Abstract Direct methanol fuel cells, DMFCs, have for long been considered as a superior alternative to rechargeable batteries for various portable applications with respect to significantly higher theoretical power densities and faster recharging by simply filling up with new liquid fuel. In reality, however, DMFCs so far have much low power densities, suffer from high fuel losses, and require extremely expensive catalysts at high loadings. Here we show that an until now not considered process at the DMFC electrodes may cause these severe losses in performance. The process is that electrons generated at nano‐structured catalyst loaded electrodes become solvated into the surrounding electrolyte. Taking this new process and resulting reaction mechanism(s) fully into account, material and catalyst/electrode design should be reconsidered to realize the true potential of DMFCs.

Silicon (Si) has shown its promises as anode material for next-generation high-energy lithium-ion batteries (LIBs) due to its high theoretical capacity 1 . However, its practical application has been impeded by the severe cyclic instability caused by a large volume change during (de) lithiation. Recently, a new family of silicon-based anode materials called “in-situ convertible-type anode materials” has emerged to resolve the cyclic instability of silicon. 2,3 This family includes sub-stoichiometric oxides, nitrides, and carbides of silicon (SiA x , where A = N, C, O). The working principle of these materials follow two mechanisms: (1) irreversible conversion and (2) reversible alloying/dealloying. During initial lithiation, the conversion reaction occurs, forming Si-Li nanodomains inside a stable Li-conductive matrix denoted as Li y Si x A (A=N, C, O). In the subsequent cycles, the Si-Li nanodomains reversibly alloying/dealloying with Li, while the Li-conductive matrix ensures stable cycling and good rate capability. Such composition mitigates the challenges associated with Si’s large volume change ensuring long-term cyclic stability. In this study, we demonstrate our approach on the development of silicon-rich, sub-stochiometric, amorphous silicon nitride (SiN x ) nanoparticles, as an in-situ convertible-type anode material and its long-term cyclic performance for LIBs. In this approach, the SiN x nanoparticles are produced via the decomposition of silane gas in the presence of ammonia using an industrially scalable, free space reactor (FSR), which is developed and customized in our research institute (IFE) (Fig. 1a). Proper proportions of silane and ammonia gases are introduced into the reactor, leading to the nucleation and growth of SiN x nanoparticles. The synthesized SiNx nanoparticles exhibited Si-rich domain and amorphous structure with particle size between 100 nm - 200 nm (Fig. 1b), as confirmed by SEM, TEM and XRD characterizations. The presence of nitrogen in silicon dominated composition is revealed by energy dispersive electron spectroscopy (EDS) and Fourier-transform infrared spectroscopy (FTIR). The scalability and reproducibility of the FSR synthesis method makes it a promising approach for the industrial production of SiNx for advance anode materials for LIBs. The electrochemical performance of the synthesized SiNx anode is evaluated by galvanostatic cycling and electrochemical impedance spectroscopy. The electrochemical performance of the SiNx performed on the electrodes with the active mass loading of 0.987 mg/cm 2 and cycled at C/5 rate has preserved its capacity about 852 mAh/g after around 600 cycles. As seen from Fig. 1c, the improved cyclic stability of the SiN x compared with pure silicon indicates that the Li-conductive matrix plays crucial role in stabilizing the anode. The authors emphasize the need for further investigation and collaboration, particularly in advance characterization, to better understand the composition and mechanisms of the Li-conductive matrix in the SiN x anode. Such detailed understanding can significantly benefit the conversion-type anode materials for their widespread use in future LIB technologies. References Zuo, X., Zhu, J., Müller-Buschbaum, P. & Cheng, Y.-J. Silicon based lithium-ion battery anodes: A chronicle perspective review. Nano Energy 31 , 113–143 (2017). Ulvestad, A. et al. Stoichiometry-Controlled Reversible Lithiation Capacity in Nanostructured Silicon Nitrides Enabled by in Situ Conversion Reaction. ACS Nano 15 , 16777–16787 (2021). Kilian, S. O. et al. Active Buffer Matrix in Nanoparticle-Based Silicon-Rich Silicon Nitride Anodes Enables High Stability and Fast Charging of Lithium-Ion Batteries. Advanced Materials Interfaces 9 , 2201389 (2022). Figure 1

Li-ion capacitors (LICs) are designed to achieve high power and energy densities using a carbon-based material as a positive electrode coupled with a negative electrode often adopted from Li-ion batteries. However, such adoption cannot be direct and requires additional materials optimization. Furthermore, for the desired device's performance, a proper design of the electrodes is necessary to balance the different charge storage mechanisms. The negative electrode with an intercalation or alloying active material must provide the high rate performance and long-term cycling ability necessary for LIC functionality-a primary challenge for the design of these energy-storage devices. In addition, the search for new active materials must also consider the need for environmentally friendly chemistry and the sustainable availability of key elements. With these factors in mind, this review evaluates advanced and emerging materials used as high-rate anodes in LICs from the perspective of their practical implementation.

