Long-term Cycling Performance Research Articles

Heterogeneous MoS2 Nanosheets on Porous TiO2 Nanofibers toward Fast and Reversible Sodium-Ion Storage.

2D layered molybdenum disulfide (MoS2) has garnered considerable attention as an attractive electrode material in sodium-ion batteries (SIBs), but sluggish mass transfer kinetic and capacity fading make it suffer from inferior cycle capability. Herein, hierarchical MoS2 nanosheets decorated porous TiO2 nanofibers (MoS2 NSs@TiO2 NFs) with rich oxygen vacancies are engineered by microemulsion electrospinning method and subsequent hydrothermal/heat treatment. The MoS2 NSs@TiO2 NFs improves ion/electron transport kinetic and long-term cycling performance through distinctive porous structure and heterogeneous component. Consequently, the electrode exhibits excellent long-term Na storage capacity (298.4mAhg-1 at 5Ag-1 over 1100 cycles and 235.6mAhg-1 at 10Ag-1 over 7200 cycles). Employing Na3V2(PO4)3 as cathode, the full cell maintains a desirable capacity of 269.6mAhg-1 over 700 cycles at 1.0Ag-1. The stepwise intercalation-conversion and insertion/extraction endows outstanding Na+ storage performance, which yields valuable insight into the advancement of fast-charging and long-cycle life SIBs anode materials.

Rational design of nitrogen-doping Ti3C2Tx microspheres with enhanced polysulfide catalytic activity for lithium-sulfur batteries

The primary challenges that impede the practical applications of lithium-sulfur batteries are the significant shuttle effect of polysulfides, huge volume expansion, and slow redox kinetics. In this work, three-dimensional nitrogen doping Ti3C2Tx MXenes (3D N-Ti3C2Tx ) were successfully synthesized by spray drying and subsequent annealing, and hydrochloric acid-treated melamine effectively reduces the oxidation of MXenes in these processes. The formation of a unique nanoflower-shaped microsphere endows 3D N-Ti3C2Tx with a significant specific surface area and pore volume. The combination of nitrogen doping and the large specific surface area increased adsorption capacity and catalytic conversion ability for polysulfide intermediates. Consequently, the obtained 3D N-Ti3C2Tx /S cathode exhibited high-capacity retention (578.5 mAh g-1 after 500 cycles at 0.5 C and 462.5 mAh g-1 after 1,000 cycles at 1 C), superior rate performance (651.2 mAh g-1 at 3 C), and excellent long-term cycling performance (capacity fading rate of 0.076% per cycle at 0.5 C and 0.046% per cycle at 1 C). This work expands the potential applications of MXenes for lithium-sulfur batteries.

Gradient fluorination engineering through interdiffusion reaction for high-voltage LiCoO2

The advancement of high charging cut-off voltage stands as a crucial avenue to enhance the energy density of LiCoO2 (LCO). However, LCO faces severe interface and bulk phase issues at high voltage (≥ 4.6 V), resulting in poor cycling stability. In this study, we reconstruct the surface structure of LCO based on the interdiffusion reaction between LCO and MgF2 in a high-temperature sintering process. Specifically, this interdiffusion reaction yields an ultra-thin LiF coating layer, artificially reinforcing the chemical structure of the cathode-electrolyte interphase (CEI) during cycling. This LiF-rich CEI not only effectively protects the surface structure of LCO, but also facilitates the lithium-ion diffusion. Furthermore, the diffusion of F and Mg into the LCO lattice significantly strengthens the structure, which inhibits unfavorable phase transitions from the O3 phase to the H1-3 phase at high voltage. Consequently, such modified LCO with concurrently enhanced interface and bulk structure exhibits outstanding long-term cycling performance within 3.0–4.6 V at 1 C, achieving a capacity retention of 84.9% after 1000 cycles. Meanwhile, it also demonstrates excellent high-temperature performance, with a capacity retention of 85.0% after 200 cycles under 45 °C.

