Cycling Performance Of Batteries Research Articles

Construction of Sulfone‐Based Polymer Electrolyte Interface Enables the High Cyclic Stability of 4.6 V LiCoO2 Cathode by In Situ Polymerization

AbstractLithium cobalt oxide (LiCoO2) is considered an indispensable cathode material in the realm of consumer electronic batteries due to its high volumetric energy density. However, at a charging cut‐off voltage as high as 4.6 V, significant interfacial side reactions between LiCoO2 and the electrolyte occur, which adversely impact the battery's cycle performance. The surface‐related issues of LiCoO2 at high charge voltages not only constrain its utilization in conventional lithium‐ion batteries with liquid electrolytes but also limit its application in solid‐state batteries. Although traditional coating methods using inert inorganic compounds can partially alleviate this issue, their point‐like coatings fail to completely prevent the surface of LiCoO2 from direct contact with the electrolyte. The exploration of novel surface protection strategies for LiCoO2 remains imperative to address the associated challenges. Herein, introducing a sulfone‐based polymer electrolyte interface is proposed on the surface of LiCoO2 using methyl vinyl sulfone (MVS) through in situ polymerization. Remarkably, LiCoO2 with sulfone‐based polymer electrolyte interface exhibits a capacity retention rate of 83% after 500 cycles when employing a carbonate electrolyte without additives at a charge cut‐off voltage of 4.6 V. Furthermore, the LiCoO2 and polymer electrolyte interface exhibits exceptional cycle stability when paired with polyether solid electrolytes that do not possess high voltage tolerance. Moreover, the incorporation of a polymer electrolyte interface not only enhances the cycle stability of LiCoO2 but also improves its thermal stability. This work presents novel research perspectives for exploring high‐voltage stable LiCoO2.

A solid-state surface-to-bulk modification with a multifunctional modified layer for 4.6 V LiCoO2

With the attempts of more than 30 years, the current commercial LiCoO2 (LCO) offers a reversible capacity of 185 mAh g−1 with a cut-off voltage of 4.5 V vs. Li+/Li. Further increasing the cut-off voltage, more lithium-ions can extract, deeply enhancing the capacity and energy density. However, it results in numerous side reactions and a significant decay in battery cycle performance. To address these issues, Nano-LiNbO3 as a coating agency is introduced by a solid-state surface-to-bulk modification process. To avoid the agglomeration and achieve uneven coating of Nano-LiNbO3 in the solid-state reaction, polyvinylpyrrolidone (PVP) is introduced as a dispersant, which effectively ensures the uniform and smooth coating along with the carbonization process. The modified LCO sample presents a specific reversible capacity of 215.5 mAh g−1 in the initial cycle and a capacity retention rate of 90 % after 100 cycles at 3–4.6 V and 0.5 C. Further analysis demonstrate that the LiNbO3 surface coating layer and the element gradient doping layer provide LCO a stable structure and an inert surface, which improves the surface stability, suppresses the oxygen release and ensures the enhanced electrochemical performance.

Nano-silica electrolyte additive enables dendrite suppression in an anode-free sodium metal battery

Sodium (Na)-based batteries are being explored as a sustainable and cost-effective alternative to Lithium (Li)-ion batteries. In particular, an “anode-free” Na metal battery offers the possibility to match or even exceed the energy density of the incumbent Li-ion technology. Nevertheless, the present lifespan of these batteries is insufficient to render them suitable as an energy source for current electronic devices and grid systems. The main reason for this is the evolution and growth of Na metal dendrites during the charge-discharge process. In this study, we report a “nano-silica modified suspension electrolyte” that improves the average coulombic efficiency and cycling performance of anode-free Na metal batteries. The nano-silica additives increase the Na+ diffusion coefficient in the electrolyte by ∼1000-fold, thereby decreasing the nucleation overpotential and inhibiting the formation of Na metal dendrites. We demonstrate that a Na|Cu half-cell with the suspension electrolyte can cycle stably for over 500 cycles at ∼1 mA cm−2 current density and an aerial capacity of ∼2 mAh cm−2. When paired with an Na3V2(PO4)3 (NVP) cathode, the anode-free NVP|Cu full-cell device with the nano-silica infused electrolyte drastically outperformed the conventional electrolyte in terms of specific capacity retention and coulombic efficiency.

