Zn-ion Hybrid Supercapacitors Research Articles

Polymer-mediated vacancy defects of graphene sheets as high-performance cathode materials for aqueous zinc-ion hybrid supercapacitors

The electrochemical behavior of graphene sheets in energy storage system is closely related to its electronic structures. Specifically, structural vacancy defects can expose more active sites and enhance the electrochemical performance. However, it is still a challenging problem to realize valid defect regulation on improving the reaction kinetics of electrode materials. Herein, vacancy-defective graphene sheets were constructed through the thermal mediated method via intercalation of polyacrylonitrile nanofibers. The vacancy defects were generated from the NH3 gas resulting from polymer decomposition at gradient carbonization temperature. The obtained composites of the graphene sheets and carbon nanofibers demonstrate that the vacancy defects benefit to charge transport, allowing more electrons to pass through the interlayered structure, and enhance the adsorption capacitance during the reversible electrochemical process. In addition, the as-assembled Zn ion hybrid supercapacitors exhibit a high energy density of 129.9 Wh kg−1 and outstanding cyclic stability (99.8 % after 10,000 cycling). The confined polymer-mediated thermal modification strategy can afford abundant vacancy defective sites and exhibit promising outlook for constructing high-performance graphene-based electrode materials for Zn ion hybrid supercapacitors.

Fallen autumn leaves – The source of highly porous carbon for Zn-ion hybrid supercapacitors

Over the years, many sophisticated synthetic two-dimensional (2D) carbon materials have become increasingly popular for supercapacitors, e.g. zinc-ion hybrid supercapacitors (ZHSC) due to their ordered structure and high energy density. Additionally, ZHSC is a very demanding device, where finding efficient materials is challenging and the energy storage mechanism remains unclear. Biomass-derived carbon materials exhibit many drawbacks due to their impurities and defective structure, low stability and poor capacitance. In this study, a ZHSC was assembled via carbonization and activation of leaves collected from city streets and utilized as a cathode material. The AC650_Zn-foil presented a high specific capacitance of 95 F·g−1 and a high energy density of 86 W·h·kg−1 at 210 W·kg−1. Furthermore, a superior power density of 40,960 W·kg−1 at 33 W·h·g−1 was presented compared to other investigated materials. In addition, we identified the processes that occurred in the following device, which demonstrated a mechanism that determines the migration of Zn ions, as well as the chemical reactions involved in Zn ions.

Layered S-Bridged Covalent Triazine Frameworks via a Bifunctional Template-Catalytic Strategy Enabling High-Performance Zinc-Ion Hybrid Supercapacitors.

Exploring covalent triazine frameworks (CTFs) with high capacitative activity is highly desirable and challenging. Herein, the S-rich CTFs cathode is pioneeringly introduced in Zn-ion hybrid supercapacitors (ZSC), achieving outstanding capacity and energy density, and satisfactory anti-freezing flexibility. Specifically, the S-bridged CTFs are synthesized by a bifunctional template-catalytic strategy, where ZnCl2 serves as both the catalyst/solvent and in situ template to construct triazine frameworks with interconnected pores and layered gaps. The resultant CTFs (CTFS-750) are employed as a reasonable pattern-like system to more deeply scrutinize the synergistic effect of S-bridged triazine and layered porous architecture for polymer-based cathodes in Zn-ion storage. The experimental results indicate that the adsorption barriers of Zn-ions on CTFS-750 are effectively weakened, and accessible Zn2+-absorption sites provided by the C─S─C and C═N bonds have been confirmed via DFT calculations. Consequently, the CTFS-750 cathode-assembled ZSC displays an ultra-high capacity of 211.6 mAh g-1 at 1.0 A g-1, an outstanding energy density of 202.7Wh kg-1, and attractive cycling performance. Moreover, the resulting flexible ZSC device shows superior capacity, good adaptability, and satisfactory anti-freezing behavior. This approach sheds new light on constructing advanced polymer-based cathodes at the atom level and paves the way for fabricating high-performance ZSC and beyond.

