Ultrafast Cycling Research Articles

Probing the glioma micro-environment: Analysis using biopsy in combination with ultra-fast cyclic immunolabeling

The interaction between gliomas and the immune system is poorly understood and thus hindering development of effective immunotherapies for glioma patients. The immune response is highly variable during tumor development, and affected by therapies such as surgery, radiation, and chemotherapy. Currently, analysis of these local changes is difficult due to poor accessibility of the tumor and high-morbidity of sampling. In this study, we developed a model for repeat-biopsy in mice to study these local immunological changes over time. Using fine needle biopsy we were able to safely and repeatedly collect cells from intracranial tumors in mice. Ultra-fast cycling technology (FAST) was used for multi-cycle immunofluorescence of retrieved cells, and provided insights in the changing immune response over time. The combination of these techniques can be utilized to study changes in the immune response in glioma or other intracranial diseases over time, and in response to treatment within the same animal.

Probing the glioma micro-environment: analysis using biopsy in combination with ultra-fast cyclic immunolabeling.

The interaction between gliomas and the immune system is poorly understood and thus hindering development of effective immunotherapies for glioma patients. The immune response is highly variable during tumor development, and affected by therapies such as surgery, radiation, and chemotherapy. Currently, analysis of these local changes is difficult due to poor accessibility of the tumor and high-morbidity of sampling. In this study, we developed a model for repeat-biopsy in mice to study these local immunological changes over time. Using fine needle biopsy we were able to safely and repeatedly collect cells from intracranial tumors in mice. Ultra-fast cycling technology (FAST) was used for multi-cycle immunofluorescence of retrieved cells, and provided insights in the changing immune response over time. The combination of these techniques can be utilized to study changes in the immune response in glioma or other intracranial diseases over time, and in response to treatment within the same animal.

Interface and Morphology Engineered Amorphous Si for Ultrafast Electrochemical Lithium Storage.

Ultrafast high-capacity lithium-ion batteries are extremely desirable for portable electronic devices, where Si is the most promising alternative to the conventional graphite anode due to its very high theoretical capacity. However, the low electronic conductivity and poor Li-diffusivity limit its rate capability. Moreover, high volume expansion/contraction upon Li-intake/uptake causes severe pulverization of the electrode, leading to drastic capacity fading. Here, interface and morphology-engineered amorphous Si matrix is being reported utilizing a few-layer vertical graphene (VG) buffer layer to retain high capacity at both slow and fast (dis)charging rates. The flexible mechanical support of VG due to the van-der-Waalsinteraction between the graphene layers, the weak adhesion between Si and graphene, and the highly porous geometry mitigated stress, while the three-dimensional mass loading enhanced specific capacity. Additionally, the high electronic conductivity of VG boosted rate-capability, resulting in a reversible gravimetric capacity of ≈1270mAhg-1 (areal capacity of ≈37µAhcm-2) even after 100 cycles at an ultrafast cycling rate of 20C, which provides a fascinating way for conductivity and stress management to obtain high-performance storage devices.

Tailored sulfur and nitrogen co-doped carbon quantum dot interfacial layer on copper foil for highly stable and ultrafast lithium-ion capacitors

Lithium-ion capacitors (LICs) are promising energy storage devices offering the advantages of lithium-ion batteries (LIBs) and supercapacitors (SCs). However, the interfacial structure between the electrode and current collector significantly affects their cycling performance and stability during ultrafast cycling. Therefore, we propose a tailored sulfur and nitrogen co-doped carbon quantum dot (SNCQD) interfacial layer on a copper foil (SNCQD/Cu) using an ultrasonic spray-coating system. A half-cell LIC electrode, fabricated with the SNCQD/Cu as the current collector, exhibited a superior specific capacity of 80.8 mAh/g and capacity retention of 90.1 % after 500 cycles at an ultrafast current density of 3000 mA/g. Furthermore, the electrode demonstrated excellent ultrafast cycling stability of 84.7 % at a capacity rate of 5C in full-cell LICs. These results are attributed to the synergistic effect of the SNCQD interfacial layer, which prevents oxidation and corrosion, enhances interfacial adhesion, and increases electrical conductivity. Therefore, the introduction of an SNCQD interfacial layer can help achieve highly stable, ultrafast LICs.

