High-capacity Lithium-ion Batteries Research Articles

Cross-linking γ-Polyglutamic Acid as a Multifunctional Binder for High-Performance SiOx Anode in Lithium-Ion Batteries.

SiOx is a highly promising anode material for realizing high-capacity lithium-ion batteries owing to its high theoretical capacity. However, the large volume change during cycling limits its practical application. The development of a binder has been demonstrated as one of the most economical and efficient strategies for enhancing the SiOx anode's electrochemical performance. In this work, a multifunctional binder (T-PGA) is fabricated by cross-linking γ-polyglutamic acid (PGA) and tannic acid (TA) for SiOx anodes. The introduction of TA into PGA helps to buffer the volume changes of the SiOx anodes, facilitate diffusion of Li+, and construct stable SEI layers. Benefiting from this proposed binder, the SiOx anode maintains a reversible capacity of 973.0 mAh g-1 after 500 cycles at 500 mA g-1 and the full cell, pairing with LiNi0.5Co0.2Mn0.3O2 cathode, delivers a reversible capacity of 133 mA h g-1 (73.2% retention) after 100 cycles. This study offers valuable insights into advanced binders that are used in high-performance Li-ion batteries.

Extending the π-Conjugation of a Donor-Acceptor Covalent Organic Framework for High-Rate and High-Capacity Lithium-Ion Batteries.

Realizing high-rate and high-capacity features of Lihium-organic batteries is essential for their practical use but remains a big challenge, which is due to the instrinsic poor conductivity, limited redox kinetics and low utility of organic electrode mateials. This work presents a well-designed donor-acceptor Covalent Organic Framework (COFs) with extended conjugation, mesoscale porosity, and dual redox-active centers to promote fast charge transfer and multi-electron processes. As anticipated, the prepared cathode with benzo [1,2-b:3,4-b':5,6-b''] trithiophene (BTT) as p-type and pyrene-4,5,9,10-tetraone (PTO) as n-type material (BTT-PTO-COF) delivers impressive specific capacity (218 mAh g-1 at 0.2 A g-1 in ether-based electrolyte and 275 mAh g-1 at 0.2 A g-1 in carbonate-based electrolyte) and outstanding rate capability (79 mAh g-1 at 50 A g-1 in ether-based electrolyte and 124 mAh g-1 at 10 A g-1 in carbonate-based electrolyte). In addition, the potential of BTT-PTO-COF electrode for prototype batteries has been demonstrated by full cells of dual-ion (FDIBs), which attain comparable electrochemical performances to the half cells. Moreover, mechanism studies combining ex situ characterization and theoratical calculations reveal the efficient dual-ion storage process and facile charge transfer of BTT-PTO-COF. This work not only expands the diversity of redox-active COFs but also provide concept of structure design for high-rate and high-capacity organic electrodes.

Remaining useful life prediction of high-capacity lithium-ion batteries based on incremental capacity analysis and Gaussian kernel function optimization

Remaining useful life (RUL) is a key indicator for assessing the health status of lithium (Li)-ion batteries, and realizing accurate and reliable RUL prediction is crucial for the proper operation of battery systems. As high-capacity Li batteries have more complex chemical properties, most of the current RUL prediction methods rely mainly on a priori knowledge to make judgments. As a result, prediction accuracy is not high. In this study, we developed a health indicator-capacity (HI-C) dual Gaussian process regression (GPR) model based on incremental capacity analysis (ICA) and optimized its kernel function to achieve accurate RUL prediction for 280 Ah high-capacity Li batteries. Validation against the United States National Aeronautics and Space Administration’s four battery test datasets showed that the use of the HI-C dual GPR model resulted in a mean absolute percentage error and root mean square error of less than 0.02 and 0.04, respectively, for the four battery-rated capacity predictions. Additionally, this model achieved an absolute error of less than five battery failure turns. Compared with a single model, the HI-C dual GPR model not only had high accuracy but also solved the problem that the HI was not measurable in the actual battery operation, which made it more suitable for RUL prediction of Li batteries.