Molten salt-assisted fabrication of hierarchical porous carbon derived from lignite for Zn-ion hybrid supercapacitors

Zn-ion hybrid supercapacitors (ZIHCs) are considered as the most potential energy storage device. Herein, a hierarchical porous carbon was prepared by molten salt-assisted one-pot activation strategy. The molten salt synthesized lignite-derived porous carbon (MLPC) has high specific surface area (3035 m2 g−1) and unique architecture with dual majority pores of size in 1–3 nm. The assembled ZIHC delivers a high specific capacitance of 570.6 F g−1 at 0.1 A g−1 and a remarkable energy density of 82.8 W h kg−1 at a power density of 16 kW kg−1. The cell achieves good long-term cycling stability with 82.2 % capacity retention at 2 A g−1 after 5000 cycles. This study provides a facile approach to utilize lignite to fabricate superior carbon cathode for high-performance aqueous ZIHCs.

Enabling Wasted A4 Papers as a Promising Carbon Source to Construct Partially Graphitic Hierarchical Porous Carbon for High-Performance Aqueous Zn-Ion Storage.

Considering the superiorities of abundance, easy collection, low cost, and nearly constant composition, the wasted A4 papers are deemed as a recyclable and scalable carbon source to fabricate functional carbon materials for Zn-ion hybrid supercapacitors (ZIHSCs), which integrate the supercapacitors' high-power output and batteries' high energy density. Herein, the wasted A4 papers are efficiently converted into an advanced carbon material owning a hierarchical porous structure with a high surface area and interconnected multiscale channels, a graphitic structure, and a good level of N/O codoping. By taking advantage of these features, an express electron/ion transfer pathway, a large accessible surface interface, and a robust architecture are achieved for swift kinetics, numerous active sites, and excellent steadiness to afford a charming Zn2+ storage capability for the aqueous coin-type ZIHSC device (a high capacity of 244 mAh g-1 at 0.1 A g-1 with a capacity conservation of 116.4 mAh g-1 even amplifying the current density by 200 times, a supreme energy density of 190.4 Wh kg-1, a supreme power output of 18 kW kg-1, and an eminent durability of 93.8% over 10,000 cycles at 10 A g-1). Excitingly, the quasi-solid ZIHSC device also bespeaks an enjoyable capacity of 211.7 mAh g-1, a high energy density of 159.3 Wh kg-1, good mechanical flexibility, and a low self-discharge rate. This work puts forward a simple and scalable strategy to enable the wasted A4 paper as a competitive carbon source to construct advanced cathode material for Zn2+ storage.

Iodine-Doped Hollow Carbon Nanocages without Templates Strategy for Boosting Zinc-Ion Storage by Nucleophilicity.

Zn-ion hybrid supercapacitors (ZHCs) combining merits of battery-type and capacitive electrodes are considered to be a prospective candidate in energy storage systems. Tailor-made carbon cathodes with high zincophilicity and abundant physi/chemisorption sites are critical but it remains a great challenge to achieve both features by a sustainable means. Herein, a hydrogen-bonding interaction-guided self-assembly strategy is presented to prepare iodine-doped carbon nanocages without templates for boosting zinc-ion storage by nucleophilicity. The biomass ellagic acid contains extensional hydroxy and acyloxy groups with electron-donating ability, which interact with melamine and ammonium iodide to form organic supermolecules. The organic supermolecules further self-assemble into a nanocage-like structure with cavities under hydrothermal processes via hydrogen-bonding and π-π stacking. The carbon nanocages as ZHCs cathodes enable the high approachability of zincophilic sites and low ion migration resistance resulting from the interconnected conductive network and nanoscale architecture. The experimental analyses and theoretical simulations reveal the pivotal role of iodine dopants. The I5-/I3- doping anions in carbon cathodes have a nucleophilicity to preferentially adsorb the Zn2+ cation by the formation of C+-I5--Zn2+ and C+-I3--Zn2+. Of these, the C+-I3- shows stronger bonding with Zn2+ than C+-I5-. As a result, the iodine-doped carbon nanocages produced via this template-free strategy deliver a high capacity of 134.2 mAh/g at 1 A/g and a maximum energy and power density of 114.1 Wh/kg and 42.5 kW/kg.