The benzothiadiazole-based COF/CNT composite as host for efficient Li-S batteries with excellent cycling stability

The cycle stability and dynamic performance of lithium-sulfur (Li-S) batteries have been major challenges, which primarily arise from the dissolution and migration of the soluble reaction intermediates during cycling, as well as the low conductivity of sulfur. In this study, a covalent organic framework containing heteroatoms (B/N/S) is uniformly wrapped on the outer surface of carbon nanotubes to form a nanocomposite (COF@CNT). The composite combines the excellent electrical conductivity of CNTs and the COF material containing evenly distributed heteroatoms that can adsorb and catalyze polysulfides. B atom on COF can be chemically adsorbed by the negatively charged SX2−, S and N atoms can interact with Li+ to reduce the “shuttle effect”. At the same time, the heteroatoms promote the liquid-to-solid phase conversion of the soluble long-chain Li2Sx (4 ≤ x ≤ 8), and the subsequent conversion of solid Li2S2 to Li2S, thereby enhancing the dynamic kinetics. As a cathode material, COF@CNT/S exhibits an initial specific capacity of 1176 mAh/g at 0.2 C, maintaining a capacity of 688 mAh/g after 1000 cycles at 1 C with a Coulombic efficiency of 99.7 %. Notably, a quite low capacity decay rate of 0.029 % per cycle has been achieved, making the COF@CNT/S cathode one of the most stable electrode material for Li-S batteries. This work provides insights into improving cycle performance of Li-S batteries, and also enriches the current study on host materials.

Improvement of rate capability and cycle life of Na-NiCl2 battery via designing a graphene anchoring porous nickel nanostructures as cathode

The integration of renewable energy with advanced energy storage technologies is essential. The sodium-based batteries, particularly sodium-nickel chloride (Na-NiCl2) batteries, show promise due to the abundance and low redox potential of sodium (−2.7 V vs. SHE). Despite their advantages in terms of cost, safety, and high efficiency, the improvement of rate and cycling performance of Na-NiCl2 batteries remains a challenge. To address this issue, a Ni nanostructure-supported reduced graphene oxide (RGO) composite is synthesized and combined with NaCl to serve as the cathode material for Na-NiCl2 batteries. Benefiting from the strong anchoring function of RGO, the growth of Ni is inhibited. As a result, the obtained cathode exhibits a notable specific capacity of 132.7 mAh/g at a high rate of 0.6C, along with excellent Coulombic efficiency of 100 % over 500 cycles and high energy efficiency (95.8 %). In addition, the outstanding conductivity, high specific surface area and abundant pore distribution of Ni@RGO contribute to enhanced conversion reaction and ion diffusion, and thus promoting rate capability. In contrast, the pure Ni nanosheets-based (Ni NSs) cathode is subjected to serious grain growth, which leads to poor rate performance and rapid capacity fading. By introducing conductive framework of RGO and constructing porous Ni nanostructure, the rapid electrons transport and diffusion of ions is achieved, and thus presenting the exceptional electrochemical properties.

Electrocatalytic tungsten boride quantum dots anchored reduced graphene oxide as the desolvation promotor for efficient sulfur redox kinetics

Lithium-sulfur (Li-S) batteries boast a multitude of compelling attributes, chief among them being their exceptional energy density and relatively low raw material costs. However, the sluggish redox kenitics of sulfur stemming from the considerable desolvation energy barrier and the notorious shuttle effect of lithium polysulfides, pose significant challenges in the commercialization of Li-S batteries. In this work, ultra-fine WB quantum dots were in-situ and uniformly dispersed on reduced graphene oxide nanosheets (WB-rGO) by mild melting-salt method, in which the abundant oxygen-containing functional groups in graphene oxide effectively prevent the agglomeration of WB. Such ultra-fine WB quantum dot as well as dual-active sites stemming from W and electronics-deficient B, confer the WB-rGO composite with improved electrochemical active surface area for dissociating Li+-solvents molecules and catalyzing polysulfides transformations, thus improving cycling and rate performance of Li-S battery. Hence, the cells with WB-rGO@PP maintained a stable long-term cycling (650 mAh g-1 after 900 cycles at 1C with an average decay rate of 0.038% per cycle) and an impressive rate capability (740 mAh g-1 at 4C). Even at a sulfur loading of 4.7mgcm-2, the cell performed a high areal capacity of 3.6 mAh cm-2 after 200 cycles.