This chapter analyzes state-of-the-art and progresses on nanomaterials’ utilization for multivalent-ion (e.g., Mg, Ca, Zn, Al) battery applications. The work comprises four sections, namely carbon-based, metal-based, metal oxide-based, and metal sulfide-based nanomaterials. These four classes of materials are evaluated in terms of structure, morphology, and electrochemical energy storage properties.

In this work we have investigated the charge storage mechanism of MnO2 electrodes in ionic liquid electrolytes. We show that by using an ionic liquid with a cation that has the ability to form hydrogen bonds with the active material (MnO2) on the surface of the electrode, a clear faradaic contribution is obtained. This situation is found for ionic liquids with cations that have a low pKa, i.e. protic ionic liquids. For a protic ionic liquid, the specific capacity at low scan rate rates can be explained by a densely packed layer of cations that are in a standing geometry, with a proton directly interacting through a hydrogen bond with the surface of the active material in the electrode. In contrast, for aprotic ionic liquids there is no interaction and only a double layer contribution to the charge storage is observed. However, by adding an alkali salt to the aprotic ionic liquid, a faradaic contribution is obtained from the insertion of Li+ into the surface of the MnO2 electrode. No effect can be observed when Li+ is added to the protic IL, suggesting that a densely packed cation layer in this case prevent Li-ions from reaching the active material surface.

Aluminum (Al) batteries are fundamentally a promising future post-Li battery technology. The recently demonstrated concept of an Al-graphite battery represents some significant progress for the technology, but the cell energy density is still very modest and limited by the quantity of the AlCl3 based electrolyte, as it relies on AlCl4‒ intercalation. For further progress, cathode materials capable of an electrochemical reaction with Al positively charged species are needed. Here such a concept of an Al metal anode ‒ organic cathode battery based on anthraquinone (AQ) electrochemistry with a discharge voltage of 1.1 V is demonstrated. Further improvement of both the cell capacity retention and rate capability is achieved by nano-structured and polymerized cathodes. The intricate electrochemical mechanism is proven to be that the anthraquinone groups undergo reduction of their carbonyl bonds during discharge and become coordinated by AlCl2+ species. Altogether the Al metal anode – AQ cathode cell has almost the double energy density of the state-of-the-art Al-graphite battery.

Solid state microbatteries are highly sought after for emerging microsensor technologies. To overcome the problem of the dwarfing capacity resulting from the miniaturization of the battery, 3D-structured platform consisting of high surface area micropillar-shaped electrodes are used. However, applying a conformal and continuous solid polymer electrolyte films onto the intricate 3D electrodes is a crucial step toward achieving functional microbatteries. In this work, we present our approach for the development of polyethylene oxide (PEO)-acrylate based ion conducting polymer thin films which function as solid polymer electrolyte (SPE) and a separator. The SPEs were electrochemically deposited on the 3D electrodes resulting in ultrathin, continuous, conformal, and pinhole-free polymer films. The electrochemical and Li+ ions transport properties of the SPEs were characterized by EIS measurements and cyclic voltammetry. Furthermore, the homogenous composition of the SPEs at various depths were confirmed by XPS depth profiling techniques. (C) The Author(s) 2019. Published by ECS.

Water-in-salt and water-in-bisalt electrolytes have recently attracted much attention due to their expanded electrochemical stability windows. The concentration limit of such electrolytes is constrained by the solubility of the lithium salts employed, ca. 21 m (mol kg(-1)) for LiTFSI (lithium bis(trifluoromethanesulfonyl)imide). By adding a second lithium salt, the total salt concentration can be increased, but the hydrogen evolution keeps limiting the application of such systems in batteries with low potential anodes. Herein we report a water-in-bisalt electrolyte with a record salt concentration (31.4 m LiTFSI + 7.9 m Li[N(CH3)(2)((CH2)(3)SO3((CH2)(4)SO3)]) in which the bulky anion completely prevents the crystallization, even at such low water contents. Although the hydrogen evolution reaction is not completely suppressed, the expanded electrochemical stability window allows for low potential reactions such as aluminum-lithium alloying. The high salt concentration favors the formation of a suitable passivation layer that can be further engineered by modifying the anion structure.

