Hollow Stair-Stepping Spherical High-Entropy Prussian Blue Analogue for High-Rate Sodium Ion Batteries.

Prussian blue analogues (PBAs) are considered to be one of the most suitable sodium storage materials, especially with the introduction of the high-entropy (HE) concept into their structure to further improve their various abilities. However, severe agglomeration of the HEPBA particles still limits the fast charging capabilities. Here, an HEPBA (Nax(FeMnCoNiCu)[Fe(CN)6]y□1-y·nH2O) with a hollow stair-stepping spherical structure has been prepared through the chemical etching process of the traditional cubic structure of HEPBA. Electrochemical characterization (sodium ion battery), kinetic analysis, and COMSOL Multiphysics simulations reveal that the nature of the high-entropy and the hollow stair-stepping spherical structure can greatly improve the diffusion behavior of Na+ ions. Moreover, the hollow structure effectively mitigates the volume change of HEPBA during SIBs operation, ultimately extending the lifespan. Consequently, the as-prepared HEPBA cathode exhibits excellent rate performance (126.5 and 76.4 mAh g-1 at 0.1 and 4.0 A g-1, respectively) and stable long-term capability (maintaining its 75.6% capacity after 1000 cycles) due to its unique structure. Furthermore, the waste of the etching process can easily be recycled to prepare more HEPBA product. This processing method holds great promise for designing nanostructures of advanced high-entropy Prussian blue analogues for sodium ion batteries.

Dynamic Covalent Amphiphilic Polymer Conetworks Based on End-Linked Pluronic F108: Preparation, Characterization, and Evaluation as Matrices for Gel Polymer Electrolytes.

We present the development of a platform of well-defined, dynamic covalent amphiphilic polymer conetworks (APCN) based on an α,ω-dibenzaldehyde end-functionalized linear amphiphilic poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol) (PEG-b-PPG-b-PEG, Pluronic) copolymer end-linked with a triacylhydrazide oligo(ethylene glycol) triarmed star cross-linker. The developed APCNs were characterized in terms of their rheological (increase in the storage modulus by a factor of 2 with increase in temperature from 10 to 50 °C), self-healing, self-assembling, and mechanical properties and evaluated as a matrix for gel polymer electrolytes (GPEs) in both the stretched and unstretched states. Our results show that water-loaded APCNs almost completely self-mend, self-organize at room temperature into a body-centered cubic structure with long-range order exhibiting an aggregation number of around 80, and display an exceptional room temperature stretchability of ∼2400%. Furthermore, ionic liquid-loaded APCNs could serve as gel polymer electrolytes (GPEs), displaying a substantial ion conductivity in the unstretched state, which was gradually reduced upon elongation up to a strain of 4, above which it gradually increased. Finally, it was found that recycled (dissolved and re-formed) ionic liquid-loaded APCNs could be reused as GPEs preserving 50-70% of their original ion conductivity.

A dicarbonate solvent electrolyte for high performance 5 V-Class Lithium-based batteries.

Rechargeable lithium batteries using 5 V positive electrode materials can deliver considerably higher energy density as compared to state-of-the-art lithium-ion batteries. However, their development remains plagued by the lack of electrolytes with concurrent anodic stability and Li metal compatibility. Here we report a new electrolyte based on dimethyl 2,5-dioxahexanedioate solvent for 5 V-class batteries. Benefiting from the particular chemical structure, weak interaction with lithium cation and resultant peculiar solvation structure, the resulting electrolyte not only enables stable, dendrite-free lithium plating-stripping, but also displays anodic stability up to 5.2 V (vs. Li/Li+), in additive or co-solvent-free formulation, and at low salt concentration of 1 M. Consequently, the Li | |LiNi0.5Mn1.5O4 cells using the 1 M LiPF6 in 2,5-dioxahexanedioate based electrolyte retain >97% of the initial capacity after 250 cycles, outperforming the conventional carbonate-based electrolyte formulations, making this, and potentially other dicarbonate solvents promising for future Lithium-based battery practical explorations.

Practical Cell Design for PTMA-Based Organic Batteries: an Experimental and Modeling Study.

