High-performance Lithium-ion Capacitors Research Articles

Nanoarchitectured MnO2 Confined to Mesoporous Carbon Microspheres as Bifunctional Electrodes for High-Performance Supercapacitors and Lithium-Ion Capacitors

Manganese dioxide (MnO2) is an outstanding electrode material to obtain high pseudocapacitance and specific capacity, but the structure pulverization and poor conductivity during the charge/discharge process are the inevitable problems. Restricting nanoscaled MnO2 in stable pore channels of mesoporous carbon spheres can effectively inhibit its pulverization and obtain an excellent conductive network. Herein, nanoarchitectured MnO2/mesoporous carbon microspheres (MCMs) as bifunctional electrodes for supercapacitors and lithium-ion capacitors (LICs) were prepared through a charily designed facile stratagem containing spray drying and the subsequent redox reaction. The MnO2/MCMs electrode delivers a gravimetric capacitance of 188 F g–1 and a volumetric capacitance of 347 F cm–3 with an outstanding cyclic performance of 90% capacitance retention after 1000 cycles at 1 A g–1, which is ideal for supercapacitors. Moreover, the assembled MnO2/MCMs//activated carbon (AC) lithium-ion capacitors exhibit a long cyclic life of 1300 times with 7.7% capacity loss at 1 A g–1 and a superior energy density of 147 Wh kg–1, as well as a power density of 4952 W kg–1, demonstrating its feasibility on LIC anodes. The excellent electrochemical performance is ascribed to the synergistic effect between MnO2 and mesoporous carbon microspheres, which improves the electrochemical capacities and cyclic stability of both systems. This work provides the possibility for applying bifunctional MnO2/MCMs as electrode materials for high-efficiency hybrid systems.

Rational Match of a Bamboo-Derived Porous Foam Carbon Cathode and Carbon Framework-Supported Nano-ZnO Anode for High-Performance Lithium-Ion Capacitors

The lithium-ion capacitor (LIC) is developed for advanced energy reserve systems, which can fulfill the requirements of long cycling capability and high power and energy density. Herein, a bamboo powder-derived porous carbon-supported ZnO composite (denoted as CZK1) was prepared and applied as an anode for the LIC. The obtained porous foam carbon (denoted as BLZACK1) acquired by acid washing of CZK1 was used as a cathode for the LIC. The assembled CZK1//BLZACK1 LIC by using CZK1 and BLZACK1 as the anode and cathode, respectively, exhibited excellent electrochemical performance. It possesses a high energy density of 134.98 W h kg–1 with a power density of 9793.58 W kg–1. Besides, after 8000 cycles at 5 A g–1, the capacitance retention is 83.90%, suggesting its outstanding cycling stability. This study shows that bamboo can be used as a derived high-performance carbon material with great potential in the field of energy storage.

Microstructured nitrogen-doped graphene-Sn composites as a negative electrode for high performance lithium-ion hybrid supercapacitors

Microstructured nitrogen-doped graphene-Sn synthetized in one step for high performance and long-term cycling stability lithium-ion capacitors.

Anthracite-derived carbon-based electrode materials for high performance lithium ion capacitors

The capacity and electrochemical kinetics mismatches between cathode and anode are two major obstacles for lithium ion capacitors. In the work, graphene coating and electrochemical prelithiation are used to reinforce the properties of activated carbon and graphitized carbon as cathode and anode. The activated carbon with high specific surface area, and the graphitized carbon with porosity are prepared with anthracite as raw material, then both of them are modified with anthracite-derived graphene. As cathode, activated carbon coated with graphene shows a capacitance of 302 F g−1 with 75% capacitance retention after 10,000 cycles. The anode, graphitized carbon coated with graphene sheets delivers a capacity of 568.1 mAh g−1 at 0.1 A g−1 with 97% capacitance retention after 300 cycles. The LICs assembled with cathode and prelithiated anode show high energy and power densities, 315.1 Wh kg−1 at 300 W kg−1 and 133.3 Wh kg−1 at 15000 W kg−1, and superior cyclic stability, 78% capacity retention after 10,000 cycles. This work illustrates surface graphene coating and prelithiation to balance the capacity and electrochemical kinetics mismatches of electrodes in LICs and blaze an efficient route to convert anthracite to high performance electrodes for LICs and other energy storage systems.

