Nowadays, new approaches to fabricate high-performance electrode materials are of vital importance in the renewable energy field. Here, we present a facile synthesis procedure of 3D Ni(OH)2/graphene hybrids for supercapacitors via synchronous electrochemical-assisted exfoliation and assembly of graphene on 3D Ni(OH)2 networks. With the assistance of an electric field, the electrochemically exfoliated high-quality graphene can be readily, uniformly assembled on the surfaces of 3D Ni(OH)2. When serving as electrode materials for supercapacitors, the resulting 3D Ni(OH)2/graphene composites exhibited excellent specific capacitance (263 mF cm−2 at 2 mA cm−2), remarkable rate capability and super-long cycle life (retention of 94.1% even after 10 000 continuous charge–discharge cycles), which may be attributed to their highly porous, stable 3D architecture as well as uniform, firm anchoring of ultrathin graphene on their surfaces. Therefore, our approach provides a facile strategy for the large-scale synthesis of high-quality graphene based composites towards various applications.

Nitrogen-doped (N-doped) porous carbons have drawn increasing attention due to their high activity for electrochemical catalysis, and high capacity for lithium-ion (Li-ion) batteries and supercapacitors. So far, the controlled synthesis of N-enriched ordered mesoporous carbons (N-OMCs) for Li-ion batteries is rarely reported due to the lack of a reliable nitrogen-doping protocol that maintains the ordered mesoporous structure. In order to realize this, in this work, ordered mesoporous carbons with controllable N contents were successfully prepared by using melamine, F127 and phenolic resin as the N-source, template and carbon-source respectively via a solvent-free ball-milling method. The as-prepared N-OMCs which showed a high N content up to 31.7 wt% were used as anodes for Li-ion batteries. Remarkably, the N-OMCs with an N content of 24.4 wt% exhibit the highest reversible capacity (506 mA h g−1) even after 300 cycles at 300 mA g−1 and a capacity retention of 103.3%. N-OMCs were also used as electrode materials in supercapacitors and a capacity of 150 F g−1 at 0.2 A g−1 with stable cycling up to 2500 times at 1 A g−1 was achieved. These attractive results encourage the design and synthesis of high heteroatom content ordered porous carbons for applications in the field of energy storage and conversion.

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This article presents a facile and effective approach for synthesizing three-dimensional (3D) graphenecoupled Schiff-base hierarchically porous polymers (GS-HPPs). The method involves the polymerization of melamine and 1,4-phthalaldehyde, yielding Schiff-base porous polymers on the interconnected macroporous frameworks of 3D graphene aerogels. The as-synthesized GS-HPPs possess hierarchically porous structures containing macro-/meso-/micropores, along with large specific surface areas up to 776 m² g⁻¹ and high nitrogen contents up to 36.8 wt%. Consequently, 3D nitrogen-enriched hierarchically porous carbon (N-HPC) materials with macro-/meso-/micropores were obtained by the pyrolysis of the GS-HPPs at a high temperature of 800 °C under a nitrogen atmosphere. With a hierarchically porous structure, good thermal stability and a high nitrogen-doping content up to 7.2 wt%, the N-HPC samples show a high specific capacitance of 335 F g⁻¹ at 0.1 A g⁻¹ in 6 M KOH, a good capacitance retention with increasing current density, and an outstanding cycling stability. The superior electrochemical performance means that the N-HPC materials have great potential as electrode materials for supercapacitors.

