Dendrite-free Zn anodes enabled by functional nitrogen-doped carbon protective layers for aqueous zinc-ion batteries

Wu, Changcai; Xie, Kaixuan; Ren, Kaixin; Yang, Shun; Wang, Qinghong

doi:10.1039/d0dt03459b

Cited by 63 publications

(39 citation statements)

References 41 publications

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“…The development of large-scale energy storage systems is highly demanded to regulate the energy output of intermittent renewable energy sources, such as solar and wind. [1] Among them, aqueous rechargeable metal batteries (ARBs) have been regarded as a promising candidate because aqueous electro-N-C networks, [36] and graphene have been reported to fabricate the composite protection layer. [34,35,37,38] In addition, due to the high specific surface area of 2D MXene materials, they have been reported to suppress the growth of Zn dendrites.…”

Section: Introductionmentioning

confidence: 99%

Dendrites‐Free Zn Metal Anodes Enabled by an Artificial Protective Layer Filled with 2D Anionic Nanosheets

et al. 2021

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Metallic zinc (Zn) has been considered to be an ideal anode material for aqueous batteries, but is impeded by the growth of Zn dendrites and its side reactions with an aqueous electrolyte. Here, it is reported that an artificial protective layer filled with novel 2D Zn2+ adsorbed Sb3P2O143− (denoted as Zn‐Sb3P2O14) nanosheets provide an effective route to mitigate the above challenging problems. The Zn‐Sb3P2O14 protection layer not only avoids the direct contact with the aqueous electrolyte to suppress the side reactions but also allows for Zn‐ions to pass through the protection layer rapidly. Moreover, the 2D Sb3P2O143− skeleton with negative charge also confines the 2D diffusion of Zn‐ion along the lateral surface of Zn anode, resulting in a uniform electron‐deposition. This unique protection layer not only enables dendrite‐free Zn plating/stripping with an average Coulombic efficiency of 99.2% for 200 cycles, but also sustains the symmetric Zn||Zn cell over 1300 h at 1 mA cm−2 and 1 mAh cm−2 as well as for 450 h at 10 mA cm−2 and 10 mAh cm−2. Such advantages bring high reversibility to full Zn batteries with MnO2 cathodes, which deliver a discharge capacity of 111.7 mAh g−1 after 1000 cycles.

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Section: Introductionmentioning

confidence: 99%

Dendrites‐Free Zn Metal Anodes Enabled by an Artificial Protective Layer Filled with 2D Anionic Nanosheets

et al. 2021

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“…The diffraction peak located between 8 and 10°proves the formation of the byproduct Zn 4 (SO 4 )(OH) 4 • 5H 2 O (PDF:39-0688) during the cycling process. 34 However, the intensity of the diffraction peak of the NGO@Zn electrode is significantly lower than that of the bare Zn electrode, indicating that the NGO coating plays a suppressive role in the formation of byproducts, which is attributed to the NGO interfacial layer effectively reducing the contact area between the electrolyte and Zn metal. Meanwhile, the mapping illustrates that the oxygen content on the surface of the NGO@Zn electrode is significantly lower than that of bare Zn after cycling (Figures S11−S12).…”

Section: Resultsmentioning

confidence: 95%

“…To further reveal the composition of the interface after deposition, XRD patterns of bare Zn and NGO@Zn electrodes after 20 cycles were further tested (Figure i). The diffraction peak located between 8 and 10° proves the formation of the byproduct Zn 4 (SO 4 )(OH) 4 ·5H 2 O (PDF:39-0688) during the cycling process . However, the intensity of the diffraction peak of the NGO@Zn electrode is significantly lower than that of the bare Zn electrode, indicating that the NGO coating plays a suppressive role in the formation of byproducts, which is attributed to the NGO interfacial layer effectively reducing the contact area between the electrolyte and Zn metal.…”

Section: Resultsmentioning

confidence: 98%

“…Inspired by the above mentioned artificial protective layers, herein, we present NGO as an artificial protective layer for the Zn anode, which inhibits dendrite growth by regulating Zn-ion deposition and interfacial electric field distribution. 34 The NGO coating has a wrinkled morphology that yields a larger specific surface area, which provides abundant nucleation sites for Zn-ions. The abundant N-doped functional groups can effectively guide the homogeneous nucleation and deposition of Zn-ions.…”

Section: Introductionmentioning

confidence: 99%

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Artificial N-doped Graphene Protective Layer Enables Stable Zn Anode for Aqueous Zn-ion Batteries

Hao

Zhou

Wei

et al. 2021

ACS Appl. Energy Mater.