Poly(2,2,6,6-tetramethyl-1-piperidinyloxy methacrylate) (PTMA) is one of the most promising organic cathode materials thanks to its relatively high redox potential, good rate performance, and cycling stability. However, being a p-type material, PTMA-based batteries pose additional challenges compared to conventional lithium-ion systems due to the involvement of anions in the redox process. This study presents a comprehensive approach to optimize such batteries, addressing challenges in electrode design, scalability, and cost. Experimental results at a laboratory scale demonstrate high active mass loadings of PTMA electrodes (up to 9.65 mg cm-2), achieving theoretical areal capacities that exceed 1 mAh cm-2. Detailed physics-based simulations and cost and performance analysis clarify the critical role of the electrolyte and the impact of the anion amount in the PTMA redox process, highlighting the benefits and the drawbacks of using highly concentrated electrolytes. The cost and energy density of lithium metal batteries with such high mass loading PTMA cathodes were simulated, finding that their performance is inferior to batteries based on inorganic cathodes even in the most optimistic conditions. In general, this work emphasizes the importance of considering a broader perspective beyond the lab scale and highlights the challenges in upscaling to realistic battery configurations.

Revealing the reversible solid-state electrochemistry of lithium-containing conjugated oximates for organic batteries.

In the rising advent of organic Li-ion positive electrode materials with increased energy content, chemistries with high redox potential and intrinsic oxidation stability remain a challenge. Here, we report the solid-phase reversible electrochemistry of the oximate organic redox functionality. The disclosed oximate chemistries, including cyclic, acyclic, aliphatic, and tetra-functional stereotypes, uncover the complex interplay between the molecular structure and the electroactivity. Among the exotic features, the most appealing one is the reversible electrochemical polymerization accompanying the charge storage process in solid phase, through intermolecular azodioxy bond coupling. The best-performing oximate delivers a high reversible capacity of 350 mAh g-1 at an average potential of 3.0 versus Li+/Li0, attaining 1 kWh kg-1 specific energy content at the material level metric. This work ascertains a strong link between electrochemistry, organic chemistry, and battery science by emphasizing on how different phases, mechanisms, and performances can be accessed using a single chemical functionality.

Chameleon Multienvironment Nanoreactors.

Nanoreactors consisting of hydrophilic porous SiO2 shells and amphiphilic copolymer cores have been prepared, which can easily self-tune their hydrophilic/hydrophobic balance depending on the environment and exhibit chameleon-like behavior. The accordingly obtained nanoparticles show excellent colloidal stability in a variety of solvents with different polarity. Most importantly, thanks to the assistance of the nitroxide radicals attached to the amphiphilic copolymers, the synthesized nanoreactors show high catalytic activity for model reactions in both polar and nonpolar environments and, more particularly, realize a high selectivity for the products resulting from the oxidation of benzyl alcohol in toluene.

Boron Nitride-Doped Polyphenylenic Organogels.

Herein, we describe the synthesis of the first boron nitride-doped polyphenylenic material obtained through a [4 + 2] cycloaddition reaction between a triethynyl borazine unit and a biscyclopentadienone derivative, which undergoes organogel formation in chlorinated solvents (the critical jellification concentration is 4% w/w in CHCl3). The polymer has been characterized extensively by Fourier-transform infrared spectroscopy, solid-state 13C NMR, solid-state 11B NMR, and by comparison with the isolated monomeric unit. Furthermore, the polymer gels formed in chlorinated solvents have been thoroughly characterized and studied, showing rheological properties comparable to those of polyacrylamide gels with a low crosslinker percentage. Given the thermal and chemical stability, the material was studied as a potential support for solid-state electrolytes. showing properties comparable to those of polyethylene glycol-based electrolytes, thus presenting great potential for the application of this new class of material in lithium-ion batteries.

High performance Li-, Na-, and K-ion storage in electrically conducting coordination polymers.