Porous V2O3@C composite anodes with pseudocapacitive characteristics for lithium-ion capacitors

Vanadium trioxide materials have attracted great interest due to their low cost and high theoretical lithium storage capacity. In this work, porous V2O3@C composites were prepared via a NaCl template-assisted freeze-drying strategy. Benefiting from the unique three-dimensional porous carbon-based structure, the V2O3@C composite anode exhibits a high-rate pseudocapacitive behavior. A lithium-ion capacitor (LIC) based on this V2O3@C composite anode and a commercial AC cathode was constructed. Results show that the as-constructed device exhibits high energy density, high power density as well as long cycle stability, indicating the great promise of our porous V2O3@C composites for the high-performance LICs.

Nitrogen-doped activated porous carbon for 4.5 V lithium-ion capacitor with high energy and power density

Lithium-ion capacitors (LICs) have become one of the most popular energy storage devices because of the combination of high energy densities and power densities. However, the kinetic imbalance of anode and cathode restricts the specific capacities and voltage windows of LICs. Herein, an in-situ nitrogen-doped activated porous carbon (ANMPC) material with high specific surface area (1894.9 m2/g) is proposed to act as both cathode and anode for the preparation of the 4.5 V “all carbon” LICs. The hierarchically porous ANMPC obtained by KOH activation and carbonization of polypyrrole (PPy) has plenty of mesopores created by surfactant (added during the PPy process) as well as micropores generated by KOH activation, thus can provide abundant active sites for ion intercalation and large area for electrostatic adsorption simultaneously, satisfying the critical requirements of high-performance anode and cathode, respectively. After coupling the pre-lithiated ANMPC anode and fresh ANMPC cathode, the complete LIC device delivers large energy density of 167.5 Wh/kg at a power density of 269.0 W/kg, and still remains 88.9 Wh/kg at an ultrahigh power density of 13,198.5 W/kg, exhibiting enormous potential for applications in high performance lithium-ion capacitors.

Construction of MoSe2 nanoparticles anchored on layered microporous carbon heterostructure anode for high-performance and low-cost lithium-ion capacitors

Lithium ion capacitors (LICs), which elaborately integrate the feature of supercapacitors and lithium-ion batteries have recently aroused extensive research attentions. Nevertheless, balancing the discrepancy of electrochemical kinetics between capacitive-type cathode and battery-type anode materials plays the pivotal role in constructing high-performance of LICs. Additionally, the cathode and anode of LICs usually adopt various material synthesis routes, making the fabrication procedures complicated and expensive from the perspective of energy storage devices. Herein, the one‑carbon dual-purpose strategy is proposed for simultaneous manipulation of MoSe2/layered microporous carbon heterostructure anode (MoSe2@LMC-1.5) and amorphous microporous carbon cathode (LMC) by using maize stalks precursor. The MoC bond formed on the interface of MoSe2 and LMC favors electron and Li-ion transfer in the composite. The amorphous microporous carbon substrate can not only ameliorate electrical conductivity of molybdenum selenide, but also tremendously suppress serious agglomeration of MoSe2 nanoparticles. The optimized mass ratio MoSe2@LMC-1.5 heterostructure remarkably improves the lithium ion storage performance. More importantly, in the potential window (0–4.5 V), LIC (MoSe2@LMC-1.5//LMC) device displays a higher energy/power output (maximum 108 Wh kg−1/221 W kg−1 and 68 Wh kg−1/2295 W kg−1) along with good cycling life.

