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Scientific Unit
An ontology for the structured storage, retrieval, and analysis of data on lithium-ion battery materials and electrode-to-cell production is presented. It provides a logical structure that is mapped onto a digital architecture and used to visualize, correlate, and make predictions in battery production, research, and development. Materials and processes are specified using a predetermined terminology; a chain of unit processes (steps) connects raw materials and products (items) of battery cell production. The ontology enables the attachment of analytical methods (characterization methods) to items. Workshops and interviews with experts in battery materials and production processes are conducted to ensure that the structure is conformable both for industrial-scale and laboratory-scale data generation and implementation. Raw materials and intermediate products are identified and defined for all steps to the final battery cell. Steps and items are defined based on current standard materials and process chains using terms that are in common use. Alternative structures and the connection of the ontology to other existing ontologies are discussed. The contribution provides a pragmatic, accessible way to unify the storage of materials-oriented lithium-ion battery production data. It aids the linkage of such data with domain knowledge and the automation of data analysis in production and research.
Supercapacitors combine efficient electrical energy storage and performance stability based on fast electrosorption of electrolyte ions at charged interfaces. They are a central element of existing and emerging energy concepts. A better understanding of capacitance enhancement options is essential to exploit the full potential of supercapacitors. Here, we report a novel hierarchically structured N-doped carbon material and a significant capacitance enhancement for a specific ionic liquid. Our studies indicate that matching of the electrode material and the ionic liquid specifically leads to a constant normalized resistance of the electrode material (voltage window up to +/-1 V vs. carbon) and a significant enhancement of the specific capacitance. Such effects are not seen for standard organic electrolytes, non-matched ionic liquids, or non-N-doped carbons. A higher N-doping of the electrode material improves the symmetric full cell capacitance of the match and considerably increases its long-term stability at +3 V cell voltage. This novel observance of enhanced specific capacitance for N-doped carbons with matched ionic liquid may enable a new platform for developing supercapacitors with enhanced energy storage capacity.
Ionic liquid mixtures show promise as electrolytes for supercapacitors with nanoporous electrodes. Herein, we investigate theoretically and with experiments how binary electrolytes comprising a common anion and two types of differently-sized cations affect capacitive energy storage. We find that such electrolytes can enhance the capacitance of single nanopores and nanoporous electrodes under potential differences negative relative to the potential of zero charge. For a two-electrode cell, however, they are beneficial only at low and intermediate cell voltages, while a neat ionic liquid performs better at higher voltages. We reveal subtle effects of how the distribution of pores accessible to different types of ions correlates with charge storage and suggest approaches to increase capacitance and stored energy density with ionic liquid mixtures.
This study presents a novel approach to developing high-performance lithium-ion battery electrodes by loading titania-carbon hybrid spherogels with sulfur. The resulting hybrid materials combine high charge storage capacity, electrical conductivity, and core-shell morphology, enabling the development of next-generation battery electrodes. We obtained homogeneous carbon spheres caging crystalline titania particles and sulfur using a template-assisted sol-gel route and carefully treated the titania-loaded carbon spherogels with hydrogen sulfide. The carbon shells maintain their microporous hollow sphere morphology, allowing for efficient sulfur deposition while protecting the titania crystals. By adjusting the sulfur impregnation of the carbon sphere and varying the titania loading, we achieved excellent lithium storage properties by successfully cycling encapsulated sulfur in the sphere while benefiting from the lithiation of titania particles. Without adding a conductive component, the optimized material provided after 150 cycles at a specific current of 250 mA g–1 a specific capacity of 825 mAh g–1 with a Coulombic efficiency of 98%.
Nanoporous carbon materials with customized structural features enable sustainable and electrochemical applications through improved performance and efficiency. Carbon spherogels (highly porous carbon aerogel materials consisting of an assembly of hollow carbon nanosphere units with uniform diameters) are desirable candidates as they combine exceptional electrical conductivity, bespoke shell porosity, tunability of the shell thickness, and a high surface area. Herein, we introduce a novel and more environmentally friendly sol-gel synthesis of resorcinol-formaldehyde (RF) templated by polystyrene spheres, forming carbon spherogels in an organic solvent. By tailoring the molar ratio of resorcinol to isopropyl alcohol (R/IPA) and the concentration of polystyrene, the appropriate synthesis conditions were identified to produce carbon spherogels with adjustable wall thicknesses. A single-step solvent exchange process from deionized water to isopropyl alcohol reduces surface tension within the porous gel network, making this approach significantly time and cost-effective. The lower surface tension of IPA enables solvent extraction under ambient conditions, allowing for direct carbonization of RF gels while maintaining a specific surface area loss of less than 20% compared to supercritically dried counterparts. The specific surface areas obtained after physical activation with carbon dioxide are 2300–3600 m2 g−1. Transmission and scanning electron microscopy verify the uniform, hollow carbon sphere network morphology. Specifically, those carbon spherogels are high-performing electrodes for energy storage in a supercapacitor setup featuring a specific capacitance of up to 204 F g−1 at 200 mA g−1 using 1 M potassium hydroxide (KOH) solution as the electrolyte.
