High-performance Li-ion Batteries Research Articles

Ultrathin composite Al2O3/LiAlO2 coating on truncated octahedral shape Co-free LiNi0.5Mn1.5O4 for enable high performance Li-ion battery

The Co-free cathode material of spinel LiNi0.5Mn1.5O4 (LNMO) has gained much interest for next-generation batteries owing to its 3D ionic channel for fast Li+ ion diffusion and high voltage operation. In this work, ultrathin composite Al2O3/LiAlO2 is adopted to modify truncated octahedral shape Fd3¯m spinel LNMO. It is found that 1 wt% Al coating modification exhibits the most excellent cycling performances, providing great capacity retention of 84.99 % for 350 cycles between 3.5 and 4.8 V at 1C. The homogeneous composite Al2O3/LiAlO2 coating on the truncated octahedral shape particle can deliver high rate capability of 40 mAh/g at 20C, charging and discharging. In addition, the ultrathin composite Al2O3/LiAlO2 coating can provide a stable interface, producing a high capacity retention of 94.82 % after 100 cycles at 45 °C. High performances of truncated octahedral shape Fd3¯m LNMO by composite Al2O3/LiAlO2 coating can enhance the safety and increase the potential applications of these cathode materials in the next-generation batteries.

A like-bulletproof glass structure flexibility-rigidity coating layer strategy for high-performance Li ion batteries Si anodes

In order to overcome the problems about the volume expansion and poor electronic conductivity of Si, a flexibility and rigidity double coating layer CNTs-rGO- PAIN was constructed. The CNTs-rGO-PANI network with porous structure and high electronic conductivity provides sufficient space to accommodate the volume change of Si, and abundant transmission path for electron and Li ion. Moreover, the coating network with flexibility and rigidity characteristic could absorb the expansion stress of Si, maintain electrode structural integrity, promote the growth of stable SEI. The polymer-nanocarbon network dual coating layer effectively safeguards the electrochemical-mechanical interplay within the electrode. The 20Si-CNTs-rGO-PANI exhibits a reversible capacity as high as 1856 mAh g−1 after 400 cycles at 0.2 A g−1 and a remarkable rate capacity of 570 and 459 mAh g−1, at 5 and 10 A g−1, respectively. The outstanding Li ion storage performance of 20Si-CNTs-rGO-PANI anode, suggests the flexibility-rigidity dual coating layer strategy is a potential way to improve the performance of alloy type anode.

Electrolyte Design Chart Reframed by Intermolecular Interactions for High-Performance Li-Ion Batteries.

Developing advanced electrolytes has been regarded as a pivotal strategy for enhancing the electrochemical performance of batteries; however, the criteria for electrolyte design remain elusive. In this study, we present an electrolyte design chart reframed through intermolecular interactions. By combining systematic nuclear magnetic resonance, Fourier transform infrared measurements, molecular dynamics (MD) simulations, and machine-learning-assisted classifications, we establish semiquantitative correlations between electrolyte components and the electrochemical reversibility of electrolytes. We propose the equivalent increment of Li salt resulting from functional cosolvent and solvent-solvent interactions for effective electrolyte design and prediction. The controllable regulation of the electrolyte design chart by the properties of solvent-solvent interactions presents varying equivalent effects of increasing Li salt concentrations in different electrolyte systems. Based on this mechanism, we demonstrate highly reversible and nonflammable phosphate-based electrolytes for graphite||NCM811 full cells. The proposed electrolyte design chart, semiquantitatively determined by intermolecular interactions, provides the necessary experimental foundation and basis for the future rapid screening and prediction of electrolytes using machine-learning methods.