N/B co-doped porous carbon with superior specific surface area derived from activation of biomass waste by novel deep eutectic solvents for Zn-ion hybrid supercapacitors

N/B co-doped porous carbon materials (NBPCs) are regarded as an ideal cathode material for Zn-ion hybrid supercapacitors (ZHSCs). As a capacitive cathode material, the improvement of specific surface area (SSA) and pore structure can efficiently enhance the capacity and rate capability of NBPCs. However, the B atom doping progress will patch up the defect and pore of NBPCs, thereby impeding the further expansion of the SSA area and porous structure. This paper designs a new route for high-efficiency fabrication of NBPCs with high SSA and rich pore structure, employing biomass waste as the carbon source and a novel deep eutectic solvent (DES) as the activation agent. The obtained NBPCs process superior SSA (2270 m2 g–1) and abundant pore structure with rich B, N-doping level. Notably, an interesting occupied effect of doped B atoms on the N-doped carbon network can be identified, which optimizes the proportion of N-contained surface functional groups, leading to the enhancement of conductivity and capacity in NBPCs. Together with the large SSA, high B, N-doping level, an appropriate proportion of N-contained surface groups, and hierarchical porous structure, the NBPC-3 sample exhibits excellent electrochemical performance as cathode materials for ZHSCs, with an energy density of 139.46 W h kg–1.

Pyrrolic-N/C = O cooperative assisted in hollow porous carbon with ultra-high electrochemical performance for Zn-ion hybrid supercapacitors

The development of high-energy–density advanced Zinc-ion hybrid supercapacitors (ZIHSs) shows significant potential, yet it remains a complex undertaking due to its heavy reliance on physical Zn2+ adsorption and the limitations imposed by insufficient cathodes. This study employs a rich in C = O and pyrrolic-N functional groups hollow porous carbon derived from cattail leaves as a cathode material for high-energy-power ZIHSs. The proposed charge storage mechanism involves the assimilation of opposite charge carriers, coupled with a multi-electron redox response, which was investigated by Ex-situ experiments and density functional theory (DFT) simulations. This process entails the alternating binding of Zn2+ and SO42− at designated active sites, along with strong relationships between Zn2+ and electronegative C = O/pyrrolic-N motifs, leading to the creation of C-O-Zn-N-C bonds. Consequently, the aqueous ZIHSs constructed with this hollow porous carbon cathode exhibit outstanding performance metrics. These include an impressive energy density of 128 Wh kg−1, a discharge specific capacity of 149 mAh/g at 10 A/g, a superb power density of 1188 W kg−1, and an extraordinary long-term lifespan, retaining 95 % of its initial capacity after 10,000 cycles. Importantly, the strategy of augmenting energy storage through chemical adsorption capability modulation can be applied to other carbon materials.

Hierarchical porous carbon guided by constructing organic-inorganic interpenetrating polymer networks to facilitate performance of zinc hybrid supercapacitors