Die vorliegende Arbeit konzentriert sich auf die Synthese von neuartigen hohlen MoSx-Nanomaterialien mit kontrollierbarer Größe und Form durch die kolloidale Template Methode. Ihre möglichen Anwendungen in wässrigen Energiespeichersystemen, einschließlich Superkondensatoren und Li-Ionen-Batterien (LIBs), wurden untersucht. Im ersten Teil wurde eine neue Nanostruktur aus hohlen Kohlenstoff-MoS2-Kohlenstoff-nanoplättchen erfolgreich durch eine L-Cystein unterstützte hydrothermale Methode unter Verwendung von Gibbsit als Templat und Polydopamin (PDA) als Kohlenstoffvorläufer synthetisiert. Nach dem Kalzinieren und Ätzen des Gibbsit Templates wurden gleichförmige Hohlplättchen erhalten, die aus einer sandwichartigen Anordnung von teilweise graphitischem Kohlenstoff und zweidimensional geschichteten MoS2 Flocken bestehen. Die Plättchen haben eine ausgezeichnete Dispergierbarkeit und Stabilität in Wasser sowie eine gute elektrische Leitfähigkeit aufgrund des durch die Kalzinierung von Polydopaminbeschichtungen erzeugten Kohlenstoffs gezeigt. Das Material wird dann in einem symmetrischen Superkondensator mit 1 M Li2SO4 als Elektrolyt aufgebracht, der eine spezifische Kapazität von 248 F/g (0.12 F/cm2) bei einer konstanten Stromdichte von 0.1 A/g und eine ausgezeichnete elektrochemische Stabilität über 3000 Zyklen aufweist, was darauf hindeutet, dass hohle Kohlenstoff-MoS2-Kohlenstoffnanoplättchen vielversprechende Materialien als Kandidaten für Superkondensatoren sind. Im zweiten Teil wurde 21 molare LiTFSI, das sogenannte "Wasser-in-Salz" (WIS) Elektrolyt, in Superkondensatoren mit hohlen Kohlenstoffnanoplättchen als Elektrodenmaterial untersucht. Im Vergleich zu dem im ersten Teil verwendeten 1 molaren Li2SO4-Elektrolyten wurden bei dem vorliegenden WIS Elektrolyt signifikante Verbesserungen in einem breiteren und stabilen Potentialfenster festgestellt, das durch die geringere Leitfähigkeit mit dem Gegenstück leicht beeinflusst wird. Die elektrochemische Impedanzspektroskopie (EIS) wurde ausgiebig eingesetzt, um einen Einblick in die Reaktionsmechanismen der WIS-Superkondensatoren zu erhalten. Zusätzlich wurde auch der Einfluss der Temperatur auf die elektrochemische Leistung im Temperaturbereich zwischen 15 und 55 °C untersucht, was eine hervorragende spezifische Kapazität von 128 F/g bei dem optimierten Zustand von 55 °C ergab. Die EIS-Messungen deckten die Abnahme der angepassten Widerstände mit der Temperaturerhöhung und umgekehrt auf und beleuchteten direkt die Beziehung zwischen elektrochemischer Leistung und Arbeitstemperatur von Superkondensatoren für zuverlässige praktische Anwendungen. Im dritten Teil wurde MoS3, ein amorphes, kettenförmig strukturiertes Übergangsmetall Trichalcogenid, als vielversprechende Anode in "Wasser-in-Salz" Li-Ionen-Batterien (WIS-LIBs) nachgewiesen. Die in diesem Teil verwendeten hohlen MoS3-Nanosphären wurden mittels einer skalierbaren Säurefällungsmethode bei Raumtemperatur synthetisiert, wobei sphärische Polyelektrolytbürsten (SPB) als Schablonen verwendet wurden. Beim Einsatz in WIS-LIBs mit LiMn2O4 als Kathodenmaterial erreicht das präparierte MoS3 eine hohe spezifische Kapazität von 127 mAh/g bei einer Stromdichte von 0.1 A/g und eine gute Stabilität über 1000 Zyklen sowohl in Knopf- als auch in Pouch-Zellen. Der Arbeitsmechanismus von MoS3 in WIS-LIBs wurde auch durch Ex-situ-Röntgenbeugungsmessungen (XRD) untersucht. Während des Betriebs wird MoS3 während der anfänglichen Li-Ionen-Aufnahme irreversibel in Li2MoO4 umgewandelt und dann allmählich in eine stabilere und reversible LixMoOy-Phase (2≤y≤4)) entlang der Zyklen umgewandelt. Amorphes Li-defizientes Lix-mMoOy/MoOz wird bei der Delithiierung gebildet. Die Ergebnisse der vorliegenden Studie zeigen einfache Ansätze zur Synthese hohler MoSx-Nanomaterialien mit kontrollierbarer Morphologie unter Verwendung einer Template-basierten Methode, die auf die vielversprechende Leistung von MoSx für wässrige Energiespeicheranwendungen zurückzuführen sind. Die elektrochemischen Untersuchungen von hohlen MoSx-Nanomaterialien