Cellulose-Encapsulated Composite Electrolyte Design: Toward Chemically and Mechanically Enhanced Solid-Sodium Batteries.

Sulfide- and halide-based ceramic ionic conductors exhibit comparable ionic conductivity with liquid electrolytes and are candidates for high-energy- and high-power-density all-solid-state batteries. These materials, however, are inherently brittle, making them unfavorable for applications. Here, we report a mechanically enhanced composite Na+ conductor that contains 92.5 wt % of sodium thioantimonate (Na3SbS4, NSS) and 7.5 wt % of sodium carboxymethyl cellulose (CMC); the latter serves as the binder and an electrochemically inert encapsulation layer. The ceramic and binder constituents were integrated at the particle level, providing ceramic NSS-level Na+ conductivity in the NSS-CMC composite. The more than 5-fold decrease of electrolyte thickness obtained in NSS-CMC composite provided a 5-fold increase in Na+ conductance compared to NSS ceramic pellets. As a result of the CMC encapsulation, this NSS-CMC composite shows increased moisture resistivity and electrochemical stability, which significantly promotes the cycling performance of NSS-based solid-state batteries. This work demonstrates a well-controlled, orthogonal process of ceramic-rich, composite electrolyte processing: independent streams for ceramic particle formation along with binder encapsulation in a solvent-assisted environment. This work also provides insights into the interplay among the solvent, the polymeric binder, and the ceramic particles in composite electrolyte synthesis and implies the critical importance of identifying the appropriate solvent/binder system for precise control of this complicated process.

Molecule Engineering of Sugar Derivatives as Electrolyte Additives for Deep-Reversible Zn Metal Anode.

The cycling performance of zinc-ion batteries is greatly affected by dendrite formation and side reactions on zinc anode, particularly in scenarios involving high depth of discharge (DOD) and low negative/positive capacity (N/P) ratios in full cells. Herein, drawing upon principles of host-guest interaction chemistry, we investigate the impact of molecular structure of electrolyte additives, specifically the -COOH and -OH groups, on the zinc negative electrode through molecular design. Our findings reveal that molecules containing these groups exhibit strong adsorption onto zinc anode surfaces and chelate with Zn2+, forming a H2O-poor inner Helmholtz plane. This effectively suppresses side reactions and promotes dendrite-free zinc deposition of exposed (002) facets, enhancing stability and reversibility of an average coulombic efficiency of 99.89% with the introduction of Lactobionic acid (LA) additive. Under harsh conditions of 92% DOD, Zn//Zn cells exhibit stable cycling at challenging current densities of 15 mA·cm-2. Even at a low N/P ratio of 1.3, Zn//NH4V4O10 full cells with LA electrolyte exhibit high-capacity retention of 73% after 300 cycles, significantly surpassing that of the blank electrolyte. Moreover, in a conversion type Zn//Br static battery with a high areal capacity (~ 5 mAh·cm-2), LA electrolyte sustains an improved cycling stability of 700 cycles.

Constructing stable electrode–electrolyte interfaces by sulfone-based additive to improve the high-voltage performance of LiCoO2

LiCoO2 battery can provide high reversible capacity at a high voltage of 4.6 V, however, maintaining its stability at high voltages remains a major challenge. To address this issue, ethyl methyl sulfone (EMS) is employed as an electrolyte additive to construct stable interfaces between the electrode and electrolyte under high-voltage condition. The characterization results indicate that the addition of EMS can inhibit the decomposition of the standard electrolyte (STD) and the dissolution of Co2+ from cathode, as well as the formation of lithium dendrites on the Li anode, thereby enhancing the stability of both cathode/electrolyte and anode/electrolyte interfaces. Consequently, the cycling performance of LiCoO2 battery using STD+3 %EMS is augmented by 16.9 % at 1 C under a cut-off voltage of 4.6 V over 100 cycles, delivering a specific capacity of 137 mA h g−1. This research provides novel insights into the design of electrolyte additives for high-voltage LiCoO2 batteries and contributes to the further development of high-voltage lithium-ion batteries.