Customized design of well-defined cathode structures with abundant adsorption sites and rapid diffusion dynamics, holds great promise in filling capacity gap of carbonaceous cathodes towards high-performance Zn-ion hybrid supercapacitors (ZHC). Herein, we fabricate a series of dynamics-oriented hierarchical porous carbons derived from the unique organic-inorganic interpenetrating polymer networks. The interpenetrating polymer networks are obtained through physically knitting polyferric chloride (PFC) network into the highly crosslinked resorcinol-formaldehyde (RF) network. Instead of covalent bonding, physical interpenetrating force in such RF-PFC networks efficiently relieves the RF skeleton shrinkage upon pyrolysis. Meanwhile, the in-situ PFC network sacrifices as a structure-directing agent to suppress the macrophase separation, and correspondingly 3D hierarchical porous structure with plentiful ion-diffusion channels (pore volume of 1.35 cm3/g) is generated in the representative HPC4via nanospace occupation and swelling effect. Further removal of Fe fillers leaves behind a large accessible specific surface area of 1550 m2/g for enhanced Zn-ion adsorption. When used as the cathode for ZHC, HPC4 demonstrates a remarkable electrochemical performance with a specific capacity of 215.1 mAh/g at 0.5 A/g and a high Zn2+ ion diffusion coefficient of 11.1 × 10−18 cm2/s. The ZHC device yields 117.0 Wh/kg energy output at a power density of 272.1 W/kg, coupled with good cycle lifespan (100,000 cycles@10 A/g). This work inspires innovative insights to accelerate Zn diffusion dynamics by structure elaboration towards high-capacity cathode materials.

Boosting the performance of Zn ion hybrid supercapacitors by regulating the chemically and physically active sites of graphene films.

Reduced graphene oxide (RGO) is an ideal material as an electrode used in the electrochemical energy storage field. However, the serious aggregation of graphene sheets and fewer chemically active sites limit it from exhibiting higher performance. Herein, we introduce a facile solvothermal reaction method to simultaneously regulate the functional groups on RGO, balance the aggregation and connection of graphene sheets, and dope the nitrogen element in a graphene network. The obtained electrode (RGO-N(DMF)) has a high content of carbonyl and nitrogen functional groups, and shows a fluffy structure as well as good electron conductivity, exhibiting both high chemically and physically actives sites. Benefiting from these advantages, RGO-N(DMF) shows a high specific capacity of 135 mA h g-1 at 0.2 A g-1 and favorable rate performance of maintaining 53% capacity at 50 A g-1, which are both higher than those of the normal hydrothermally obtained RGO electrodes. More interestingly, RGO-N(DMF) can maintain the high electrochemical performance at a high mass loading of 5.1 mg cm-2. In addition, when the RGO-N(DMF) electrode is used in the flexible Zn-ion hybrid supercapacitor (ZHS), the capacity retention remains at 100% after 500-time bending, showing excellent mechanical flexibility. This study not only provides an effective strategy for constructing carbon-based cathode materials with excellent properties, but also provides prospects and enlightenment for the practical application of aqueous ZHSs.

Nitridation-boosted V eg occupation of a VN@CNT flexible electrode for high-rate Zn-ion hybrid supercapacitors

Nitridation-boosted V e_g occupation of a VN@CNT flexible electrode for high-rate Zn-ion hybrid supercapacitors

From wasted polymers to N/O co-doped partially graphitic carbon with hierarchical porous architecture as a promising cathode for high performance Zn-ion hybrid supercapacitors

N/O co-doped graphitic hierarchical porous carbon is yielded from wasted polymers. A capacity of 257.9 mA h g−1 with an ultrahigh energy density of 226.5 W h kg−1 is delivered. Excellent energy storage ability is also obtained for wearable devices.

2D metal–organic framework derived ultra-thin nitrogen-doped oxygen rich porous carbon nanosheets for zinc-ion hybrid supercapacitors

2D MOF derived ultra-thin carbon nanosheets with high reactivity, super-hydrophilicity and hierarchical porosity are prepared. The corresponding Zn-ion hybrid supercapacitor delivers exceptional energy storage capability with long cycling stability.