Deoxygenated porous carbon with highly stable electrochemical reaction interface for practical high-performance lithium-ion capacitors

Metal-ion capacitors, especially lithium-ion capacitors (LICs), are promising energy storage devices with much higher energy density than conventional electrochemical double-layer capacitors (EDLC). While compared with the EDLCs, the stable voltage window of the cathode in LICs is much narrower than that in EDLCs because of the different energy storage mechanisms, which restricts the energy density of LICs. In this work, the porous carbon (D-HAC) with an ultra-low oxygen element content of 0.973 wt.% is synthesized by heating the starch-based porous carbon (HAC) in the hydrogen-argon mixing atmosphere. The specific capacitance of D-HAC reaches up to 106.7 F g−1 at 50 mA g−1. Owing to high specific capacitance of D-HAC, LIC constructed with D-HAC cathode and soft carbon anode can provide a high energy density of 123.5 Wh kg−1. More importantly, the D-HAC//SC LIC shows excellent capacity retention of 96.77% after 10 000 cycles at a high rate of 50 C due to the stable electrochemical interface of D-HAC. This work provides a simple and efficient method to remove the unstable oxygen element of the porous carbon materials and shows a promising approach to develop advanced metal-ion capacitors with high energy density and long cycle life.

Co3ZnC@NC Material Derived from ZIF-8 for Lithium-Ion Capacitors.

Metal–organic framework (MOF)-derived carbon materials were widely reported as the anodes of lithium-ion capacitors (LICs). However, tunning the structure and electrochemical performance of the MOF-derived carbon materials is still challenging. Herein, metal carbide materials of Co3ZnC@NC-8:2 were obtained by the pyrolysis of the MOF materials of Co0.2Zn0.8ZIF-8 (Zn/Co ratio of 8:2). A half-cell assembled with the Co3ZnC@NC-8:2 electrode exhibits a discharge capacity of the electrode material of 598 mAh g–1 at a current density of 0.1 A g–1. After 100 cycles, the retention rate of discharge specific capacity is about 90%. The high performance of Co3ZnC@NC-8:2 is ascribed to its high crystalline degree and well-defined structure, which facilitates the intercalation/deintercalation of lithium ions and buffers the volume change during the charge/discharge process. The high capacitance contribution ratio calculated by cyclic voltammetry (CV) curves at different scanning rates indicates the pseudocapacitance storage mechanism. LICs constructed from the Co3ZnC@NC-8:2 material have a rectangular CV curve, while the charge–discharge curve has a symmetrical triangular shape. This study indicates that MOF-derived carbon is one of the promising materials for high-performance LICs.

High-Performance Lithium-Ion Capacitors Produced by Atom-Thick Carbon Cathode and Nitrogen-Doped Porous Carbon Anode

High-Performance Lithium-Ion Capacitors Produced by Atom-Thick Carbon Cathode and Nitrogen-Doped Porous Carbon Anode

Preparation of the 3D Porous Carbon Based on Vacuum residue and Its Application in Lithium Ion Capacitors

Two porous carbon materials were prepared from vacuum residue using the hard template method to construct high-performance dual-carbon lithium-ion capacitors. The results show that the mixture of vacuum residue for removing toluene insoluble matter and sodium citrate were subjected to aerobic rapid polycondensation, and the vacuum residue after polycondensation was heated at 700 °C to obtain ZYC-7 porous carbon with a specific surface area of about 181 m2 g-1. The ZYC-7 was further etched by KOH under 700 °C to obtain ZYCK-7 super porous carbon with a specific surface area than 997 m2 g-1. The ZYC-7 porous carbon exhibited a specific capacity of 600 and 300 mA h g-1 at a current density of 0.1 and 2.0A g-1, under 0-3 V vs. Li+/Li, while the ZYCK-7 super porous carbon revealed a specific capacity of more than 70 mA h g-1 at a current density of 1.0 A g-1 under 2.0-4.3 V vs. Li+/Li; The ZYC-7 and ZYCK-7 were assembled into a double-carbon lithium-ion capacitor with an energy density higher than 55 Wh kg-1 at a power density of 10 kW Kg-1, and its capacity retention rate was still greater than 85% after 3000 cycles of charge and discharge at a current density of 1.0 A g-1.

