Research Progress of Bentonite-based Functional Materials in Electrochemical Energy Storage

doi:10.15541/jim20240240

Abstract

Abstract:

Bentonite is an abundant, cheap and readily available natural clay mineral, with montmorillonite (MMT) as its main mineral composition. MMT possesses excellent ion exchange, adsorption and ion transport properties due to its unique two-dimensional layered nanostructure, abundant pore structure, and high specific surface area. Moreover, it also possesses excellent thermal, chemical and mechanical stabilities. In recent years, MMT has attracted extensive attention in the field of electrochemical energy storage owing to the above excellent characteristics, especially the inherent fast ion (Li⁺, Na⁺, Zn²⁺, etc.) transport properties. Thus, the bentonite-based functional materials have been widely applied to the key components (i.e., electrodes, polymer electrolytes, and separators) of electrochemical energy storage devices and show good application prospects. In this review, the structure and physicochemical properties of bentonite are firstly introduced, and then the research progress of bentonite-based functional materials in the field of electrochemical energy storage, mainly including metal anodes, lithium-sulfur battery cathodes, solid/gel polymer electrolytes, and polymer separators, is comprehensively summarized. On the basis of these facts, the ion transport promotion mechanism of bentonite-based functional materials during the process of electrochemical energy storage is elaborated. Finally, the current problems and challenges faced by application of bentonite-based materials in electrochemical energy storage devices are pondered, and the possible future research directions are prospected. This review provides useful guidance for the design and development of bentonite-based electrochemical energy storage functional materials.

Key words: electrochemical energy storage, bentonite, electrode, electrolyte, separator, review

CLC Number:

TB332

WEN Zhipeng, WEI Yi, HOU Xianghua, GUO Jiawen, LI Qu, ZHU Manqing, ZHANG Jiahao, PAN Kai, WU Lian. Research Progress of Bentonite-based Functional Materials in Electrochemical Energy Storage[J]. Journal of Inorganic Materials, 2024, 39(12): 1301-1315.

Figures/Tables 9

Fig. 1 Schematic illustration of MMT crystal structure

Fig. 2 Application of bentonite in electrochemical energy storage devices

Fig. 3 Applications of bentonite-based functional materials in metal anodes (a) Schematic diagram of the lithium ion pumping effect in the interlayers of Ag-montmorillonite (AMMT); (b) Voltage profiles of the AMMT/Cu@Li||AMMT/Cu@Li and Li||Li symmetrical batteries under 1 mA·cm-2 and 1 mAh·cm-2 conditions with insets showing voltage profiles at different cycles[38]; (c) Preparation schematic of hexadecyl trimethyl ammonium bromide (CTAB)-pillared organic-montmorillonite (OMMT) mixed ZnSO4/MnSO4 liquid electrolyte as a protective layer (denoted as ZnOMMT) for zinc-ion batteries (ZIBs); (d) Long-term cycling performance of ZIBs with ZnOMMT protective layer at 2.0 A·g−1 [40]; (e) Preparation schematic and SEM image of the Na-montmorillonite (Na-MMT) modified Na metal anode (Na@Na-MMT); (f) Rate performance at different current densities and (g) cycling performance at 2C of the Na||Na3V2(PO4)3 (NVP), Na@Ca-montmorillonite (Ca-MMT)||NVP, and Na@Na-MMT||NVP batteries[42]

Fig. 4 Preparation, action mechanism and electrochemical performance of bentonite-based host materials for lithium-sulfur battery cathodes (a) Adsorption conformations of Li-montmorillonite (Li-MMT) on various lithium polysulfides (Li2S, Li2S2, Li2S3, Li2S4, Li2S6, and Li2S8); (b) Crystal structure of Li-MMT[28]; (c) Preparation schematic of the S/CoS2@montmorillonite (S/CoS2@MMT) composite materials; (d) SEM image of CoS2@MMT; (e) Rate performance of the S/CoS2@MMT, S/CoS2, and S/MMT cathodes; (f) Cycling performance of the S/CoS2@MMT with a sulfur loading of 4.0 mg·cm-2[47]