P2-type low-cost and moisture-stable cathode for sodium-ion batteries

Mn-based P2-type oxides are considered as promising cathodes for Na-ion batteries; however, they face significant challenges, including structural degradation when charged at high cutoff voltages and structural changes upon storing in a humid atmosphere. In response to these issues, we have designed an oxide with co-doping of Cu and Al which can balance both cost and structural stability. The redox reaction of Cu2+/3+ can provide certain charge compensation, and the introduction of Al can further suppress the Jahn-Teller effect of Mn, thereby achieving superior long-term cycling performance. The ex-situ XRD testing indicates that Cu/Al co-doping can effectively suppress the phase transition of P2-O2 at high voltage, thereby explaining the improvement in electrochemical performance. DFT calculations reveal a high chemical tolerance to moisture, with lower adsorption energy for H2O compared to pure Na0.67Cu0.25Mn0.75O2. A representative Na0.67Cu0.20Al0.05Mn0.75O2 cathode demonstrates impressive reversible capacities of 148.7 mAh/g at 0.2 C, along with a remarkable capacity retention of 79.1% (2 C, 500 cycles).

Tuning the morphology of argan shells-based activated carbon towards applications as an anode for lithium-ion battery

The application of carbonaceous materials other than graphite as an anode for lithium-ion batteries can generate significant advantages, mainly in terms of cost and sustainability while achieving high specific capacities. In this work, we successfully managed to tune the morphology of activated carbon prepared from argan shells to be used as an electrode material for lithium-ion batteries. Both Nanosphere-AC and Honeycomb-AC are obtained from the same precursor. The AC samples were comprehensively characterized using sorption isotherms, scanning electron microscopy, X-ray diffraction and Fourier-transforming infrared spectroscopy. Both materials were tested as anodes for lithium-ion batteries. It was found that Nanosphere-AC permitted great specific capacity (700 mAh.g−1at 50 mAh.g−1) and long-term cycling, showing no apparent capacity fade even after 200 cycles, offering promising application potential. Whereas Honeycomb-AC only achieved 220 mAh.g−1 at 50 mAh.g−1, but still exhibited great long-term cycling performance after 200 cycles and rate capability properties.

Porous Si/Ca-Si-O nanocomposite lithium storage materials by calciothermic reduction of Si with CaH2

Silicon monoxide (SiO)-based anode materials are one of the most intensively investigated class of materials for use as high-capacity anodes in lithium-ion batteries. However, their low initial Coulombic efficiency (ICE), resulting from the irreversible electrochemical reaction of the amorphous SiO2 (a-SiO2) phase in the SiO, restricts the wide-spread adoption of SiO-based anode materials in lithium-ion batteries. Pre-emptive formation of an irreversible phase that converts a-SiO2 to a non-reactive state with lithium prior to cell assembly has received much attention for enhancing ICE. However, this process has the drawback of not ensuring long-term cycle performance. Herein, the pre-emptive formation of irreversible phase combined with the high-energy mechanical milling (HEMM) process is proposed to simultaneously improve both the ICE and long-term cycle performance. The resulting porous Si/Ca-Si-O nanocomposite electrode exhibits an impressive ICE of 86.4 % and maintains 55 % of its capacity over 200 cycles. The key factor in the significant ICE improvement is the irreversible Ca-Si-O phase, which is formed by the calciothermic reduction of Si with CaH2. In addition, the microstructural changes induced by the HEMM process effectively mitigate the volume expansion of Si during cycling, resulting in improved long-term cycle stability.

In situ polymerization design of a quasi-solid electrolyte enhanced by NMP additive for lithium metal batteries

Solid polymer electrolytes (SPEs) are considered one promising candidate for lithium metal batteries due to their high flexibility, low cost, and roll-to-roll scalability. However, conventional SPEs prepared via ex situ methods are confronted with challenges such as poor contact and high resistance at the electrode|SPE interface, as well as low ionic conductivity at room temperature. In this study, we developed a quasi-solid electrolyte (QSE) using an in situ polymerization approach, employing butyl acrylate as the monomer and incorporating NMP as an additive. Spectroscopic investigations and DFT calculations revealed that NMP tends to form an overleaf-structured [Li(NMP)3][TFSI] complex with LiTFSI, promoting lithium salt dissociation. Owing to this advantage, the QSE exhibits high room-temperature ionic conductivity (6.94 × 10−4 S cm−1) and an extensive electrochemical stability window (5.01 V vs. Li+/Li). Furthermore, the in situ polymerization method facilitates full contact at the interface, enhancing the interfacial stability and reducing the interface resistance, thus resulting in stable cycling of Li|Built-in QSE|Li symmetric cell for 1100 h at 0.1 mA cm−2. The assembled LiFePO4|Built-in QSE|Li cell also demonstrates excellent rate and long-term cycling performance. Our findings offer valuable insights into the interaction between organic additives and lithium salts and present a novel strategy for the development of polymer electrolytes.