We report on a novel, simple, and environmentally benign synthesis route for a free-standing reduced graphene oxide (r-GO) aerogel and its application as supporting electrode for the electrochemical redox reaction of sulphur in a catholyte-based lithium-sulphur battery. A mesoporous matrix is formed by a layers of r-GO, providing sites for electrochemical reactions and a highly conducting pathway for electrons. The highly porous structure is easily infiltrated by a catholyte solution providing a homogeneous distribution of the sulphur active material in the conductive graphene matrix and ensuring efficient electrochemical reactions. This is demonstrated by a high capacity, 3.4 mAh cm(-2), at high mass loading, 3.2 mg cm(-2) of sulphur in the cathode and in total the sulphur loading in the Li-S cell is even double (6.4 mg cm(-2)). Additionally, the presence of oxygen groups in the r-GO aerogel structure stabilizes the cycling performance and the Li-S cell with the fluorine free catholyte shows a capacity retention of 85% after 350 cycles.

Mixing the standard battery salt LiTFSI with various Li-salts of novel pseudo-delocalized organic anions [N(CH3)2((CH2)nSO3)((CH2)mSO3)]- (MMnm11), results in super-cooled solvent-free liquid electrolytes with glass transition temperatures of ca. 50 °C. Synthesis routes and full chemical characterisation of the new pseudo-delocalized anions are presented, as well as phase and thermal stabilities. The ion conductivities and electrochemical stabilities are evaluated towards lithium and sodium battery application.

AbstractConsidering the excellent chemical and physical properties of conducting polymers (CPs), such as high surface area as well as short path lengths for electronic and ionic transport, along with their flexible nature, places CPs in the spotlight as one of the most widely studied materials for energy storage, and especially for supercapacitor electrodes. This article briefly covers the theory behind CPs, their methods of production and customization, and what makes CPs as desirable materials for supercapacitor applications. In addition, the synthesis of thiophene derivatives, used to impove the stability of the resultant CP, is also presented. One negative effect of using CPs is often associated with the increase of their molecular weight,which results in lower gravimetric performance. Therefore, we discuss the important difference between practical gravimetric capacitance and theoretical gravimetric capacitance. Some of the limitations of CPs (such as limited cycle life) can be improved upon via compositing with carbon materials or metal oxide materials. Finally, a discussion of real‐world devices and prototypes concludes the article. Devices utilizing CPs as the main active component are mainly limited to trial devices and prototypes. Nonetheless, CPs continue to attract interest in the academic world as prospective supercapacitor materials with great potential to outperform the existing commercial devices.

In this paper, the electropolymerisation of pre-synthesised N-ethylanilinium trifluoroacetate, a protic ionic liquid (PIL), was carried out. The PIL served as the monomer precursor, solvent, and supporting electrolyte for the polymerisation process, and no additional acid was required due to the protic nature of the PIL. Two different morphologies of the poly(N-ethylaniline) were achieved by using different electropolymerisation approaches and the resultant films were soluble in the PIL precursor as well as a wide range of organic solvents. The use of anilinium based PILs, as polymerisation precursors, promises a greener approach for the production of polyanilines, as well as highly processable polymers.

The demand for catalysts that are highly active and stable for electron-transfer reactions has been boosted by the discovery that [Pt(NH3)4](TCNQF4)2 (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) is an efficient catalyst. In this work, we prepare and characterize the two related [Pt(NH3)4]2+ complexes, [Pt(NH3)4](TCNQ)2·(DMF)2 (1) and [Pt(NH3)4](TCNQ)2 (2). Reaction of [Pt(NH3)4](NO3)2 with LiTCNQ in a mixed solvent (methanol/dimethylformamide, 4 : 1 v/v) gives [Pt(NH3)4](TCNQ)2·(DMF)2 (1), whereas the same reaction in water affords [Pt(NH3)4](TCNQ)2 (2). 2 has been previously reported. Both 1 and 2 have now been characterized by single-crystal X-ray crystallography, Fourier-transform (FT)IR, Raman and UV-vis spectroscopy, and electrochemistry. Structurally, in 1, the TCNQ1− anions form infinite stacks with a separation between adjacent anions within the stack alternating between 3.12 and 3.42 Å. The solvated structure 1 differs from the non-solvated form 2 in that pairs of TCNQ1− anions are clearly displaced from each other. The conductivities of pressed pellets of 1 and 2 are both in the semi-conducting range at room temperature. 2 can be electrochemically synthesized by reduction of a TCNQ-modified electrode in contact with an aqueous solution of [Pt(NH3)4](NO3)2 via a nucleation growth mechanism. Interestingly, we discovered that 1 and 2 are not catalysts for the ferricyanide and thiosulfate reaction. Li+ and tetraalkylammonium salts of TCNQ1−/2− and TCNQF41−/2− were tested for potential catalytic activity towards ferricyanide and thiosulfate. Only TCNQF41−/2− salts were active, suggesting that the dianion redox level needs to be accessible for efficient catalytic activity and explaining why 1 and 2 are not good catalysts. Importantly, the origin of the catalytic activity of the highly active [Pt(NH3)4](TCNQF4)2 catalyst is now understood, enabling other families of catalysts to be developed for important electron-transfer reactions.