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Zinc (Zn) metal anode is one of the promising aqueous anodes due to its lower reduction potential and high capacity; however, the unstable interface during cycling severely inhibits the development of aqueous Zn-ion batteries (ZIBs). Here, we constructed a protective layer of nitrogen (N)-doped graphene (NGO) on Zn foil using a simple squeegee coating process. In situ optical microscopy and mass spectrometry analyses further demonstrated that this graphene protective layer alleviates the release of hydrogen as well as the hydrolysis of Zn. Meanwhile, the abundant N-doped functional groups modulate the deposition morphology of the Zn metal and inhibit the growth of porous dendrites. Based on this, the NGO@Zn||NGO@Zn symmetric cell presents a stable cycling performance over 500 h with a low overpotential (19 mV). Meanwhile, the full cell of the LiMn2O4 (LMO)||NGO@Zn battery delivers a capacity of 89.1 mAh g–1 after 600 cycles at the rate of 1C and a high specific capacity at the rate of 5C. Moreover, the LMO||NGO@Zn pouch cell (1.32 mAh cm–2) exhibits a capacity of up to 124.7 mAh g–1 at 0.5C and retains a capacity of 72.9 mAh g–1 after 90 cycles under no stress test conditions. This work offers a feasible synthesis approach and promising performance to accelerate the industrial application of aqueous ZIBs.

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“…[35,36] Besides the modification of electrolyte compositions, the surface engineering of Zn has also been extensively studied, in which artificial layers were introduced on the Zn surface to enhance the electronic conductivity and/or the attraction with Zn 2+ . The conductive materials investigated for surface-coating have included reduced graphene oxide, [37] N-doped graphene oxide, [38] graphite, [39] N-doped carbon, [40] carbon nanofiber, [41] carbon nanotube (CNT) foam, [42] free-standing CNT/paper scaffold, [43] MXene, [44] Zn-Cu alloy, [45,46] polypyrrole, [47] Tin, [48] ZnF 2 /Ag, [49] ZnF 2 , [50,51] and Ag, [52] all of which were reported to be effective in suppressing dendrites because the "tip effect" could be alleviated by a uniform distribution of the electric field. Nonconductive materials were also applied to enhance the attractive force toward Zn 2+ ions.…”

Section: Introductionmentioning

confidence: 99%

Zinc Anodes Modified by One‐Molecular‐Thick Self‐Assembled Monolayers for Simultaneous Suppression of Side‐Reactions and Dendrite‐Formation in Aqueous Zinc‐Ion Batteries

Mwemezi

Prabakar

Han

et al. 2022

Small

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Repeated charge/discharge in aqueous zinc‐ion batteries (ZIBs) commonly results in surface corrosion/passivation and dendrite formation on zinc anodes, which is a major challenge for the commercialization of zinc‐based batteries. In this work, metallic Zn modified by self‐assembled monolayers is described as a viable anode for ZIBs. ω‐mercaptoundecanoic acid that is spontaneously adsorbed on Zn (MUDA/Zn) contributes to the simultaneous suppression of side reactions and dendrite formation in ZIBs. Though one‐molecular‐thick, densely packed alkyl chains prohibit H2O and H+ from making direct contact with the underlying Zn, and surface carboxylate moieties (–COO‐) effectively repel anionic species (OH‐) in a solution, which renders a Zn anode inert against zincate formation within a wide range of pH. In contrast, the electrostatic attraction between surface‐carboxylates and cations increases the concentration of Zn2+ on the surface of MUDA/Zn to facilitate Zn plating/stripping with less overpotentials. The high concentration of Zn2+ also results in an increased number of nucleation sites, which enhances the lateral growth of Zn with no formation of dendrites. As a result, MUDA/Zn shows excellent stability during prolonged Zn plating/stripping within a wide range of pH. The advantageous properties of MUDA/Zn are also retained in full‐cells coupled with δ‐MnO2 cathodes.

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Dendrite-free Zn anodes enabled by functional nitrogen-doped carbon protective layers for aqueous zinc-ion batteries

Abstract: Rechargeable aqueous zinc-ion batteries possess the merits of good environmental benignity, high operational safety and high-energy density. Nevertheless, the practical application of zinc-ion batteries are severely obstructed by the inhomogeneous...

Cited by 63 publications

References 41 publications

Dendrites‐Free Zn Metal Anodes Enabled by an Artificial Protective Layer Filled with 2D Anionic Nanosheets

Dendrites‐Free Zn Metal Anodes Enabled by an Artificial Protective Layer Filled with 2D Anionic Nanosheets

Artificial N-doped Graphene Protective Layer Enables Stable Zn Anode for Aqueous Zn-ion Batteries

Zinc Anodes Modified by One‐Molecular‐Thick Self‐Assembled Monolayers for Simultaneous Suppression of Side‐Reactions and Dendrite‐Formation in Aqueous Zinc‐Ion Batteries

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