Eliminating H2O/HF and regulating interphase with bifunctional tolylene-2, 4-diisocyanate (TDI) additive for long life Li-ion battery

Lithium-ion batteries (LIBs) featuring a Ni-rich cathode exhibit increased specific capacity, but the establishment of a stable interphase through the implementation of a functional electrolyte strategy remains challenging. Especially when the battery is operated under high temperature, the trace water present in the electrolyte will accelerate the hydrolysis of the electrolyte and the resulting HF will further erode the interphase. In order to enhance the long-term cycling performance of graphite/LiNi0.8Co0.1Mn0.1O2 (NCM811) LIBs, herein, Tolylene-2,4-diisocyanate (TDI) additive containing lone-pair electrons is employed to formulate a novel bifunctional electrolyte aimed at eliminating H2O/HF generated at elevated temperature. After 1000 cycles at 25 °C, the battery incorporating the TDI-containing electrolyte exhibits an impressive capacity retention of 94% at 1 C. In contrast, the battery utilizing the blank electrolyte has a lower capacity retention of only 78%. Furthermore, after undergoing 550 cycles at 1 C under 45 °C, the inclusion of TDI results in a notable enhancement of capacity, increasing it from 68% to 80%. This indicates TDI has a favorable influence on the cycling performance of LIBs, especially at elevated temperatures. The analysis of the film formation mechanism suggests that the lone pair of electrons of the isocyanate group in TDI play a crucial role in inhibiting the generation of H2O and HF, which leads to the formation of a thin and dense interphase. The existence of this interphase is thought to substantially enhance the cycling performance of the LIBs. This work not only improves the performance of graphite/NCM811 batteries at room temperature and high temperature by eliminating H2O/HF but also presents a novel strategy for advancing functional electrolyte development.

Reusable Cell Design for High-Temperature (600 °C) Liquid Metal Battery Cycling

This paper presents the cycling of a novel low-cost Na-Zn liquid metal battery. Its 600 °C operating temperature presents multiple challenges that must be overcome to achieve commercial viability, both from a structural and electrochemical perspective. To enable long-term cycling of the Na-Zn battery in a realistic environment, we have developed a reusable, hermetically sealed, high temperature and sufficiently corrosion resistant cell concept. The design as well as various approaches for assembling and filling the cell are presented. The factors considered when selecting specific components are documented and explained. The active volume of the cell design can be up to 40 ml, corresponding to a nominal capacity of 1 A h, while the entire cell body weighs around 800 g and costs approximately €200 ($215). The performance of the cell is demonstrated in terms of longevity (1000 h) and high discharge current density (100 mA cm-2). The manuscript not only presents the first long-term cycling performance of the novel Na-Zn chemistry achieving Coulombic efficiency of up to 80%, but also demonstrates the design’s versatility with in situ dynamic neutron radiography of the cell.

Li6.28La3Zr2Al0.24O12-reinforced Single-ion Conducting Composite Polymer Electrolyte for Room-Temperature Li-Metal Batteries

Composite polymer electrolytes composed of inorganic fillers and organic polymers are promising electrolyte candidates for Li metal batteries, with benefits of improved safety and suppressed lithium dendrite growth. However, a severe concentration polarization effect often occurs when using conventional dual-ion electrolytes, and the increase in internal impedance during cycling results in decreased lifespan of the battery. To address this challenge, a plasticized single-ion conducting composite polymer electrolyte (SICE) was designed and fabricated by polymerizing the monomers of lithium (4-styrenesulfonyl) (trifluoromethanesulfonyl) imide (LiSTFSI) and poly(ethylene glycol) methyl ether acrylate (PEGMEA), crosslinker poly(ethylene glycol) diacrylate (PEGDA), silane-modified Li6.28La3Al0.24Zr2O12 nanofibers (s@LLAZO NFs), along with a PEG-based plasticizer tetraethylene glycol dimethyl ether (TEGDME), by heat-initiation. The anions were restrained and delocalized so that only Li cation migration occurred during the charging/discharging process, leading to a superior lithium-ion transference number. The s@LLAZO NFs enabled direct monomer grafting with the polymer matrix, resulting in controlled formation of an organic-inorganic network with increased filler content and improved filler distribution in the SICE system. The SICE membrane exhibited high ionic conductivity at room temperature, reduced activation energy and excellent oxidation stability. Most importantly, the all-solid-state Li-metal batteries assembled with the fabricated SICE demonstrated stable long-term cycling performance and remarkable rate capability at room temperature.

