Cycle Life Performance Research Articles

Aqueous Supercapacitor with Wide-Temperature Operability and over 100,000 Cycles Enabled by Water-in-Salt Electrolyte.

Supercapacitors are crucial in renewable energy integration, satellite power systems, and rapid power delivery applications for mitigating voltage fluctuations and storing excess energy. Aqueous electrolytes offer a promising solution for low-cost and safe supercapacitors. However, they still face limitations in cycle life and wide-temperature range performance. Here, we present a symmetric supercapacitor utilizing activated carbon electrodes and a "water-in-salt" electrolyte (WiSE) based on lithium perchlorate. The WiSE electrolyte exhibits an expanded electrochemical stability window, endowing the aqueous supercapacitor with remarkable stability and long cycle life of over 100,000 cycles at 500 mA g-1 with more than 91 % capacity retention. Moreover, the supercapacitor demonstrates good rate capability and wide temperature operability ranging from -20 to 80 °C. The use of high concentrations of salt in the aqueous electrolyte contributes not only to the enhancement of supercapacitor performance and cycle life but also to the temperature stability range, enabling all-season operability.

Eco-Friendly High-Performance Symmetric All-COF/Graphene Aqueous Zinc-Ion Batteries.

Developing high-performance aqueous symmetric all-organic batteries (SAOBs) by replacing metal-based batteries or batteries with organic electrolytes is highly attractive to achieve a greener rechargeable world. However, such a new energy storage system still exhibits unsatisfactory rate capability and cycling stability due to the limitations in electrode materials screening. Here, a novel covalent organic framework (COF) containing abundant CN and CO for the electrode material is designed, which is combined with graphene and assembled into all-COF/graphene batteries for the first time. Moreover, the co-storage of Zn2+ and H+ in COF can be achieved in a mild aqueous electrolyte. Impressively, benefiting from the extended porous structure of COF, plentiful active reaction sites, more extensive electron delocalization from CO modification at molecular level, as well as enhanced fast H+ storage capacity of graphene and CO in COF, this kind of SAOBs show excellent cycle life and high rate performance (over 15000 cycles with a capacity of 80 mAh g-1 at a high current density of 5 A g-1 in pouch cell). This work will open a new window for the design of high-performance aqueous organic batteries, further moving toward a more eco-friendly electrochemical world.

A donor-acceptor conjugated bipolar polymer with multielectron redox sites for long-cycle-life and high-rate aqueous zinc dual-ion batteries

Aqueous zinc-ion batteries (AZIBs) have hugely latent advantages in large-scale energy storage due to its innate safety, reasonable price, and sustainability. However, most AZIB cathode materials suffer from short cycling life and poor rate performance. Herein, a bipolar donor-acceptor (D-A) conjugated microporous polymer (PTZ-BDTB), consisting of electron-withdrawing benzo[1,2-b:4,5-b’]dithiophene-4,8-dione (BDTB) units and electron-donating phenothiazine (PTZ) units, is developed as the cathode material of aqueous zinc dual-ion batteries (AZDIBs). The D-A type structure design could reduce the band gap, thus promoting electron transfer in the polymer framework. Therefore, the PTZ-BDTB cathode in a 30 mol/kg (m) ZnCl2 water-in-salt electrolyte exhibits a high reversible capacity of 202 mA h g−1 at 0.05 A g−1 with excellent rate performance (109 mA h g−1 at 15 A g−1), which is far superior to its counterpart polymers PPTZ and PB-BDTB. Impressively, PTZ-BDTB shows ultra-stable cycle performance with capacity retention ratios of 76.2% after 460 cycles at 0.05 A g−1 and 96% after 27000 cycles at 5 A g−1. PTZ-BDTB also exhibits a low self-discharge ability with capacity retention about 76.4% after resting the battery for 28 days. These results demonstrate that D-A type structural design is a promising strategy for constructing high performance cathode materials for AZDIBs.

Synergistic Interaction of Strongly Polar Zinc Selenide and Highly Conductive Carbon Nanoframeworks Accelerates Redox Kinetics of Polysulfides.