High-entropy materials (HEMs) with promising energy storage and conversion properties have recently attracted worldwide increasing research interest. Nevertheless, most research on the synthesis of HEMs focuses on a “trial and error” method without any guidance, which is very laborious and time-consuming. This review aims to provide an instructive approach to searching and developing new high-entropy energy materials in a much more efficient way. Toward materials design for future technologies, a fundamental understanding of the process/structure/property/performance linkage on an atomistic level will promote prescreening and selection of material candidates. With the help of computational material science, in which the fast development of computational capabilities that have a rapidly growing impact on new materials design, this fundamental understanding can be approached. Furthermore, high-throughput experimental methods, enabled by the advances in instrumentation and electronics, will accelerate the production of large quantities of results and stimulate the identification of the target products, adding knowledge in computational design. This review shows that combining computational preselection and verification by high-throughput can be an efficient approach to unveil the complexities of HEMs and design novel HEMs with enhanced properties for energy-related applications.
Batteries employing transition-metal sulfides enable high-charge storage capacities, but polysulfide shuttling and volume expansion cause structural disintegration and early capacity fading. The design of heterostructures combining metal sulfides and carbon with an optimized morphology can effectively address these issues. Our work introduces dopamine-coated copper Prussian blue (CuPB) analogue as a template to prepare nanostructured mixed copper–iron sulfide electrodes. The material was prepared by coprecipitation of CuPB with in situ dopamine polymerization, followed by thermal sulfidation. Dopamine controls the particle size and favors K-rich CuPB due to its polymerization mechanism. While the presence of the coating prevents particle agglomeration during thermal sulfidation, its thickness demonstrates a key effect on the electrochemical performance of the derived sulfides. After a two-step activation process during cycling, the C-coated KCuFeS2 electrodes showed capacities up to 800 mAh/g at 10 mA/g with nearly 100% capacity recovery after rate handling and a capacity of 380 mAh/g at 250 mA/g after 500 cycles.
A novel, two step synthesis is presented combining the formation of carbide-derived carbon (CDC) and redox-active vanadium pentoxide (V2O5) in a core-shell manner using solely vanadium carbide (VC) as the precursor. In a first step, the outer part of VC particles is transformed to nanoporous CDC owing to the in situ formation of chlorine gas from NiCl2 at 700 [degree]C. In a second step, the remaining VC core is calcined in synthetic air to obtain V2O5/CDC core-shell particles. Materials characterization by means of electron microscopy, Raman spectroscopy, and X-ray diffraction clearly demonstrates the partial transformation from VC to CDC, as well as the successive oxidation to V2O5/CDC core-shell particles. Electrochemical performance was tested in organic 1 M LiClO4 in acetonitrile using half- and asymmetric full-cell configuration. High specific capacities of 420 mA h g-1 (normalized to V2O5) and 310 mA h g-1 (normalized to V2O5/CDC) were achieved. The unique nanotextured core-shell architecture enables high power retention with ultrafast charging and discharging, achieving more than 100 mA h g-1 at 5 A g-1 (rate of 12C). Asymmetric cell design with CDC on the positive polarization side leads to a high specific energy of up to 80 W h kg-1 with a superior retention of more than 80% over 10 000 cycles and an overall energy efficiency of up to 80% at low rates.
