixation of CO 2 in molten salts is the insufficient functionality of the deposited carbon on cathode. [6] Amorphous and disordered carbon is commonly obtained by electrochemical conversion of CO 2 in molten salts, which contradicts with the demands of application devices for carbonaceous materials with high graphitization degree. [6] For example, aluminum-ion (Al-ion) battery (AIB) possesses the merits of low cost, high volumetric capacity, and high safety. Many cathode materials are reported for Al-ion batteries, including carbon-based materials, metal sulfides, and V 2 O 5. [25-27] For carbon-based materials, the carbon with higher graphitization degree commonly possesses better performance for reversible Al storage. [26,27] In this regard, pioneering works were conducted by Lu and coworkers. [7,28-33] In their strategy, a highly porous 3D graphene foam is used as the cathode for rechargeable Al-ion batteries,

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Section: Resultsmentioning

confidence: 99%

Electrochemical Fixation of Carbon Dioxide in Molten Salts on Liquid Zinc Cathode to Zinc@Graphitic Carbon Spheres for Enhanced Energy Storage

Xiao

Weng

et al. 2020

Advanced Energy Materials

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“…On the other hand, these Zn protrusions caused by hydrogen evolution reaction will attract more Zn 2+ flux (“tip” effect) [ 22 ] under concentrated electric field during electrochemical cycling, thus accelerating the vertical growth of Zn dendrites instead of planar growth and hydrogen production further flourish (Figure 1g). Up to now, various strategies have been evolved to prohibit the Zn dendrite growth, such as electrolyte optimization, [ 8,23–25 ] Zn surface coating, [ 9,21,26–29 ] and alloying. [ 30 ] To some extent, these strategies stabilize Zn metal, but they do not follow the original nature of Zn dendrite growth in aqueous environment, and batteries are operated with low current density and loading mass of cathode materials, far from practical implementation.…”

Section: Figurementioning

confidence: 99%

Toward Practical High‐Areal‐Capacity Aqueous Zinc‐Metal Batteries: Quantifying Hydrogen Evolution and a Solid‐Ion Conductor for Stable Zinc Anodes

et al. 2021

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environments, [7-12] where Zn deposition even during shelf time is continuously interfered by competitive hydrogen evolution through H 2 O decomposition (Zn + 2H 2 O → Zn(OH) 2 + H 2) and by consuming both the electrolyte and active Zn metal. This long-neglected problem will remarkably affect calendar life of batteries, which is equivalently important with the intensively studied cycling life of batteries. As revealed in our preliminary quantitative study shown in Figure 1a, immersing Zn in 2 m ZnSO 4 electrolyte will induce an ≈0.25 mmol h-1 cm-2 hydrogen flux. The continuous hydrogen evolution will cause local pH changes, which further induce the formation of loose and brittle Zn 4 SO 4 (OH) 6 •xH 2 O (3Zn(OH) 2 + ZnSO 4 •xH 2 O → Zn 4 SO 4 (OH) 6 •xH 2 O), as revealed in Figure 1b. [13-18] It is generally assumed that these by-products augment the tortuosity and irregularity at the electrode/electrolyte interface with physical contact surface being increased (Figure 1c-h), which will further accelerate hydrogen evolution reaction. The above issues necessitate an effective method to detect hydrogen evolution. Nevertheless, for a Zn-based battery, these assumption and hypotheses are only based on oversimplified observations of battery swelling, gas bubbles, or conducting polarization curve in the absence of Zn 2+ condition, not reflecting physical truth of battery. [19-21] Hydrogen production during electrochemical procedure and even shelf time has not been precisely quantified. Consequently, efforts to make Zn metal a valid anode material may be misdirected. Quantifying the hydrogen production on the electrode during Zn deposition is key to understanding the mechanisms leading to capacity loss and battery failure. On the other hand, these Zn protrusions caused by hydrogen evolution reaction will attract more Zn 2+ flux ("tip" effect) [22] under concentrated electric field during electrochemical cycling, thus accelerating the vertical growth of Zn dendrites instead of planar growth and hydrogen production further flourish (Figure 1g). Up to now, various strategies have been evolved to prohibit the Zn dendrite growth, such as electrolyte optimization, [8,23-25] Zn surface coating, [9,21,26-29] and alloying. [30] To some extent, these strategies stabilize Zn metal, but they do The hydrogen evolution in Zn metal battery is accurately quantified by in situ battery-gas chromatography-mass analysis. The hydrogen fluxes reach 3.76 mmol h −1 cm −2 in a Zn//Zn symmetric cell in each segment, and 7.70 mmol h −1 cm −2 in a Zn//MnO 2 full cell. Then, a highly electronically insulating (0.11 mS cm −1) but highly Zn 2+ ion conductive (80.2 mS cm −1) ZnF 2 solid ion conductor with high Zn 2+ transfer number (0.65) is constructed to isolate Zn metal from liquid electrolyte, which not only prohibits over 99.2% parasitic hydrogen evolution but also guides uniform Zn electrodeposition. Precisely quantitated, the Zn@ZnF 2 //Zn@ZnF 2 cell only produces 0.02 mmol h −1 cm −2 of hydrogen (0.53% of the Zn//Zn cell). Encouragingly, a hig...

