Professor Feng Jinkui's team of Shandong University: Lightweight, self-supporting, galvanizing MXene@ porous oxide-modified diaphragm for aqueous zinc metal batteries
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First author: EYing
Corresponding author: Professor Feng Jinkui
Communication unit: Shandong University
Thesis DOI: 10.1021/acsnano.2c01571
Full text at a glance
A self-supporting, flexible, galvanistic, MXene@ porous oxide-modified diaphragm is designed to stabilize the metal zinc anode. The porous oxides prepared by vacuum distillation in one step have a large specific surface area, high porosity and a uniform pore structure. MXene@ porous oxide modified layer can uniformly distribute the electric field, promote ion diffusion, and reduce local current density, so the modified diaphragm can induce uniform zinc deposition.
Background
The rechargeable secondary battery has the advantages of high safety, low cost, green pollution-free, etc., so it is considered to be one of the most potential energy storage devices. Zinc metal has the advantages of high theoretical specific capacity, low redox potential, excellent electrochemical stability, and abundant reserves, which makes zinc metal batteries attract much attention. However, the formation and growth of zinc dendrites during the cycle can lead to poor Coulomb efficiency and even puncture of the diaphragm, ultimately causing a short circuit in the battery.
Highlights of this article
1. A lightweight, galvanistic diaphragm is constructed. By MXene@ the heterogeneous structure of porous oxides to modify the diaphragm, so that it can uniformly distribute the electric field, promote ion diffusion, and reduce the local current density, so that uniform zinc deposition can be induced and a long-life zinc anode can be obtained.
2. The porous oxide prepared by the one-step vacuum distillation method has a large specific surface area, high porosity and uniform pore structure, and this method can also be used to synthesize other porous materials.
3. Construct a high-magnification aqueous zinc-ion battery. Using the synthetic self-supporting NS/MXene@MnO2 as the positive electrode, a high-rate full battery was obtained.
4. The modified separator can also be used in other metal battery systems, such as lithium, sodium, potassium, magnesium, calcium and other metal batteries.
Graphic and text analysis
Fig. 1 Schematic diagram of the synthesis of nanoporous oxides by vacuum distillation.
Fig. 2 Transmission electron microscopy and high-power transmission electron microscopy (cm) of nanoporous nickel oxide (a,d), cobalt oxide (b,e), copper oxide (c,f), magnesium oxide (g,j), indium trioxide (h, k), titanium dioxide (f, l).
Fig. 3 X-ray diffraction pattern and specific surface area plot of nanoporous nickel oxide (a,g), cobalt oxide (b,h), copper oxide (c,i), magnesium oxide (d,j), indium trioxide (e,k), titanium dioxide (f,l).
Fig. 4 Schematic diagram of the synthesis of MXene@ porous nickel oxide modified diaphragm.
Fig. 5 MXene@ relevant characterization of porous nickel oxide modified diaphragms. (a) X-ray diffraction pattern, (b) infrared spectrogram and (c) X-ray photoelectron spectra of the unmodified and modified diaphragm. (i,j) Unmodified and (k,l) modified diaphragm scan electron microscopy. (m) scanning electron microscopy element distribution map, (n-q) transmission electron microscope distribution map, and (r) transmission electron microscope element distribution pattern of the modified diaphragm.
Fig. 6 Schematic diagram of the evolution of the deposition behavior of zinc metal on stainless steel collectors when using unmodified and MXene@ porous nickel oxide modified diaphragms and (c-j) scanning electron microscopy diagrams.
Fig. 7 (a-f) Zn || assembled using unmodified and MXene@ porous nickel oxide modified diaphragms Coulomb efficiency diagram of Ti batteries. (g) Zn || assembled with unmodified and MXene@ porous nickel oxide modified diaphragms Graph of the cyclic performance of the Zn battery. Zn || assembled with MXene@ porous nickel oxide-modified diaphragm Zn battery (h) magnification performance diagram and (i) cycle performance diagram at high current density.
Figure 8 (a) Synthetic schematic of the cathode material NS/MXene@MnO2, (b) XRD of MXene, MnO2 and NS/MXene@MnO2, (c) Raman and (d) XPS spectra. (e) Ti 2p, (f) Mn 2p, (g) O 1s, (h) N 1s, (i) S 2p, (j-m) SEM and (n, o) EDS mapping maps for NS/MXene@MnO2.
Fig. 9 Electrochemical performance diagram of a full battery assembled using NS/MXene@MnO2 cathode material and unmodified and modified separators. (a) Cyclic voltammetry, (b) charge-discharge curve, (c) charge-discharge curve for week 50, (d,e) cyclic performance plot, (f) magnification performance plot, (g) capacity retention rate, and (h) cyclic performance plot at large current density.
Fig. 10 Analysis of the energy storage mechanism of a full battery assembled using NS/MXene@MnO2 cathode material and modified diaphragm. (a,b) GITT curve, (c) impedance curve, (d)Z′ and ω–1/2 curves, (e) cyclic voltammetry at different sweep rates, (f,g) graph of peak current and sweep velocity, (h) diffusion and contribution plot of pseudocapacity.
Figure 11 Evolution of metal zinc deposition in a full battery under different diaphragm systems.
Summary and outlook
Stabilize the metal zinc anode by designing a self-supporting, flexible, galvanistic MXene@ porous oxide-modified diaphragm. (1) The porous oxide prepared by one-step vacuum distillation method has a large specific surface area, high porosity and uniform pore structure. (2) Through vacuum distillation, a series of multi-antioxidants are synthesized, such as porous cobalt oxide, porous copper oxide, porous magnesium oxide, porous indium trioxide, porous titanium dioxide and so on. (3) MXene@ porous oxide modification layer can uniformly distribute the electric field, promote ion diffusion, and reduce the local current density, so the modified diaphragm can induce uniform zinc deposition. (4) The modified layer of zinc prophilia can promote the uniform distribution of zinc ion flow. Based on the above advantages, the obtained zinc metal anode has a long cycle life. In addition, this modification method can also be applied to other metal battery systems, such as lithium, sodium, potassium, magnesium, calcium and other metal batteries.
Corresponding Author Introduction
Feng Jinkui, Professor of School of Materials Science and Engineering, Shandong University, Doctoral Supervisor, National High-level Young Talents Inductees, Shandong Taishan Scholar Young Expert, Shandong Jieqing, Qian Yitai Academician Team Member, Main Research Direction, Key Materials for Secondary Batteries. Nearly five years as corresponding author in Energy Environ. Sci. (2)、ACS Nano (7)、Adv. Energy Mater.、 Adv. Funct. Mater (3) 、Energy Storage Mater (4)、Nano Today. Journals such as NanoEnergy (2) have published more than 80 SCI papers, including more than 30 if >10 papers. He has cited more than 8,000 times and cited 16 papers.
Introduction of the first author
Ernst & Young Ling, a 2019 doctoral student at Shandong University, graduated with a Ph.D. in June 2023. His research direction is the controllable preparation and performance and mechanism of high-safety and high-energy density electrode materials, and he has published more than 20 SCI papers in the international top journals Nano Today, Advanced Functional Materials (2), Nano Energy, Energy Storage Materials, ACS Nano (8), with a total of more than 1100 citations, including 3 ESI papers. It has applied for more than 50 patents and authorized 22 patents ([email protected]).
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