Coordination polymers (CPs) made of redox-active organic moieties and metal ions emerge as an important class of electroactive materials for battery applications. However, the design and synthesis of high voltage alkali-cation reservoir anionic CPs remains challenging, hindering their practical applications. Herein, we report a family of electrically conducting alkali-cation reservoir CPs with the general formula of A2-TM-PTtSA (wherein A = Li+, Na+, or K+; TM = Fe2+, Co2+, or Mn2+; and PTtSA = benzene-1,2,4,5-tetra-methylsulfonamide). The incorporation of transition metal centers not only enables intrinsic high electrical conductivity, but also shows an impressive redox potential increase of as high as 1 V as compared to A4-PTtSA analogues, resulting in a class of organometallic cathode materials with a high average redox potential of 2.95-3.25 V for Li-, Na- and K-ion batteries. A detailed structure - composition - physicochemical properties - performance correlation study is provided relying on experimental and computational analysis. The best performing candidate shows excellent rate capability (86% of the nominal capacity retained at 10C rate), remarkable cycling stability (96.5% after 1000 cycles), outstanding tolerance to low carbon content (5 wt%), high mass loading (50 mg cm-2), and extreme utilisation conditions of low earth orbit space environment tests. The significance of the disclosed alkali-ion reservoir cathodes is further emphasized by utilizing conventional Li-host graphite anode for full cell assembly, attaining a record voltage of 3 V in an organic cathode Li-ion proof-of-concept cell.

Bio-Based Solid Electrolytes Bearing Cyclic Carbonates for Solid-State Lithium Metal Batteries.

Green resources for lithium-based batteries excite many researchers due to their eco-friendly nature. In this work, a sustainable bio-based solid-state electrolyte was developed based on carbonated soybean oil (CSBO), obtained by organocatalyzed coupling of CO2 to epoxidized soybean oil. CSBO coupled with lithium bis(trifluoromethanesulfonyl)imide salt on a bio-based cellulose separator resulted in free-standing membranes. Those membranes on electrochemical measurements exhibited ionic conductivity of around 10-3  S cm-1 at 100 °C and around 10-6  S cm-1 at room temperature with wide electrochemical stability window (up to 4.6 V vs. Li/Li+ ) and transference number up to 0.39 at RT. Further investigations on the galvanostatic charge-discharge of LiFePO4 cathodes with CSBO-based electrolyte membranes and lithium metal anodes delivered the gravimetric capacity of 112 and 157 mAh g-1 at RT and 60 °C, respectively, providing a promising direction to further develop bio-based solid electrolytes for sustainable solid-state lithium batteries.

New Cathode Materials in the Fe-PO4 -F Chemical Space for High-Performance Sodium-Ion Storage.

Sodium and iron make up the perfect combination for the growing demand for sustainable energy storage systems, given the natural abundance and sustainability of the two building block elements. However, most sodium-iron electrode chemistries are plagued by intrinsic low energy densities with continuous ongoing efforts to solve this. Herein, the chemical space of a series of (meta)stable, off-stoichiometric Fe-PO4 -F phases is analyzed. Some are found to display markedly improved electrochemical activity for sodium storage, as compared to the amorphous or thermodynamically stable phases of equivalent composition. The metastable crystalline Na1.2 Fe1.2 PO4 F0.6 delivers a reversible capacity of more than 140 mAh g-1 with an average discharge potential of 2.9 V (vs Na+ /Na0 ) resulting in a practical specific energy density of 400 Wh kg-1 (estimated at the material level), outperforming many developed Fe-PO4 analogs thus far, with further multiple possibilities to be explored toward improved energy storage metrics. Overall, this study unlocks the possibilities of off-stoichiometric Fe-PO4 -F cathode materials and reveals the importance to explore the oft-overlooked metastable or transient state materials for energy storage.

High Salt-Content Plasticized Flame-Retardant Polymer Electrolytes.