Lithium-sulfur batteries (LSBs) have become strong competitors in secondary battery systems because of their superior theoretical capacity and energy density. However, due to the serious shuttle effect of soluble long-chain lithium polysulfides (LiPSs) and the slow solid-solid reaction kinetics, LSBs face some specific challenges, such as a short cycle life and low rate performance. The introduction of selenide/carbon composites derived from zeolite imidazolate frameworks (ZIFs) into separator coatings is a direct and effective solution to the aforementioned problems. Here, a zinc selenide/carbon catalyst material (ZnSe@C) was constructed and employed to modify commercial polypropylene (PP) separators to accelerate the conversion of intermediates. The highly polar ZnSe effectively fixes the active material on the cathode side by transferring electrons between elements with LiPSs and improves the utilization rate of sulfur. Concurrently, the highly conductive carbon nanoskeleton generated following the pyrolysis of ZIF-8 ensures the rapid transfer of charges during the catalytic reaction. The prepared ZnSe@C has a large specific surface area (250.07 m2 g-1) and mesoporous ratio (78.03%), which not only enhances adsorption and catalysis but also promotes the penetration of the electrolyte and the transport of Li+. Based on this, ZnSe@C/PP separator cells exhibit a low average capacity decay rate of 0.051% per cycle after 500 cycles at 1 C.

A Versatile InF3 Substituted Argyrodite Sulfide Electrolyte Toward Ultrathin Films for All‐Solid‐State Lithium Batteries

AbstractAll‐solid‐state lithium batteries (ASSLBs) incorporating sulfide solid electrolytes capture great attention due to their intrinsic safety features and high energy density. Nevertheless, the implementation of sulfide solid electrolytes faces significant challenges, including moisture sensitivity, narrow intrinsic electrochemical windows, and excessively thick solid electrolyte layers. Here, the substitution of In for P and F for Cl in argyrodite sulfide Li5.7PS4.7Cl1.3 is presented. With appropriate elemental substitutions, the Li symmetric cells exhibit a high critical current density value of 2.5 mA cm−2 and deliver prolonged plating/stripping over 1000 h at 1 mA cm−2 and 25 °C. Further, the Li5.82P0.94In0.06S4.7Cl1.12F0.18 displays high chemical stability toward organic solvents, which is further demonstrated by the density functional theory (DFT) calculations. Using polyisobutylene as a binder, a uniform sulfide film (35 µm) is prepared by slurry casting and hot pressing process, delivering a high ionic conductivity of 1.4 mS cm−1 at 25 °C. Coupled with FeS2 and LiCoO2 cathode, the all‐solid‐state lithium metal cell exhibits a long cycling life and excellent rate performance. This study provides a design strategy and reveals the importance of high‐performance sulfide SEs in the scalable production of sulfide film.

Copper-Based Para-Phthalic Acid Metal-Organic Framework: An Efficient Anodic material for Super-capattery Hybrid Systems

The battery-supercapacitor hybrid, an asymmetric energy storage system, has garnered considerable attention due to its outstanding energy storage capabilities. Anodic materials have become a central focus, driven by the quest for enhanced energy density, power density, cycle life, and overall performance. In this study, we have synthesized copper-based para-phthalic acid (PTA) metal-organic frameworks (MOFs) via a facile hydrothermal method to be employed as the positive electrode material in a battery-supercapacitor hybrid matrix. The initial testing indicates the battery-type nature of the prepared electrode along with maximum specific capacity of 260.5 C g-1 at 0.7 A g-1. Subjection of Cu-PTA MOF electrode to real device configuration (Super-capattery device) results in considerable specific capacity of 152.2 C g-1 along with specific energy and power of 35.9 Wh kg-1 and 5950 W kg-1, respectively at 0.3 A g-1. The device also demonstrated a stability potential of 92.15% when tested for 5000 continuous charge-discharge cycles. The present study presents Cu-PTA MOF an exciting addition for advancing current state of research in the field of energy storage technology.