Enhancing Electrochemical Performance of Si@CNT Anode by Integrating SrTiO3 Material for High-Capacity Lithium-Ion Batteries

Silicon (Si) has attracted worldwide attention for its ultrahigh theoretical storage capacity (4200 mA h g−1), low mass density (2.33 g cm−3), low operating potential (0.4 V vs. Li/Li+), abundant reserves, environmentally benign nature, and low cost. It is a promising high-energy-density anode material for next-generation lithium-ion batteries (LIBs), offering a replacement for graphite anodes owing to the escalating energy demands in booming automobile and energy storage applications. Unfortunately, the commercialization of silicon anodes is stringently hindered by large volume expansion during lithiation–delithiation, the unstable and detrimental growth of electrode/electrolyte interface layers, sluggish Li-ion diffusion, poor rate performance, and inherently low ion/electron conductivity. These present major safety challenges lead to quick capacity degradation in LIBs. Herein, we present the synergistic effects of nanostructured silicon and SrTiO3 (STO) for use as anodes in Li-ion batteries. Si and STO nanoparticles were incorporated into a multiwalled carbon nanotube (CNT) matrix using a planetary ball-milling process. The mechanical stress resulting from the expansion of Si was transferred via the CNT matrix to the STO. We discovered that the introduction of STO can improve the electrochemical performance of Si/CNT nanocomposite anodes. Experimental measurements and electrochemical impedance spectroscopy provide evidence for the enhanced mobility of Li-ions facilitated by STO. Hence, incorporating STO into the Si@CNT anode yields promising results, exhibiting a high initial Coulombic efficiency of approximately 85%, a reversible specific capacity of ~800 mA h g−1 after 100 cycles at 100 mA g−1, and a high-rate capability of 1400 mA g−1 with a capacity of 800 mA h g−1. Interestingly, it exhibits a capacity of 350 mAh g−1 after 1000 lithiation and delithiation cycles at a high rate of 600 mA hg−1. This result unveils and sheds light on the design of a scalable method for manufacturing Si anodes for next-generation LIBs.

Enhancing micro-scale SiOx anode durability: Electro-mechanical strengthening of binder networks via anchoring carbon nanotubes with carboxymethyl cellulose

With the increasing prevalence of lithium-ion batteries (LIBs) applications, the demand for high-capacity next-generation materials has also increased. SiOx is currently considered a promising anode material due to its exceptionally high capacity for LIBs. However, the significant volumetric changes of SiOx during cycling and its initial Coulombic efficiency (ICE) complicate its use, whether alone or in combination with graphite materials. In this study, a three-dimensional conductive binder network with high electronic conductivity and robust elasticity for graphite/SiOx blended anodes was proposed by chemically anchoring carbon nanotubes and carboxymethyl cellulose binders using tannic acid as a chemical cross-linker. In addition, a dehydrogenation-based prelithiation strategy employing lithium hydride was utilized to enhance the ICE of SiOx. The combination of these two strategies increased the CE of SiOx from 74% to 87% and effectively mitigated its volume expansion in the graphite/SiOx blended electrode, resulting in an efficient electron-conductive binder network. This led to a remarkable capacity retention of 94% after 30 cycles, even under challenging conditions, with a high capacity of 550 mA h g−1 and a current density of 4 mA cm−2. Furthermore, to validate the feasibility of utilizing prelithiated SiOx anode materials and the conductive binder network in LIBs, a full cell incorporating these materials and a single-crystalline Ni-rich cathode was used. This cell demonstrated a ∼27.3% increase in discharge capacity of the first cycle (∼185.7 mA h g−1) and exhibited a cycling stability of 300 cycles. Thus, this study reports a simple, feasible, and insightful method for designing high-performance LIB electrodes.