Fig. 5 Structure and Li ion transport properties of fast Li ion transport path constructed by bentonite nanosheets in solid polymer electrolytes[74] (a) Schematic illustration of dual Li+ transportation pathways in the Li-montmorillonite (Li-MMT)/polyvinylidene difluoride-hexafluoropropylene (PVDF-HFP) solid electrolyte (Li-MPSE); (b) Electrochemical impedance spectra (EIS) of PVDF-HFP solid electrolyte (PSE), montmorillonite/PVDF-HFP solid electrolyte (MPSE), and Li-MPSE; (c) Chronoamperometry curve of Li/Li-MPSE/Li with 10 mV at room temperature with inset showing the initial and steady-state EIS of the cell; (d) Cycling performance of Li/Li-MPSE/LiFePO4 (LFP) and Li/PSE/LFP batteries

Fig. 6 Directional ion transport pathways constructed by vertically arranging bentonite nanosheets in gel polymer electrolytes (GPEs)[75] (a, b) Schematic illustration of (a) vertical-aligned montmorillonite prepared by directional freezing technology and (b) fabrication process of GPEs with/without vertical-aligned ion pathways; (c) Top view SEM image of the ion-conducting arrays GPEs

Fig. 7 Preparation process and thermostability of bentonite-based functional material filling modified polymer separator[93] (a) Preparation of organic-montmorillonite (OMMT) via the intercalation modification of Na-montmorillonite (Na-MMT) by hexadecyl trimethyl ammonium bromide (CTAB) and preparation of polyimide (PI)/OMMT nanofibrous membrane via the thermal imidization of polyamide acid (PAA)/OMMT; (b) Photographs of Celgard 2400 and PI/OMMT hybrid separators before and after exposure to 180 ℃ for 0.5 h and (c) the corresponding thermal shrinkage changes at different OMMT mass fractions of 0, 3%, 5%, 7%, and 10% (denoted as PI/0 wt%-OMMT, PI/3 wt%-OMMT, PI/5 wt%-OMMT, PI/7 wt%-OMMT, and PI/10 wt%-OMMT, respectively)

Fig. 8 Structure, action mechanism and electrochemical performance of bentonite-based functional coating on the surface of separators for lithium sulfur batteries (a) SEM image of Keggin Al13-pillared montmorillonite (AlMMT)@polypropylene (PP) separator with inset showing its optical image; (b) Cross- sectional SEM image and EDS mappings of AlMMT@PP separator[99]; (c) Schematic illustration of functions of the selenium-doped sulfurized-polyacrylonitrile (Se0.06SPAN)/montmorillonite (MMT) coating layer; (d) Cycling performance at 1C of different separators (PP, MMT@PP, Se0.06SPAN@PP, and Se0.06SPAN/MMT@PP) with a sulfur loading of 0.8 mg·cm-2; (e) First cycle charge and discharge curves of Li-S battery with Se0.06SPAN/MMT@PP separator at a sulfur loading of 26.75 mg·cm-2[101]; (f) Surface and cross-sectional SEM images of FeS2@MMT/PP separator; (g) Binding energies of lithium polysulfides (Li2Sx, x=1, 2, 4, 6, 8) on MMT and FeS2 (200) surface (left), energy profiles for the reactions from Li2S8 to Li2S (upper right), and energy barrier profiles of Li2S decomposition on MMT and FeS2 (200) surface (lower right)[102]

Fig. 9 Promotion mechanism of ion transport by bentonite-based functional materials during electrochemical energy storage process (a) Finite element simulations of the current distribution in cross-linked methoxy poly(ethylene glycol) acrylate (CMP)/vertical-aligned montmorillonite (VAMMT), CMP/MMT, and CMP GPEs[75]; (b) Molecular dynamics simulations of the electrolyte system (LiPF6 in ethylene carbonate (EC)/diethyl carbonate (DEC)) with/without MMT, and the corresponding (c) radial distribution function and (d) distribution of Li ion clusters[69]; (e) Migration pathways and energy barriers of Zn2+ along the a axis and b axis of the Zn-MMT (001) surface[105]

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