Indium Nitride Nanowires: Low Redox Potential Anodes for Lithium-Ion Batteries.

Advanced lithium-ion batteries (LIBs) are crucial to portable devices and electric vehicles. However, it is still challenging to further develop the current anodic materials such as graphite due to the intrinsic limited capacity and sluggish Li-ion diffusion. Indium nitride (InN), which is a new type of anodic material with low redox potential (<0.7V vs Li/Li+) and narrow bandgap (0.69eV), may serve as a new high-energy density anode material for LIBs. Here, the growth of 1D single crystalline InN nanowires is reported on Au-decorated carbon fibers (InN/Au-CFs) via chemical vapor deposition, possessing a high aspect ratio of 400. The binder-free Au-CFs with high conductivity can provide abundant sites and enhance binding force for the dense growth of InN nanowires, displaying shortened Li ion diffusion paths, high structural stability, and fast Li+ kinetics. The InN/Au-CFs can offer stable and high-rate Li delithiation/lithiation without Li deposition, and achieve a remarkable capacity of 632.5 mAh g-1 at 0.1 A g-1 after 450 cycles and 416 mAh g-1 at a high rate of 30 A g-1. The InN nanowires as battery anodes shall hold substantial promise for fulfilling superior long-term cycling performance and high-rate capability for advanced LIBs.

Reinforced flexible solid-state electrolyte membrane by polyurethane polymer of intrinsic microporosity for high-energy-density lithium metal battery

Poly (ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) are restricted in commercial applications due to the low ionic conductivity at ambient temperature and fragile mechanical properties. Polyurethanes (PUs) are unique materials coupled with superior rigidity and flexibility. Herein, we designed a novel polyurethane polymer of intrinsic microporosity (PPU), which was incorporated with PEO-based polymer electrolyte to prepare composite polymer electrolyte (CPE). The physicochemical and electrochemical properties of CPE membranes were explored. The high ionic conductivity (1.82 × 10−3 S cm−1 at 50 °C) and superior interfacial stability with the lithium anode was obtained. Furthermore, the rate performances and the cycling properties of CPE in LiFePO4 (LFP) batteries were extensively studied. The CPE-15% PPU film showed the excellent electrochemical stability of 84.3% capacity retention after 890 cycles at 0.5 C and 82.4% capacity retention after 500 cycles at 1.0 C at 50 °C. Especially, the CPE matched with high-voltage LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode delivered long-term stable cycling performances. The novel polymer electrolyte acquired could open up a new horizon to achieve high stable lithium metal batteries.

A self-assembled carbon nanotube/silicon composite battery anode stabilized with chemically reduced graphene oxide sheets

This study presents a streamlined fabrication process for lithium-ion battery (LIB) electrodes, involving the dispersion of carbon nanotubes (CNT), silicon (Si), and graphene oxide (GO) in an aqueous solution, followed by vacuum filtration to produce self-standing composite electrodes. Two reduction routes are employed to form reduced graphene oxide (rGO). The chemically reduced CNT/Si/rGO-5 %-Chem anode exhibits superior mechanical resilience compared to thermally reduced counterparts, which suffer from reduced strength and structural integrity. Chemical reduction also enhances electrochemical performance, increasing the initial capacity of the non-reduced CNT/Si/GO-5 % composite anode from 1,461 to 2,342 mAh g−1, with improved long-term cycling performance. Electrochemical impedance spectroscopy shows lower pre-cycle charge transfer resistance (148 Ω) and superior solid electrolyte interphase (SEI) resistance (43 Ω) for chemically reduced anodes compared to thermally reduced ones. After cycling, the chemically reduced composite anode exhibits reduced electrolyte resistance and charge transfer resistance, indicating stable electrochemical reactions. The composite structure undergoes adaptive rearrangements during cycling, optimizing active material utilization. In summary, CNTs accommodate silicon swelling, while chemically reduced rGO promotes stable SEI formation, highlighting the benefits of chemical reduction in enhancing mechanical durability and electrochemical performance, making the self-standing CNT/Si/rGO composite film a promising LIB anode.