New solid polymer electrolytes are of particular interest for next-generation high-energy batteries since they can overcome the limited voltage window of conventional polyether-based electrolytes. Herein, a flame-retardant phosphorus-containing polymer, poly(dimethyl(methacryloyloxy)methyl phosphonate) (PMAPC1) is introduced as a promising polymer matrix. Free-standing membranes are easily obtained by mixing PMAPC1 with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and a small amount of acetonitrile (AN). LiTFSI/AN mixed aggregates are formed that act as plasticizers and enable ionic conductivities up to 1.6 × 10-3 S cm-1 at 100 °C. The high content of LiTFSI used in our electrolytes leads to the formation of a stable LiF solid-electrolyte interphase, which can effectively suppress Li dendrites and the chemical degradation of AN in contact with Li. Accordingly the electrolyte membranes exhibit a wide electrochemical stability window above 4.7 V versus Li+/Li and fire-retardant properties due to the presence of the phosphorus-containing polymer. Atomistic molecular modeling simulations have been performed to determine the structure of the electrolytes on the microscopic scale and to rationalize the trends in ionic conductivity and the transport regime as a function of the electrolyte composition. Finally, our electrolyte membranes enable stable cycling performance for LiFePO4|PMAPC1 + LiTFSI + AN|Li batteries.

Application of Redox-Responsive Hydrogels Based on 2,2,6,6-Tetramethyl-1-Piperidinyloxy Methacrylate and Oligo(Ethyleneglycol) Methacrylate in Controlled Release and Catalysis.

Hydrogels have reached momentum due to their potential application in a variety of fields including their ability to deliver active molecules upon application of a specific chemical or physical stimulus and to act as easily recyclable catalysts in a green chemistry approach. In this paper, we demonstrate that the same redox-responsive hydrogels based on polymer networks containing 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) stable nitroxide radicals and oligoethylene glycol methyl ether methacrylate (OEGMA) can be successfully used either for the electrochemically triggered release of aspirin or as catalysts for the oxidation of primary alcohols into aldehydes. For the first application, we take the opportunity of the positive charges present on the oxoammonium groups of oxidized TEMPO to encapsulate negatively charged aspirin molecules. The further electrochemical reduction of oxoammonium groups into nitroxide radicals triggers the release of aspirin molecules. For the second application, our hydrogels are swelled with benzylic alcohol and tert-butyl nitrite as co-catalyst and the temperature is raised to 50 °C to start the oxidation reaction. Interestingly enough, benzaldehyde is not miscible with our hydrogels and phase-separate on top of them allowing the easy recovery of the reaction product and the recyclability of the hydrogel catalyst.

High Power Cathodes from Poly(2,2,6,6-Tetramethyl-1-Piperidinyloxy Methacrylate)/Li(NixMnyCoz)O2 Hybrid Composites.

Lithium-ion batteries are today among the most efficient devices for electrochemical energy storage. However, an improvement of their performance is required to address the challenges of modern grid management, portable technology, and electric mobility. One of the most important limitations to solve is the slow kinetics of redox reactions associated to inorganic cathodic materials, directly impacting on the charging time and the power characteristics of the cells. In sharp contrast, redox polymers such as poly(2,2,6,6-tetramethyl-1-piperidinyloxy methacrylate) (PTMA) exhibit fast redox reaction kinetics and pseudocapacitors characteristics. In this contribution, we have hybridized high energy Li(NixMnyCoz)O2 mixed oxides (NMC) with PTMA. In this hybrid cathode configuration, the higher voltage NMC (ca. 3.7 V vs. Li/Li+) is able to transfer its energy to the lower voltage PTMA (3.6 V vs. Li/Li+) improving the discharge power performances and allowing high power cathodes to be obtained. However, the NMC-PTMA hybrid cathodes show an important capacity fading. Our investigations indicate the presence of an interface degradation reaction between NMC and PTMA transforming NMC into an electrochemically dead material. Moreover, the aqueous process used here to prepare the cathode is also shown to enable the degradation of NMC. Indeed, once NMC is immersed in water, alkaline surface species dissolve, increasing the pH of the slurry, and corroding the aluminum current collector. Additionally, the NMC surface is altered due to delithiation which enables the interface degradation reaction to take place. This reaction by surface passivation of NMC particles did not succeed in preventing the interfacial degradation. Degradation was, however, notably decreased when Li(Ni0.8Mn0.1Co0.1)O2 NMC was used and even further when alumina-coated Li(Ni0.8Mn0.1Co0.1)O2 NMC was considered. For the latter at a 20C discharge rate, the hybrids presented higher power performances compared to the single constituents, clearly emphasizing the benefits of the hybrid cathode concept.