Nitrogen substituted graphdiyne as electrode for high-performance lithium-ion batteries and capacitors

Herein, pyridinic nitrogen substituted graphdiyne (PyN-GDY) is directly prepared on the surface of copper foil via a facile Glaser-Hay reaction. PyN-GDY comprises GDY-like hybridized sp2 and sp-carbon structures, meanwhile one of the C atom in the benzene ring is replaced by a pyridinic-N atom. Hence, the lithium (Li) atoms intercalated into the PyN-GDY framework can be stabilized due to the interaction between the Li atoms and the pyridinic-N, which can be further confirmed through theoretical analysis on the binding energy of complex containing Li and PyN-GDY. Moreover, the different arrangement of monomers during the preparation process formed plenty of hierarchical pores in the 2D plane, which would shorten the diffusion path and facilitate the delivery of Li-ions. Based on the unique pyridine N doping structure, PyN-GDY exhibits outstanding electrochemical performance with superior cycling stability when applied as electrode in Li-ion half batteries and Li-ion capacitors.

Robust and Fast Lithium Storage Enabled by Polypyrrole-Coated Nitrogen and Phosphorus Co-Doped Hollow Carbon Nanospheres for Lithium-Ion Capacitors.

Lithium-ion capacitors (LICs) have been proposed as an emerging technological innovation that integrates the advantages of lithium-ion batteries and supercapacitors. However, the high-power output of LICs still suffers from intractable challenges due to the sluggish reaction kinetics of battery-type anodes. Herein, polypyrrole-coated nitrogen and phosphorus co-doped hollow carbon nanospheres (NPHCS@PPy) were synthesized by a facile method and employed as anode materials for LICs. The unique hybrid architecture composed of porous hollow carbon nanospheres and PPy coating layer can expedite the mass/charge transport and enhance the structural stability during repetitive lithiation/delithiation process. The N and P dual doping plays a significant role on expanding the carbon layer spacing, enhancing electrode wettability, and increasing active sites for pseudocapacitive reactions. Benefiting from these merits, the NPHCS@PPy composite exhibits excellent lithium-storage performances including high rate capability and good cycling stability. Furthermore, a novel LIC device based on the NPHCS@PPy anode and the nitrogen-doped porous carbon cathode delivers a high energy density of 149 Wh kg−1 and a high power density of 22,500 W kg−1 as well as decent cycling stability with a capacity retention rate of 92% after 7,500 cycles. This work offers an applicable and alternative way for the development of high-performance LICs.

A high specific surface area porous carbon skeleton derived from MOF for high-performance Lithium-ion capacitors

Lithium-ion capacitor (LICs) is expected to replace the traditional double-layer capacitor and lithium-ion battery as a new energy storage device. However, the slow de/intercalation of Li+ in battery-type electrodes (anode) limits the power density of lithium-ion capacitors (LICs). In this work, a high specific surface area porous carbon skeleton (Z-T-PC) is synthesized derived from MOF (Zn-TFBDC). Benefit from the large specific surface area and 3D conductive skeleton, the Z-T-PC shows that the sample has a high specific capacity and stable cycling performance as the LIC anode. The assembled asymmetric LICs exhibit high power density and energy density with Z-T-PC anode. The work provides new thinking for the application of the novel anode material of LICs.