Highly Durable and Ultrafast Cycling of Dual‐Ion Batteries via In Situ Construction of Cathode–Electrolyte Interphase

AbstractDual‐ion batteries have shown promising prospect in energy storage, owing to their low material costs, high power capability, and environmental friendliness. However, graphite as the cathode always suffers from structural damage and electrode/electrolyte interface instability, which greatly deteriorate their electrochemical performance. Here, tris(trimethyl‐silyl) phosphite (TMSP) is added as an electrolyte additive to improve the electrochemical performance. TMSP not only scavenges the deleterious species generated by electrolytes, but also produces a thin and uniform cathode–electrolyte interphase layer on graphite. Hence, the electrochemical performance is greatly promoted. In graphite||graphite, the capacity retention is ≈96.8% at 30 °C or 92.5% after 3000 cycles in the presence of TMSP, much better than those without TMSP (62% at 30 °C or 27% after 200 cycles).

Improved‐quality graphene film decorated with ultrafine MnO 2 nanoparticles as a multifunctional current collector for high‐reversibility zinc‐ion batteries

Zinc-ion batteries (ZIBs) are considered as a reasonable alternative to lithium-ion batteries (LIBs) due to their satisfactory safety levels, low cost, and eco-friendliness. Nevertheless, the ZIBs have suffered from rapid capacity fading and unstable cycling stability due to poor reversibility. To overcome this issue, a suitable current collector with high electrical conductivity and good interfacial adhesion to the electrode material is essential. Herein, for the first time, an improved-quality graphene film (IQGF) is uniformly decorated with ultrafine manganese oxide nanoparticles (UFMP) and the resulting UFMP@IQGF composite is used as a multifunctional current collector. The as-fabricated ZIB exhibits a superb energy storage performance and reversibility, with an improved specific capacity of 404.7 mA h g−1 at a current density of 0.1 A g−1, and an excellent ultrafast cycling stability, with a capacity retention of 83.7% for up to 300 cycles at a current density of 2.0 A g−1. Moreover, the all-solid-state ZIB using a gel-electrolyte exhibits a good energy storage performance, mechanical flexibility, and feasibility for practical applications.

Reversible faradaic reactions involving redox mediators and oxygen-containing groups on carbon fiber electrode for high-performance flexible fibrous supercapacitors

Flexible fibrous supercapacitors (FFS) are taking account of as the energy storage devices for wearable electronics owing to their high power density, high safety, long cycle life, and simple manufacturing process. Nevertheless, FFSs have the disadvantage of low specific capacitance that results from the electrochemical characteristics of the electrical double layer on the carbon fiber electrode. In this study, for the first time, an FFS comprising surface-activated carbon fibers as an electrode/current collector and a redox additive gel polymer electrolyte (FFS-SARE) was fabricated for use as a wearable energy storage device. The FFS-SARE showed outstanding electrochemical performance, namely, high specific capacitances of 891 and 399 mF cm−2 at current densities of 70.0 and 400 μA cm−2, respectively, and remarkable ultrafast cycling stability over 5000 cycles with 92% capacitance retention at a current density of 400.0 μA cm−2. Moreover, they exhibited mechanical flexibility and had high feasibility, and they showed good energy storage performance that renders them suitable for use in wearable electronic textiles.