Incorporating Sodium-Conductive Polymeric Interfacial Adhesive with Inorganic Solid-State Electrolytes for Quasi-Solid-State Sodium Metal Batteries.

Inorganic solid-state electrolytes have attracted enormous attention due to their potential safety, increased energy density, and long cycle-life benefits. However, their application in solid-state batteries is limited by unstable electrode-electrolyte interface, poor point-to-point physical contact, and low utilization of metallic anodes. Herein, interfacial engineering based on sodium (Na)-conductive polymeric solid-state interfacial adhesive is studied to improve interface stability and optimize physical contacts, constructing a robust organic-rich solid electrolyte interphaselayer to prevent dendrite-induced crack propagation and security issues. The interfacial adhesive strategy significantly increases the room-temperature critical current density of inorganic Na-ion conductors from 0.8 to 3.2mAcm-2 and markedly enhances the cycling performance of solid-state batteries up to 500 cycles, respectively. Particularly, the Na3V2(PO4)3-based full solid-state batteries with high cathode loading of 10.16mgcm-2 also deliver an excellent cycling performance, further realizing the stable operation of solid-state laminated pouch cells. The research provides fundamental perspectives into the role of interfacial chemistry and takes the field a step closer to realizing practical solid-state batteries.

Correction: Enhanced cycle performance of Li ion battery by graphene sheets covering with SnO@SnO2 anode materials

Correction: Enhanced cycle performance of Li ion battery by graphene sheets covering with SnO@SnO2 anode materials

Enhanced cycle performance of Li ion battery by graphene sheets covering with SnO@SnO2 anode materials

Enhanced cycle performance of Li ion battery by graphene sheets covering with SnO@SnO2 anode materials

Micro-cracking on the surface of zinc metal improves the cycle performance of aqueous zinc ion batteries

The notorious zinc dendrite is a severe constraint to the practical application of zinc-based batteries, as the metal tips growing vertically in two dimensions on the surface of the electrodes during cycling and loosely packed sharp edges may pierce through the diaphragm, posing a safety hazard. In this study, physical stress extrusion was used to generate micron- or submicron-sized cracks on zinc metal anodes, which significantly increased the specific surface area of the electrodes and mitigated the local current density of the electrodes. Zinc ion fluxes were significantly dispersed, producing a dense Zn2SO4(OH)6-xH2O (ZHS) layer, which differed distinctly from the by-products of the loose upright growth on the surface of Raw Zn (RZn). Additionally, three-dimensional structure of cracked zinc composition allows it to adjust the zinc volume variations during electroplating/stripping, and the abundance of nucleation sites significantly reduces the Zn polarization voltage, resulting in uniform Zn deposition. The average cycle life of the symmetric cell was >400 h at 1 mA cm−2 current density, and nearly 500 cycles at 5 mA cm−2 current density for the asymmetric cell, with an average Coulombic efficiency of 99.3 %. The activation energy substantially declined with the increase in Zn ion flux per unit time (29.615 KJ mol−1 vs. 44.041 KJ mol−1), demonstrating efficient desolvation kinetics. Furthermore, the Crack Zn || V2O5 full cell also exhibits outstanding self-discharge performance, with 85 % capacity retention in a 48 h resting charge/discharge testing, superior to the raw zinc foil anode (78.3 %). Herein, a method of creating microcrack configurations on the surface of zinc anodes using stress extrusion was presented, sparing the current density while optimizing the undesirable growth patterns of ZHS by-products.

Improving the structural stability and reaction kinetic of Na3V2(PO4)3 through tungsten doping towards the ultralong cycle performance and excellent temperature tolerance of sodium ion batteries

A series of carbon-coated tungsten doping NVP (Na(3-x)V(2-x)Wx(PO4)3@C, x = 0, 0.05, 0.1, 0.2, 0.3) was synthesized by sol–gel method. Characterization reveals that partial substitution of V by the larger W has beneficial influences on the structure and diffusion kinetics of NVP. Consequently, the optimized NVP-W0.1@C electrode releases a reversible initial capacity of 116 mA h g−1 at 1C, that is quite near to the theoretical value of pure NVP (117 mA h g−1). Furthermore, it delivers a high reversible capacity of 83.6 mA h g−1 at 50C with marvelous 94.3 % retention over 18,000 cycles. Desirable performances are demonstrated at −20 °C and 45 °C respectively, suggesting its viability in harsh environment. This work shed a light on scalable and feasible routine to regulate SIBs-based cathodes with promising performances.