Well-dispersed Sb particles embedded on N-doped carbon nanofibers toward high-performance Li-ion battery

Well-dispersed Sb particles embedded on N-doped carbon nanofibers toward high-performance Li-ion battery

Unlocking the power of lithium trifluoride, LiMF3 (M = Mn, Co, Fe, Ni, and V), materials through DFT: a paradigm shift in electrode candidates for high-performance Li-ion batteries

Unlocking the power of lithium trifluoride, LiMF3 (M = Mn, Co, Fe, Ni, and V), materials through DFT: a paradigm shift in electrode candidates for high-performance Li-ion batteries

Synergistic construction of uniform LiAlO2 coating on LiNi0.8Co0.1Mn0.1O2 cathode materials by acid etching and polyvinylpyrrolidone cross-linking approaches for high-performance Li-ion batteries

A uniform and conductive LiAlO2 coating on the LiNi0.8Co0.1Mn0.1O2 cathode material was successfully constructed by the synergistic effects of acid etching and polyvinylpyrrolidone (PVP) cross-linking approaches. Hydrolysis of Al sources (Al(NO3)3) generates H+ ions to etch the inert surfaces of hydroxide precursors, which leaves highly active sites exposed on the Ni0.8Co0.1Mn0.1(OH)2 surfaces for subsequent coating. Furthermore, PVP polymeric chains act as cross-linkers to anchor Al(OH)3 onto the highly active Ni0.8Co0.1Mn0.1(OH)2 surfaces for the formation of uniform LiAlO2 coating layers after chemical lithiation of calcination. The synergistically constructed LiAlO2 coating layers could effectively reduce the gas production and improve the cycling stability of the LiNi0.8Co0.1Mn0.1O2 cathode materials with a high reversible capacity of 212.0 mAh g−1 at 0.1 C for the initial cycle and 172.3 mAh g−1 at 1 C for the 200th cycle.

A Macromolecule Cathode for High-Performance Li-Ion and Na-Ion Batteries

A Macromolecule Cathode for High-Performance Li-Ion and Na-Ion Batteries

Bi-Directional H-Bonding Modulated Soft/Hard Polyethylene Glycol-Polyaniline Coated Si-Anode for High-Performance Li-Ion Batteries.

Ultrahigh-capacity silicon (Si) anodes are essential for the escalating energy demands driven by the booming e-transportation and energy storage field. However, their practical applications are strictly hampered by their intrinsically low electroconductivity, sluggish Li-ion diffusion, and undesirably large volume change. Herein, a high-performance Si anode, comprised of a modulated soft/hard coating of polyethylene glycol (PEG) (as Li-ion conductor) and polyaniline (PANI) (as electron conductor) on the surface of Si nanoparticles (NPs) through H-bonding network, is introduced. In this design, the abundant ─OH groups of soft PEG allow it to uniformly cover Si NPs while the hard PANI binds to PEG through its ─N─H group, thus constructing a tight connectin between Si and PEG-PANI (PP). Consequently, the elastic PP allows Si@PP to accommodate the huge volume expansion while possessing fine electronic/ionic conductivity. Therefore, the Si@PP anode exhibits a high initial Coulombic efficiency of 90.5% and a stable capacity of 1871mAhg-1 after 100 cycles at 1Ag-1 with a retention of 85.7%. Additionally, the Si@PP anode also demonstrates a high areal capacity of 3.01mAhcm-2 after 100 cycles at 0.5Ag-1 . This work reveals a scalable interface design of multi-layer multifunctional coatings for high-performance electrode materials in next-generation Li-ion batteries.

High-performance solid-state Li-ion batteries enabled by homogeneous, large-area ferroelectric PVDF-TrFE solid polymer electrolytes via horizontal centrifugal casting method

Solid polymer electrolytes (SPEs) have emerged as promising alternatives for enhancing the safety features of lithium-ion batteries (LIBs) while remaining compatible with established LIB manufacturing processes. However, a persistent challenge has been the relatively limited yield achieved via traditional fabrication techniques such as solution casting and doctor blade methods. In this study, we present a novel strategy to produce extensive and uniform films of solid polymer electrolytes using a ferroelectric polyvinylidene fluoride-trifluoroethylene (PVDF-TrFE) polymer. This approach employs horizontal centrifugal casting (HCC), a technique hitherto unutilized for SPE production. The substantial centrifugal forces generated during the HCC process yield SPE films characterized by uniform thickness across the surface and elevated ionic conductivity at ambient temperature. Compared to conventional solution casting techniques, the Li//Li cell featuring the SPE derived from HCC manifests stable electrochemical performance and increased cycle endurance. Additionally, a full cell incorporating a Li iron phosphate cathode displays consistent electrochemical behavior at room temperature. Notably, a 3 × 4 cm2 pouch cell maintains its performance attributes even under mechanical stress conditions such as folding and punching. These findings underscore the potential effectiveness of employing the HCC method in the development of high-performance SPE-based LIB systems.