Structural and surface engineering promotes Zn-ion energy storage capability of commercial carbon cloth

Aqueous Zn-ion hybrid supercapacitors (AZHSCs) combining the advantages of high-energy batteries and high-power supercapacitors see a bright future, but they still suffer from the poor capacity of carbonic cathodes. Herein, a functionalized porous carbon cloth (denoted as FPCC) electrode is demonstrated based on commercial carbon cloth (denoted as CC) tuning by structural and surface engineering. The constructed exfoliated porous carbon layer and the negatively charged functionalized interface not only increase the electrical double layer capacitance but also favor the chemical adsorption of Zn2+ to obtain additional pseudocapacitance. Consequently, the FPCC electrode delivers a high capacity of 0.16 mAh cm−2 at 4 mA cm−2, which is 923.8 times higher than CC, and a long cycle life (85.0% capacity retention after 30 000 cycles). More importantly, the Zn//FPCC AZHSC possesses an impressive energy density (3.3 mWh cm−3) and power density (240 mW cm−3), superior to many advanced batteries and supercapacitors. The quasi-solid-state device is also assembled as a demo. This modification strategy may provide new opportunities for high-performance AZHSCs.

Surface protection and nucleation enhancement of zinc anode with graphene and doped carbon nanotubes for high-performance energy storage

Owing to their high-power density, long cycling performance, excellent safety, and eco-friendliness, Zn-ion hybrid supercapacitors (ZIHC) have attracted attention as a next-generation energy storage technology to replace conventional lithium-ion batteries. However, the dissolution of Zn in ZIHCs, their low wettability and limited number of nucleation sites for Zn plating have limited their further application. To address these, research has been undertaken to enhance safety by applying a protective layer, such as carbon, ceramics, or polymers, onto the zinc anodes. Nevertheless, achieving exceptional energy storage performance remains insufficient. In this study sequentially coated Zn electrode surface with graphene and carbon nanotubes (CNT), and F and N were simultaneously doped in the carbon lattice of the top layer of the CNTs. Owing to its excellent safety, improved wettability, and numerous nucleation sites for Zn plating, the surface-engineered Zn anode exhibited improved energy–power density (255 to 141 Wh kg−1 between 800 and 32,000 W kg−1) and long lifespan capability of 93 % after 45,000 cycles. The proposed strategy is a highly promising approach for enhancing the energy storage performance of ZIHCs.

A soft implantable energy supply system that integrates wireless charging and biodegradable Zn-ion hybrid supercapacitors.

The advent of implantable bioelectronic devices offers prospective solutions toward health monitoring and disease diagnosis and treatments. However, advances in power modules have lagged far behind the tissue-integrated sensor nodes and circuit units. Here, we report a soft implantable power system that monolithically integrates wireless energy transmission and storage modules. The energy storage unit comprises biodegradable Zn-ion hybrid supercapacitors that use molybdenum sulfide (MoS2) nanosheets as cathode, ion-crosslinked alginate gel as electrolyte, and zinc foil as anode, achieving high capacitance (93.5 mF cm-2) and output voltage (1.3 V). Systematic investigations have been conducted to elucidate the charge storage mechanism of the supercapacitor and to assess the biodegradability and biocompatibility of the materials. Furthermore, the wirelessly transmitted energy can not only supply power directly to applications but also charge supercapacitors to ensure a constant, reliable power output. Its power supply capabilities have also been successfully demonstrated for controlled drug delivery.

Fluorinated Laser-induced Graphene towards High Performance Zn-ion Hybrid Supercapacitors

Fluorinated Laser-induced Graphene towards High Performance Zn-ion Hybrid Supercapacitors

High energy density flexible Zn-ion hybrid supercapacitors with conductive cotton fabric constructed by rGO/CNT/PPy nanocomposite

