中南大学潘安强教授、常智教授Advanced Functional Materials：电响应二维黑磷纳米片诱导水系锌金属电池均匀Zn2+沉积
【Article Information】
Electrically responsive two-dimensional black phosphorus nanosheets induce uniform Zn2+ deposition in aqueous zinc-metal cells
First Author: Li Weihang
Contact: PAN An-qiang*, CHANG Zhi*
Affiliation: Central South University, Xinjiang University
【Background】
Aqueous zinc-metal batteries (AZMBs) are receiving increasing attention due to their abundant zinc metal reserves, high theoretical capacity, low redox potential, and environmental sustainability. However, due to the hydrogen evolution corrosion of active H2O, a large number of Zn4(OH)6SO4·xH2O(ZHS) insulation by-products will be produced on the surface of zinc metal, which will reduce its coulombic efficiency. In addition, the irregular protrusions on the zinc metal lead to the uneven distribution of local currents, which in turn leads to the accumulation of a large amount of Zn2+ around it, resulting in dendrite growth and battery failure.
【Introduction】
近日，来自中南大学、新疆大学的潘安强教授与中南大学的常智教授合作，在国际知名期刊Advanced Functional Materials上发表题为“Electric-responded Two-dimensional Black Phosphorus Nanosheets Induce Uniform Zn2+ Deposition for Efficient Aqueous Zinc-metal Batteries”的文章。 该论文使用二维黑磷（BP）纳米片作为添加剂对水系电解液进行改性。 二维BP纳米片具有独特的电子定向迁移特性，因此在电场作用下，BP纳米片能够迅速迁移至电极表面屏蔽“尖端效应”。
The nanosheets overlaid on the protrusions can induce stable and uniform Zn2+ deposition, effectively inhibiting the formation of dendrites. In addition, the protective layer formed by BP nanosheets can isolate the direct contact between zinc metal and active H2O, thereby inhibiting the occurrence of side reactions. The addition of BP nanosheets significantly improved the cycling stability of AZMB. The results show that the Zn//Zn symmetrical battery based on the modified electrolyte assembly can achieve a stable cycle of 2800 hours at 1 mA cm-2 and 1 mAh cm-2. Zn//NVO (Zn//NH4V4O10) whole battery can still achieve 78.85% capacity retention rate after 1000 cycles at 5 A g-1. The BP nanosheet additive strategy provides a new research idea to promote the practical application of AZMB.
Fig.1 Schematic diagram of the adsorption behavior of BP under electric field and its induced deposition behavior of Zn2+ (a). XRD (b), SEM (c), AFM (d, f) and height distribution (e, g) of 2D-BP. Digital photographs of 0.1, 0.3, 0.5, and 1 P-ZSO (h). XRD patterns of zinc electrodes after immersion in different electrolytes for 3 days (i) and 5 days (j). SEM images of zinc electrodes collected from 0.3 P-ZSO electrolytes after 3 days (k) and 5 days (l), and SEM images of zinc electrodes collected from ZSO electrolytes after 3 days (m) and 5 days (n).
图2 分别基于ZSO和0.3 P-ZSO电解液组装的Zn//Zn对称电池在0.25 mA cm-2和0.25 mAh cm-2(a),1 mA cm-2和1 mAh cm-2(b)、2 mA cm-2和1 mAh cm-2(c)及5 mA cm-2和1 mA cm-2(d)条件下的长循环性能及倍率循环性能(e)。 分别基于ZSO和0.3 P-ZSO电解液组装的Zn//Cu电池在2 mA cm-2和1 mAh cm-2(f)、5 mA cm-2和1 mA cm-2(g)及10 mA cm-2和1 mAh cm-2(h)的条件下的CE。
Fig. 3 In-situ optical observation of zinc deposition in ZSO(a) and 0.3 P-ZSO(b) electrolytes. SEM images of ZSO electrolyte-based zinc electrode after 10 cycles (c) and 100 cycles (d) at 1 mA cm-2 and 1 mAh cm-2. SEM images of a zinc electrode based on 0.3 P-ZSO electrolyte after 10 cycles (e) and 100 cycles (f) at 1 mA cm-2 and 1 mAh cm-2. Cross-sectional SEM images based on ZSO (g) and 0.3 P-ZSO electrolyte (h) after 50 cycles. 3D height images of zinc electrodes based on ZSO(i) and 0.3 P-ZSO electrolytes (j) after 50 cycles at 1 mA cm-2 and 1 mAh cm-2. P2p XPS fit (k) on zinc electrode surface based on 0.3 P-ZSO electrolyte after 50 cycles. XRD profiles of zinc electrodes collected from 0.3 P-ZSO electrolyte at 1 mA cm-2 and 1 mAh cm-2 after different cycles (l).
Fig. 4 Electric field distribution in ZSO(a) and 0.3 P-ZSO(c) electrolytes and Zn2+ concentration gradient distributions in ZSO(b) and 0.3 P-ZSO(d) electrolytes. The interaction energy (e) of the crystal planes of Zn2+-BP and Zn2+-Zinc electrodes (002) and the interaction energy (f) of the crystal planes of H+-BP and H+-Zinc electrodes (002). Nyquist plots (g) and chronogalvanometric curves (h) of Zn//Zn symmetrical cells assembled based on ZSO and 0.3 P-ZSO electrolytes, respectively. Tafel plot of zinc electrode in ZSO and 0.3 P-ZSO electrolyte (i).