F-doped Co-free LiNixMn1-xO2 (0.7 ≤ x ≤ 0.9) cathodes for ameliorating electrochemical performance of Li-ion batteries

Ni-rich LiNiCoMnO2 cathodes, which exhibit high energy densities and layered structures, have been studied For Li-ion batteries (LIBs) with high capacities and excellent stabilities. However, the high cost and price fluctuation of Co as the main element in the cathodes remain severe issues for the stable development of LIBs. Therefore, in this study, F-doped Co-free Ni-rich LiNixMn1-xO2 (0.7 ≤ x ≤ 0.9) cathodes were prepared for high-performance LIBs. With increasing Ni content, the undoped Ni-rich LiNixMn1-xO2 cathodes exhibited increased discharge capacities and decreased stabilities. In contrast, the F-doped Ni-rich LiNixMn1-xO2 cathodes delivered higher cycle retentions at 0.5 C for 100 cycles compared to the undoped cathodes. In addition, the F doping of Ni-rich LiNixMn1-xO2 cathodes can facilitate Li-ion diffusion, retaining their reversibility and high capacities at high current densities.

Robust chemo-mechanical stability of additives-free SiO2 anode realized by honeycomb nanolattice for high performance Li-ion batteries

Silicon-based anodes including Si, SiOx and SiO2 could deliver ultra-large capacities, but degrade fast owing to huge volume change and low conductivity. Generally, large amounts of elastic binder and conductive additives were composited with nanosized silicon-based materials to yield reasonable cycling stability, which nevertheless not only decrease specific capacity but also induce inhomogeneous lithiation/delithiation as well as uneven stress variations. Artificial nanolattice has exhibited superior mechanical properties which could be ideal structure for silicon-based anodes, but yet faces challenges in integration of chemical reactivity, conductivity and mechanical stability. Herein, we fabricate artificial SiO2 honeycomb nanolattice consisting of numerous nanoscale SiO2 cells interconnected by through-holes, and conformal coating of highly graphitic carbon on the nanolattice is achieved through in situ catalytic graphitization. Moreover, the nanolattice is firmly bonded on Cu substrate through atomic interdiffusion irrespective of surface roughness. This unique structure allows fast charge transportation and homogeneous lithiation/delithiation throughout the micron-meter nanolattice, which results in excellent stability and large reversible capacity over 500 cycles at 1 A/g. The results highlight design and constructing artificial nanolattice can be an effective way to prevent chemo-mechanical degradation of silicon-based anode materials.

Electrophoretic deposition of graphene oxide as a stabilizing layer on the Ni-rich layered oxide electrodes for enhancing the cycling stability of Li-ion cathodes

One of the critical challenges for layered Ni-rich cathode material is the surface degradation caused by the parasitic reaction between the cathode material and the organic electrolytes. Herein, we develop an overall electrode modification strategy to improve the cathode surface's structural stability by integrating graphene oxide (GO) coating on the surface of the cathode electrode with the assistance of the electrophoretic deposition technique (EPD). The attenuated total reflectance (ATR) and scanning electron microscope (SEM) results confirm the formation of the uniform thin GO layer on the surface of the Ni-rich cathode. The electrochemical studies such as galvanostatic charge-discharge, galvanostatic intermittent titration Technique (GITT), and incremental capacity analysis (ICA) tests show that the existence of thin layers of GO not only does not hinder the intercalation of Li+ ions but also can facilitate the charge transfer and intercalation of Li+ ions by decreasing the charge transfer resistance of the electrode. The cycling stability of the cathode coated with GO in 30 s of EPD shows better performance over 150 charge-discharge cycles and lower Rct than the pristine electrode. Our work provides a design idea for stabilizing the surface/bulk structure of advanced Ni-rich cathode for high-performance Li-ion batteries.

