Magnesium-ion batteries (MIBs) are considered strong candidates for next-generation energy-storage systems owing to their high theoretical capacity, divalent nature and the natural abundancy of magnesium (Mg) resources on Earth. However, the development of MIBs has been mainly limited by the incompatibility of Mg anodes with several Mg salts and conventional organic-liquid electrolytes. Therefore, one major challenge faced by MIBs technology lies on developing safe electrolytes, which demonstrate appropriate electrochemical voltage window and compatibility with Mg anode. This review discusses the development of MIBs from the point-of-view of the electrolyte syntheses. A systematic assessment of promising electrolyte design strategies is proposed including liquid and solid-state electrolytes. Liquid-based electrolytes have been largely explored and can be categorized by solvent-type: organic solvent, aqueous solvent, and ionic-liquids. Organic-liquid electrolytes usually present high electrochemical and chemical stability but are rather dangerous, while aqueous electrolytes present high ionic conductivity and eco-friendliness but narrow electrochemical stability window. Some ionic-liquid electrolytes have proved outstanding performance but are fairly expensive. As alternative to liquid electrolytes, solid-state electrolytes are increasingly attractive to increase energy density and safety. However, improving the ionic conductivity of Mg ions in these types of electrolytes is extremely challenging. We believe that this comprehensive review will enable researchers to rapidly grasp the problems faced by electrolytes for MIBs and the electrolyte design strategies proposed to this date.

Research development on electrolytes for magnesium-ion batteries

In recent years, titanium(IV) dioxide nanoparticles (TiO2NPs) have shown promising potential in various biological applications such as antimicrobials, drug delivery, photodynamic therapy, biosensors, and tissue engineering. For employing TiO2NPs in these fields, their nanosurface must be coated or conjugated with organic and/or inorganic agents. This modification can improve their stability, photochemical properties, biocompatibility, and even surface area for further conjugation with other molecules such as drugs, targeting molecules, polymers, etc. This review describes the organic-based modification of TiO2NPs and their potential applications in the mentioned biological fields. In the first part of this review, around 75 recent publications (2017-2022) are mentioned on the common TiO2NP modifiers including organosilanes, polymers, small molecules, and hydrogels, which improve the photochemical features of TiO2NPs. In the second part of this review, we presented 149 recent papers (2020-2022) about the use of modified TiO2NPs in biological applications, in which specific bioactive modifiers are introduced in this part with their advantages. In this review, the following information is presented: (1) the common organic modifiers for TiO2NPs, (2) biologically important modifiers and their benefits, and (3) recent publications on biological studies on the modified TiO2NPs with their achievements. This review shows the paramount significance of the organic-based modification of TiO2NPs to enhance their biological effectiveness, paving the way toward the development of advanced TiO2-based nanomaterials in nanomedicine.

Surface modification of TiO2 nanoparticles with organic molecules and their biological applications.

Rational design of artificial interphase buffer layer with 3D porous channel for uniform deposition in magnesium metal anodes

Non-nucleophilic and non-fluorinated compounds are the most important class of solvent to enable sustainable rechargeable magnesium (Mg) batteries, however, they suffer from poor stability due to the formation of unstable...

Non-nucleophilic electrolyte with non-fluorinated hybrid-solvents for long-life magnesium metal batteries

Non‐passivating and chlorine‐free electrolytes are crucial for making rechargeable magnesium batteries practically feasible. Rational design of a brand‐new electrolyte should balance both Mg salt and solvent considering that the interfacial reactions occurring at electrolyte/electrode interface involve with ion solvation structure. Herein, nitrogenous 2‐methoxyethylamine (MOEA) is employed as co‐solvent to regulate the coordination behavior of cations/anions in Mg(CF3SO3)2‐G2 electrolyte after a series of screenings, which enables significantly ameliorated physiochemical properties. In‐depth insight on the mechanism of MOEA participating in the solvation structure formation and interfacial reactions is deduced via density functional theory calculations and molecular dynamics simulations. The decompositions of MOEA‐tailored cationic/anionic complexes shield Mg anode and Mo6S8 cathode with Mg3N2 and CxNy‐rich layers, respectively, which enable to suppress side reaction and accelerate Mg2+ transportation with competing desolvation at the interfacial layer. All the merits endow remarkable performances of symmetric/asymmetric cells with ultralong‐cycle lives over 5000 h and a remarkable average Coulombic efficiency of 98.3% after 8200 cycles (≈11 months), respectively. Additionally, a cheerful discharge capacity of ≈59.3 mAh g−1 is obtained over 1000 cycles at 0.5 C in Mo6S8||Mg full cell.