in wässrigen Elektrolyten geben Einblick in die Reaktionsmechanismen von wässrigen Energiespeichersystemen und treiben die Entwicklung von Metallsulfiden für wässrige Energiespeicheranwendungen voran. / The present thesis focuses on the synthesis of novel hollow MoSx nanomaterials with controllable size and shape through the colloidal template method. Their possible applications in aqueous energy storage systems, including supercapacitors and Li-ion batteries (LIBs), have been studied. In the first part, hollow carbon-MoS2-carbon nanoplates have been successfully synthesized through an L-cysteine-assisted hydrothermal method by using gibbsite as the template and polydopamine (PDA) as the carbon precursor. After calcination and etching of the gibbsite template, uniform hollow platelets, which are made of a sandwich-like assembly of partial graphitic carbon and two-dimensional layered MoS2 flakes, have been obtained. The platelets have shown excellent dispersibility and stability in water, and good electrical conductivity due to carbon coating generated by the calcination of polydopamine. The material is then applied in a symmetric supercapacitor using 1 M Li2SO4 as the electrolyte, which exhibits a specific capacitance of 248 F/g (0.12 F/cm2) at a constant current density of 0.1 A/g and an excellent electrochemical stability over 3000 cycles, suggesting that hollow carbon-MoS2-carbon nanoplates are promising candidate materials for supercapacitors. In the second part, 21 m LiTFSI, so-called “water-in-salt” (WIS) electrolyte, has been studied in supercapacitors with hollow carbon nanoplates as electrode materials. In comparison with 1 M Li2SO4 electrolyte used in the first part, significant improvements on a broader and stable potential window have been revealed in the present WISE, which is slightly influenced by the lower conductivity with the counterpart. The electrochemical impedance spectroscopy (EIS) has been extensively employed to provide an insight look on the formation of solid electrolyte interphase in the WIS-supercapacitors. Additionally, the effect of temperature on the electrochemical performance has also been investigated in the temperature range between 15 and 55 °C, yielding eminent specific capacitance of 128 F/g at the optimized condition of 55 °C. The EIS measurements disclosed the decrease of fitted resistances with the increase of temperature and vise versa, directly illuminating the relationship between electrochemical output and working temperature of supercapacitors for reliable practical applications. In the third part, MoS3, an amorphous chain-like structured transitional metal trichalcogenide, has been demonstrated as a promising anode in the “water-in-salt” Li-ion batteries (WIS-LIBs). Hollow MoS3 nanospheres used in this part have been synthesized via a scalable room-temperature acid precipitation method using spherical polyelectrolyte brushes (SPB) as the template. When applied in WIS-LIBs with LiMn2O4 as the cathode material, the prepared MoS3 achieves a high specific capacity of 127 mAh/g at the current density of 0.1 A/g and good stability over 1000 cycles in both coin cells and pouch cells. The working mechanism of MoS3 in WIS-LIBs has also been studied by ex-situ X-ray diffraction (XRD) measurements. During operation, MoS3 undergoes irreversible conversion to Li2MoO4 during the initial Li ion uptake, and is then gradually converted to a more stable and reversible LixMoOy (2≤y≤4)) phase along cycling. Amorphous Li-deficient Lix-mMoOy/MoOz is formed upon delithiation. The results in the present thesis demonstrate facile approaches for synthesizing hollow MoSx nanomaterials with controllable morphologies using a template-based method, which attribute to the promising performance of MoSx for aqueous energy storage applications. The electrochemical studies of hollow MoSx nanomaterials in aqueous electrolytes provide insight into the reaction mechanisms of aqueous energy storage systems and push forward the development of metal sulfides for aqueous energy storage applications.

