Effective Suppression of Dendritic Lithium Growth Using an Ultrathin Coating of Nitrogen and Sulfur Codoped Graphene Nanosheets on Polymer Separator for Lithium Metal Batteries

Shin, Won-Kyung; Kannan, Aravindaraj G.; Kim, Dong-Won

doi:10.1021/acsami.5b07730

Cited by 215 publications

(136 citation statements)

References 42 publications

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“…The suppressed bulk/dendritic deposition of Zn in the V‐3M‐Nafion cell can be due to the combined contribution from the inherent single ion conducting property and the presence of the anionic —

{SO}_{3}^{-}

group in the Nafion ionomer. The electrostatic interaction between electron‐rich

{SO}_{3}^{-}

groups in the Nafion ionomer, and the positively charged Zn can provide a strong interfacial interaction that suppresses the dendritic growth during prolonged cycling and facilitates the uniform deposition of Zn . This interfacial interaction assists in maintaining an efficient contact between the Zn anode and the Nafion ionomer membrane.…”

Section: Resultsmentioning

confidence: 99%

Dendrite Growth Suppression by Zn²⁺‐Integrated Nafion Ionomer Membranes: Beyond Porous Separators toward Aqueous Zn/V₂O₅ Batteries with Extended Cycle Life

2019

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The dendritic/irregular growth of zinc deposits in the anode surface is often considered as a major intricacy limiting the lifespan of aqueous zinc‐ion batteries. The effect of separators on the evolution of the surface morphology of the anode/cathode is never thoroughly studied. Herein, for the first time, the efficacy of the Zn2+‐integrated Nafion ionomer membrane is demonstrated as a separator to effectively suppress the growth of irregular zinc deposits in the metallic anode of an aqueous Zn/V2O5 battery. The Zn2+‐ions coordinated with the SO3− moieties in Nafion result in a high transference number of the Zn2+ cation, all the while facilitating a high ionic conductivity. The Zn2+‐integrated Nafion membrane enables the Zn/V2O5 cell to deliver a high specific capacity of 510 mAh g−1 at a current of 0.25 A g−1, which is close to the theoretical capacity of anhydrous V2O5 (589 mAh g−1). Moreover, the same cell exhibits an excellent cycling stability of 88% retention of the initial capacity even after 1800 charge–discharge cycles, superior to that of the Zn/V2O5 cells comprising conventional porous separators.

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{SO}_{3}^{-}

group in the Nafion ionomer. The electrostatic interaction between electron‐rich

{SO}_{3}^{-}

Section: Resultsmentioning

confidence: 99%

Dendrite Growth Suppression by Zn²⁺‐Integrated Nafion Ionomer Membranes: Beyond Porous Separators toward Aqueous Zn/V₂O₅ Batteries with Extended Cycle Life

2019

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“…The morphological evolution of Li plating/stripping on the 3DCu@NG at 0.5 mA cm −2 were observed by ex situ scanning electron microscope (SEM) as shown in Figure 2b-g, and all the images were taken from the middle area of the crosssection. [46,47] The deposition of Li above NG could maintain the integrity of the graphene. There were a number of tiny nanoparticles embedded on the inner surface of 3D current collector (Figure 2b ( Figure 2c).…”

Section: Morphology Of LI Metal Deposition On 3dcu@ng and 3dcumentioning

confidence: 99%

N‐Doped Graphene Modified 3D Porous Cu Current Collector toward Microscale Homogeneous Li Deposition for Li Metal Anodes