High-Volumetric-Energy-Density Cathode Material from Single-Sized Precursor via Precise Additive Control

To overcome the energy density limitations of current layered cathode materials, high-nickel cathode materials with a bimodal distribution composed of ∼ 15um-sized secondary particles and micron-sized single crystals are synthesized from a single-sized high-nickel precursor by incorporating the grain-growth promoting/inhibiting additive. Synthesized cathode material effectively reduces the pores within the electrode and shows an excellent electrode density of > 3.9 g/cm3, exceeding ∼ 80 % of the theoretical density. In addition, due to efficient contact between large secondary particles and small single crystals, bimodal particles with additives show higher electrical conductivity compared to additive-free monomodal secondary particles, and a capacity of ∼ 220 mAh/g is achieved even at a high loading level of ∼ 30 mg/cm2 and 96 % active-material fraction. Based on remarkable electrode density and high capacity, it is possible to realize a volumetric energy density of more than 700 mAh/cm3. To the best of our knowledge, this is the highest energy density result for electrodes made from layered cathode materials. Moreover, through the synergistic effect of morphology control by selective additives and surface coating, the synthesized bimodal cathode simultaneously exhibits excellent capacity as well as improved cycle-life performance compared to a bare cathode without additives. The enhanced electrochemical performance is attributed to increased connectivity between individual cathode particles, decreased bulk/surface resistance, and reduced intergranular cracks after cycling through structure design by additives, which is confirmed through various electrochemical analyses and electrode observations.

Three-dimensional CNTs boosting the conductive confinement structure of silicon/carbon anodes in lithium-ion batteries

In this study, a surface functionalization strategy was proposed to involve carbon nanotubes and silicon nanoparticles encapsulated within carbon derived from a zeolite imidazole framework (ZIF-67). Multidimensional interconnected carbon nanotubes bolster the structural stability and facilitate ion/electron transfer within silicon/carbon composites. Silicon nanoparticles were successfully encapsulated in ZIF-67-derived carbon shells, with carbon nanotubes effectively transferring interfacial stress between silicon and carbon shell during lithiation, where ZIF-67-derived carbon reduces the volume expansion in silicon anodes. As a consequence, the outstanding cycle life and rate performance were demonstrated in the silicon/carbon composites. The specific capacity was maintained at 660 mAh g-1 over 200 cycles at 1 A g-1. The in-situ construction of this conductive confinement structure based on three-dimensional carbon nanotubes offers a promising design approach for advancing silicon/carbon anode technologies.

All-Cobalt-Free Layered/Olivine Mixed Cathode Material for High-Electrode Density and Enhanced Cycle-Life Performance

All-Cobalt-Free Layered/Olivine Mixed Cathode Material for High-Electrode Density and Enhanced Cycle-Life Performance

Improving High-Voltage Cycling Stability and High-Rate Capability of Sodium-Ion Layered Cathode Oxides through Trace Amounts of Low-Valence Metals.

With the increasing demand for clean energy sources, the need for large-scale energy storage systems to ensure the stable output of renewable energy sources, such as wind and solar, has also increased. Sodium-ion batteries have emerged as a potential solution for these storage systems owing to their high energy density, abundance in the Earth's crust, and low cost. However, the larger atomic radius of sodium ions results in higher energy barriers for ion migration in cathode materials, which can affect the cycle life and rate performance of the battery. Therefore, developing a suitable structure that facilitates rapid sodiation and desodiation and maintains good cycling stability remains a significant challenge. This study aimed to reduce the content of trivalent manganese ions and minimize the impact of the Jahn-Teller effect to enhance the capacity retention of manganese-based layered oxides. Additionally, a series of P2-type Na0.78Li0.1ZnxNi0.15-xMn0.75O2 compounds were successfully synthesized through doping with divalent zinc ions. Structural analyses of the doped material indicated that Zn doping did not alter the crystal structure but increased the interlayer distance of the transition metals. Electrochemical performance tests revealed that appropriate Zn2+ doping promoted sodium-ion diffusion and improved the reversible capacity of the battery. This study provides a promising approach for developing sodium-ion batteries with rapid charging and discharging capabilities.

