Stabilizing Interface pH by N-Modified Graphdiyne for Dendrite-Free and High-Rate Aqueous Zn-Ion Batteries

Qi Yang; Liang Li; Tanveer Hussain; Donghong Wang; Lan Hui; Ying Guo; Guojin Liang; Xinliang Li; Ze Chen; Zhaodong Huang; Yongjun Li; Yurui Xue; Zicheng Zuo; Jieshan Qiu; Yuliang Li; Chunyi Zhi

doi:10.1002/anie.202112304

Stabilizing Interface pH by N-Modified Graphdiyne for Dendrite-Free and High-Rate Aqueous Zn-Ion Batteries

Angew Chem Int Ed Engl. 2022 Feb 1;61(6):e202112304. doi: 10.1002/anie.202112304. Epub 2021 Dec 20.

Authors

Qi Yang^{1

2}, Liang Li³, Tanveer Hussain⁴, Donghong Wang², Lan Hui³, Ying Guo², Guojin Liang², Xinliang Li², Ze Chen², Zhaodong Huang², Yongjun Li³, Yurui Xue³, Zicheng Zuo³, Jieshan Qiu⁵, Yuliang Li³, Chunyi Zhi^{1

2}

Affiliations

¹ Hong Kong Center for Cerebro-Cardiovascular Health Engineering, Hong Kong SAR, 999077, China.
² Department of Materials Science and Engineering, City University of Hong Kong, 83 Tat Chee Avenue, Hong Kong SAR, 999077, China.
³ Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
⁴ School of Chemical Engineering, The University of Queensland, St Lucia, QLD, 4072, Australia.
⁵ State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, China.

PMID: 34799952
DOI: 10.1002/anie.202112304

Abstract

Zn dendrite issue was intensively studied via tuning zinc ion flux. pH change seriously influences dendrite formation, while its importance has not been revealed. Here, we construct a N-modification graphdiyne interface (NGI) to stabilize pH by mediating hydrated zinc ion desolvation. Operando pH detection reveals pH stabilization by NGI. This works with pores in NGI to achieve dendrite-free Zn deposition and an increased symmetric cell lifespan by 116 times. Experimental and theoretical results owe pH stabilization to desolvation with a reduced activation energy achieved by electron transfer from solvation sheath to N atom. The efficient desolvation ensures that electron directly transfers from substrate to Zn²⁺ (rather than the coordinated H₂ O), avoiding O-H bond splitting. Hence, Zn-V₆ O₁₃ battery achieves a long lifespan at 20.65 mA cm^-2 and 1.07 mAh cm^-2 . This work reveals the significance of interface pH and provides a new approach to address Zn dendrite issue.

Keywords: Zn batteries; Zn dendrite; desolvation; graphdiyne; interface pH.

Grants and funding

CityU 11305218/GRF Scheme