Kinked Silicon Nanowires: Superstructures by Metal-Assisted Chemical Etching.

We report on metal-assisted chemical etching of Si for the synthesis of mechanically stable, hybrid crystallographic orientation Si superstructures with high aspect ratio, above 200. This method sustains high etching rates and facilitates reproducible results. The protocol enables the control of the number, angle, and location of the kinks via successive etch-quench sequences. We analyzed relevant Au mask catalyst features to systematically assess their impact on a wide spectrum of etched morphologies that can be easily attained and customized by fine-tuning of the critical etching parameters. For instance, the designed kinked Si nanowires can be incorporated in biological cells without affecting their viability. An accessible numerical model is provided to explain the etch profiles and the physicochemical events at the Si/Au-electrolyte interface and offers guidelines for the development of finite-element modeling of metal-assisted Si chemical etching.

Linear and Nonlinear Dynamic Behavior of Polymer Micellar Assemblies Connected by Metallo-Supramolecular Interactions.

The linear and nonlinear rheology of associative colloidal polymer assemblies with metallo-supramolecular interactions is herein studied. Polystyrene-b-poly(tert-butylacrylate) with a terpyridine ligand at the end of the acrylate block is self-assembled into micelles in ethanol, a selective solvent for the latter block, and supramolecularly connected by complexation to divalent metal ions. The dependence of the system elasticity on polymer concentration can be semi-quantitatively understood by a geometrical packing model. For strongly associated (Ni2+, Fe2+) and sufficiently concentrated systems (15 w/v%), any given ligand end-group has a virtually 100% probability of being located in an overlapping hairy region between two micelles. By assuming a 50% probability of intermicellar crosslinks being formed, an excellent prediction of the plateau modulus was achieved and compared with the experimental results. For strongly associated but somewhat more dilute systems (12 w/v%) that still have significant overlap between hairy regions, the experimental modulus was lower than the predicted value, as the effective number of crosslinkers was further reduced along with possible density heterogeneities. The reversible destruction of the network by shear forces can be observed from the strain dependence of the storage and loss moduli. The storage moduli of the Ni2+ and Zn2+ systems at a lower concentration (12 w/v%) showed a rarely observed feature (i.e., a peak at the transition from linear to nonlinear regime). This peak disappeared at a higher concentration (15 w/v%). This behavior can be rationalized based on concentration-dependent network stretchability.

Ion-Conducting Redox-Active Polymer Gels Based on Stable Nitroxide Radicals.

Redox-active polymer networks based on stable nitroxide radicals are a very promising class of materials to be used in the so-called organic radical batteries. In order to obtain fast-charging and high power electrodes, however, excellent ionic conductivity inside the electrode material is required to allow easy diffusion of ions and fast redox reactions. In this contribution, we investigated redox-active poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) chains cross-linked through ionic liquid-like 1,2,3-triazolium groups. Different networks were prepared in which the amount of cross-linker and the counter-anion associated to the 1,2,3-triazolium group were varied. The ionic conductivities of the different polymer networks were first measured in the solid state by electrochemical impedance spectroscopy at different temperatures, and an increased ionic conductivity was measured when 1,2,3-triazolium groups were present in the network. The effects of the chemical nature of the counterions associated to the 1,2,3-triazolium groups and of the crosslinking density were then studied. The best ionic conductivities were obtained when bis (trifluoromethane)sulfonamide (TFSI) counter-anions were used, and when the crosslinking density of the TFSI-containing gel was higher. Finally, those ion-conducting gels were loaded with free LiTFSI and the transference number of lithium ions was accordingly measured. The good ionic conductivities and lithium ions transference numbers measured for the investigated redox-active gels make them ideal candidates for application as electrode materials for either organic radical batteries or pseudo-capacitors energy storage devices.

Synthesis and characterisation of redox hydrogels based on stable nitroxide radicals.