Multifunctional zinc-nickel alloy enabling high-performance aqueous zinc ion batteries

Aqueous zinc ion batteries are considered to be the new type of secondary batteries that have the potential to replace lithium-ion batteries as the most widely used in the future due to their green environment, high specific capacity and abundant zinc resources. However, due to the contact between the zinc anode and electrolyte, the generation of by-products and corrosion phenomena are not completely avoided, which can easily lead to problems such as short cycle life and poor electrochemical performance of the battery. In this study, uniform zinc-nickel alloy (ZnNi) was prepared by melting method. The element nickel has excellent corrosion resistance and is widely used to improve the corrosion resistance of metal alloys, so the introduction of nickel effectively enhances the corrosion resistance of ZnNi alloys. In addition, metallic nickel shows strong attraction to Zn2+, which can promote the uniform distribution and deposition of Zn2+ and inhibit the dendrites growth to prolong the battery life. Notably, the ZnNi-assembled symmetric cell exhibited excellent cycling performance compared with the Zn//Zn cell (100 h), with a cycle life of up to 1000 h at 2 mA cm−2. In addition, the capacity retention rate of the ZnNi//MnO2 full cell was still as high as 90.6 % after 1000 cycles. The preparation of the ZnNi alloy anode may provide a new idea for future alloying strategies.

MIL-125 (Ti) and porous dielectric polymer substrate introducing composite gel polymer electrolyte with enhanced mechanical property, thermal stability and electrochemical property

Lithium metal batteries have potentially high energy density, but severe uncontrolled lithium dendrites and unstable side reactions prevent large-scale applications. Serial three-dimensional porous poly (vinylidene fluoride) and copolymer membrane-based composite gel electrolytes are designed by introducing MIL-125 (Ti) and ethylene carbonate. Abundant lithium-ion transportation channels and homogeneous ion transport microregion are provided the new type porous fluoropolymer substrate. We also find that crystalline phase and dielectric properties of serial polymer membrane have significant impact on electrochemical performance for composite gel electrolytes. The mechanical and dielectric property of composite electrolyte enhanced by incorporating uniform and well distribution MIL-125 (Ti), which improve the electrolyte/electrode interface charge distribution and promote uniform lithium deposition, leading to lithium dendrite suppression. MIL-125 (Ti)/P(VDF-TrFE-CTFE) composite membrane shows the enhanced maximum strain of 181 %, thermal stability (188 °C) and corresponding composite gel electrolyte reflects higher ionic conductivity of 1.7 × 10–3 S cm-1 and wider electrochemical window at room temperature than PVDF and PVDF-HFP composite electrolytes. Expectedly, quasi-solid state lithium metal battery of MIL-125 (Ti)/P(VDF-TrFE-CTFE) composite gel electrolyte exhibits higher discharge capacity (152.8 mAh g-1) at 240th cycle and 1 C, longer cycling life and better rate performance under large current density than PVDF and PVDF-HFP composite electrolytes.

Enhanced Supercapacitor and Cycle-Life Performance: Self-Supported Nanohybrid Electrodes of Hydrothermally Grown MnO2 Nanorods on Carbon Nanotubes in Neutral Electrolyte.

Efficient and sustainable energy storage remains a critical challenge in the advancement of energy technologies. This study presents the fabrication and electrochemical evaluation of a self-supporting electrode material composed of MnO2 nanorods grown directly on a carbon paper and carbon nanotube (CNT) substrate using a hydrothermal method. The resulting CNT/MnO2 electrodes exhibit a unique structural architecture with a high surface area and a three-dimensional hierarchical arrangement, contributing to a substantial electrochemical surface area. Electrochemical testing reveals remarkable performance characteristics, including a specific capacitance of up to 316.5 F/g, which is 11 times greater than that of conventional CP/MnO2 electrodes. Moreover, the CNT/MnO2 electrodes demonstrate outstanding retention capacity, exhibiting a remarkable 165% increase over 10,000 cycles. Symmetric supercapacitor devices utilizing CNT/MnO2 electrodes maintain a large voltage window of 3 V and a specific capacitance as high as 200 F/g. These results underscore the potential of free-standing CNT/MnO2 electrodes to advance the development of high-performance supercapacitors, which can be crucial for efficient and sustainable energy storage solutions in various industrial and manufacturing applications.

