Traditional Lithium-ion Batteries Research Articles

Lithium-Ion Battery Modeling and State of Charge Prediction Based on Fractional-Order Calculus

Predicting lithium-ion batteries’ state of charge (SOC) is essential to electric vehicle battery management systems. Traditional lithium-ion battery models mainly include equivalent circuit models (ECMs) and electrochemical models (EMs). ECMs are based on integer-order component modeling, which cannot characterize the internal electrochemical reaction mechanism of the battery, resulting in lower SOC prediction accuracy. In contrast, due to their complex structure, EMs are limited in their application. This study takes lithium batteries as the research object and proposes a fractional-order impedance model (FOIM) that characterizes the dynamic properties of the internal behavior of lithium-ion batteries using fractional-order elements. Considering the highly nonlinear characteristics of lithium-ion batteries, this study introduces the theory of fractional-order calculus into the extended Kalman filter (EKF) algorithm, and proposes the fractional-order extended Kalman filter (FEKF) algorithm applied to the prediction of battery charge state. Comparative analysis of simulation and experimental results shows that the accuracy of the FOIM, compared to ECMs, is significantly improved. The FEKF algorithm has good robustness in estimating the SOC, and the SOC prediction accuracy achieved with the algorithm is also improved compared with that obtained using the EKF algorithm of the integer-order model.

Dual-Coordination-Induced Poly(vinylidene fluoride)/Li6.4Ga0.2La3Zr2O12/Succinonitrile Composite Solid Electrolytes Toward Enhanced Rate Performance in All-Solid-State Lithium Batteries.

Pursuing high energy and power density in all-solid-state lithium batteries (ASSLBs) has been the focus of attention. However, due to their inferior ion transport, their rate performance is limited compared to traditional lithium-ion batteries. Herein, a dual-coordination mechanism is first proposed to construct a high-performance poly(vinylidene fluoride)/Li6.4Ga0.2La3Zr2O12/succinonitrile (PVDF/LLZO/SN) composite solid electrolyte. The dual-coordination interactions of SN with both LLZO and Li+ in lithium salts allow SN to act like a branched chain of PVDF, realizing an increase in the free volume of the composite electrolyte. Meanwhile, SN molecules are immobilized within the electrolyte membrane by coordinating with LLZO, ensuring good interfacial stability. Profiting from the dual-coordination mechanism, the PVDF/LLZO/SN composite solid electrolyte combines enhanced electrochemical performance and interfacial compatibility. When applied to ASSLBs, the composite solid electrolyte enables the battery to operate at rates up to 6 C. The LiFePO4/Li batteries operated at 4 C can still deliver a high capacity retention rate of 96.4% after 50 cycles. Notably, these batteries also exhibit good long-cycle stability. After 500 cycles at 0.5 C, the discharge capacity was maintained at 145.9 mAh g-1.

Recent Advances in All-Solid-State Lithium–Oxygen Batteries: Challenges, Strategies, Future

Digital platforms, electric vehicles, and renewable energy grids all rely on energy storage systems, with lithium-ion batteries (LIBs) as the predominant technology. However, the current energy density of LIBs is insufficient to meet the long-term objectives of these applications, and traditional LIBs with flammable liquid electrolytes pose safety concerns. All-solid-state lithium–oxygen batteries (ASSLOBs) are emerging as a promising next-generation energy storage technology with potential energy densities up to ten times higher than those of current LIBs. ASSLOBs utilize non-flammable solid-state electrolytes (SSEs) and offer superior safety and mechanical stability. However, ASSLOBs face challenges, including high solid-state interface resistances and unstable lithium-metal anodes. In recent years, significant progress has been proceeded in developing new materials and interfaces that improve the performance and stability of ASSLOBs. This review provides a comprehensive overview of the recent advances and challenges in the ASSLOB technology, including the design principles and strategies for developing high-performance ASSLOBs and advances in SSEs, cathodes, anodes, and interface engineering. Overall, this review highlights valuable insights into the current state of the art and future directions for ASSLOB technology.

Double Perovskite La2 MnNiO6 as a High-Performance Anode for Lithium-Ion Batteries.