ZnO-PANI nanocomposite: Enhanced electrochemical performance towards energy storage

In the present investigation a novel nanocomposite composed of Polyaniline (PANI) and Zinc Oxide (ZnO) has been evaluated for its structural, morphological, and electrochemical properties for its application as high-performance Li-ion battery electrode. The X-ray diffraction (XRD) and Furrier transform infrared (FTIR) spectral analysis confirmed the synthesis of ZnO-PANI nanocomposite. The Field emission- scanning electron microscopy (FE-SEM) images confirmed the uniform distribution of ZnO nanoparticle in PANI matrix, while BET surface area analysis revealed a narrow mesoporous pore distribution with high surface area, enhancing its potential for energy storage. The electrochemical assessment using CR2032 coin cells showcased the remarkable performance of the ZnO-PANI nanocomposite as an electrode material for energy storage. Cyclic voltammetry (CV) analysis revealed distinct reduction and reformation peaks related to ZnO and Li+ insertion into the PANI matrix. The nanocomposite displayed a high specific capacity, with an initial discharge capacity of 1052 mA h g−1, followed by stable performance in subsequent cycles. Notably, Coulombic efficiency consistently exceeded 98 % from the 10th cycle, demonstrating excellent performance. The rate capability was equally impressive, delivering discharge capacities from 1052 mA h g−1 at 0.1C to 771 mA h g−1 at 2C. Long-term cycling tests illustrated exceptional capacity retention, with 92.99 % capacity retained after 500 cycles and outstanding Coulombic efficiency consistently above 99 %. In conclusion, the ZnO-PANI nanocomposite exhibits desirable structural and morphological attributes, exceptional electrochemical performance, and potential for advanced energy applications, particularly in Li-ion batteries.

Electrochemical elucidation of phosphorus-doped and 3D graphene aerogel surface-modified SiOx porous nanocomposite electrode material for high-performance lithium-ion batteries

Silicon oxide (SiOx) is promising as an earth abundant eco-friendly cost-effective anode material for lithium-ion batteries (LIBs), boasts a higher capacity compared to commercial graphite, garnering significant interest. Nevertheless, its practical application is hindered by issues related to poor cycling performance and low electronic conductivity. In this investigation, graphene aerogel-wrapped (GA) red phosphorus (P) doped SiOx (P-SiOx@GA) composite material is successfully constructed through ball-milling followed by freeze-drying and thermal treatment processes. The prepared materials are characterized the physico-chemical properties. The electrochemical performance is evaluated through Li-ion half and full (LiFePO4//P-SiOx@GA) cells configuration. The synthesized P-SiOx@GA electrode exhibits outstanding cyclic performance, demonstrating a specific capacity of 1094 mAh g−1 at 0.5C with a capacity retention of 80.3 % over 200 cycles in half-cell test. Furthermore, it demonstrates superior rate capability and delivers a reversible rate capacity of 754 mAh g−1 at 2C. Besides, the Li-ion punch cell configuration of LiFePO4//P-SiOx@GA shows good reversible capacity of 1.4 mAh at 0.5C over 300 cycles. The doping of P and porous 3D structure of GA forms an SiOx matrix network is facilitate the establishment of a 3D conductive pathway for electron transport and Li+ diffusion but also acts as a flexible matrix to accommodate the volume changes of SiOx. Therefore, the results and way of preparation promotes a practical feasibility of high-performance Si-based Li-ion batteries applications.