Surface Engineering of Carbon via Coupled Porosity Tuning and Heteroatom‐Doping for High‐Performance Flexible Fibrous Supercapacitors

AbstractFlexible fibrous supercapacitors (FFS) are considered the next‐generation wearable energy storage devices because they provide reliable safety, eco‐friendliness, and high power density. In particular, the FFS is desirable for application to wearable electronics because it can overcome disadvantages of the lithium‐ion battery (LIB), such as the hazard of explosion and the complex manufacturing process. Nevertheless, the practical application of the FFS continues to be inhibited by the poor energy storage performance due to the limited specific surface area, poor electrical properties, and low wettability of the carbon fiber electrode. Herein, for the first time, the surface engineering of an FFS using nitrogen and fluorine codoped mesoporous carbon fibers (FFS‐NFMCF) is described, and the synergistic effect of porosity tuning and heteroatom codoping upon the electrochemical performance is demonstrated. The resultant supercapacitor shows a high specific capacitance of 243.9 mF cm−2 at a current density of 10.0 µA cm−2 and good ultrafast cycling stability with capacitance retention of 91.3% for up to 10 000 cycles at a current density of 250.0 µA cm−2. More interestingly, the FFS‐NFMCF exhibits good mechanical properties and remarkable safety in practical application, thus demonstrating its feasibility for use in wearable electronic textiles.

Preparation of Current Collectors with Uniform Multi-Pits by Physical Rolling for Improving Full Battery Rate Performance

Reasonable design and modification of the current collector’s surface is an important means to improve the rate performance of a full battery. However, despite considerable structural engineering efforts focused on current collectors, these modifications are still challenging to apply in actual production for various reasons. To solve these problems, a low-cost physical rolling method is used to produce an Al foil with uniform multi-pits for the current collector (PEAL) of the electrode. The pits formed by this method increase the effective contact area of the current collector, thus increasing the electron collection capacity and slurry loading capacity. The improved adhesion of the electrode leads to a reduction in the amount of binder, further increasing the electron migration rate. The results show that full battery with PEAL as current collector has higher rate performance (867.5 mAh at 15C) and higher ultrafast cycling stability (1005.8 mAh with the capacity retention of 76.1% at 10C after 1000 cycles) than other samples. The rate performance of the full battery is further improved (increase from 867.5 mAh to 962.4 mAh at 15C) by reducing the binder ratio from 2.5% to 1.9%.

Boosting ultrafast Li storage kinetics of conductive Nb-doped TiO2 functional layer coated on LiMn2O4

Interface engineering of LiMn2O4 (LMO) is a promising strategy to enhance the lithium storage capability and cycling stability of cathode materials in Li-ion batteries (LIBs). This is because the strategy prevents structural degradation; however, Li storage kinetics remains unsatisfactory, resulting in poor ultrafast cycling performance. Therefore, we fabricated an Nb-doped TiO2 (NTO) functional layer as a conductive passivation layer on the LMO surface by horizontal ultrasonic spray pyrolysis deposition. The NTO functional layer suppressed the volume expansion of LMO and exhibited high electrical and ionic conductivity, which resulted in improved structural stability of LMO (related to cycling stability) and increased electron/ion transfer rate (related to ultrafast cycling performance). In the TiO2 structure, Ti4+ ions were replaced by Nb5+ ions, which possess high electrical conductivity and a wide c-axis as a Li-ion diffusion route. As a result, the NTO-coated LMO cathode material showed an outstanding specific capacity of 112.7 mAh/g with a remarkable capacity retention of 96.2% after 100 cycles at a current density of 1 C and excellent ultrafast cycling capacity and stability of 70.0 mAh/g after 500 cycles at a current density of 10 C.

Hierarchical hybrid nanostructure of 1T-tungsten disulfide quantum dots/multihollow capillary bundle-type mesoporous carbon for ultrafast and ultrastable lithium storage