Constructing high-toughness polyimide binder with robust polarity and ion-conductive mechanisms ensuring long-term operational stability of silicon-based anodes

Silicon-based materials have demonstrated remarkable potential in high-energy–density batteries owing to their high theoretical capacity. However, the significant volume expansion of silicon seriously hinders its utilization as a lithium-ion anode. Herein, a functionalized high-toughness polyimide (PDMI) is synthesized by copolymerizing the 4,4′-Oxydiphthalic anhydride (ODPA) with 4,4′-oxydianiline (ODA), 2,3-diaminobenzoic acid (DABA), and 1,3-bis(3-aminopropyl)-tetramethyl disiloxane (DMS). The combination of rigid benzene rings and flexible oxygen groups (-O-) in the PDMI molecular chain via a rigidness/softness coupling mechanism contributes to high toughness. The plentiful polar carboxyl (–COOH) groups establish robust bonding strength. Rapid ionic transport is achieved by incorporating the flexible siloxane segment (Si-O-Si), which imparts high molecular chain motility and augments free volume holes to facilitate lithium-ion transport (9.8 × 10−10 cm2 s−1 vs. 16 × 10−10 cm2 s−1). As expected, the SiOx@PDMI-1.5 electrode delivers brilliant long-term cycle performance with a remarkable capacity retention of 85% over 500 cycles at 1.3 A g−1. The well-designed functionalized polyimide also significantly enhances the electrochemical properties of Si nanoparticles electrode. Meanwhile, the assembled SiOx@PDMI-1.5/NCM811 full cell delivers a high retention of 80% after 100 cycles. The perspective of the binder design strategy based on polyimide modification delivers a novel path toward high-capacity electrodes for high-energy–density batteries.

Vertically-Aligned Card-House Structure for Composite Solid Polymer Electrolyte with Fast and Stable Ion Transport Channels.

All-solid-state lithium batteries (ASSLBs) are highly promising as next-generation energy storage devices owing to their potential for great safety and high energy density. This work demonstrates that composite solid polymer electrolyte with vertically-aligned card-house structure can simultaneously improve the high rate and long-term cycling performance of ASSLBs. The vertical alignment of laponite nanosheets creates fast and uniform Li+ ion transport channels at the nanosheets/polymer interphase, resulting in high ionic conductivity of 8.9 × 10-4 S cm-1 and Li+ transference number of 0.32 at 60°C, as well as uniformly distributed solid electrolyte interphase. Such electrolyte is characterized by high mechanical strength, low flammability, excellent structural stability and stable ion transport channels. In addition, the ASSLB cell with the electrolyte and LiFePO4 cathode delivers a high discharge specific capacity of 124.8 mAh g-1 , which accounts for 85.6% of its initial capacity after 500 cycles at 1C. The reasonable design through structural control strategy by interconnecting the vertically-aligned nanosheets open a way to fabricate high performance composite solid polymer electrolytes.

Pristine cobalt humic acid xerogels embedded with ultrafine cobalt sulfide for enhanced and stable lithium-ion storage

The electrochemical performance of pristine metal–organic xerogels as anodes in lithium-ion batteries is reported for the first time. We propose a novel synthesis approach for the in situ generation of highly dispersed, ultrafine cobalt sulfide nanoparticles on humic acid gels (CoSHA). The CoS nanoparticles in CoSHA have an average diameter of approximately 3 nm. CoSHA electrodes demonstrate enhanced lithium storage capacity, delivering a capacity of 662 mAh g−1 at 0.1 A g−1. They also show stable long-term cycling performance, with no capacity decay after 900 cycles at 1.0 A g−1. Furthermore, our experiments indicate that the improved lithium-ion adsorption results from the oxygen-containing functional groups in humic acid and the ultrafine CoS active sites. This study offers a practical methodology for synthesizing ultrafine metal sulfides and new insights into using pristine gel-based electrodes for energy storage and conversion.