Spray-assisted synthesis of ant-cave-structured Ni-rich cathode microspheres with Li-reactive coating layer for high-performance Li-ion batteries

In this study, a spray-assisted synthetic method for preparation of Ni-rich Li [NixCoyMn1-x-y]O2 (NCM) cathode microspheres is introduced. Unlike the co-precipitation method, which necessitates pH control, the use of complexing agent, and further lithiation step, the spray-assisted approach can produce Li-containing precursors with homogeneous elemental distribution in a few seconds. To overcome the high energy density loss arising from the morphological traits of the hollow/porous microspheres produced from the spray process, a two-step spraying methodology is adopted. Planetary ball milling efficiently pulverizes the spray-pyrolyzed product, which is then dispersed in an aqueous solution to form colloids. Spray drying and subsequent oxidation of the colloidal solution yield ant-cave-structured NCM microspheres with fine primary particles. By simply changing the stoichiometry of the metal salts dissolved in the aqueous solution, NCM cathodes with the desired composition (NCM622 and NCM811) are obtained. Additionally, a Li-reactive coating layer is introduced on the surface of the fine particles comprising NCM microspheres by a 10-min gas-phase coating method. The delicate design of NCM622 cathode with a coating layer enables stable cycle performance (capacity retention of 82.0 % after the 150th cycle) and high rate capability (136.8 mA h g−1 at 10 C) when operated under high-voltage conditions (2.5–4.5 V).

Ultrafast, in-situ Transformation of Protective Layer on Lithium-Rich Manganese-Based Layered Oxides for High-performance Li-ion Batteries

Ultrafast, in-situ Transformation of Protective Layer on Lithium-Rich Manganese-Based Layered Oxides for High-performance Li-ion Batteries

An in-situ bicomponent polymeric matrix solid electrolyte for solid-state Lithium metal batteries with extended cycling-life

The utilization of ceramic-polymer hybrid electrolytes has gained popularity in the development of all-solid-state lithium batteries that are capable of high-energy and long-lasting performance. This research presents a novel dual hybrid in-situ solid electrolyte membrane (iHSE) that is tailored for high-performance Li-ion batteries, consisting of LATP and PVDF-HFP. The hybrid membrane is comprised of LATP particles and PVDF-HFP with PEG polymer matrix (HSE), and the migration of Li+ ions in LATP particles was simulated through molecular dynamics. At a temperature of 40 °C, the hybrid membrane demonstrates an ionic conductivity of 7.36 × 10−4 S·cm−1 and a lithium-ion migration number of 0.61. The interface between the cathode and electrolyte membrane is effectively enhanced through in situ polymerization with the resulting all-solid-state lithium battery exhibits a reversible discharge capacity of 160 mAh·g−1 at a current density of 0.1C multiplier at ambient temperature and can function normally for over 1000 cycles of charge and discharge at 1C multiplier. Moreover, the discharge capacity trend exhibits greater uniformity in comparison to a battery lacking interface enhancement.

Projection Micro Stereolithography of Skin Layered Microporous Polymer Membranes As a Separator for Li-Ion Batteries

Commercial liquid electrolyte lithium-ion batteries (LIBs) traditionally incorporate microporous polymer membranes, or separators, to isolate electrode contact and enable ionic transport. Although they do not actively participate in cell chemistry, well-designed separators can influence cell performance and safety, and thus, are essential components of a cell. Current separator manufacturing processes include "wet" or "dry" mechanical stretching , phase inversion, and evaporation-induced phase separation. However, these processes have limited morphological control of geometry and layered structures. Additive manufacturing techniques have been used to rapidly prototype materials that have both high customizability and fine microstructural control. We investigate hexanediol diacrylate (HDDA) as a polymer system using projection micro-stereolithography, a layer-by-layer photopolymerization technique, to develop separators with controlled microstructures for Li-ion batteries. We successfully fabricate a unique polymer architecture of alternating nanometer thin skin layers and microporous network. The fine control of printing parameters (i.e., printing platform, skin layers, and exposure time), results in tunable porosity and morphology. This unique approach to manufacturing LIB separators provides hierarchical homogeneity for more uniform Li-ion transport. It’s potential as a LIB separator is explored by characterizing its electrolyte wettability, thermal tolerance, electrochemical properties, and mechanical stability. Finally, lithium symmetric cells using the HDDA microporous membranes are evaluated against Celgard 2325 separators. This work provides a promising new route for developing separators using additive manufacturing techniques to enable high performance Li-ion batteries.