Traditional lithium-ion batteries cannot meet the ever-increasing energy demands due to the unsatisfied graphite anode with sluggish electrochemical kinetics. Recently, the perovskite material family as anode attracts growing attention due to their advantages on specific capacity, rate capability, lifetime, and safety. Herein, a double perovskite La2 MnNiO6 synthesized by solid-state reaction method as a high-performance anode material for LIBs is reported. La2 MnNiO6 with an average operating potential of <0.8V versus Li+ /Li exhibits a good rate capability. Besides, the Li|La2 MnNiO6 cells perform long cycle life without decay after 1000 cycles at 1C and a high cycling retention of 93% is observed after 3000 cycles at 6C. It reveals that this material maintains stable perovskite structure with cycling. Theoretical calculations further demonstrate the high electronic conductivity, low diffusion energy barrier, and structural stability of the lithiated La2 MnNiO6 . This study highlights the double perovskite type material as a promising anode for next-generation batteries.

Tellurium filled carbon nanotubes cathodes for Li-Te batteries with high capacity and long-term cyclability

Li-Te batteries, compared with traditional lithium-ion batteries and Li-other group VIA elements (including O, S, Se) batteries, have shown overwhelming features of high specific volumetric capacity and superior electrical conductivity. These features make the Li-Te batteries possess great importance in modern portable electronics and electric vehicles with limited battery package size. However, the Achilles' Heel in Li-Te batteries is the huge volume change and inevitable dissolution of polytellurides during cycling. Herein, we synthesize a cathode material based on polycrystalline Te encapsulated in N-doped multiwall carbon nanotubes (Te-filled CNTs) by physical vapor transport (PVT) method. With unique spatial restriction of the CNT hosts, the electrochemically active Te content can be well preserved, and the prepared Te-filled CNTs cathodes deliver a high specific capacity of 590 mAh g−1 based on Te content. More importantly, the reaction kinetics and electrochemical reversibility of the cathodes have been significantly improved by using nanoscale cavities (4–6 nm) which stabilize the polytellurides (Li2Ten). Meanwhile, a series of in situ characterizations are carried out to straightforwardly reveal a two-step discharge/charge mechanism for Te-filled CNTs. In addition, theoretical calculations prove that the encapsulated Te ensure a lower energy barrier for lithiation compared with bare CNT. This work sheds light on the nanoconfinement effect of CNT for improving the utilization and cycling stability of Te based cathodes in Li-Te batteries.

An ultrafast rechargeable and high durability lithium metal battery using composite electrolyte with the three-dimensional inorganic framework by Li6.4La3Zr1.4Ta0.6O12 surface functionalization

The liquid electrolyte used in traditional lithium-ion batteries has risks of leakage, combustion and explosion. Solid electrolyte is one of the effective strategies to solve the safety problems of lithium-ion batteries. And the use of solid electrolytes makes it possible to use lithium metal as an anode to achieve higher energy densities. At present, the main factors restricting the performance improvement of all-solid-state lithium batteries are the low electrochemical performance of electrolytes and poor solid-solid interface contact. The composite electrolyte has the advantages of both inorganic materials and polymers, but its electrochemical performance is still not up to the requirements of use. In situ synthesis of LaRuO3 with perovskite structure on the surface of Li6.4La3Zr1.4Ta0.6O12(LLZTO) induces the formation of Li2Zr2O7 while introducing defects. The Li2Zr2O7 phase "welds" inorganic particles into three-dimensional(3D) inorganic framework, increasing the reaction sites between inorganic fillers and polymers. Compared with the primitive sample, the ionic conductivity of the modified electrolyte is increased by an order of magnitude at room temperature, wherein the lithium-ion conductivity of the composite electrolyte with 3% LaRuO3 is as high as 6.06 × 10−4 S cm−1. At 5C, the discharge specific capacity of LiFePO4 | [email protected] 3% LRO | Li can reach 114.6 mAh g−1; After 400 cycles, the discharge specific capacity remains at 129.6 mAh g−1. Under the same conditions, the discharge specific capacities of the unmodified samples are only 92.4 mAh g−1 and 35 mAh g−1. The high rate discharge performance of solid-state lithium metal battery supports the high torque output of motor, which improves the acceleration performance of electric vehicles or ships. The high capacity and excellent cycle performance of solid-state lithium metal battery can significantly extend the driving range and service life of electric vehicles.