Fiber-shaped energy-storage devices for high energy and power density are crucial to power wearable electronics. In this work, reduced graphene oxide/carbon nanotubes/polypyrrole (GCP-op) cotton fabric with the optimal performance is prepared via a facile and cost-effective dipping-drying together with chemical polymerization approach. The structural characterizations confirm that the GCP-op cotton fabric has been successfully attached with numerous nanoparticles and carbon nanotubes, which can serve as a channel for electronical transfer. And GCP-op cotton fabric electrode displays admirable areal specific capacitance with 8397 mF cm−2 at 1 mA cm−2. By combining GCP-op cathode with zinc anode, a GCP-op//PAM/ZnCl2//Zn flexible Zn-ion hybrid supercapacitor (FZHSC) is produced with 2 M polyacrylamide/ZnCl2 (PAM/ZnCl2) hydrogel as the gel electrolyte. The FZHSC has superior cycle stability of 88.2%, outstanding energy density of up to 158 μWh cm−2 and power density at 0.5 mW cm−2. The remarkable performance proves that PPy-based material can provide more options for design and fabricate high energy flexible Zn-ion hybrid supercapacitors.

Ni3S2/Ni2O3 heterojunction anchored on N-doped carbon nanosheet aerogels for dual-ion hybrid supercapacitors

As a member of transition metal sulfides, Ni3S2 has been reported as one type of the effective pseudocapacitive electrode materials for supercapacitors, due to its good electrical conductivity and high electrochemical activity. To further improve the energy density of the Ni3S2-based supercapacitors, we propose a novel approach to the Ni3S2/Ni2O3 heterojunction anchored on N-doped carbon nanosheet aerogels (Ni3S2/Ni2O3@N-CNA), which is used as the cathode for Zn-ion hybrid supercapacitors with the dual-ion electrolytes. The Ni3S2/Ni2O3@N-CNA samples can be prepared through the bubble-templated polymerization of pyrrole and the carbonization of the polypyrrole nanosheet hydrogel/Ni2+. The Ni3S2/Ni2O3@N-CNA cathode is immersed into the Li-ion catholyte for Li+ storage, while the Zn foil anode is immersed into the Zn-ion anolyte for Zn2+ storage. Electrochemical kinetic analysis of the dual-ion hybrid supercapacitor indicates its evident capacitance characteristic. Additionally, theoretical calculations reveal that the Ni3S2/Ni2O3 heterojunction can facilitate the adsorption and dehydration of a hydrated Li+ ion to further play a great role in the enhancement of pseudocapacitance. Based on the novel strategy of the alkaline dual-ion electrolytes, this dual-ion hybrid supercapacitor with the high energy density (64.2 Wh kg−1) opens up a new avenue to develop high-performance Zn-ion hybrid supercapacitors.

Customizable Metal Micromesh Electrode Enabling Flexible Transparent Zn-Ion Hybrid Supercapacitors with High Energy Density.

Emerging flexible and wearable electronic products are placing a compelling demand on lightweight transparent energy storage devices. Owing to their distinguishing features of safety, high specific energy, cycling stability, and rapid charge/discharge advantages, Zn-ion hybrid supercapacitors are a current topic of discussion. However, the trade-off for optical transmittance and energy density remains a great challenge. Here, a high-performance Zn-ion hybrid supercapacitor based on the customizable ultrathin (5µm), ultralight (0.45mg cm-2), and ultra-transparent (87.6%) Ni micromesh based cathode and Zn micromesh anode with the highest figure of merit (84843) is proposed. The developed flexible transparent Zn-ion hybrid supercapacitors reveal excellent cycle stability (no decline after 20000 cycles), high areal energy density (31.69 µWh cm-2), and high power density (512 µW cm-2). In addition, the assembled solid flexible and transparent Zn-ion hybrid supercapacitor with polyacrylamide gel electrolyte shows extraordinary mechanical properties even under extreme bending and twisting operation. Furthermore, the full device displays a high optical transmittance over 55.04% and can be conformally integrated with diverse devices as a flexible transparent power supply. The fabrication technology offers seamless compatibility with industrial manufacturing, making it an ideal model for the advancement of portable and wearable devices.