Cost-Effective Milled Silicon and Exfoliated Graphene Anode for High-Performance Li-Ion Batteries

Lithium-ion batteries play a significant role in modern electronics and electric vehicles. However, current lithium-ion battery chemistries are unable to satisfy the increasingly heightened expectations regarding energy demand and reliability. To boost the overall energy density while ensuring the safety of Li batteries, researchers have focused on developing the battery materials [1]. Silicon has an ultrahigh theoretical capacity and has been regarded as the best choice for next-generation lithium-ion battery anodes, but it also suffers from dramatic expansion during cycling [2]. Hence mitigating volume expansion is one of the main challenges towards developing a successful Si based anodes. Herein, a facile air-controlled electrospray method to directly deposit silicon/graphene (Si/Gr) onto current collectors was described. This method is inspired by an electrospinning process and possesses all the advantages that electrospinning has such as low cost, easy scaling up, and simultaneous solvent evaporation during the spraying process. Cost-effective silicon/graphene (Si/Gr) composite electrodes have been investigated for the multiple benefits of Gr in providing mechanical integrity to buffer the silicon volume expansion while maintaining electronic contact with Si to provide a Li-ion transport pathway and to form a uniform solid electrolyte interface (SEI) layer. Our results revealed a superior battery performance including a capacity of 1000 mAh/g at 2C rates and minor capacity loss during long cycling. The details of synthesis, characterization, and lithium-ion battery results of the hybrid anodes will be presented.

Microstructural Refinement and Surface Modification of Ni-Rich Cathodes for High-Performance Li-Ion Battery

Li[Ni1–x–y–zCoxMnyAlz]O2 (NCMA) cathodes have attracted public attention owing to their improved durability by leveraging the advantages of NCM and NCA cathodes. The combination of Mn and Al in a NCMA cathode effectively stabilizes the host layered structure to increase its resistance to microcracking; consequently, NCMA cathodes outperform both NCM and NCA cathodes with the same Ni contents, in terms of cycle life, without sacrificing energy density. However, as the Ni contents of the cathodes exceed 90%, a simple, compositionally engineered NCMA cathode lacks the chemical and mechanical stability to suppress surface degradation and the development of permanent microcracks due to the high incidence of highly reactive Ni4+ species on its surface.1,2 Considering the limitations of NCMA cathodes, a combination strategy involving microstructural engineering to inhibit microcracking, by enabling the efficient dissipation of local strain,3 and the modification of the exposed cathode surface, to protect it against deleterious electrolyte attack, is expected to afford superior Ni-rich layered cathodes.In this study, we improved the cycling stability of a conventional NCMA cathode with a Ni content of 93% (a NCMA93 cathode) using a combination strategy involving microstructural engineering and surface modification. To this end, we prepared a Sb-doped NCMA93 (denoted as Sb-NCMA93) cathode; Sb was incorporated to refine its microstructure and radially align and elongate its primary particles. Furthermore, we generated a protective F layer on the cathode surface through a chemical reaction between residual lithium compounds and a NH4F coating agent. To comprehensively investigate the synergetic effect of this combination strategy, conventional and Sb-doped NCMA93 cathodes with and without F coatings were synthesized and characterized and their fundamental properties and electrochemical performances compared. Post-mortem analyses were performed to elucidate the origins of the remarkable long-term cycling stability of the optimized cathodes. Reference s : [1] H.-J. Noh, S. Youn, C. S. Yoon, Y.-K. Sun, J. Power Sources, 2013, 233, 121.[2] H.-H. Ryu, K.-J. Park, C. S. Yoon, Y.-K. Sun, Chem. Mater. 2018, 30, 1155.[3] U.-H. Kim, H.-H. Ryu, J.-H. Kim, R. Mücke, P. Kaghazchi, C. S. Yoon, Y.-K. Sun, Adv. Energy Mater. 2019, 9, 1803902.