Ultrathin poly(cyclocarbonate-ether)-based composite electrolyte reinforced with high-strength functional skeleton

Composite polymer electrolytes (CPEs) are considered to be the most promising to break through the performance and safety limitations of traditional lithium-ion batteries because of their excellent electrochemical and mechanical properties. Aiming at the performance limitations of the most common polyether matrix such as poly(ethylene oxide) (PEO), a novel poly(cyclocarbonate-ether) polymer matrix was prepared by in-situ thermal curing, the weaker interaction between its C = O bond and Li+ can promote the rapid transport of Li+. Adding ionic liquid and active filler LLZTO to the matrix can synergistically reduce the crystallinity of matrix and promote the dissociation of lithium salts. In addition, a 3D functional skeleton made of polyacrylonitrile (PAN) and lithium fluoride (LiF) can greatly improve the mechanical strength of polymer matrix after cold pressing, and LiF is also conducive to interface stability. The thickness of the optimal sample (VP6L/CPL) was only 25 μm, and its ionic conductivity, lithium ion transference number, and electrochemical stability window were as high as 7.17 × 10−4 S cm−1 (25 °C), 0.54 and 5.4 V, respectively, while the mechanical strength reaches 6.1 MPa, which can fully inhibit the growth of lithium dendrites. The excellent electrochemical performance and mechanical strength enable the assembled Li|VP6L/CPL|Li battery to be continuously charged for over 200 h and cycled stably for more than 2300 h, and Li|VP6L/CPL|LFP battery can be stably cycled for more than 400 and 550 cycles at 1 C (40 °C) and 0.5 C (25 °C), respectively.

Review of the Developments and Difficulties in Inorganic Solid-State Electrolytes.

All-solid-state lithium-ion batteries (ASSLIBs), with their exceptional attributes, have captured the attention of researchers. They offer a viable solution to the inherent flaws of traditional lithium-ion batteries. The crux of an ASSLB lies in its solid-state electrolyte (SSE) which shows higher stability and safety compared to liquid electrolyte. Additionally, it holds the promise of being compatible with Li metal anode, thereby realizing higher capacity. Inorganic SSEs have undergone tremendous developments in the last few decades; however, their practical applications still face difficulties such as the electrode-electrolyte interface, air stability, and so on. The structural composition of inorganic electrolytes is inherently linked to the advantages and difficulties they present. This article provides a comprehensive explanation of the development, structure, and Li-ion transport mechanism of representative inorganic SSEs. Moreover, corresponding difficulties such as interface issues and air stability as well as possible solutions are also discussed.

Electrolyte Engineering for Safer Lithium‐Ion Batteries: A Review

Comprehensive SummaryDespite being widely used in people's daily life, the safety issue of lithium‐ion batteries (LIBs) has become the major barrier for them to be applied in electrical vehicles (EVs) or large‐scale energy storage. Typically, due to the use of liquid electrolytes containing flammable solvents which are easily oxidized by excessive and accumulated heat, the potential thermal runaway is a major safety concern for traditional LIBs. A strategy for a safer electrolyte design is controlling the flammability and volatility of the liquid electrolytes, to effectively prevent thermal runaway, thus avoiding fire or other risks. Through this study, the mechanisms of thermal runaway and the recent progress in electrolyte engineering toward LIBs were summarized, covering the major strategies including adding flame‐retardants, the utilization of ionic liquid electrolytes and solid electrolytes. The characteristics, strengths and weaknesses of different strategies were discussed. New designing directions of safer electrolytes for the LIBs were also provided.

Preparation and characterization of LLZO-LATP composite solid electrolyte for solid-state lithium-ion battery

All-solid-state lithium-ion batteries (ASSLB) demonstrate significant advancements in energy density and safety comparing the traditional lithium-ion batteries, which using liquid electrolyte. The performance of ASSLBs strongly depends on the characteristics of solid electrolyte materials. Currently, Li1.3Al0.3Ti1.7(PO4)3 (LATP) and Li7La3Zr2O12 (LLZO) have the best individual performances in the field of solid ceramic electrolytes. The purpose of this study is to investigate the characteristics of the LLZO-LATP composite electrolyte sintering at various temperatures. The dense LLZO-LATP solid composited electrolyte with acceptable electrochemical performance is successfully prepared using planetary ball-mill method. The phase and morphology of the samples were assisted by X-ray diffraction and Field-emission scanning electron microscopy. The LLZO-LATP composite sintered at 800 °C has less chemical reaction with small amount of second phase with high sintering density of 88.4%. The ionic conductivity of LLZO-LATP sintered at 800 °C is 1.3 × 10−6 Scm−1. This study addresses the lowering of sintering temperature of a composite solid electrolyte with two different structure electrolyte materials, is informative for its future research and to be promising in solid-state batteries.