2d van der Waal SiC/borophene heterostructure as a promising anode for high-capacity Li ion battery: First principles study

We constructed SiC/borophene heterostructure based on the method of commensurate lattice with supercell approach and studied the structural, electronic and electrochemical properties using density functional theory (DFT). The interfacial binding energy of SiC/borophene is as high as −26.07 meV/Å2. Significant amounts of charge were found to drift from SiC to borophene, resulting in interfacial charge redistribution and increased Li binding affinity on the surfaces. The electronic properties of SiC/borophene showed pronounced metallic conductivity, a trait conducive to anodic applications in electrochemical cells. The calculated Li adsorption energy at the interface of SiC/borophene is −2.23 eV. Multiple layer adsorption is also observed, with the heterostructure retaining much of its structural integrity after adatom adsorption, indicating possible good cycling stability. At the maximum concentration, the Li storage capacity for SiC/borophene is 1980.63 mAh/g, surpassing a large variety of other reported 2D complexes. Also, an overall average operating voltage of 1.06 V is maintained in the structure, which is in proximity of the optimal 1.5 V threshold requisite for anodic operations. The diffusion energy barriers associated with lithium ion migration across the three distinct adsorption sites of the heterostructure all reveal a nominal magnitude with the lowest barrier energy of 0.54 eV at the top of borophene adsorption layer and site. These findings show that SiC/borophene could be used as an anode in very high-capacity lithium-ion batteries.

Tin-Antimony Oxide-Graphite Composite as Anode Material with high Capacity for Lithium-Ion Batteries

Tin-Antimony Oxide-Graphite Composite as Anode Material with high Capacity for Lithium-Ion Batteries

An optimized quantum particle swarm optimization–extended Kalman filter algorithm for the online state of charge estimation of high-capacity lithium-ion batteries under varying temperature conditions

An optimized quantum particle swarm optimization–extended Kalman filter algorithm for the online state of charge estimation of high-capacity lithium-ion batteries under varying temperature conditions

Anisotropic, free-standing anodic films with aligned anatase-bronze TiO2-integrated graphene for high-capacity lithium-ion batteries

The composition modification and structure manipulation of carbon-based battery electrodes is becoming an increasingly urgent need for safer, more reliable, and effective electric vehicles. Herein, we fabricate a free-standing hybrid anatase-bronze TiO2-grafted reduced graphene oxide (TiO2-rGO) through a one-pot solvothermal procedure. The TiO2-rGO composite was transformed into a film with an anisotropic alignment and assembled as an anode into lithium-ion batteries (LIBs) to enhance its performance. Our previously developed “Pulse Freezing” process, with modifications including: (1) dimensional and structural optimization for larger and faster film production and (2) optimal microfluidic condition for vertical porous alignment, is utilized for assembling this nanocomposite anodic film. During the microfluidic assembly process, we achieved the desirable flowrate, flow patterns, and alignments of the integrated TiO2-rGO layers while forming porous microstructures through freeze drying. The porous and aligned TiO2-integrated rGO film exhibits a significantly enhanced specific capacity of 400 mAh/g at 0.2 A/g, which is a drastic increase compared to traditional TiO2 and carbon black electrodes possessing <50 mAh/g capacity, attributed to the anisotropic alignment and porous microstructure of rGO in combination with TiO2 grafting. The developed TiO2-rGO composite film provides a promising application of Ti-based electrodes in LIBs for commercial battery industries.

Advancing Lithium-Ion Batteries' Electrochemical Performance: Ultrathin Alumina Coating on Li(Ni0.8Co0.1Mn0.1)O2 Cathode Materials.

Ni-rich Li(NixCoyMnz)O2 (x ≥ 0.8)-layered oxide materials are highly promising as cathode materials for high-energy-density lithium-ion batteries in electric and hybrid vehicles. However, their tendency to undergo side reactions with electrolytes and their structural instability during cyclic lithiation/delithiation impairs their electrochemical cycling performance, posing challenges for large-scale applications. This paper explores the application of an Al2O3 coating using an atomic layer deposition (ALD) system on Ni-enriched Li(Ni0.8Co0.1Mn0.1)O2 (NCM811) cathode material. Characterization techniques, including X-ray diffraction, scanning electron microscopy, and transmission electron microscopy, were used to assess the impact of alumina coating on the morphology and crystal structure of NCM811. The results confirmed that an ultrathin Al2O3 coating was achieved without altering the microstructure and lattice structure of NCM811. The alumina-coated NCM811 exhibited improved cycling stability and capacity retention in the voltage range of 2.8-4.5 V at a 1 C rate. Specifically, the capacity retention of the modified NCM811 was 5%, 9.11%, and 11.28% higher than the pristine material at operating voltages of 4.3, 4.4, and 4.5 V, respectively. This enhanced performance is attributed to reduced electrode-electrolyte interaction, leading to fewer side reactions and improved structural stability. Thus, NCM811@Al2O3 with this coating process emerges as a highly attractive candidate for high-capacity lithium-ion battery cathode materials.