In this work, a block copolymer (BCP) consisting of poly((butyl methacrylate-co-benzophenone methacrylate-co-methyl methacrylate)-block-(2-hydroxyethyl methacrylate)) (P(BMA-co-BPMA-co-MMA)-b-P(HEMA)) is prepared by a two-step atom-transfer radical polymerization (ATRP) procedure. BCP membranes are fabricated applying the self-assembly and nonsolvent induced phase separation (SNIPS) process from a ternary solvent mixture of tetrahydrofuran (THF), 1,4-dioxane, and dimethylformamide (DMF). The presence of a porous top layer of the integral asymmetric membrane featuring pores of about 30 nm is confirmed via scanning electron microscopy (SEM). UV-mediated cross-linking protocols for the nanoporous membrane are adjusted to maintain the open and isoporous top layer. The swelling capability of the noncross-linked and cross-linked BCP membranes is investigated in water, water/ethanol mixture (1:1), and pure ethanol using atomic force microscopy, proving a stabilizing effect of the UV cross-linking on the porous structures. Finally, the influence of the herein described cross-linking protocols on water-flux measurements for the obtained membranes is explored. As a result, an increased swelling resistance for all tested solvents is found, leading to an increased water flux compared to the pristine membrane. The herein established UV-mediated cross-linking protocol is expected to pave the way to a new generation of porous and stabilized membranes within the fields of separation technologies.
The Faradaic processes related to electrochemical water reduction at the nanoporous carbon electrode under negative polarization are reduced when the concentration of aqueous sodium nitrate (NaNO3) is increased or the temperature is decreased. This effect enhances the relative contribution of ion electrosorption to the total charge storage process. Hydrogen chemisorption is reduced in aqueous 8.0 m NaNO3 due to the low degree of hydration of the Na+ cation; consequently, less free water is available for redox contributions, driving the system to exhibit electrical double-layer capacitive characteristics. Hydrogen adsorption/desorption is facilitated in 1.0 m NaNO3 due to the high molar ratio. The excess of water shifts the local pH in carbon nanopores to neutral values, giving rise to a high overpotential for dihydrogen evolution in the latter. The dilution effect on local pH shift in 1.0 m NaNO3 can be reduced by decreasing the temperature. A symmetric activated carbon cell assembled with 8.0 m NaNO3 exhibits a high capacitance and coulombic efficiency, a larger contribution of ion electrosorption to the overall charge storage process, and a stable capacitance performance at 1.6 V.
Abstract Continuous and low-energy desalination technologies are in high demand to enable sustainable water remediation. Our work introduces a continuous desalination process based on the redox reaction of a dual-zinc electrode. The system consists of two zinc foils as redox electrodes with flowing ZnCl2 electrolyte, concentrated and diluted salt streams with three anion- and cation-exchange membranes (AEM and CEM) separated configuration (AEM|CEM|AEM). If a constant current is applied, the negative zinc electrode is oxidized, and electrons are released to the external circuit, whereas the positive zinc electrode is reduced, causing salt removal in the dilution stream. The results showed that brackish water can be directly desalted to 380.6 ppm during a continuous batch-mode process. The energy consumption can be as low as 35.30 kJ mol−1 at a current density of 0.25 mA cm−2, which is comparable to reverse osmosis. In addition, the dual-zinc electrode electrochemical desalination demonstrates excellent rate performance, reversibility, and batch cyclability through electrode exchange regeneration. Our research provides a route for continuous low-energy desalination based on metal redox mediators.
In this study, we explore carbon onions (diameter below 10 nm), for the first time, as a substrate material for lithium sulfur cathodes. We introduce several scalable synthesis routes to fabricate carbon onion-sulfur hybrids by adopting in situ and melt diffusion strategies with sulfur fractions up to 68 mass%. The conducting skeleton of agglomerated carbon onions proved to be responsible for keeping active sulfur always in close vicinity to the conducting matrix. Therefore, the hybrids are found to be efficient cathodes for Li-S batteries, yielding 97-98% Coulombic efficiency over 150 cycles with a slow fading of the specific capacity (ca. 660 mA h g-1 after 150 cycles) in long term cycle test and rate capability experiments.