ZIF-8/ZIF-67 derived ZnS@Co-N-C hollow core-shell composite and its application in lithium‑sulfur battery

Lithium‑sulfur batteries are energy conversion devices that possess much higher energy densities than traditional lithium-ion batteries. However, the shuttle effect of the chemical reaction in the positive electrode of lithium‑sulfur batteries significantly reduces their specific capacity and charge retention characteristics. Therefore, we fabricated a novel hollow core-shell structure to serve as a separator modification layer and inhibit the shuttle effect. A ZIF-8/ZIF-67 core-shell precursor was first prepared by a room temperature solution reaction. This precursor was then treated by a vulcanization and calcination process to form the end product, in which ZnS was the core active site and CoN doped carbon nanocages were the outer shell. The discharge capacity and the cycling durability of a lithium‑sulfur battery were significantly improved by coating this novel structure on a polyethylene (PE) separator. Electrochemical measurements and microstructural analysis demonstrated that the unique hollow structure served as a polysulfide reservoir. Moreover, the Co-N-C shell and ZnS core of this structure also chemically interacted with and had a catalytic effect on the polysulfides, which enhanced the cycle and rate performance of the battery. Therefore, the lithium‑sulfur battery prepared using a ZnS@Co-N-C core-shell composite-coated PE separator showed excellent electrochemical performance.

Research Progress of All-Solid-State Lithium-Ion Batteries

In order to reach the peak in carbon dioxide emissions by 2030 and achieve carbon neutrality by 2060, it is necessary to perform technical research to reduce carbon emissions. Key core technologies such as zero emissions/reductions, hydrogen industry, and energy storage are particularly important in energy conservation and emissions reduction. In terms of energy storage, lithium-ion batteries (LIBs) are more advanced. However, traditional LIBs have risks such as swelling, leakage, and flammability. The creation of solid-state lithium-ion batteries (SSLBs) will be thoroughly described in this article, along with the benefits and drawbacks of various electrolytes and electrode materials. Additionally, the future development prospects of SSLBs will be discussed. In the long run, with the continuous optimization of SSLBs performance, the positive electrode material system is a higher specific capacity of lithium-rich materials, and the lithium-ion batteries with negative metal lithium will become mainstream, and the SSLBs technology with a higher energy density, lower cost, more security, and better stability will play a vital supporting role in the clean energy transformation.

One-dimensional H2V3O8 nanorods and two-dimensional lamellar MXene composites as efficient cathode materials for aqueous rechargeable zinc ion batteries.

The energy crisis is a the worldwide problem which needs humans to solve immediately. To solve this problem, it is necessary to develop energy storage batteries. It is worth mentioning the aqueous rechargeable zinc ion batteries (ARZBs) which have some advantages, such as low cost, good safety and no need for an organic electrolyte as in the traditional lithium-ion batteries. However, it is still a challenge to find suitable and reliable electrode materials. In this work, as-prepared H2V3O8 nanorods and MXene composites are used as cathode materials in ARZBs which were designed well using a hydrothermal method after optimizing the reaction time. The results showed that H2V3O8/MXene ARZBs could provide a good transport path for zinc ions, which were based on special 1D H2V3O8 nanorods and 2D multi-layered MXene materials, which exhibited an outstanding initial specific discharge capacity of 373 mA h g-1 at 200 mA g-1, good rate capability and a long lifecycle with only 15.8% capacity decay at 500 mA g-1 after 5000 cycles. The H2V3O8/MXene composites with a good electrochemical performance bring insight into their promising applications for energy storage batteries. They provided enhanced rate performance and excellent cycling stability, which was ascribed to the multi-step and multi-mode zinc ion insertion/extraction process. This was confirmed by the use of the 1D/2D integrated structure of the H2V3O8/MXene composites, which was conductive to zinc ion diffusion.

