Long-life Lithium-ion Batteries Research Articles

Surface N Sites Mediate the Formation of Li Metal Cluster@N-Enriched Hierarchically Porous Carbon for Ultrahigh-Capacity Lithium Storage.

Graphite is the popular anode material of current lithium-ion batteries (LIBs). However, its low specific capacity and poor lithium intercalation potential hinder its use for high-power and large-scale energy storage. To meet the demand for energy storage, novel anode materials with high capacity, fast chargeable capability, and long cycle life are of great interest. Herein, we demonstrate an advanced nitrogen-enriched hierarchical porous carbon serving as a lithiophilic anode material for ultrahigh capacity and long-life LIBs. NHPC-700 (under optimal synthetic conditions), featuring a high surface area, rich N-doping, high porosity, and partially graphitized nanosheet structures, is successfully fabricated from a Schiff-base copolymer via a template-incipient wetness impregnation method. NHPC-700 exhibits an ultrahigh reversible lithium storage capacity of 2796 mA h g-1 at 0.1 A g-1 while still maintaining a high capacity of 526 mA h g-1 at 10 A g-1 after 1000 cycles. Theoretical and experimental studies reveal that this remarkable Li storage performance can be attributed to the large number of N lithiophilic sites on the inner surface of the small mesoporous pores. These sites guide Li metal nucleation in the initial period and control well the volume variation during charge/discharge cycles, thus exhibiting excellent cycle stability and great potential for practical application.

Interface Engineering of MOF-Derived Co3O4@CNT and CoS2@CNT Anodes with Long Cycle Life and High-Rate Properties in Lithium/Sodium-Ion Batteries.

Metal-organic framework materials can be converted into carbon-based nanoporous materials by pyrolysis, which have a wide range of applications in energy storage. Here, we design special interface engineering to combine the carbon skeleton and nitrogen-doped carbon nanotubes (CNTs) with the transition metal compounds (TMCs) well, which mitigates the bulk effect of the TMCs and improves the conductivity of the electrodes. Zeolitic imidazolate framework-67 is used as a precursor to form a carbon skeleton and a large number of nitrogen-doped CNTs by pyrolysis followed by the in situ formation of Co3O4 and CoS2, and finally, Co3O4@CNTs and CoS2@CNTs are synthesized. The obtained anode electrodes exhibit a long cycle life and high-rate properties. In lithium-ion batteries (LIBs), Co3O4@CNTs have a high capacity of 581 mAh g-1 at a high current of 5 A g-1, and their reversible capacity is still 1037.6 mAh g-1 after 200 cycles at 1 A g-1. In sodium-ion batteries (SIBs), CoS2@CNTs have a capacity of 859.9 mAh g-1 at 0.1 A g-1 and can be retained at 801.2 mAh g-1 after 50 cycles. The unique interface engineering and excellent electrochemical properties make them ideal anode materials for high-rate, long-life LIBs and SIBs.

Flexible bidirectional pulse charging regulation achieving long-life lithium-ion batteries

Typical application scenarios, such as vehicle to grid (V2G) and frequency regulation, have imposed significant long-life demands on lithium-ion batteries. Herein, we propose an advanced battery life-extension method employing bidirectional pulse charging (BPC) strategy. Unlike traditional constant current charging methods, BPC strategy not only achieves comparable charging speeds but also facilitates V2G frequency regulation simultaneously. It significantly enhances battery cycle ampere-hour throughput and demonstrates remarkable life extension capabilities. For this interesting conclusion, adopting model identification and postmortem characterization to reveal the life regulation mechanism of BPC: it mitigates battery capacity loss attributed to loss of lithium-ion inventory (LLI) in graphite anodes by intermittently regulating the overall battery voltage and anode potential using a negative charging current. Then, from the perspective of internal side reaction, the life extension mechanism is further revealed as inhibition of solid electrolyte interphase (SEI) and lithium dendrite growth by regulating voltage with a bidirectional pulse current, and a semi-empirical life degradation model combining SEI and lithium dendrite growth is developed for BPC scenarios health management, the model parameters are identified by genetic algorithm with the life simulation exhibiting an accuracy exceeding 99%. This finding indicates that under typical rate conditions, adaptable BPC strategies can extend the service life of LFP battery by approximately 123%. Consequently, the developed advanced BPC strategy offers innovative perspectives and insights for the development of long-life battery applications in the future.

SnO2-MoO2 nanoparticles coated on graphene oxide as a high-capacity, high-speed, long-life lithium-ion battery anode

Ternary SnO2-MoO2-GO (SMGO) nanocomposites were synthesized by hydrothermal method, modified Hummers method, and ball milling method. SMGO nanocomposites have the following advantages, including mitigating volume expansion during cycling, enhancing conductivity, and reducing the transmission path length for both electrons and Li+. Consequently, the SMGO composite material demonstrates a capacity of 1215.2 mAh/g after 200 cycles at 0.2 Ag−1, and a capacity of 1032.9 mAh/g after 1000 cycles at 1.0 Ag−1. Moreover, subsequent SEM analysis of the electrode material reveals the absence of accumulation or notable cracks, underscoring the remarkable cycling stability of the SMGO composite material.