Zhang

Wen

Wang

et al. 2018

Advanced Energy Materials

169

105

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standard hydrogen electrode). [6][7][8][9][10] Unfortunately, the uneven plating/stripping of Li metal causes uncontrolled Li dendrite growth, which induces a series of problems. First, the continuous growth of Li dendrites may puncture the separator and cause short circuit, consequently resulting in serious safety issues. [11][12][13][14] Second, Li dendrite growth can consume electrolyte and dendritic Li may lose its electronic contact with electrode (called "dead Li") during Li stripping process, accordingly reducing the Coulombic efficiency (CE) and leading to capacity fading. [15][16][17] In addition, different from the other anode materials, the relative volume change of Li metal anodes is infinite due to its "hostless" nature, leading to internal pressure changes and interfacial fluctuations. The solid electrolyte interface (SEI) layer on the surface of the electrodes, which may not accommodate the volume change, will be repeatedly break and form during continuous cycling. [18][19][20] Moreover, the broken SEI will greatly exacerbate the uneven Li electrodeposits nucleate and accelerate the growth of Li dendrites. [21,22] These severe problems impede the practical applications of Li metal anodes and the approach to solve these multifaceted problems would be imperative.To tackle these critical issues, tremendous efforts have been taken to improve the stability of Li metal anodes and the SEI from different perspectives. In order to stabilize the SEI layer, various electrolyte additives, such as Cs + and Rb + ions, LiF, Li 2 S 8 , and LiNO 3 , were used. [23][24][25] Introducing nanoscale interfacial layers has also been intensively investigated (such as interconnected carbon nanospheres [26] and hexagonal boron nitride [27] ), where repeated deposition/stripping of Li under the layers exhibited stable CE. However, the above-mentioned methods based on Li foil (2D Li metal anodes) could not effectually prevent the huge volume change upon stripping/plating of Li metal. Thus, the internal pressure changes and interfacial fluctuations still happened during cycling. [28] To solve this problem, the 3D porous current collectors were used as host structures for Li metal in recent studies, such as 3D porous copper current collectors, [29][30][31][32][33] 3D nickel foam host, [34] and graphene [35,36] electrode. As a major part of Li metal batteries, the current collector has direct influence Lithium metal is the most promising anode material for high-energy-density batteries due to its high specific capacity of 3860 mAh g −1 and low reduction potential of −3.04 V versus standard hydrogen electrode. However, huge volume change, safety concerns, and low efficiency impede the practical applications of Li metal anodes. Herein, it is shown that the nitrogen-doped graphene modified 3D porous Cu (3DCu@NG) current collector can mitigate the above problems. The N-doped graphene, coating on the surface of 3D current collector, not only contributes to a uniform Li + flux, but also leads to a scattered distribution of electrons t...

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“…The Li dendrite would grow out through the bigger nanopores more easily, so the CE gradually decayed during cycling and maintained only ≈80% after 100 cycles. [12][13][14][15][16] In the past decades, considerable efforts have been carried out to address these problems. After a longtime etching, a larger area of Cu foil was exposed, resulting in an unstable CE during cycling.…”

mentioning

confidence: 99%

Poly(dimethylsiloxane) Thin Film as a Stable Interfacial Layer for High‐Performance Lithium‐Metal Battery Anodes

et al. 2016

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Effective Suppression of Dendritic Lithium Growth Using an Ultrathin Coating of Nitrogen and Sulfur Codoped Graphene Nanosheets on Polymer Separator for Lithium Metal Batteries

Cited by 215 publications

References 42 publications

Dendrite Growth Suppression by Zn²⁺‐Integrated Nafion Ionomer Membranes: Beyond Porous Separators toward Aqueous Zn/V₂O₅ Batteries with Extended Cycle Life

Dendrite Growth Suppression by Zn²⁺‐Integrated Nafion Ionomer Membranes: Beyond Porous Separators toward Aqueous Zn/V₂O₅ Batteries with Extended Cycle Life

N‐Doped Graphene Modified 3D Porous Cu Current Collector toward Microscale Homogeneous Li Deposition for Li Metal Anodes

Poly(dimethylsiloxane) Thin Film as a Stable Interfacial Layer for High‐Performance Lithium‐Metal Battery Anodes

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Effective Suppression of Dendritic Lithium Growth Using an Ultrathin Coating of Nitrogen and Sulfur Codoped Graphene Nanosheets on Polymer Separator for Lithium Metal Batteries

Cited by 215 publications

References 42 publications

Dendrite Growth Suppression by Zn2+‐Integrated Nafion Ionomer Membranes: Beyond Porous Separators toward Aqueous Zn/V2O5 Batteries with Extended Cycle Life

Dendrite Growth Suppression by Zn2+‐Integrated Nafion Ionomer Membranes: Beyond Porous Separators toward Aqueous Zn/V2O5 Batteries with Extended Cycle Life

N‐Doped Graphene Modified 3D Porous Cu Current Collector toward Microscale Homogeneous Li Deposition for Li Metal Anodes

Poly(dimethylsiloxane) Thin Film as a Stable Interfacial Layer for High‐Performance Lithium‐Metal Battery Anodes

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Dendrite Growth Suppression by Zn²⁺‐Integrated Nafion Ionomer Membranes: Beyond Porous Separators toward Aqueous Zn/V₂O₅ Batteries with Extended Cycle Life

Dendrite Growth Suppression by Zn²⁺‐Integrated Nafion Ionomer Membranes: Beyond Porous Separators toward Aqueous Zn/V₂O₅ Batteries with Extended Cycle Life