Transition metal dichalcogenides such as tungsten disulfide (WS2), a typical 2D layered structure, have attracted increasing attention as promissing anode materials for ultrafast Li-ion batteries (LIBs), because of their high theoretical specific capacity and excellent Li-ion diffusion kinetics. Furthermore, the ionic/electrical properties of WS2, which can improve ultrafast cycling performance, can be effectively enhanced by its unique metallic phase (1T-WS2). Despite these significant advantages, the application of WS2 anodes is limited by critical issues such as large volume expansion and poor ultrafast cycling performance, because the control and synthesis of nano-sized 1T-WS2 crystals is difficult.Therefore, to improve the ultrafast and ultrastable Li storage of LIBs, herein, a novel architecture comprising 1T-WS2 quantum dots (QDs) embedded in mesoporous carbon nanofibers (PCNFs) with multihollow capillary bundle-type mesopores is proposed. This novel hierarchical hybrid nanostructure exhibits a high specific capacity (716.5 mAh g−1 after 100 cycles at 100 mA g−1) and an outstanding rate capability, because of increased Li-ion storage sites and fast Li-ion diffusion and significant ultrafast cycling capacity (528.1 mAh g−1) and long-term cycling stability (87.8% after 1000 cycles) under ultrafast cycling conditions (2000 mA g−1). The increase in the Li storage sites is attributed to the high specific capacity due to the well-dispersed 1T-WS2 QDs in the PCNFs; the increased Li-ion transfer rate is attributed to the high rate capability due to the multihollow capillary bundle-type mesopores; the long-term cycling stability is attributed to the WS2 QDs embedded within the PCNFs, which effectively prevent volume expansion.

Non-Equilibrium Lattice Heterogeneity As the Unified Kinetic Hurdle of Ni-Rich Layered Cathode for Ultrafast Lithium Ion Batteries

The significantly reduced capacity at a fast cycling rate is one of the most serious bottlenecks that prevent the large-scale application of Ni-rich layered oxide cathode for electrical vehicle batteries. Figuring out the capacity decline mechanism is crucial to addressing such hurdle and developing ultrafast lithium ion batteries. In this work, with operando synchrotron-based spectroscopy, we captured the formation of non-equilibrium separated phases during the extremely fast cycling of various Ni-rich layered oxides, in contrast to their solid-solution structural evolution pathway at slow cycling rate. Further, such non-equilibrium phase heterogeneity was demonstrated to be an effective capacity retention descriptor for Ni-rich layered oxide cathode: the capacity retention ratio is liner inversely proportional to the lattice heterogeneity at an extremely fast cycling rate (e.g., 10C), regardless of the composition and Ni content. Those detrimental non-equilibrium phase heterogeneity could be eliminated by raising the operation temperature, contributing to much higher lithium ion transport kinetics and better capacity retention during ultrafast cycling

Highly Efficient Multicomponent Gel Biopolymer Binder Enables Ultrafast Cycling and Applicability in Diverse Battery Formats.

Electrode materials with a high performance and stable cycling have been commercialized, but the utilization of state-of-the-art Li-ion batteries in high-current rate applications is restricted because of limitations in other battery components, in particular, the lack of an efficient binder. Herein, a novel multicomponent polymer gel binder (PGB) is presented, comprising the biopolymer chitosan as the host, embedded with the 1-butyl-1-methylpyrrolidinium dicyanamide (PYR14DCA) ionic liquid and the lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. The multicomponent approach leads to carbon black arrangement along well-distributed chitosan chains in the electrodes, forming a highly electronic conductive network. Furthermore, the plasticizing effect of the ionic liquid leads to an enhanced ionic conductivity. As a result, shorter charge-transfer paths are enabled, leading to an exceptionally high rate capability in LiFePO4 and Li4Ti5O12 half cells, up to 50C. LiFePO4||Li4Ti5O12 full cells using the PGB for both electrodes also demonstrated stable cycling at 10C, with an impressively high discharge capacity of 173 mA h·g-1 after 1000 cycles. In addition, freestanding electrodes could also be realized and functioning flexible Li-ion cells were successfully demonstrated. Thus, the novel water-processable binder offers multifaceted advantages, making the approach highly promising for industrial implementation.

Fluorine-doped carbon quantum dot interfacial layer on stockade-like etched copper foil for boosting Li-ion storage