Constructing Efficient Mg(CF3SO3)2 Electrolyte via Tailoring Solvation and Interface Chemistry for High‐Performance Rechargeable Magnesium Batteries

Passivation of the Mg anode surface in conventional electrolytes constitutes a critical issue for practical Mg batteries. In this work, a perfluorinated tert‐butoxide magnesium salt, Mg(pftb)2, is codissolved with MgCl2 in tetrahydrofuran (THF) to form an all‐magnesium salt electrolyte. Raman spectroscopy and density function theory calculation confirm that [Mg2Cl3·6THF]+[Mg(pftb)3]− is the main electrochemically active species of the electrolyte. The proper lowest unoccupied molecular orbital energy level of the [Mg(pftb)3]− anion enables in situ formation of a stable solid electrolyte interphase (SEI) on Mg anodes. A detailed analysis of the SEI reveals that its stability originates from a dual‐layered organic/inorganic hybrid structure. Mg//Cu and Mg//Mg cells using the electrolyte achieve a high Coulombic efficiency of 99.7% over 3000 cycles, and low overpotentials over ultralong‐cycle lives of 8100, 3000, and 1500 h at current densities of 0.5, 1.0, and 2.0 mA cm−2, respectively. The robust SEI layer, once formed on a Mg electrode, is also shown highly effective in suppressing side‐reactions in a TFSI−‐containing electrolyte. A high Coulombic efficiency of 99.5% over 800 cycles is also demonstrated for a Mg//Mo6S8 full cell, showing great promise of the SEI forming electrolyte in future Mg batteries.

Stable Solid Electrolyte Interphase In Situ Formed on Magnesium‐Metal Anode by using a Perfluorinated Alkoxide‐Based All‐Magnesium Salt Electrolyte

Circulating tumor cells (CTCs) can be the seeds of tumor metastasis and are closely linked to cancer-related death. Fast and effective detection of CTCs is important for the early diagnosis of cancer and the evaluation of micrometastasis. However, the extreme rarity and heterogeneity of CTCs in peripheral blood make sensitive detection of CTCs a big challenge. In this paper, a TiO2-based surface-enhanced Raman scattering (SERS) bioprobe is reported for the first time with outstanding ultrasensitive specificity, excellent stability of the signal, and good biocompatibility for the detection of CTCs. The TiO2 NPs were encoded with alizarin red (AR) and functionalized with reduced bovine serum protein (rBSA) and folic acid (FA). The limit of detection (LOD) for 4-mercaptobenzoic acid (4-MBA) and AR molecules adsorbed on the TiO2 SERS substrate is 5 × 10-7 M. The designed TiO2-based SERS bioprobe can be effectively utilized in detecting four diverse types of cancer cells in rabbit blood, which shows good sensitivity of the SERS detection technology. Finally, precise targeting of CTCs based on the SERS bioprobe with the function of fluorescence imaging is also confirmed by the fluorescence colouration test. This work offers a novel strategy for CTC detection and the development of non-noble metal semiconductor-based SERS platforms for tumor diagnosis.

A TiO2-based bioprobe enabling excellent SERS activity in the detection of diverse circulating tumor cells.

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Stable Solid Electrolyte Interphase In Situ Formed on Magnesium‐Metal Anode by using a Perfluorinated Alkoxide‐Based All‐Magnesium Salt Electrolyte

A TiO2-based bioprobe enabling excellent SERS activity in the detection of diverse circulating tumor cells.