Resolving the mismatch between the practical potential window (PPW) and the available capacitive potential window of supercapacitor electrodes provides a feasible way to expand the operating voltage of supercapacitors, which further boosts energy density. Here, our research unveils a unique approach to manually control the PPW of the corresponding carbon-based supercapacitors (CSCs) by rational functionalization with amino groups. The extra pair of electrons from amino N atoms naturally adsorbs cations in the electrolyte, which rationalizes the surface charge of the carbon electrode and adjusts the PPW. A remarkable voltage expansion is achieved for CSCs, from 1.4 V to its maximum limit, 1.8 V, correspondently resulting in an approximately 1-fold increase in the energy density. Importantly, such a simple strategy endows our CSCs with an outstanding maximum energy density of 7.7 mWh cm⁻³, which is not only among the best values reported for thin-film CSCs but also comparable to those reported for Li thin-film batteries. These encouraging results are believed to bring fundamental insights into the nature of potential control in energy storage devices.

This paper reports a simple self-assembly strategy towards bowl-shaped carbon-containing hollow particles, as well as an unprecedented potential application for block copolymer vesicles in energy storage. Kippah vesicles (fully collapsed vesicles), formed by solution self-assembly of an amphiphilic polystyrene-block-poly(ethylene oxide) block copolymer, were employed as the template to guide the formation of bowl-shaped nitrogen-doped carbon hollow particles (BNCHPs). As electrode materials of supercapacitors, BNCHPs exhibit superior electrochemical performance. In particular, compared with their spherical counterpart, BNCHPs largely increase their volumetric packing density, leading to much higher volumetric capacitance or volume reduction of electrodes, which is desired for practical supercapacitor devices.

The great popularity of portable, wearable, and implantable smart electronics has intensively boosted the development of flexible miniaturized power supplies. Owing to the fast charge/discharge capability, high power delivery, long cycling lifetime, easy fabrication and integration, flexible in-plane micro-supercapacitors (FPMSCs) are of significance as the micropower sources for the next-generation flexible on-chip electronics. In this review, we provide a comprehensive overview about FPMSCs and discuss the recent advances in their fabrication and applications. Particular emphasis is put on the emergent device fabrication technologies of FPMSCs, including deposition techniques, coating strategies, etching methods, and printing technologies. Moreover, we highlight the unique applications of FPMSCs in constructing smart responses and self-powered integrated systems in terms of multifunctional operation modes. Finally, the remaining challenges regarding flexibility, performance improvement, smart response, and microdevice integration of FPMSCs are discussed, which will stimulate further research in this thriving field.

In-plane micro-supercapacitors (MSCs), as promising power candidates for micro-devices, typically exhibit high power densities, large charge/discharge rates, and long cycling lifetimes. The high areal/volumetric capacitances, high energy/power densities, high rate capability, as well as flexibility are the main scientific pursue in recent years. Among diverse electrode materials for MSCs, coordination polymer frameworks are emerging due to the designable porous structure and tunable functionality. However, the unsatisfied electrochemical performance still hinders their practical applications. In this work, we demonstrate the first time an efficient in-situ growth approach to precisely modify the vacancy of Prussian-blue nano-thin films with pyridine by coordination reaction for high energy-density MSCs. Confirmed by the experimental results and density functional theory calculation, the vacancy modification within Prussian-blue network improved the film-forming property, hydrophilicity, and electrochemical activity of the thin films. The resultant MSCs based on pyridine-modified Prussian-blue exhibited an ultrahigh energy density of up to 12.1 mWh cm⁻³ and an ultra-low time constant (t₀) of 0.038 ms, which are the best values among the state-of-the-art in-plane MSCs. This work provides an attractive solution for structural engineering of promising active materials on molecule level toward high-performance micro-energy devices.