Dynamically Interfacial pH‐Buffering Effect Enabled by
            <i>N</i>
            ‐Methylimidazole Molecules as Spontaneous Proton Pumps toward Highly Reversible Zinc‐Metal Anodes

Zhang, Minghao; Hua, Haiming; Dai, Pengpeng; Zheng, He; Han, Lianhuan; Tang, Peiwen; Yang, Jae Young; Lin, Pengxiang; Zhang, Yufei; Zhan, Dongping; Chen, Jianken; Qiao, Yu; Li, Cheng Chao; Zhao, Jinbao; Yang, Yang

doi:10.1002/adma.202208630

Cited by 72 publications

(50 citation statements)

References 68 publications

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“…This is attributed to the fact that CYC, which is also negatively charged, replaces SO 4 2– at the interface by atomic pinning, thereby homogenizing the surface electric field and promoting uniform Zn deposition. The mechanism is further demonstrated by the CV-based electrochemical quartz crystal microbalance (EQCM) tests. , To avoid the mass changes associated with Zn plating, 0.2 M Na 2 SO 4 is used as the electrolyte. When the potential is swept from 0.6 to −0.6 V, the Δ m value in the electrode surface of the system without CYC-Na is only about 10 ng and decreases to 0 when the potential is returned to 0.6 V (Figure f).…”

Section: Results and Discussionmentioning

confidence: 99%

Atomic Pinning of Trace Additives Induces Interfacial Solvation for Highly Reversible Zn Metal Anodes

Duan,

Wang,

Sun

et al. 2023

ACS Nano

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Aqueous Zn metal batteries are considered promising energy storage devices due to their high energy density and low cost. Unfortunately, such great potential is at present obscured by two clouds called dendrite growth and parasitic reactions. Herein, trace amounts of sodium cyclamate (CYC-Na) are introduced as an electrolyte additive, and accordingly, an atomic-pinning-induced interfacial solvation mechanism is proposed to summarize the effect of trace addition. Specifically, coadsorption of −NH– and −SO3 groups overcomes the ring-flipping effect and pins the CYC anion near the Zn anode surface in parallel, which significantly modifies the Zn2+ solvation sheath at the interface. This process homogenizes the surface Zn2+ flux and reduces the H2O and SO4 2– content on the surface, thus eliminating byproducts and leveling Zn deposition. Cells with trace CYC-Na cycle stably for 3650 h and still cycle for 330 h at high depths of discharge of 56.9%. This work dispels the clouds for efficient trace additives for AZMBs.

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Section: Results and Discussionmentioning

confidence: 99%

Atomic Pinning of Trace Additives Induces Interfacial Solvation for Highly Reversible Zn Metal Anodes

Duan,

Wang,

Sun

et al. 2023

ACS Nano

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“…[24] Here, nitrogen functional sites are expected to improve the electronic conductivity and the reversibility of the Zn anode (Figure S2c-f, Supporting Information). [25] However, when the annealing temperature was higher than the boiling point (907 °C) of Zn metal, only two characteristic peaks at 44°and 51°corresponding to the (111), (200) crystal planes of the metal Co phase and a wide characteristic peak at ≈25°, corresponding to the (002) crystal plane of amorphous carbon, can be observed in the XRD pattern of ZCDC, indicating that ZnCo ZIF-L has been completely carbonized and Zn 0 no longer exists (Figure S1b, Supporting Information). [24] Specific surface area and pore structure of a 3D host are critical to the ionic migration and volume accommodation within metal anodes.…”

Section: Resultsmentioning

confidence: 99%

A Lean‐Zinc and Zincophilic Anode for Highly Reversible Zinc Metal Batteries

Shao

Luo

et al. 2023

Adv Funct Materials

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Lean‐zinc anode is a promising configuration that can eliminate the trade‐off of energy density and cycle lifetime of zinc metal (Zn0) batteries. However, there are rare investigations of lean‐Zn anode designs and it remains a grand change to sustain high zinc reversibility under lean zinc conditions. Herein, a lean‐Zn anode design based on a hierarchical and zincophilic cobalt metal (Co0) nanowire‐decorated carbon host, which is derived from a ZnCo bimetallic organic framework, is reported. Within the lean‐Zn anode, the trace amount of Zn0 acts as a zinc reservoir to make up for any irreversible loss of zinc source upon cycling, while the zincophilic Co0 nanowires can guide uniform zinc nucleation and growth through a lattice matching mechanism. Consequently, high Zn0 reversibility (average Coulomb efficiency of 99.6% for 4250 cycles), low nucleation overpotential (50.8 mV at 1 mA cm−2), and uniform and compact zinc electrodeposition are realized. When coupling the lean‐Zn anode with a Zn‐containing cathode, the full cell delivers high Coulomb efficiency (99.6% for 4250 cycles on average) and a long lifetime of more than 5000 cycles.

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“…Obvious frequency change (Δ f ) of can be observed, confirming the additive adsorption at the interface. According to the Sauerbrey relation, the mass change is estimated as 35.6 ng . After the baseline electrolyte was reintroduced in the final step, the frequency increased but failed to recover to the initial value in the first step, suggesting the structural stability of the adsorption layer.…”

mentioning

confidence: 99%

“…According to the Sauerbrey relation, the mass change is estimated as 35.6 ng. 28 After the baseline electrolyte was reintroduced in the final step, the frequency increased but failed to recover to the initial value in the first step, suggesting the structural stability of the adsorption layer. Complementary support comes from the electrochemical impedance spectroscopy (EIS), where the ZSO-2959 electrolyte shows much higher charge transfer resistance than the baseline electrolyte after 2 h of rest, while there is no obvious difference initially (Figure S2).…”

mentioning

confidence: 99%

Interfacial Molecule Engineering for Reversible Zn Electrochemistry

Lin

Luo

et al. 2023

ACS Energy Lett.

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The unstable Zn interface caused by undesired dendrites and parasitic side reactions greatly impedes the deployment of aqueous Zn metal batteries. Herein, an efficient adsorptive additive strategy is proposed to reshape the electric double layer and regulate Zn interfacial chemistry. 2-Hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone (Irgacure 2959) was selected owing to its strong adsorption ability, intermolecular hydrogen bonding, and exposed strong electronegative carbonyl group. The constructed self-adaptive adlayer contributes to a localized H 2 O, SO 4 2− -poor environment and horizontal alignment of Zn deposits along the (002) plane, thus endowing thermodynamically stable and highly reversible Zn electrochemistry. As a result, reversible plating/stripping of 3800 h and high Coulombic efficiency of 99.8% are achieved. Intriguingly for practical application, the economical additive (0.016 USD L −1 ) enables stable discharge output for 500 cycles in Zn/VS 2 cells at a low negative-to-positive capacity ratio of 2.5 (cathode mass loading: 10.8 mg cm −2 ), holding great promise for use in a scalable, low-cost, rechargeable battery.

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Dynamically Interfacial pH‐Buffering Effect Enabled by N ‐Methylimidazole Molecules as Spontaneous Proton Pumps toward Highly Reversible Zinc‐Metal Anodes

Cited by 72 publications

References 68 publications

Atomic Pinning of Trace Additives Induces Interfacial Solvation for Highly Reversible Zn Metal Anodes

Atomic Pinning of Trace Additives Induces Interfacial Solvation for Highly Reversible Zn Metal Anodes

A Lean‐Zinc and Zincophilic Anode for Highly Reversible Zinc Metal Batteries

Interfacial Molecule Engineering for Reversible Zn Electrochemistry

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