A Dynamic and Self‐Adapting Interface Coating for Stable Zn‐Metal Anodes

Guo, Zhikun; Fan, Longlong; Zhao, Chenyang; Chen, Aosai; Liu, Nannan; Zhang, Yu; Zhang, Naiqing

doi:10.1002/adma.202105133

Cited by 211 publications

(146 citation statements)

References 38 publications

Supporting

Mentioning

142

Contrasting

Order By: Relevance

“…As depicted in Figure 1c and Figure S2, Supporting Information, an uneven electric field resulting from the tip effect would trigger local Zn 2+ concentration polarization, which serves as the rich-charge center and constitutes to drive more ions to accumulate at the initial nuclei location, further evolving into dendrites growth. [18] In sharp contrast, when introducing quantum-size CDs functional layer, the electrode exhibits a relatively homogeneous electric fled distribution, which mainly benefits from abundant nucleation sites provided by CDs leading to the fact that Zn ions could be adsorbed on the whole electrode thus inducing uniform nucleation and avoid dendrite formation (Figure 1d). These computations strongly illustrate high affinity and uniform electric field distributions play a vital role for CDs in modulating Zn nucleation/deposition behavior.…”

Section: Resultsmentioning

confidence: 99%

High‐Yield Carbon Dots Interlayer for Ultra‐Stable Zinc Batteries

Zhang

et al. 2022

Advanced Energy Materials

114

View full text Add to dashboard Cite

natural abundance, and operational safety, which is considered to be one of the most promising next-generation batteries. [3] However, Zn anode in the mildly acidic condition is plagued by notorious dendritic growth, inevitable corrosion, as well as hydrogen evolution due to thermodynamic instability, which gives rise to a low coulombic efficiency and poor cycling reversibility during the plating/stripping process. [4] Similar to Li/Na metal batteries, the Zn 2+ ion prefers to form nuclei at dislocated sites due to relatively high potential, and subsequent zinc ions deposit at initial nucleation sites with higher curvature and lower activation energy, further growing into protuberances. The sharp tips of protuberances with the considerably higher electric field would serve as charge center, eventually resulting in furious dendrites growth after long-term accumulation. [5] Most disturbingly, the persistent dendrites growth would result in loose porous morphology and a mass of "dead Zn", which further exacerbates the interfacial parasitic reaction due to excessive exposure between the electrolyte and Zn anode. [6] Therefore, uniform Zn deposition and less contact with water are of great significance to achieving the long cycle life of the Zn anode.Recently, to obtain a robust zinc anode, modification of electrolyte/anode interfaces has been proposed to suppress the formation of Zn dendrites. Electrolyte engineering, [7] including regulation of the electrolyte composition and introduction of additive, one easy and effective strategy, is adopted to enhance the stability of zinc anode via tailoring solvated structure or forming a solid electrolyte interface. However, expensive costs for highly concentrated electrolytes and continual consumption of functional additives seriously impede the large-scale practical application of ZMBs. Another strategy of amending Zn anode structure, such as surface-preferred crystal plane and nano-sized Zn anode, has attracted a great deal of attention, which could greatly reduce the nucleation barrier leading to the inhibition of dendrites growth. [8] Unsatisfactorily, regulating the preferred orientation crystal involves complicated operation techniques, and nano-structured Zn with extensive specific area results in excessive contact between electrode and electrolyte, which may aggravate hydrogen evolution reaction (HER) and Zn corrosion. In addition to the above two strategies to solve the issue of zinc dendrites, constructing an artificial interfacial layer with a similar function to SEI via ex situ coating or in situ growth has been widely studied to ameliorate problems of electrode/electrolyte interface. [9] The metal coating layer exhibits strong affiliationThe practical implementation of Zn metal anodes with high volumetric capacity is seriously plagued by the dendritic growth and accompanying interfacial parasitic reactions. Herein, high yield carbon dots (CDs) with abundant polar functional groups (CHO and CN), as a functional artificial interface layer, are rationally de...

show abstract

Section: Resultsmentioning

confidence: 99%

High‐Yield Carbon Dots Interlayer for Ultra‐Stable Zinc Batteries

Zhang

et al. 2022

Advanced Energy Materials

114

View full text Add to dashboard Cite

show abstract

“…Such a result should be mainly attributed to the rapid growth of Zn dendrite and dead Zn, which would damage the anode-electrolyte interface, extending the transport path of ions/electrons and even pierce the separator, as described in Figure S26, Supporting Information. [49,50] Unlike that, the DIE-modified cell can keep a stable contact impedance in the whole process. Furthermore, although the charge-transfer impedance of modified cell would also gradually decrease in the initial cycling, it can tend to being stable in the subsequent cycles, confirming the high stability of the anode-electrolyte interface (Figure 5k).…”

Section: Resultsmentioning

confidence: 99%

Novel Concept of Separator Design: Efficient Ions Transport Modulator Enabled by Dual‐Interface Engineering Toward Ultra‐Stable Zn Metal Anodes