A set-up of a sodium metal anode vs. a solid polymer electrolyte (SPE) comprising poly(ethylene oxide) (PEO) and sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) has been evaluated in detail for the feasibility to use sodium metal as a pseudo-reference electrode (pseudo-RE). To evaluate the stability and reproducibility, we monitored the half-wave potential (E-1/2) of added decamethylferrocene (Me(10)Fc) and the stability of the interface by electrochemical impedance spectroscopy (EIS). The sodium/SPE interface resistance (R-Na/SPE) increases with time, up to 2.8k Omega cm(-2), and causes the E-1/2 of the Me(10)Fc(+/0) reference redox couple to drift up to 15mV during 88hours. Moreover, the sodium potential is very irreproducible, even initially after cell assembling the values can differ by 60mV, likely due to extreme sensitivity of the metal surface even to an "inert and dry" glove box environment. Indeed, freshly cut sodium readily reacts with water, forming NaOH, and adsorbs impurities that can be present even in a glove box atmosphere. The oxidation layer and the amount of adsorbed impurities increase with the exposure to the glove box atmosphere, as revealed by ATR-FTIR spectroscopy. Altogether, this calls for attention when evaluating any battery materials in half-cell configurations using sodium metal as the pseudo-RE.

•Thiophene is grafted to silicon to allow for intimate contact.•Modification with the thiophene layer acts as a pre-existing SEI layer.•The thiophene layer results in improved cycle life.•Further improvements will be possible by forming conducting polymer composites.

Presented in this work is a facile and quick electrochemical method for controlling the morphology of thick polyaniline (PANi) films, without the use of templates. By stepping the polymerization potential from high voltages to a lower (or series of lower) voltage(s), we successfully controlled the morphology of the polymer, and fibrous structures, unique to each potential step, were achieved. In addition, the resultant film was tested electrochemically for its viability as an electrode material for flexible batteries and supercapacitors. Furthermore, the PANi film was decorated with gold and platinum nanoparticles via an electroless deposition process for possible electrocatalytic applications, whereby the oxidation of hydrazine at the composite was investigated.

The trans-activator of transcription (TAT) peptide is regarded as the “gold standard” for cell-penetrating peptides, capable of traversing a mammalian membrane passively into the cytosolic space. This characteristic has been exploited through conjugation of TAT for applications such as drug delivery. However, the process by which TAT achieves membrane penetration remains ambiguous and unresolved. Mechanistic details of TAT peptide action are revealed herein by using three complementary methods: quartz crystal microbalance with dissipation (QCM-D), scanning electrochemical microscopy (SECM) and atomic force microscopy (AFM). When combined, these three scales of measurement define that the membrane uptake of the TAT peptide is by trans-membrane insertion using a “worm-hole” pore that leads to ion permeability across the membrane layer. AFM data provided nanometre-scale visualisation of TAT punctuation using a mammalian-mimetic membrane bilayer. The TAT peptide does not show the same specificity towards a bacterial mimetic membrane and QCM-D and SECM showed that the TAT peptide demonstrates a disruptive action towards these membranes. This investigation supports the energy-independent uptake of the cationic TAT peptide and provides empirical data that clarify the mechanism by which the TAT peptide achieves its membrane activity. The novel use of these three biophysical techniques provides valuable insight into the mechanism for TAT peptide translocation, which is essential for improvements in the cellular delivery of TAT-conjugated cargoes including therapeutic agents required to target specific intracellular locations.

Conducting polymers have become the focus of research due to their interesting properties, such as a wide range of conductivity, facile production, mechanical stability, light weight and low cost and the ease with which conducting polymers can be nanostructured to meet the specific application. They have become valuable materials for many applications, such as energy storage and generation. Recently, conducting polymers have been studied for use in supercapacitors, batteries and fuel cells. This article is to briefly discuss the background & theory behind their conductivity as well as to highlight the recent contributions of conducting polymers to the field of energy. Furthermore, the methods of production of the conducting polymers in addition to the different ways utilised to nano-engineer special morphologies are discussed.

The chemistry of oxidized forms of TTF in acidified CH3CN has been established using electrochemical and spectroscopic techniques.