Atomic layer deposition has proven to be a particularly attractive approach for decorating mesoporous carbon substrates with redox active metal oxides for electrochemical energy storage. This study, for the first time, capitalizes on the cyclic character of atomic layer deposition to obtain a highly conformal and atomically controlled decoration of carbon onions with alternating stacks of vanadia and titania. The addition of 25 mass% TiO2 leads to an expansion of the VO2 unit cell, thus greatly enhancing lithium intercalation capacity and kinetics. Electrochemical characterization revealed ultrahigh discharge capacity of up to 382 mAh[middle dot]g-1 of the composite electrode (554 mAh[middle dot]g-1 per metal oxide) with an impressive capacity retention of 82 mAh[middle dot]g-1 (120 mAh[middle dot]g-1 per metal oxide) at a high discharge rate of 20 A[middle dot]g-1 or 52 C. Rigorous stability benchmarking showed superior stability over 3,000 cycles when discharging to a reduced potential of -1.8 V vs. carbon. These capacity values are among the highest reported for any metal oxide system, while in addition, supercapacitor-like power performance and longevity are achieved. On a device level, high specific energy and power of up to 110 Wh[middle dot]kg-1 and 6 kW[middle dot]kg-1, respectively, were achieved when employing the hybrid material as anode versus activated carbon cathode.
A detailed understanding of ion adsorption within porous carbon is key to the design and improvement of electric double-layer capacitors, more commonly known as supercapacitors. In this work nuclear magnetic resonance (NMR) spectroscopy is used to study ion adsorption in porous carbide-derived carbons. These predominantly microporous materials have a tuneable pore size which enables a systematic study of the effect of pore size on ion adsorption. Multinuclear NMR experiments performed on the electrolyte anions and cations reveal two main environments inside the carbon. In-pore ions (observed at low frequencies) are adsorbed inside the pores, whilst ex-pore ions (observed at higher frequencies) are not adsorbed and are in large reservoirs of electrolyte between carbon particles. All our experiments were carried out in the absence of an applied electrical potential in order to assess the mechanisms related to ion adsorption without the contribution of electrosorption. Our results indicate similar adsorption behaviour for anions and cations. Furthermore, we probe the effect of sample orientation, which is shown to have a marked effect on the NMR spectra. Finally, we show that a 13 C -> 1 H cross polarisation experiment enables magnetisation transfer from the carbon architecture to the adsorbed species, allowing selective observation of the adsorbed ions and confirming our spectral assignments.
This work presents the synthesis of MoO2/MoS2 core/shell nanoparticles within a carbon nanotube network and their detailed electron microscopy investigation in up to three dimensions. The triple-hybrid core/shell material was prepared by atomic layer deposition of molybdenum oxide onto carbon nanotube networks, followed by annealing in a sulfur-containing gas atmosphere. High-resolution transmission electron microscopy together with electron diffraction, supported by chemical analysis via energy dispersive X-ray and electron energy loss spectroscopy, gave proof of a MoO2 core covered by few layers of a MoS2 shell within an entangled network of carbon nanotubes. To gain further insights into this complex material, the analysis was completed with 3D electron tomography. By using Z-contrast imaging, distinct reconstruction of core and shell material was possible, enabling the analysis of the 3D structure of the material. These investigations showed imperfections in the nanoparticles which can impact material performance, i.e. for faradaic charge storage or electrocatalysis.
Heat-to-current conversion of low-grade heat from a thermocapacitive cycle by supercapacitors
(2015)
Thermal energy is abundantly available, and especially low-grade heat is often wasted in industrial processes as a by-product. Tapping into this vast energy reservoir with cost-attractive technologies may become a key element for the transition to an energy-sustainable economy and society. We propose a novel heat-to-current converter which is based on the temperature dependence of the cell voltage of charged supercapacitors. Using a commercially available supercapacitor, we observed a thermal cell-voltage rise of around 0.6 mV K-1 over a temperature window of 0 [degree]C to 65 [degree]C. Within our theoretical model, this can be used to operate a Stirling-like charge-voltage cycle whose efficiency is competitive to the most-efficient thermoelectric (Seebeck) engines. Our proposed heat-to-current converter is built from cheap materials, contains no moving parts, and could operate with a plethora of electrolytes which can be chosen for optimal performance at specific working temperatures. Therefore, this heat-to-current converter is interesting for small-scale, domestic, and industrial applications.
Our investigations into molecular hydrogen (H2) confined in microporous carbons with different pore geometries at 77 K have provided detailed information on effects of pore shape on densification of confined H2 at pressures up to 15 MPa. We selected three materials: a disordered, phenolic resin-based activated carbon, a graphitic carbon with slit-shaped pores (titanium carbide-derived carbon), and single-walled carbon nanotubes, all with comparable pore sizes of <1 nm. We show via a combination of in situ inelastic neutron scattering studies, high-pressure H2 adsorption measurements, and molecular modelling that both slit-shaped and cylindrical pores with a diameter of ∼0.7 nm lead to significant H2 densification compared to bulk hydrogen under the same conditions, with only subtle differences in hydrogen packing (and hence density) due to geometric constraints. While pore geometry may play some part in influencing the diffusion kinetics and packing arrangement of hydrogen molecules in pores, pore size remains the critical factor determining hydrogen storage capacities. This confirmation of the effects of pore geometry and pore size on the confinement of molecules is essential in understanding and guiding the development and scale-up of porous adsorbents that are tailored for maximising H2 storage capacities, in particular for sustainable energy applications.