Anion exchange membrane based on poly(arylene ether sulfone)s functionalized with quinuclidinium-piperidinium dual cations for vanadium redox flow battery applications

Vanadium redox flow batteries (VRFBs) have gained significant interest as a prospective energy storage solution due to their scalability and extended cycle durability. The efficient functioning of VRFBs relies significantly on anion exchange membranes (AEMs), which facilitate the selective transport of ions while preventing crossover. In this study, we present a novel AEM based on poly(arylene ether sulfone)s (PAES) functionalized with dual cations (quinuclidinium-piperidinium) (DC-PAES) bearing a butyl spacer, explicitly designed for VRFB applications. The DC-PAES membrane containing dual cations separated by a butyl spacer results in a balanced combination of hydrophilicity and hydrophobicity, which enables efficient ion transport across the membrane. The DC-PAES membrane showed hydroxide conductivity of 0.085 S/cm at 80 °C, having an ion exchange capacity (IEC) of 1.42 mmol/g. The resulting DC-PAES membrane displayed low permeability (2.1 × 10−7 cm2 min−1) and high selectivity (12.3 × 105 S min cm−3) to vanadium. The performance of the AEMs fabricated for VRFB application showed better Coulombic (97.1 %), energy (90.0 %), and voltage efficiency (92.63 %) at 40 mAcm−2 higher than Nafion 117. The reported AEMs revealed excellent stability due to the steric and ring constraints of quinuclidinium and piperidinium cation, hindering the attack of oxidative species. Furthermore, the DC-PAES membrane demonstrated improved battery cycling performance lasting up to 150 cycles under in-situ conditions, making it a promising separator material for VRFB applications.

LFO modified separator for the initial anode irreversibility compensation in lithium-ion rechargeable full cells

Lithium-ion batteries (LIBs) dominate portable electronics and electric vehicles for their high energy density and long cycle life. However, a part of active Li loss in the initial charge process for the solid electrolyte interphase (SEI) formation at the anode surface, which reduces the energy density and cycle life of LIBs. Prelithiation attempts have been widely regarded as providing additional active lithium to address this issue. Li5FeO4 (LFO) as a cathode prelithiation additive with high donable lithium ions is very promising. But the residues of the gas release limited its further application due to its low conductivity in the first charge process. Here, we prepared CNT/ Polyacrylonitrile (PAN) /LFO/polypropylene (PP) separator by an electrospinning method, the CNT/PAN/LFO/PP separator can effectively improve cycle performance of LFP batteries, benefiting from Li2O participation in the construction of SEI and higher infiltration rate of the electrolyte resulting in faster interfacial Li+ transfer kinetics. The LFP pouch cell with CNT/PAN/LFO/PP separator can maintain a stable output over 1000 cycles (capacity fade rate per cycle of 0.005 %) with a highercapacity increased by 6.2 %.

Electrochemical-Thermal-Mechanical Coupling Analysis of Lithium-Ion Batteries under Fast Charging

Thermal runaway and volume expansion caused by temperature rise under fast charging of lithium-ion batteries (LIBs) are the major reasons of battery explosion and cycle performance degradation. In this work, considering the radiation heat transfer on the battery surface, an electrochemical-thermal-mechanical coupling model of cylindrical LIBs under fast charging (state of charge (SOC) ≤80%) is developed in order to investigate the distributions of the temperature and stress. Then, choosing 18650 LIBs as the object, the charge efficiency, temperature, and stress distributions are compared between fast charging and galvanostatic operation under SOC≤80%, respectively. Finally, the influences of the thickness, particle radius, the maximum lithium-ion concentration of the cathode, and initial electrolyte concentration on the temperature, radial stress, and hoop stress of LIB during charge are explored, respectively. Numerical results show that fast charging improves 20.8% of the charge efficiency. Increasing the cathodic thickness and decreasing the cathodic maximum lithium-ion concentration or initial electrolyte concentration can reduce the temperature of LIB during the charge. The results of this work will provide some reference value for the design of LIBs under fast charging.