Application of Solid Polymer Electrolytes for Solid-State Sodium Batteries

Rechargeable sodium-ion batteries have become more attractive because of its advantages such as abundant sodium resources and lower costs compared to traditional lithium-ion batteries. In keeping with the future development of high-capacity secondary batteries, solid-state batteries, which use solid electrolytes instead of liquid organic electrolytes, are expected to overcome the challenges of traditional lithium-ion batteries in terms of energy density, cycle life and safety. Among various electrolytes, polymer matrices have great potential and application in flexible solid-state sodium batteries, as they can form large molecular structures with sodium salts, exhibit low flammability and excellent flexibility. But there are still challenges including low ionic conductivity, poor wettability, electrode/electrolyte interface stability and compatibility, which can limit battery performance and hinder practical applications. The preparation, benefits, and drawbacks of polymer-based solid-state sodium batteries (SSBs) are examined in this article based on an overview of solid electrolytes from the perspectives of polymer-based sodium battery materials, solid polymer electrolytes, and composition polymer electrolytes. Finally, it provides insights into the challenges and potential developments for polymer-based solid-state sodium batteries in the future.

Locally regulating Li+ distribution on an electrode surface with Li-Sn alloying nanoparticles for stable lithium metal anodes.

Despite the fact that lithium metal batteries (LMBs) have the advantage of higher energy density than traditional lithium-ion batteries (LIBs), the development of Li anodes is hindered by the issues of dendritic Li growth and parasitic reactions during cycling, which can cause a coulombic efficiency decrease and capacity decay. Herein, a Li-Sn composite anode is developed by a facile rolling method. The in situ generated Li22Sn5 nanoparticles are uniformly distributed in the Li-Sn anode after the rolling process. The Li22Sn5 nanoparticles on the surface of the electrode exhibit excellent lithiophilicity, reducing the Li nucleation barrier. Multiphysics phase simulation discloses the distribution of local current density around the holes, guiding Li preferentially to deposit back onto the sites of previous Li stripping, and then realizing a controllable plating/stripping behavior of Li on the Li-Sn composite anode. Consequently, the symmetrical cell of Li-Sn||Li-Sn achieves a stable cycling lifetime of more than 1200 h at a current density of 1 mA cm-2 with a fixed capacity of 1 mA h cm-2. Besides, the full cell pairing with the LiFePO4 cathode delivers excellent rate performance and capacity retention after long cycles. This work provides new insight to modify the Li metal for preparing dendrite-free anodes.

SnO2/h-BN nanocomposite modified separator as a high-efficiency polysulfide trap in lithium–sulfur batteries

The illustration shows that the SnO2/10%-h-BN composite coated on the separator interlayer decreases the migration of soluble polysulfides compared to the SnO2/5%-h-BN and SnO2/25%-h-BN composite coated on the separator.

In-situ polymerized electrolyte modified with oligomeric cyclotetrasiloxane for all-solid-state lithium metal batteries

High energy density and high-safety is expected for the ongoing revolution of lithium-ion batteries (LIBs). All-solid-state lithium metal batteries (ASSLMBs) are promising to break through the bottleneck of traditional liquid LIBs. However, the huge interfacial resistance between solid electrolytes and cathode is a hinder to the develop ASSLMBs. Herein, we report an in-situ polymerized solid-state electrolytes (SPE) based on oligomeric cyclotetrasiloxane (CTS) and polyethylene glycol diglycidyl ether (PEGDE) to solve this problem. CTS can provide a three-dimensional skeleton for the cross-linked SPE, which can effectively improve the properties of SPE. When the CTS content is 10 wt%, SPE exhibits a high ionic conductivity at 28 °C (0.37 mS cm−1) and a wide electrochemical stable window of 5.02 V (vs Li/Li+). Benefiting from the in-situ polymerization properties, ionic transportation at the cathode/electrolyte interface can be enhanced. Especially, the in-situ SPE exhibits outstanding compatibility against lithium metal over 600 h at a current density of 0.2 mA cm−2, the Li/SPE/LiCoO2 can deliver a capacity of 120.5 mAh g−1 at 0.05 C after 100 cycles. Our study, therefore, provides a new type of SPE to meet both interfacial and bulk conductivity requirements for ASSLMBs.