Fig.5 CV curves (a) and rate performance (b) of Zn//NVO whole cells assembled based on ZSO and 0.3 P-ZSO electrolytes, respectively. GCD curves (c) of Zn//NVO whole cells assembled based on 0.3 P-ZSO electrolyte at different current densities. Long-cycle performance of Zn//NVO based on ZSO and 0.3 P-ZSO electrolyte assembly at a current density of 5 A g-1 (d). Voltage distribution of a Zn//NVO whole cell assembled based on 0.3 P-ZSO(e) and ZSO electrolyte (f) at a current density of 5 A g-1. Stepwise voltage distribution (g) of a Zn//NVO whole cell assembled based on ZSO and 0.3 P-ZSO electrolytes at a current density of 5 A g-1.
【Main points of the text】
Point 1: The electric double-layer mechanism induced by electron migration in nanosheets can make nanosheets migrate to the electrode surface faster
There are a large number of delocalized π bond electrons in BP nanosheets, and the external electric field can interact with the electrons, thereby inducing the directional migration of electrons to one end of the nanosheet and the formation of an electric double layer (EDL), which in turn causes the nanosheets to migrate rapidly to the electrode surface under the action of the electric field. The protective layer formed by BP nanosheets can effectively isolate the direct contact between zinc metal and active H2O, thereby inhibiting the occurrence of side reactions.
Point 2: The addition of nanosheets can shield the "tip effect" and promote the uniform deposition of Zn2+
BP nanosheets can periodically and dynamically overlay the surface protrusions, weakening the "tip effect" of the electrode, so that the electric field strength of the electrode near the surface remains uniform. The uniform electric field distribution ensured that the concentration distribution of Zn2+ remained stable, and the uniform deposition of Zn2+ was realized, which effectively inhibited the growth of dendrites.
Point 3: The introduction of BP nanosheets slows down electrode corrosion and reduces the generation of ZHS
The direct contact between the BP nanosheet and the zinc electrode isolates the direct contact between the negative electrode and the active H2O, thereby slowing down the corrosion rate of the electrode. In addition, BP nanosheets exhibit weaker interactions with H+ relative to the (002) crystal plane of the zinc anode. Therefore, BP nanosheets covering the surface of zinc metal can improve the energy barrier of hydrogen evolution reaction and slow down the occurrence of side reactions.
【Article Link】
Electric-responded Two-dimensional Black Phosphorus Nanosheets Induce Uniform Zn2+ Deposition for Efficient Aqueous Zinc-metal Batteries
https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.202404146
【About the Corresponding Author】
Professor Pan Anqiang's profile: National high-level young talent, Hunan Province leading talent in science and technology innovation, distinguished professor of sublimation scholar of Central South University, doctoral supervisor, director of the Department of Materials Physics. New Century Outstanding Talent of the Ministry of Education, Huxiang Young Talent (Science and Technology Innovation), and winner of "Outstanding Youth" of Hunan Provincial Natural Science Foundation. He is a member of the 8th and 9th Youth Committee of the Chinese Materials Research Society, and a director of the Hunan Ceramic Society. At present, he has presided over and participated in the National High-level Talent Project, the National High-tech Development Program (863) Project, the National Key R&D Program, the National Natural Science Foundation of China, and the General Project.
湖南省重点研发计划，湖南省自然科学基金杰出青年基金、教育部新世纪优秀人才等项目20余项；迄今为止在 Nat. Commun.，Angew. Chem. Int. Ed., Adv. Mater., Adv. Energy Mater., Adv. Funct. Mater., Energy Environ. Sci., ACS Energy Lett., Nano Energy., Energy Storage Mater.等国际期刊上发表论文180余篇，论文引用>13000次，H指数66。 授权中国发明专利20余项。
Professor Chang Zhi's profile: Professor, Sublimation Scholar (Top Notch Gang), Doctoral Supervisor, selected into the National Overseas High-level Young Talents Program (Overseas Excellent Youth) in 2022. Ph.D. and postdoctoral fellow under the supervision of Prof. Haoshen Zhou, an internationally renowned electrochemist (National University of Tsukuba & National Institute of Advanced Industrial Science and Technology (AIST), Japan. He is mainly engaged in the research of high specific energy lithium-ion battery/lithium metal battery electrolyte, functional separator, solid electrolyte, metal anode protection and other directions.
近五年发表SCI论文90余篇，其中以第一及通讯作者在Joule，Nat. Commun. (x 2)，Angew. Chem. Int. Ed. (x 5) ，Adv. Mater. (x 2) ，Energy Environ. Sci. (x 3) ，Adv. Energy Mater.，Adv. Sci.，Adv. Funct. Mater. (x4) ，Energy Storage Mater. (x 2) ，Small (x 2) ，J. Mater. Chem. A (x 4) 等刊物上发表论文34篇，他引超过5500次，H因子38，申请国家发明专利8项。 担任SCI期刊Materials客座编辑，eScience期刊青年编委以及Nat. Com., AM, Angew, EES, JACS, AFM, AEM, EnSM等国际期刊的审稿人。