Improving the cycling performance of lithium-air batteries using a nitrite salt electrolyte

Lithium nitrate (LiNO3) has been used as the electrolyte salt for Lithium-air battery (LAB), both to protect the lithium metal anode and to generate NO2− anions that function as the redox mediator (RM) reducing the charging voltage. However, this RM effect minimally improves cycling performance because only a low NO2− concentration is produced. Instead, the use of lithium nitrite (LiNO2) as the supporting electrolyte salt can overcome this limitation. In this study, 1 M solutions of LiNO3 or LiNO2 in tetraethylene glycol dimethyl ether (TEGDME) or N-methyl-2-pyrrolidone (NMP) were prepared as LAB electrolytes. Walden plots of these electrolytes established a higher degree of dissociation in the NMP having a greater dielectric constant, thus enhancing ionic conductivity. Electrochemical impedance spectroscopy determined that an LAB cell incorporating the LiNO2/NMP electrolyte exhibited reduced diffusion resistance during discharge-charge cycling as a consequence of the enhanced RM effect of NO2− anions. Microscopic observation and pore distribution analysis of cathodes confirmed that the clogging of pores was minimized with the LiNO2/NMP electrolyte. As a result, the LAB cell using this electrolyte extended the cycle performance, more than doubling the cycle life. LiNO2 is considered to be an effective alternative for electrolyte salt for LAB.

Additives for Aqueous Zinc-Ion Batteries: Recent Progress, Mechanism Analysis, and Future Perspectives.

Aqueous zinc-ion batteries (ZIBs) stand out as a promising next-generation electrochemical energy storage technology, offering notable advantages such as high specific capacity, enhanced safety, and cost-effectiveness. However, the application of aqueous electrolytes introduces challenges: Zn dendrite formation and parasitic reactions at the anode, as well as dissolution, electrostatic interaction, and by-product formation at the cathode. In addressing these electrode-centric problems, additive engineering has emerged as an effective strategy. This review delves into the latest advancements in electrolyte additives for ZIBs, emphasizing their role in resolving the existing issues. Key focus areas include improving morphology and reducing side reactions during battery cycling using synergistic effects of modulating anode interface regulation, zinc facet control, and restructuring of hydrogen bonds and solvation sheaths. Special attention is given to the efficacy of amino acids and zwitterions due to their multifunction to improve the cycling performance of batteries concerning cycle stability and lifespan. Additionally, the recent additive advancements are studied for low-temperature and extreme weather applications meticulously. This review concludes with a holistic look at the future of additive engineering, underscoring its critical role in advancing ZIB performance amidst the complexities and challenges of electrolyte additives.

Multilayer hybrid solid-state electrolyte membrane for the high rate and long-life cycle performance of lithium-metal batteries

Hybrid solid-state electrolytes (HSEs) can be used to increase the electrochemical performance of lithium-metal batteries (LMBs), while also suppressing dendrite formation and preventing flammable behavior and electrolyte leakage, which are frequently present in conventional organic-liquid electrolytes. Notably, multilayer HSE membranes have received increasing emphasis since they can significantly ameliorate the interface contact toward electrodes and the mechanical strength. In this current work, we fabricated multilayer HSE membranes via a solution-casting technique that incorporated poly(vinylidene fluoride–co–hexafluoropropylene) (PVDF-HFP), polydopamine-modified Li6.28La3Zr2Al0.24O12 (PDA@LLZAO) filler, succinonitrile (SN) and lithium bis(trifluoromethane sulfonyl)imide (LiTFSI). The resulting HSE membrane exhibited a high ionic conductivity (2.49 ×10−4 S cm−1 at 30 ℃), transference number of 0.65, and excellent electrochemical window (4.80 V). The symmetrical cell featuring Li/HSE/Li was stable and cycled without short circuiting for 1000 h during the Li plating/stripping cycles. Furthermore, the coin-type cell assembled with LiFePO4/HSE/Li showed an initial discharge capacity of 134.7 mAh g1 and exhibited superior retained capacity and average coulombic efficiency of 93.45% and 99.39%, respectively, after 687 cycles at 2 C and 30 ℃. Therefore, the as-prepared multilayer HSE is a promising SSE for next-generation LMBs.