Constructing High‐Performance Li‐ion Capacitors via Cobalt Fluoride with Excellent Cyclic Stability as Anode and Coconut Shell Biomass‐Derived Carbon as Cathode Materials

AbstractThe Lithium‐ion capacitor (LIC) is a potential candidate for the next generation of energy storage devices due to high power density, high energy density and excellent cycle stability. Nonetheless, the problem of matching optimization is still faced for LIC. Many different approaches are explored to find a balance between the two storage mechanisms so that high performance LICs can be obtained. Here, CoF2, prepared by solvothermal method, showed reversible specific capacity of 307 mAh g−1 after 900 cycles at 0.1 A g−1 and 81 mAh g−1 after 10,000 cycles at 4 A g−1. Meanwhile, coconut shell is used as precursor for preparing natural porous carbon as cathode materials of LIC. The coconut shell biomass carbon (CSBC‐5), outstanding specific surface area (2767 m2 g−1), holds a capacity of 120 mAh g−1 after 1000 cycles at 1 A g−1. The LIC, CoF2 as anode and CSBC‐5 as cathode, shows excellent cycle stability (65 % capacity retention after 5000 cycles), higher energy density of 82 Wh kg−1 (at power density of 190 W kg−1) and higher power density of 3800 W kg−1(at energy density of 50 Wh kg−1). Therefore, the material of CoF2 is a promising choice for the future anode and promotes the development of LIC.

Facile Synthesis of Graphene with Fast Ion/Electron Channels for High-Performance Symmetric Lithium-Ion Capacitors.

With the battery-type anode and capacitor-type cathode, lithium-ion capacitors (LICs) are expected to exhibit both high energy and high power density but suffer from the mismatch of the electrode reaction kinetics and capacity. Herein, to alleviate the mismatch between the two electrodes and synergistically enhance the energy/power density, we design a method of microwave irradiation reduction to prepare graphene-based electrode material (MRPG/CNT) with fast ion/electron pathway. The three-dimensional structure of CNT intercalation to graphene inhibits the restacking of graphene sheets and improves the conductivity of the electrode material, resulting a rapid ion and electron diffusion channel. Due to its specific properties, MRPG/CNT materials can be used as both anode and cathode electrodes of LICs at the same time. As anode, MRPG/CNT shows a high capacity of 1200 mAh g-1 as well as high rate performance. As cathode, MRPG/CNT displays a high capacity of 108 mAh g-1 and the capacity retention of 100% after 8000 cycles. Coupling the prelithiated MRPG/CNT anode with MRPG/CNT cathode gives a full-graphene-based symmetric LIC, which achieves a high energy density of 232.6 Wh kg-1 at 226.0 W kg-1, 111.2 Wh kg-1 at the ultrahigh power density of 45.2 kW kg-1, and superior capacity retention of 86% after 5000 cycles. The structure design of this electrode provides a new strategy for alleviating the mismatch of LIC electrodes and constructing high-performance symmetrical LICs.

An instantaneous metal organic framework to prepare ultra-high pore volume porous carbon for lithium ion capacitors

The wide application of lithium ion capacitors (LICs) is now seriously limited by the complex synthesis process of cathode carbon with a demand for high capacity. In this study, a metal organic frameworks (MOFs)-derived porous carbon with super large porous volume (3.504 cm3 g−1) and specific surface area (3132 m2 g−1) is obtained by carbonization at a reasonable temperature and acid pickling. The MOF can be facilely and efficiently synthesized by the coprecipitation method (for a few seconds) in deionized water from fluorine-containing organic precursors and zinc-based salts. Moreover, benefiting from the reasonable graphitization and optimized O doping, the porous carbon has a high specific capacity (123.4 mAh g−1) and excellent cycling stability (10000 cycles) in a half-cell with organic electrolyte. The porous carbon was also used as the cathode in LICs devices with the sucrose hard carbon as an anode. The LICs devices can possess an energy density of 157 Wh kg−1 and a power density of 40 KW kg−1, as well as the the capacities remain ~ 85% after 4000 cycles. This preparation method of ultra-high pore volume MOFs-derived carbon and high-performance LICs devices can provide a unique pathway toward the more advanced energy storage equipment.