Modification of Li3PO4 layer effectively boosting lithium storage and thermal safety performance for LiCoO2 batteries

To meet the demand for high-performance LiCoO2 batteries, it is necessary to overcome challenges such as interface degradation and rapid capacity degradation caused by changes in bulk structure, especially under deep delithiation and high temperature conditions. The ion conductive coating layer of Li3PO4 has been directly modified on the surface of LiCoO2 particles using magnetron sputtering method, significantly improving the lithium storage performance of LiCoO2@Li3PO4 composites. Compared to pure LiCoO2, the modified LiCoO2 sample exhibits obviously better cycle life and high-temperature performance. Especially, under the conditions of 2 and 1 C, the LiCoO2@Li3PO4 electrode delivers excellent cycling performance at high voltage of 4.5 V, with capacity retention rates of 89.7% and 75.7% at room temperature and high temperature of 45 °C, being far greater than those of 12.3% and 29.1% for bare LiCoO2 electrodes. It is discovered that the Li3PO4 coating layer not only effectively enhances interface compatibility and suppresses the irreversible phase transition of LiCoO2, but also further improves the Li+ transport kinetics and significantly reduces battery polarization, ultimately enabling the modified LiCoO2 electrode to exhibit excellent lithium storage performance and thermal safety characteristics under high voltage conditions. Thus, such effective modified strategy can undoubtedly provide an important academic inspiration for LiCoO2 implication.

Electrophoretically deposited nickel titanate/CNT composite as promising anode for lithium/sodium ion batteries

In this study, we have demonstrated that electrophoretically fabricated NiTiO3 (NTO)/CNT composite is a viable negative electrode for lithium and sodium ion batteries, with favorable electrochemical performance. NTO/CNT exhibited initial discharge capacity of 1032 mAhg−1 and 751 mAhg−1 at 100 mAg−1 with a retained capacity of ∼ 412 mAhg−1 and ∼ 180 mAhg−1 even after 100 cycles against lithium and sodium ion respectively. CNT helps in buffering the volume fluctuations by giving structural stability and enables good cycle life performance. Also such good performance can be ascribed to the porous microstructure, good adherence property with the current collector and uniform active material distribution with carbon black and CNT on the deposited film.

Heterointerfaces Chemistry of Transition Metal-Shielded Zinc Anode for High-Performance Aqueous Zinc Batteries

Aqueous zinc metal batteries confront impediments such as severe side reactions and dendrite formation on the zinc metal anode, impeding its commercialization. Although various metals and zinc-metal alloys aim to optimize the zinc anode, the preferential order and reaction mechanisms at the metal/electrolyte interface remain unclear. Here, we utilized magnetron sputtering to create nanolayered metal coatings (Cu, Ti, Ag, Au, Al) on the zinc surface. Notably, the Cu@Zn anode exhibited moderate binding energy with Zn atoms and lower nucleation overpotential than bare Zn, resulting in excellent cycling life (1600 h) and rate performance. Even at a high depth of discharge (80%), the cycling life can still over 200h. In full cells, Cu@Zn//VO2 demonstrated outstanding stability, retaining 95.5% capacity after 600 cycles. Comparison with other metal-coated zinc anodes revealed that Cu@Zn excels due to its moderate binding energy and superior kinetic properties. This study provides valuable insights for optimizing the heterointerface chemistry in zinc anodes, offering general guidelines to regulate various metal anodes suffering the similar challenges.Keywords: Aqueous Zinc ion battery, Metal-nanolayer, Magnetron sputtering, High Zn utilization

Improved Silicon/Graphite Composite Anode for High-Energy Li-Ion Battery

High-specific capacity of Silicon (~ reaching up to 3600 mAh/g corresponds to Li15Si4) and relatively higher lithiation potential (~0.4V Vs Li+; helpful in avoiding plating) makes it an ideal candidate for high-energy Li-ion batteries (LIBs). However, it is faced with severe issues like high crystallographic expansion (~320%), slow lithium diffusion, and high reactivity with electrolyte at higher SOCs. All of it leads to particle cracking, isolation, and electrode delamination resulting into poor cycle life performance. To harness the true potential of Silicon, we proposed an improvised Si/Gr composite anode balancing the high-specific capacity and cycle life. We investigated a novel binder formulation for Si-rich/Gr composite to enable high-specific capacity without compromising on life cycle. We demonstrated a robust and stable solid-electrolyte interface (SEI) formation by optimizing the electrolyte additive and formation protocol. Coupling our Si/Gr anode with high-energy Ni-rich cathode at appropriate capacity ratio (N/P) provides high-energy density (> 400 Wh/Kg) for LIBs.