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Section: Dendrite Inhibition Strategies On Zn Anodementioning

confidence: 99%

Strategies for the Stabilization of Zn Metal Anodes for Zn‐Ion Batteries

Chen

Hou

et al. 2020

Advanced Energy Materials

531

374

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scenario, the utilization of alternative and sustainable energy types, such as solar energy, [2] wind energy, [3] biomass energy, [4] tidal energy, [5] and geothermal energy, [6] is essential. Although these types of energy are generally accessible and clean, the direct storage and transportation of them are extremely difficult, and their highly fluctuating nature makes things even worse. [7] Alternatively, electrical energy is often generated from these energy types and serves as an intermediate between the direct energy harvest and the terminal utilization. In this regard, the development of energy storage systems (ESSs) is essential to provide a more versatile and stable energy supply for individual, household, and industrial applications, which has consequently been extensively investigated. [8] Among all current ESSs, batteries play a major role [9] and have been indispensably utilized for portable electronics, tools, electric vehicles (EVs), and even power grids. [10] Owing to their lightweight, high energy density, and extended cycle life, lithium-ion batteries (LIBs), initially developed in the early 1990s, are regarded as a milestone of ESS technologies. [11] Since then, LIBs have been widely applied, which have reshaped our lifestyle. Despite their success in mass production, commercial LIBs still suffer from high cost due to the limited lithium resource and the high cost of other components (e.g., Co-based cathode), [12] which is further worsened by the rigid requirement for their manufacture. Besides, the safety concerns, which stem from the flammable organic electrolyte and highly reactive lithium species, also significantly hinder the deployment of LIBs on a large scale. [13] Considering these limitations of LIBs, it is necessary to develop alternative ESSs with comparable energy/power density but better costeffectiveness and higher safety characteristics. [14] To achieve this, the exploration of high capacity yet relatively inert anode materials and nonflammable electrolytes is essential. Zinc-ion batteries (ZIBs) have been prospected as a new generation of inexpensive and safe ESS devices. Different from typical LIBs, a ZIB is composed of a Zn 2+ ion storage cathode and a Zn metal anode, which is favorable for high anode capacity. Furthermore, aqueous electrolytes are frequently used for ZIBs rather than the organic ones. [15] As a result, energy is stored and released via the reversible Zn stripping/plating at the anode and Zn 2+ insertion/desertion at Zinc-ion batteries (ZIBs) are regarded as a promising candidate for next-generation energy storage systems due to their high safety, resource availability, and environmental friendliness. Nevertheless, the instability of the Zn metal anode has impeded ZIBs from being reliably deployed in their proposed applications. Specifically, dendrite formation and the hydrogen evolution reaction (HER) on the Zn surface significantly compromise the Coulombic efficiency and cycling stability of ZIBs. In recent years, increasing efforts have been devoted t...

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Dendrite-free Zn anode with dual channel 3D porous frameworks for rechargeable Zn batteries

Cited by 264 publications

References 62 publications

Electrochemical Fixation of Carbon Dioxide in Molten Salts on Liquid Zinc Cathode to Zinc@Graphitic Carbon Spheres for Enhanced Energy Storage

Electrochemical Fixation of Carbon Dioxide in Molten Salts on Liquid Zinc Cathode to Zinc@Graphitic Carbon Spheres for Enhanced Energy Storage

Toward Practical High‐Areal‐Capacity Aqueous Zinc‐Metal Batteries: Quantifying Hydrogen Evolution and a Solid‐Ion Conductor for Stable Zinc Anodes

Strategies for the Stabilization of Zn Metal Anodes for Zn‐Ion Batteries

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