Battery Performance Evaluation through Decision Tree

This study addresses the pervasive concern surrounding battery performance degradation in electronic devices. While some attribute this decline to device aging, a significant portion of the population lacks awareness of the precise factors contributing to diminished battery efficiency. Consequently, the research investigates the factors related to battery performance, aiming to identify the determinants of reduced efficiency. Decision trees are used to meticulously analyze the intricate relationships between variables and discern the factors that respondents perceive as causative of diminished battery performance. This algorithm is chosen since, in predicting high-capacity lithium-ion battery performance, the decision tree outperforms other algorithms in machine learning in accuracy. The study elucidates diverse user preferences, with 55.38% favoring Android and 44.62% expressing a preference for iOS, indicating disparate perceptions of battery health: 61.54% consider their batteries as "Good," while 38.46% acknowledge a decline. The decision tree analysis of 195 participants underscores the pronounced impact of prolonged usage on battery health, revealing that 95% maintain good battery performance. In contrast, 27.69% of Android users face reduced battery performance, emphasizing the need for targeted user education and Android manufacturers to prioritize device longevity. The ultimate objective is to give readers a comprehensive understanding of the dynamics of battery performance in the context of device aging and its contributing factors and give some input to manufacturers and service providers.

A three-dimensional Ge@C anode with a hollow and micro/nano structure for high-capacity lithium-ion battery

Aiming at the key issues of low intrinsic conductivity and large volume expansion during the cycling existed in high-capacity Ge anode material system, a micro/nano structured Ge@C hybrid material was designed and prepared through a facile and controllable method. The as-prepared micron conductive cage with a dodecahedral structure is composed of interconnected ultra-thin walled Ge nanotubes encapsulated in the porous N-containing carbon network, which can not only reserve more buffer space for the volume expansion of Ge and assist in building a stable SEI film during the cycling, improves the conductivity and stability of the material, but also provide a rich and penetrating channel for the transmission of ions, realizing high dynamics. When applied to the anode of lithium-ion battery, the three-dimensional micro/nano structured germanium-based hybrid material (Ge-3D@C) delivers a high initial specific capacity of 1500 mAh g−1 at 0.2 A g−1, and after 350 cycles, it can still maintain a high reversible specific capacity of 1147 mAh g−1. Even at high current densities of 1 A g−1 and 2 A g−1, high reversible specific capacities of 752 and 631 mAh g−1 can still be obtained. Importantly, the rational design can be used to prepare Ge hybrids doped with other metals or metal oxides, as well as different structures, by adjusting the layer materials and the types of germanates, so as to adapt to different application environments.

Advanced-design cross-linked binder enables high-performance silicon-based anodes through in-situ crosslinking based on sodium carboxymethyl cellulose and poly-lysine

Practical employment of silicon (Si) electrodes in lithium-ion batteries (LIBs) is limited due to the severe volume changes suffered during charging-discharging process, causing serious capacity fading. Here, a composite polymer (CP-10) containing sodium carboxymethyl cellulose (CMC-Na) and poly-lysine (PL) is proposed for the binder of Si-based anodes, and a multifunctional strategy of “in-situ crosslinking” is achieved to alleviate the severe capacity degradation effectively. A cross-linked three-dimensional (3D) network is established through the strong hydrogen bonding interaction and reversible electrostatic interactions within CP-10, offering favorable mechanical tolerance for the extreme volume expansion of Si. Moreover, hydrogen bonding interaction along with ion-dipole interaction formed between CP-10 and Si surface enhance the bonding capability of Si-based anodes, promoting the maintenance of anodes' integrity. Consequently, over 800 cycles are achieved for the Si@CP-10 at 0.5C while maintaining a fixed discharge specific capacity of 1000 mAh g−1. Moreover, the Si/C@CP-10 can stably operate over 500 cycles with a capacity retention of 77.12 % at 1C. The prolonged cycling lifetime of Si/C and Si anodes suggests great potential for this strategy in promoting the implementation of high-capacity LIBs.