Benchmarking the Match of Porous Carbon Substrate Pore Volume on Silicon Anode Materials for Lithium-Ion Batteries.

Silicon (Si) is one of the most promising anode materials for high-energy-density lithium-ion batteries. However, the huge volume expansion hinders its commercial application. Embedding amorphous Si nanoparticles in a porous carbon framework is an effective way to alleviate Si volume expansion, with the pore volume of the carbon substrates playing a pivotal role. This work demonstrates the impact of pore volume on the electrochemical performance of the silicon/carbon porous composites from two perspectives: 1) pore volume affects the loadings of Si particles; 2) pore volume affects the structural stability and mechanical properties. The smaller pore volume of the carbon substrate cannot support the high Si loadings, which results in forming a thick Si shell on the surface, thereby being detrimental to cycling stability and the diffusion of electrons and ions. On top of that, the carbon substrate with a larger pore volume has poor structural stability due to its fragility, which is also not conducive to realizing long cycle life and high rate performance. Achieving excellent electrochemical performances should match the proper pore volume with Si content. This study will provide important insights into the rational design of the silicon/carbon porous composites based on the pore volume of the carbon substrates.

Electrochemical and structural performances of carbon and glass fiber-reinforced structural supercapacitor composite at elevated temperatures

The structural supercapacitor can store electrical energy and withstand structural loads while saving substantial weight in many structural applications. This study investigated the development of a structural supercapacitor with a fiber-reinforced polymer composite system and explored the operating temperature’s influence on its performance. The electrochemical and mechanical properties of structural supercapacitors beyond the ambient temperature have not yet been studied; hence, evaluating parameters such as specific capacitance, energy density, cycle life, and structural performance at elevated temperatures are highly desired. We have designed and manufactured single and parallelly connected multilayer structural supercapacitor composites in this research. Carbon fibers were used as a bifunctional component, acting both as a current collector while acting as a mechanical reinforcement. In addition, glass fibers were added as the separator which is also acting as an integral reinforcement. The electrochemical and mechanical behavior of structural supercapacitors at elevated temperatures up to 85 °C were experimentally investigated. The test results revealed that at room temperature, the developed double-cell structural supercapacitor, which demonstrated an area-specific capacitance of 1.16 mF cm−2 and energy density of 0.36 mWh cm−2 at 0.24 mA cm−2, which are comparable to current achievements in structural supercapacitor research. The structural supercapacitor’s tensile, flexural, and compression strengths were measured as 109.5 MPa, 47.0 MPa, and 50.4 MPa, respectively. The specific capacitance and energy density reached 2.58 mF cm−2 and 0.81 mWh cm−2, while tensile, flexural, and compression strengths were reduced to 70.9 MPa, 14.2 MPa, and 8.8 MPa, respectively, at 85 °C. These findings provide new comprehensive knowledge on structural supercapacitor devices suitable for applications operating within a temperature range from ambient conditions to 85 °C.

Off-Stoichiometry of Sodium Iron Pyrophosphate as Cathode Materials for Sodium-Ion Batteries with Superior Cycling Stability.

As one of the important devices for large-scale electrochemical energy storage, sodium-ion batteries have received much attention due to the abundant resources of raw materials. However, whether it is a base station power source, an energy storage power station, or a start-stop power supply, long energy cycle life (more than 5000 cycles), high stability, and safety performance are application prerequisites. Regrettably, currently, few sodium-ion batteries can meet this requirement, mainly due to shortcomings in positive electrode performance. We report a sufficiently stable sodium-ion battery cathode material, Na2Fe0.95P2O7, that retains 97.5% capacity after 5000 charge/discharge cycles. The use of nonstoichiometry in the lattice enables simultaneous modification of the crystal and electronic structure, promoting Na2Fe0.95P2O7 to be extremely stable while still being able to achieve a capacity of 92 mAh g-1 and stable cycling at high temperatures up to 60 °C. Our results confirm the positive effect of nonstoichiometric ratios on the performance of Na2Fe0.95P2O7 and provide a reliable idea to promote the practical application of sodium-ion batteries.