In-situ polymerisation of fluorene to achieve theoretical capacity in LiFePO4 cells

This study aims to enhance the electrochemical properties of solid-state lithium-ion batteries by modifying the cathode material, LiFePO4 (LFP), via fluorene addition and in-situ polymerisation. The first modification process involves creating a shell structure (the film thickness of 10 nm) around each LFP particle and establishing a net-like structure to connect the particles before the in-situ polymerisation. Then, electrochemical in-situ polymerisation during battery cycling with a low current and obtaining the composite cathode of lithium iron phosphate (LFP) and polyfluorene. The results demonstrate that adding 20 wt.% fluorene significantly reduces the transfer resistance and enhances the rate performance with the capacity retention of 95.2 % (from 0.1C to 2C and return to 0.2C) of the solid-state batteries. Additionally, the modified LFP cathode demonstrates excellent long-term cycling performance and exhibits capacity (167.2 mAh/g in 0.2 C) close to the theoretical limit, and Coulombic efficiency remains at 99.2 %.

In Situ Construction of Elastic Solid-State Polymer Electrolyte with Fast Ionic Transport for Dendrite-Free Solid-State Lithium Metal Batteries.

Solid-state lithium metal batteries (LMBs) have been extensively investigated owing to their safer and higher energy density. In this work, we prepared a novel elastic solid-state polymer electrolyte based on an in situ-formed elastomer polymer matrix with ion-conductive plasticizer crystal embedded with Li6.5La3Zr1.5Ta0.5O12 (LLZTO) nanoparticles, denoted as LZT/SN-SPE. The unique structure of LZT/SN-SPE shows excellent elasticity and flexibility, good electrochemical oxidation tolerance, high ionic conductivity, and high Li+ transference number. The role of LLZTO filler in suppressing the side reactions between succinonitrile (SN) and the lithium metal anode and propelling the Li+ diffusion kinetics can be affirmed. The Li symmetric cells with LZT/SN-SPE cycled stably over 1100 h under a current density of 5 mA cm-2, and Li||LiFePO4 cells realized an excellent rate (92.40 mAh g-1 at 5 C) and long-term cycling performance (98.6% retention after 420 cycles at 1 C). Hence, it can provide a promising strategy for achieving high energy density solid-state LMBs.

Cobalt nanoparticles embedded in nitrogen-doped carbon nanofibers to enhance redox kinetics for long-cycling sodium–sulfur batteries

The shuttle effect resulting from severe volume expansion and polysulfide dissolution imposes limitations to the application of sodium–sulfur (Na–S) batteries. Herein, a three-dimensional self-supported electrode comprised of cobalt nanoparticles embedded in nitrogen-doped carbon nanofibers (CoNCNFs) is constructed to accommodate sulfur as the cathode for Na–S batteries. The carbon fiber framework facilitates direct electrons transmission and reduces the overall contact impedance of the electrode. The abundant pore structure not only promotes electrolyte infiltration but also ensures high loading of sulfur and provides space for volume expansion during charging and discharging. Most significantly, the CoNCNF carrier accelerates the conversion rate of sodium polysulfides into Na2S and guide Na2S deposition on its surface in a three-dimensional progressive nucleation (3DP) mode, resulting in a high Na2S deposition capacity and outstanding long-term cycling performance. When coupled with a Na-metal anode, the CoNCNF/S composite cathode exhibits stable electrochemical properties with a capacity up to 1030.2 mA h/g after 300 cycles at 0.2 C and excellent rate performance.

A Study on Long-Term Cycling Performance by External Pressure Change for Pouch-Type Lithium Metal Batteries

&lt;p&gt;Lithium dendrite formation is one of the most significant problems with lithium metal batteries. The lithium dendrite reduces the lithium metal batteries’ cycling life and safety. To apply consistent external pressure to a lithium metal pouch cell, we design a press jig in this study. External pressure creates dense lithium morphology by preventing lithium dendrite formation. After 300 cycles at 1 C, the cells with the external pressure perform far better than the cells without it, with a cycling retention of 97.8%. The formation of stable lithium metal is made possible by external pressure, which also enhances safety and cyclability.&lt;/p&gt;