Lithium-electroactive peroxidase-like MnO2 nanomaterials as an ultrasensitive and selective sensing platform for carcinogenic 3,3′-diaminobenzidine and high-capacity lithium-ion batteries cathode materials

Lithium-electroactive peroxidase-like MnO2 nanomaterials as an ultrasensitive and selective sensing platform for carcinogenic 3,3′-diaminobenzidine and high-capacity lithium-ion batteries cathode materials

Mitigating Gas Evolution in Electron Beam-Induced Gel Polymer Electrolytes Through Bi-Functional Cross-Linkable Additives.

The current high-capacity lithium-ion batteries (LIBs), reliant on flammable liquid electrolytes (LEs) and nickel-rich cathodes, are plagued by safety hazards, especially the risk of hazardous gas release stemming from internal side reactions. To address these safety concerns, an electron beam (E-beam)-induced gel polymer electrolyte (E-Gel) is introduced, employing dipentaerythritol hexaacrylate (DPH) as a bi-functional cross-linkable additive (CIA). The dual roles of DPH are exploited through a strategically designed E-beam irradiation process. Applying E-beam irradiation on the pre-cycled cells allows DPH to function as an additive during the initial cycle, establishing a protective layer on the surface of the anode and cathode and as a cross-linker during the E-beam irradiation step, forming a polymer framework. The prepared E-Gel with CIA has superior interfacial compatibility, facilitating lithium-ion diffusion at the electrode/E-Gel interface. The electrochemical assessment of 1.2 Ah pouch cells demonstrates that E-Gel substantially reduces gas release by 2.5 times compared to commercial LEs during the initial formation stage and ensures superior reversible capacity retention even after prolonged cycling at 55°C. The research underscores the synergy of bifunctional CIA with E-beam technology, paving the way for large-scale production of safe, high-capacity, and commercially viable LIBs.

Structural Reversibility of Nanoscaled Sn Anodes.

Alloying-type anode materials provide high capacity for lithium-ion batteries; however, they suffer pulverization problems resulting from the volume change during cycling. Realizing the cycling reversibility of these anodes is therefore critical for sustaining their electrochemical performance. Here, we investigate the structural reversibility of Sn NPs during cycling at atomic-level resolution utilizing in situ high-resolution TEM. We observed a surprisingly near-perfect structural reversibility after a complete cycle. A three-step phase transition happens during lithiation, accompanied by the generation of a significant number of defects, grain boundaries, and up to 202% volume expansion. In subsequent delithiation, the volume, morphology, and crystallinity of the Sn NPs were restored to their initial state. Theoretical calculations show that compressive stress drives the removal of vacancies generated within the NPs during delithiation, therefore maintaining their intact morphology. This work demonstrates that removing vacancies during cycling can efficiently improve the structural reversibility of high-capacity anode materials.

Dilithium pyridine-2, 5-dicarboxylate as potential anode material for Li-ion battery

Amongst various small molecules with different functional groups, conjugated carbonyls are the most promising materials for lithium storage at low potential. This work reports lithium storage in dilithium pyridine-2, 5-dicarboxylate small molecule. We show here that dilithium pyridine-2, 5-dicarboxylate reversibly stores 2 mol of Li-ion per molecule, giving a reversible capacity of 307 mAh/g at an average voltage of 1.0 V. The capacity retention after 500 cycles at 1C rate is 69 %. This material shows impressive rate performance with a capacity retention of 140 mAh/g at 5C rate. The inclusion of electronegative nitrogen in the benzene ring helps in improving the storage performance compared to lithium terephthalate. Further ex-situ studies demonstrate possible mechanism for reversible lithium storage. Our findings showcase that the deliberately engineered organic electrode material facilitates the development of high capacity lithium-ion battery.