Antimony Telluride Nanocomposite As a High Performance Anode for Rechargeable Potassium-Ion Batteries

The development of high-capacity and low-cost energy storage systems are a top priority in electric vehicles and smart grids. Room temperature potassium-ion batteries (PIBs), which have the advantages of high theoretical capacity, abundant earth reserves, and low potassium costs, have recently emerged as an appealing alternative to traditional lithium-ion batteries (LIBs). In particular, finding advanced anode materials with suitable operation potential and high capacity is of significance for next-generation PIBs. In this regard, Sb-based materials have recently gained popularity as promising anode materials for batteries in terms of their suitable working potential, high density, and theoretical capacity. Among them, Sb2Te3 has a much higher density (6.66 g/cm3) than other Sb-based materials such as Sb2O3, Sb2S3, and Sb2Se3. This suggests that Sb2Te3 can have a high theoretical capacity. In addition, Te exhibits a higher conductivity than S or Se. Accordingly, the Sb2Te3 is appealing as an ideal anode for PIBs. Unfortunately, the Sb2Se3 has poor cycling stability and rate performances, which is primarily owing to the large volume change during alloying and dealloying.In this study, using a simple hydrothermal strategy, we synthesized a carbon-coated Sb2Te3 nanocomposite (Sb2Te3@C). In the novel design, the Sb2Te3@C nanocomposite is compactly encapsulated by a uniform carbon layer, which effectively relieves structural stress leading to preventing structural pulverization and stabilize the solid electrolyte interface layer. As expected with this optimal design, the Sb2Te3@C nanocomposite electrode performed nicely suitable for PIBs. In addition, the effect of the alloying/dealloying process on the crystal structure of Sb2Te3@C was investigated using in- situ/ex-situ XRD patterns recorded at various stages of discharge and charge to clarify the alloying mechanism. Furthermore, a full cell made up of a Sb2Te3@C anode and a potassium Prussian blue type cathode also exhibited successful operation.

High-rate and durable sulfide-based all-solid-state lithium battery with in situ Li2O buffering

Sulfide electrolytes (SEs)-based all-solid-state lithium batteries (ASSLBs) are advantageous over traditional lithium-ion batteries (LIBs) because of high energy density and safety. Unfortunately, the commercialization of SEs-based ASSLBs is presently hindered by interfacial instability between SEs and active materials, sluggish dynamics and poor cycling performance. Here we report, for the first time, a stable and conductive Li2O buffering coating for Ni-rich LiNi0.8Co0.1Mn0.1O2 (NCM811) in ASSLBs using SEs of Li6PS5Cl via a facile one-step sintering. We show using judiciously combined computation and experiment that Li2O buffering improves the stability of NCM811 and significantly boosts transfer of Li+. Via tuning the thickness of the Li2O buffer, we demonstrate the high initial discharge capacity of 189.66 mAh g − 1 (0.1C) and rate capability of 61.71 mAh g − 1 (3C), together with outstanding long-term cycling performance of ∼ 2600 cycles at 1C with capacity retention of 81.47%, and Coulombic efficiency of 99.9%. We conclude that conductive Li2O buffering can be used to obviate interfacial instability between SEs and active materials and to boost dynamics and cycling performance. Findings will be of immediate benefit to a range of researchers in design for high-performance ASSLBs for practical application and commercialization.

Recent progress of solid-state lithium batteries in China

Different from traditional lithium-ion battery, the solid-state lithium batteries (SSLBs) using solid electrolytes (SEs) have attracted much attention for their potential of high safety, high energy density, good rate performance, and wide operating temperature range in recent years. In China, the SSLB-relevant fundamental research and industrialization exploration are progressing rapidly. In this perspective, we present a timely overview of the recent research and development of SSLBs in China in the past 1 year, covering the latest achievements of SSLBs which used sulfide SEs, oxide SEs, solid polymer electrolytes, and halide SEs, respectively. Moreover, the government policies and the latest company industrialization process relative to SSLBs are comprehensively summarized.