Liang

Zhao

et al. 2022

Adv Funct Materials

101

View full text Add to dashboard Cite

Sluggish transport kinetics and rapid dendrite growth are considered the main obstacles that impair the performance of Zn metal batteries. This work has developed a unique strategy of dual‐interface engineering (DIE) to design the separator as efficient ions transport modulator. The dual function of spontaneous polarization effect and high zincophilicity of BaTiO3 (BTO) is revealed by combining the theoretical and experimental studies. Benefiting from the decoration of BTO on glass fiber and well filling of the surface interspace, the DIE‐modified separator can not only effectively capture and accelerate Zn2+ transport between the fiber–electrolyte interface, but also redistribute the ions transport into homogenization in the separator–anode interface. Therefore, the modified Zn anodes perform highly reversible Zn plating/stripping with ultrahigh cumulative capacity even up to 9500 mAh cm−2 at the high current density of 10 mA cm−2. Meanwhile, the modified Zn‐MnO2 battery can retain a specific capacity of 108 mAh g−1 after 1800 cycles at 1 A g−1. Furthermore, the capacity retention of the battery also can be improved from 37.5% up to 115% at 0.2 A g−1 after 100 cycles. Such a novel concept for separator engineering provides a new perspective to enable ultra‐stable Zn metal anodes and high‐performance Zn metal batteries.

show abstract

“…Undoubtedly, the CPE strategy shows a remarkable improvement and surpasses the performance of Zn//Cu cells in the latest reported works (Table S2, Supporting Information). [26][27][28][29][30][31][32][33][34][35][36][37][38][39] To demonstrate the feasibility and efficiency of the CPE in full cell, NVO nanofibers are used as the cathodes to pair with Zn metal anodes. [40] The Zn//NVO full cell demonstrates nearly no capacity decay over 5000 cycles at a high rate of 5 A g −1 as shown in Figure 5f, featuring decent capacity ≈100 mAh g −1 and CE of >99%.…”

Section: Efficacy Of the Designed Cpementioning

confidence: 99%

Diminishing Interfacial Turbulence by Colloid‐Polymer Electrolyte to Stabilize Zinc Ion Flux for Deep‐Cycling Zn Metal Batteries

et al. 2022

View full text Add to dashboard Cite

volumetric capacity of 5855 mAh cm −3 ) of metallic Zn. [1] However, nonuniform Zn deposition aggravates formation of dendrites and leads to a low Coulombic efficiency (CE), resulting in battery performance deterioration. It is believed that regulated Zn 2+ distribution is beneficial to the uniform Zn plating. [1,2] Many works in the field of Zn anode realize uniform Zn 2+ distribution and improve Zn electrochemistry by constructing efficient Zn 2+ transport path. [1][2][3] However, we find that at deep cycling (high current densities and capacities), the interfacial turbulence is a severe problem that cannot be ignored to destroy the stability of Zn 2+ transport path. In details, the Zn 2+ ions flux distribution is affected by two factors: construction and stabilization of Zn 2+ transport path. Homogeneous Zn 2+ channels are helpful to realize uniform ion flux distribution; while Zn 2+ transport path would be destructed due to inevitable severe interfacial turbulence caused by fluidity of electrolyte and undesired H 2 evolution reaction (HER), which would lead to the disturbance of ion flux and uneven Zn deposition. In addition, the HER is usually accompanied by metal corrosion. [3] This not only consumes water in the electrolyte, but also the generated H 2 would result in swelling of the cell and even cell rupture. Meanwhile, the consumption of H + in water results in the accumulation of residual OH − ions, driving the corrosion reaction to form inactive Zn 4 SO 4 (OH) 6 •xH 2 O byproducts. [4,5] Moreover, the operation of ZMBs with high capacities is limited owing to the incomplete Zn discharging process because accumulated Zn leads to increased polarization of the battery; High current density can also cause an inhomogeneous electric field, incomplete metal stripping, and excessive polarization especially current and concentration polarization. [6,7] These issues can cause more serious interfacial instability and disturbance for deep-cycling batteries with high areal capacities and high current densities, significantly undermining the performance of ZMBs and plaguing their scale-up implementation. Aqueous deeply rechargeable Zn metal electrodes can only be achieved when the interfacial turbulence is rectified. Considering that free water molecules in electrolytes induce H 2 evolution and interfacial corrosion, highly concentrated The fluidity of aqueous electrolytes and undesired H 2 evolution reaction (HER) can cause severe interfacial turbulence in aqueous Zn metal batteries (ZMBs) at deep cycling with high capacities and current densities, which would further perturb ion flux and aggravate Zn dendrite growth. In this study, a colloid-polymer electrolyte (CPE) with special colloidal phase and suppressed HER is designed to diminish interfacial turbulence and boost deep Zn electrochemistry. Density functional theory calculations confirm that the quantitative migratory barriers of Zn 2+ along the transport pathway in CPE demonstrate much smaller fluctuations compared with normal aqueous electrolyte, indicating...

show abstract

A Dynamic and Self‐Adapting Interface Coating for Stable Zn‐Metal Anodes

Cited by 211 publications

References 38 publications

High‐Yield Carbon Dots Interlayer for Ultra‐Stable Zinc Batteries

High‐Yield Carbon Dots Interlayer for Ultra‐Stable Zinc Batteries

Novel Concept of Separator Design: Efficient Ions Transport Modulator Enabled by Dual‐Interface Engineering Toward Ultra‐Stable Zn Metal Anodes

Diminishing Interfacial Turbulence by Colloid‐Polymer Electrolyte to Stabilize Zinc Ion Flux for Deep‐Cycling Zn Metal Batteries

Contact Info

Product

Resources

About