Polyoxovanadate Li7[V15O36(CO3)] and its derivative γ-LiV2O5 as superior performance cathode materials for aqueous zinc-ion batteries

Recently, many reports have been published about polyoxovanadates (POVs) with multiple electrons redox activity for energy storage. However, they are easily transformed into solid-state oxides after calcination. We noted that although dehydrated Li7[V15O36(CO3)] (Li7V15) exhibited a high capacity for lithium-ion batteries (LIBs), it was reported that the electrochemical behavior of the dehydrated sample same as γ-LiV2O5 (γ-LVO) which prepared by annealing the cluster and undehydrated Li7V15 was not redox-active. Interestingly, we were surprised to find that undehydrated Li7V15 and its derivative γ-LVO showed better electrochemical performance than LIBs when first proposed as the cathode to store Zn2+. Both Li7V15 and γ-LVO electrodes provided excellent rate performance and satisfied cyclability (135.0 and 214.1 mAh g−1 at 3 A g−1 after 1000 cycles, respectively). The fast kinetics of Li7V15 and γ-LVO were verified by pseudocapacitive analysis, GITT and EIS tests. Moreover, the Zn2+ storage mechanism and redox behavior of Li7V15 and γ-LVO were examined by ex-situ measurements. First-principles calculations revealed that the Zn2+ was chemisorbed on the clusters and physisorbed between the clusters. This work enriches the POVs cathode chemistry in aqueous energy storage.

Synergistic Protecting-Etching Synthesis of Carbon Nanoboxes@Silicon for High-Capacity Lithium-Ion Battery.

Silicon (Si) is considered as the most likely choice for the high-capacity lithium-ion batteries owing to its ultrahigh theoretical capacity (4200 mA h g-1) being over 10 times than that of traditional graphite anode materials (372 mA h g-1). However, its widespread application is limited by problems such as a large volume expansion and low electrical conductivity. Herein, we design a hollow nitrogen-doped carbon-coated silicon (Si@Co-HNC) composite in a water-based system via a synergistic protecting-etching strategy of tannic acid. The prepared Si@Co-HNC composite can effectively mitigate the volume change of silicon and improve the electrical conductivity. Moreover, the abundant voids inside the carbon layer and the porous carbon layer accelerate the transport of electrons and lithium ions, resulting in excellent electrochemical performance. The reversible discharge capacity of 1205 mA h g-1 can be retained after 120 cycles at a current density of 0.5 A g-1. In particular, the discharge capacity can be maintained at 1066 mA h g-1 after 300 cycles at a high current density of 1 A g-1. This study provides a new strategy for the design of Si-based anode materials with excellent electrical conductivity and structural stability.

Interface and Morphology Engineered Amorphous Si for Ultrafast Electrochemical Lithium Storage.

Ultrafast high-capacity lithium-ion batteries are extremely desirable for portable electronic devices, where Si is the most promising alternative to the conventional graphite anode due to its very high theoretical capacity. However, the low electronic conductivity and poor Li-diffusivity limit its rate capability. Moreover, high volume expansion/contraction upon Li-intake/uptake causes severe pulverization of the electrode, leading to drastic capacity fading. Here, interface and morphology-engineered amorphous Si matrix is being reported utilizing a few-layer vertical graphene (VG) buffer layer to retain high capacity at both slow and fast (dis)charging rates. The flexible mechanical support of VG due to the van-der-Waalsinteraction between the graphene layers, the weak adhesion between Si and graphene, and the highly porous geometry mitigated stress, while the three-dimensional mass loading enhanced specific capacity. Additionally, the high electronic conductivity of VG boosted rate-capability, resulting in a reversible gravimetric capacity of ≈1270mAhg-1 (areal capacity of ≈37µAhcm-2) even after 100 cycles at an ultrafast cycling rate of 20C, which provides a fascinating way for conductivity and stress management to obtain high-performance storage devices.