The interface engineering of anode electrodes in lithium-ion batteries (LIBs) is a key strategy in improving the Li-ion storage kinetics and interface stability to achieve outstanding ultrafast cycling capacities and cycling stabilities of LIBs. However, despite extensive research on the interfacial engineering of electrode materials, studies on the interface design between the electrode and current collector to improve the ultrafast cycling performance are rare. In this study, we designed a novel interface architecture for a fluorine-doped carbon quantum dot (F-CQD) interfacial layer on a stockade-like etched Cu foil via electrochemical modification and a spray coating process. The anode electrode assembled with the resultant Cu foil showed enhanced adhesion, high reaction kinetics, and excellent interface stability between the electrode and Cu foil due to the F-CQD interfacial layer on the stockade-like etched Cu foil, leading to an improved ultrafast cycling performance. Consequently, the novel architecture of a Cu foil having stockade-like etching patterns with an F-CQD interfacial layer showed an increased ultrafast cycling capacity of 82.9 mAh g−1 and excellent ultrafast cycling stability of 94.1% after 500 cycles under ultrafast cycling conditions. These improved ultrafast cycling performances are due to the high contact area between the electrode and Cu foil, excellent reaction sites, and superb corrosion resistance.

Nanoengineered Organic Electrodes for Highly Durable and Ultrafast Cycling of Organic Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have become increasingly important as next-generation energy storage systems for application in large-scale energy storage. It is very crucial to develop an eco-friendly and green SIB technique with superior performance for sustainable future use. Replacing the conventional inorganic electrode materials with green and safe organic electrodes will be a promising approach. However, the poor electrochemical kinetics, unstable electrode-electrolyte interface, high solubility of the electrodes in the electrolyte, and large amount of conductive carbon present great challenges for organic SIBs. In this study, the issues of organic electrodes are addressed through atomic-level manipulation of these organic molecules using a series of ultrathin (Å-level) metal oxide coatings (Al2 O3 , ZnO, and TiO2 ). Uniform and precise coatings on the perylene-3,4,9,10-tetracarboxylicacid dianhydride by gas-phase atomic layer deposition technique shows a stable interphase, enhanced electrochemical kinetics (71C, 10 A g-1 ), and excellent stability (89%-500 cycles) compared to conventional organic electrode (70%-200 cycles). Further studies reveal that the chemical stability of the metal oxide coating layer plays a critical role in influencing the redox behavior, and improving kinetics of organic electrodes. This study opens a new avenue for developing high-energy organic SIBs with performance equivalent to inorganic counterparts.

Fabrication of Boron-Doped Activated Carbon for Zinc-Ion Hybrid Supercapacitors

Zinc-ion hybrid supercapacitors (ZICs) have recently been spotlighted as energy storage devices due to their high energy and high power densities. However, despite these merits, ZICs face many challenges related to their cathode materials, activated carbon (AC). AC as a cathode material has restrictive electrical conductivity, which leads to low capacity and lifetime at high current densities. To overcome this demerit, a novel boron (B) doped AC is suggested herein with improved electrical conductivity thanks to B-doping effect. Especially, in order to optimize B-doped AC, amounts of precursors are regulated. The optimized B-doped AC electrode shows a good charge-transfer process and superior electrochemical performance, including high specific capacity of 157.4 mAh g−1 at current density of 0.5 A g−1, high-rate performance with 66.6 mAh g−1 at a current density of 10 A g−1, and remarkable, ultrafast cycling stability (90.7 % after 10,000 cycles at a current density of 5 A g−1). The superior energy storage performance is attributed to the B-doping effect, which leads to an excellent charge-transfer process of the AC cathode. Thus, our strategy can provide a rational design for ultrafast cycling stability of next-generation supercapacitors in the near future.

Accelerating lithium storage capability of cobalt sulfide encapsulated within anion dual-doped mesoporous carbon nanofibers

Metal sulfide materials are promising for the anodes of ultrafast lithium ion batteries (LIBs) for many potential high-technology devices because of their high electrical conductivity, high theoretical capacity, and chemical/electrochemical stability resulting from their unique crystal structures. Despite their significant advantages, these materials face an important challenge related to structural degradation, owing to the significant volume expansion of metal sulfide under ultrafast cycling conditions. This phenomenon leads to rapid capacity fading and must be improved for the practical application of ultrafast LIBs. In the present study, a unique architecture of cobalt sulfide encapsulated within anion dual (nitrogen and sulfur)-doped mesoporous carbon nanofibers (referred to as CoS-NS-PCNF) was fabricated via electrospinning and carbonization. The CoS-NS-PCNF exhibited superb ultrafast cycling performance including outstanding cycling stability (748.6 mAh g−1 with capacity retention of 96.5% at 100 mA g−1 after 100 cycles), a superb ultrafast cycling capacity (550.1 mAh g−1 at 2000 mA g−1), and excellent ultrafast cycling stability (514.6 mAh g−1 with capacity retention of 93.5% at 2000 mA g−1 after 500 cycles). Thus, the novel architecture has significant advantages for ultrafast lithium storage kinetics including a short lithium-ion diffusion length, a high ion/electron transfer rate, and effective prevention of volume expansion.