This work introduces the facile and scalable two-step synthesis of Ti 2 Nb 10 O 29 (TNO)/carbon hybrid material as a promising anode for lithium-ion batteries (LIBs). The first step uses a mechanically-induced self-sustaining reaction via ball-milling at room temperature to produce titanium niobium carbide with a stoichiometric ratio of Ti and Nb of 1 to 5. The second step involves the oxidation of as-synthesized titanium niobium carbide to produce TNO. Synthetic air yields fully oxidized TNO, while annealing in CO 2 results in TNO/carbon hybrids. The electrochemical performance for the hybrid and non-hybrid electrodes was surveyed for a narrow potential window (1.0-2.5 V vs. Li/Li + ) and a large potential window (0.05-2.5 V vs. Li/Li + ). The best hybrid material displayed a specific capacity of 350 mAh/g at a rate of 0.01 A/g (144 mAh/g at 1 A/g) in the large potential window regime. The electrochemical performance of hybrid materials is superior compared to non-hybrid materials for operation within the large potential window. Due to the advantage of carbon in hybrid material, the rate handling is faster than that of the non-hybrid one. The hybrid materials display robust cycling stability and maintain ca. 70% of their initial capacities after 500 cycles. In contrast, only ca. 26% of the initial capacity is maintained after the first 40 cycles for non-hybrid materials. We also applied our hybrid material as an anode in a full-cell lithium-ion battery by coupling it with commercial LiMn 2 O 4 .
In this work, the preparation and fabrication of elastomeric opal films revealing reversible mechanochromic and pH-responsive features are reported. The core–interlayer–shell (CIS) particles are synthesized via stepwise emulsion polymerization leading to hard core (polystyrene), crosslinked interlayer (poly(methyl methacrylate-co-allyl methacrylate), and soft poly(ethyl acrylate-co-butyl acrylate-co-(2-hydroxyethyl) methacrylate) shell particles featuring a size of 294.9 ± 14.8 nm. This particle architecture enables the application of the melt-shear organization technique leading to elastomeric opal films with orange, respectively, green brilliant reflection colors dependent on the angle of view. Moreover, the hydroxyl moieties as part of the particle shell are advantageously used for subsequent thermally induced crosslinking reactions enabling the preparation of reversibly tunable mechanochromic structural colors based on Bragg's law of diffraction. Additionally, the CIS particles can be loaded upon extrusion or chemically by a postfunctionalization strategy with organic dyes implying pH-responsive features. This convenient protocol for preparing multi-responsive, reversibly stretch-tunable opal films is expected to enable a new material family for anti-counterfeiting applications based on external triggers.
P2-type layered oxides with the general Na-deficient composition Na x TMO2 (x < 1, TM: transition metal) are a promising class of cathode materials for sodium-ion batteries. The open Na+ transport pathways present in the structure lead to low diffusion barriers and enable high charge/discharge rates. However, a phase transition from P2 to O2 structure occurring above 4.2 V and metal dissolution at low potentials upon discharge results in rapid capacity degradation. In this work, we demonstrate the positive effect of configurational entropy on the stability of the crystal structure during battery operation. Three different compositions of layered P2-type oxides were synthesized by solid-state chemistry, Na0.67(Mn0.55Ni0.21Co0.24)O2, Na0.67(Mn0.45Ni0.18Co0.24Ti0.1Mg0.03)O2 and Na0.67(Mn0.45Ni0.18Co0.18Ti0.1Mg0.03Al0.04Fe0.02)O2 with low, medium and high configurational entropy, respectively. The high-entropy cathode material shows lower structural transformation and Mn dissolution upon cycling in a wide voltage range from 1.5 to 4.6 V. Advanced operando techniques and post-mortem analysis were used to probe the underlying reaction mechanism thoroughly. Overall, the high-entropy strategy is a promising route for improving the electrochemical performance of P2 layered oxide cathodes for advanced sodium-ion battery applications.