The principle of encapsulation/release of a guest molecule from stimuli responsive hydrogels (SRHs) is mainly realised with pH, temperature or light stimuli. However, only a limited number of redox responsive hydrogels have been investigated so far. We report here the development of a SRH that can release its guest molecule upon a redox stimulus. To obtain this redox hydrogel, we have introduced into the hydrogel the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) stable nitroxide radical, which can be reversibly oxidized into an oxoammonium cation (TEMPO+). Water solubility is provided by the presence of the (oligoethyleneglycol)methacrylate (OEGMA) comonomer. Electrochemical and mechanical characterization showed that those gels exhibit interesting physicochemical properties, making them very promising candidates for practical use in a wide range of applications.

A H-bond stabilized quinone electrode material for Li-organic batteries: the strength of weak bonds.

Small organic materials are generally plagued by their high solubility in battery electrolytes. Finding approaches to suppress solubilization while not penalizing gravimetric capacity remains a challenge. Here we propose the concept of a hydrogen bond stabilized organic battery framework as a viable solution. This is illustrated for 2,5-diamino-1,4-benzoquinone (DABQ), an electrically neutral and low mass organic chemical, yet with unusual thermal stability and low solubility in battery electrolytes. These properties are shown to arise from hydrogen bond molecular crystal stabilization, confirmed by a suite of techniques including X-ray diffraction and infrared spectroscopy. We also establish a quantitative correlation between the electrolyte solvent polarity, molecular structure of the electrolyte and DABQ solubility - then correlate these to the cycling stability. Notably, DABQ displays a highly reversible (above 99%) sequential 2-electron electrochemical activity in the solid phase, a process rarely observed for similar small molecular battery chemistries. Taken together, these results reveal a potential new strategy towards stable and practical organic battery chemistries through intramolecular hydrogen-bonding crystal stabilization.

Carbonyl-Based π-Conjugated Materials: From Synthesis to Applications in Lithium-Ion Batteries.

The constant growth in the global energy demand together with the increasing awareness of clean and sustainable development has strongly pushed scientists to search for metal-free, low-cost, environmentally friendly functional energy-storage systems (ESSs). Among the reported organic electrode materials, carbonyl-based π-conjugated compounds show excellent rate capabilities and cycling stabilities and are powerful candidates for the next generation of rechargeable lithium-ion batteries (LIBs). Benefiting from the molecular structure versatility and design feasibility, the electrochemical properties of organic and polymeric materials can be easily tuned. This Review summarizes recent efforts in the search for carbonyl-based π-conjugated electrode materials in LIBs with a focus on the synthetic strategies developed to improve their electrochemical performance. The use of these materials in flexible, all-organic LIBs is highlighted as a unique direction towards widespread applications of LIBs.

Kinked silicon nanowires-enabled interweaving electrode configuration for lithium-ion batteries.

A tri-dimensional interweaving kinked silicon nanowires (k-SiNWs) assembly, with a Ni current collector co-integrated, is evaluated as electrode configuration for lithium ion batteries. The large-scale fabrication of k-SiNWs is based on a procedure for continuous metal assisted chemical etching of Si, supported by a chemical peeling step that enables the reuse of the Si substrate. The kinks are triggered by a simple, repetitive etch-quench sequence in a HF and H2O2-based etchant. We find that the inter-locking frameworks of k-SiNWs and multi-walled carbon nanotubes exhibit beneficial mechanical properties with a foam-like behavior amplified by the kinks and a suitable porosity for a minimal electrode deformation upon Li insertion. In addition, ionic liquid electrolyte systems associated with the integrated Ni current collector repress the detrimental effects related to the Si-Li alloying reaction, enabling high cycling stability with 80% capacity retention (1695 mAh/gSi) after 100 cycles. Areal capacities of 2.42 mAh/cm2 (1276 mAh/gelectrode) can be achieved at the maximum evaluated thickness (corresponding to 1.3 mgSi/cm2). This work emphasizes the versatility of the metal assisted chemical etching for the synthesis of advanced Si nanostructures for high performance lithium ion battery electrodes.