Interfacial Engineering of a Heteroatom-Doped Graphene Layer on Patterned Aluminum Foil for Ultrafast Lithium Storage Kinetics.

The design of the interfacial architecture between the electrode and the current collector in lithium-ion batteries (LIB) plays a key role in achieving ultrafast lithium storage kinetics with respect to efficient charge transfer and cycle stability. However, in recent years, despite considerable efforts in the structural and chemical engineering of active materials (anode and cathode materials), interfacial architectures between the electrode and the current collector have received relatively insufficient attention in the case of ultrafast LIBs. Here, the interface architecture of a micropatterned Al current collector with a heteroatom-doped graphene interfacial layer is developed using roll pressing and dip coating processes. The cathode electrode fabricated with the resultant current collector offers increased contact area with enhanced interfacial stability between the electrode and the current collector because of micropatterns with heteroatom-doped graphene formed on the current collector, leading to outstanding ultrafast cycling capacity (105.8 mA h g-1) at 20 C. Furthermore, at extremely high rate and long-term cycling performance, significant ultrafast cycling stability (specific capacity of 87.1 mA h g-1 with capacity retention of 82.3% at 20 C after 1000 cycles) is noted. These improved ultrafast and ultra-stable performances are explained in terms of the increased electron collection/provision site with a high contact area between the electrode and the current collector for enhanced ultrafast cycling capacity and the effective corrosion prevention of the current collector with fast charge transfer for ultrafast cycling stability.

Ultra-fast cycling for multiplexed cellular fluorescence imaging.

Rapid analysis of single and scant cell populations is essential in modern diagnostics, yet existing methods are often limited and slow. Here we describe an ultra-fast, highly efficient cycling method for the analysis of single cells based on unique linkers for tetrazine (Tz) / trans-cyclooctene (TCO) mediated quenching. Surprisingly, the quenching reaction rates were more than 3 orders of magnitude faster (t1/2 < 1 sec) than predicted. This allowed multi-cycle staining and immune cell profiling within an hour, leveraging the accelerated kinetics to open new diagnostic possibilities for rapid cellular analyses.

Synergistic effect of heteroatom-doped activated carbon for ultrafast charge storage kinetics

Providing a crystallographic and electronic modification of carbon-based materials in electrical double-layer capacitors (EDLCs) is an essential technology needed to improve the charge storage kinetics and to enhance ultrafast cycling performances. However, despite numerous structural composite and morphological modification efforts focused on active materials, ultrafast charge storage kinetics still indicated a poor ultrafast capacitance and low cycling stability. To solve these problems, in the present study, we propose a novel heteroatom (N, P, and B)-doped activated carbon (AC) that has the synergistic effects of N-, P-, and B-doping using the one-pot doping calcination process. Compared to the bare-AC, N-doped AC, P-doped AC, and B-doped AC, the novel heteroatom-doped AC indicates an improved ultrafast charge storage kinetics, such as high specific capacitance (243.9 F g−1 at the scan rate of 10 mV s−1), good cycling stability (216.7 F g−1 at 100 mV s−1 after 500 cycles), and superb ultrafast cycling capacitance (199.7 F g−1 at 300 mV s−1). These superb electrochemical performances can be attributed by synergistic effects of increased active sites by N-doping related to a high charge storage area, improved functional groups by P-doping related to an excellent wettability between the electrode and the electrolyte, and enhanced electrical properties by B-doping related to a good electron acceptability.