Lithium/sodium-ion capacitors based on 3D graphene-based materials

Metal ionic capacitors (MICs) are a new type of hybrid electrochemical energy storage (EES) devices that integrate the advantages of high-power output in supercapacitors and high energy density in batteries. These materials show potential to be commercialized, but their practical application is still limited due to the imbalance of kinetics and capacity between the electrodes, the slow ion/electron diffusion rate and the poor structural stability of the electrodes. 3D graphene-based materials with unique structure and appealing properties have recently received attentions for application in MICs due to their remarkable improvement from charge storage capacity to reaction kinetics. In this article, we reviewed the research progress of 3D graphene-based materials in lithium-ion capacitors (LICs) and sodium ion capacitors (SICs). Firstly, the energy storage principle and development requirements of LICs and SICs are introduced. The fabrication of 3D graphene materials is then summarized. The key advantages and important roles of 3D graphene-based materials in the construction of LICs and SICs are discussed. Finally, the challenges and prospects regarding the application of 3D graphene-based materials in high-performance LICs and SICs are presented.

Reduced graphene oxide encapsulated MnO microspheres as an anode for high-rate lithium ion capacitors

Developing an anode material with high-rate Li+ intercalation and stable charge/discharge platform is important for achieving high performance lithium ion capacitors (LICs). Reduced graphene oxide (rGO)-encapsulated MnO microspheres (∼2 μm) are obtained by a simple process including solvothermal and calcination techniques. The material contains a large number of mesopores (∼2.8 nm diameter). The MnO/rGO has a favorable cycling stability (846 mAh g−1 at 0.1 A g−1 after 110 cycles) and an outstanding rate performance (207 mAh g−1 at 6.4 A g−1). Kinetic analysis reveals that a pseudocapacitive contribution plays a dominant role for the energy storage. The improvement in the pseudocapacitive behavior is ascribed to the fact that the uniform rGO coating on the MnO provides continuous pathways for electron transport, and the mesoporous structure provides numerous migration paths for Li-ions. Furthermore, MnO/rGO//activated carbon (AC) LICs have a high energy density of 98 Wh kg−1 at a relatively high power density of 10,350 W kg−1, and have a capacity retention of 71% after 5000 cycles at 1.6 A g−1. These outstanding results indicate that the enhanced Li+ intercalation of the anode offsets the kinetic imbalance between the two electrodes.

Tuning the microstructures of uniform carbon spheres by controlling the annealing conditions for high-performance lithium-ion full batteries and lithium-ion capacitors

Microstructures include graphited microcrystal structures, micro-pores, specific areas, and pore volume of hard carbon spheres (CSs), have been tuned to optimize their Li+ storage performance by annealing at different temperature. The sample annealed at 650 °C (CS-650) exhibits the best performance for Li+ storage with high specific capacity, stable cycling stability, and superior rate performance. The CS-650 displays an initial capacity of 284 mAh g–1 at a specific current of 0.3 A g–1 with 277 mAh g–1 can be retained after 400 cycles, and a specific capacity of 180 mAh g–1 can be achieved at a high specific current of 2.0 A g–1. More significantly, the CS-650 exhibits a high capacitive contribution ratio from 62.2% to 76.0% as the scan rate increases from 0.3 to 1.0 mV s−1 due to its high specific area and large pore volume. The capacitive behaviour of CS-650 enhances the reaction kinetics for high energy and high-power applications in both full battery and Li-ion capacitor (LIC), which are assembled with LiNi0.5Co0.2Mn0.3O2 cathode and activated carbon positive electrode, respectively. The CS-650-based full battery shows a specific capacity of 66.1 mAh g−1 at 0.1 A g−1 combined with high cycling stability. The LIC displays a specific energy of 115 Wh kg−1 at 242 W kg−1 with a specific energy of 48 Wh kg−1 at 2364 W kg−1. Our work indicates that the Li+ storage performance of hard carbon can be tuned by the microstructure and both high energy and high power performances can be achieved.