Three-dimensional interwoven CoS2/reduced graphene oxide/carbon nanotubes composite as anode materials for high-performance lithium-ion batteries

CoS2 exhibits abundant redox reactions, high theoretical capacity, excellent, mechanical properties, and is regarded as a prospective electrode material. However, rational design of CoS2 composites with high capacity and ultra-long cycle life remains a major challenge. In this work, we formed CoS2/rGO/CNT electrode materials by compositing reduced graphene oxide (rGO), carbon nanotubes (CNT) and CoS2 with a three-dimensional interwoven network. The elemental composition and three-dimensional network morphology were described using SEM, TEM, XRD, Raman, BET, TGA and XPS. The large loading area provided by the three-dimensional network for Li+ facilitates the effective diffusion of Li+ during the cycling process. In addition, the three-dimensional network acts as an adhesion substrate for CoS2 nanoparticles, mitigating the bulk change and reducing the aggregation of CoS2 nanoparticles. On the other hand, the tight bonding of CNT with CoS2/rGO facilitates fast transfer of electron in CoS2/rGO/CNT. The electrochemical measurement results show that after 1000 cycles, the capacity is 615.8 mAh/g at 2000 mA/g and can still reach 233.7 mAh/g at 5000 mA/g after 2000 cycles. The favorable electrochemical properties prove that CoS2/rGO/CNT is an excellent anode material for long-life lithium-ion batteries.

Long-Life Lithium-Ion Sulfur Pouch Battery Enabled by Regulating Solvent Molecules and Using Lithiated Graphite Anode.

The development of lithium-sulfur (Li-S) batteries is severely limited by the shuttle effect and instability of Li-metal anode. Constructing Li-ion S batteries (LISBs), by using more stable commercial graphite (Gr) anode instead of Li-metal, is an effective way to realize long-cycle-life Li-S batteries. However, Gr electrode is usually incompatible with the ether-based electrolytes commonly used for Li-S batteries due to the Li+ -ether complex co-intercalation into Gr interlayers. Herein, a solvent molecule structure regulation strategy is provided to weaken the Li+ -solvent binding by increasing steric hindrance and electronegativity, to accelerate Li+ de-solvation process and prevent Li+ -ether complex co-intercalation into Gr anode. Meanwhile, the weakly solvating power of solvent can suppress the shuttle effect of lithium polysulfides and makes more anions participate in Li+ solvation structure to generate a stable anion-derived solid electrolyte interface on Gr surface. Therefore, a LISB coin-cell consisting of lithiated graphite anode and S@C cathode displays a stable capacity of ≈770 mAh g-1 within 200 cycles. Furthermore, an unprecedented practical LISB pouch-cell with a high Gr loading (≈10.5mg cm-2 ) also delivers a high initial capacity of 802.3 mAh g-1 and releases a stable capacity of 499.1 mAh g-1 with a high Coulombic efficiency (≈95.9%) after 120 cycles.

Atomic pins bridging integrated surface to assist high-rate stability for Co-free Li-rich cathode

Li- and Mn-rich oxides (LMR) have emerged as promising cathode materials for next-generation Li-ion batteries due to their cost effectiveness, impressive capacity, and high energy density. However, the poor electrochemical kinetics and structural instability in hostile interface environments have result in continuous voltage/capacity decay and undesirable rate performance, impeding the large-scale commercial application of LMR materials. In this study, we introduce an atomic pins-assisted integrated surface reconstruction (AISR) strategy to address the interfacial degradation and instability issues. Utilizing the bidirectional diffusion effect of the aluminum-containing intermediate layer during the heat treatment process, we employ aluminum atoms as bridging centers to in situ construct a composite interface structure. This approach capitalizes on the element diffusion reaction and anchoring effect to achieve multifunctional modification through the Al-based ionic conductor network constructing and near-surface Al doping for LMR material. Intriguingly multiple kinetic investigations and calculations reveal that the epitaxial ionic conductor layer suppresses interfacial side reactions, enhances ionic conductivity, and improves electronic conductivity by regulating cationic/anionic redox activity through Al surface doping.Impressively, the modified electrodes exhibited an increased reversible capacity at both 0.1C/5C rates (0.1C, 2 ∼ 4.8 V, from 264.2 mAh∙g−1 to 274 mAh∙g−1; 5C, 2 ∼ 4.6 V, from 145.5 mAh∙g−1 to 197.9 mAh∙g−1) and improved capacity retention after 250 cycles at 1C/5C rates (2 ∼ 4.6 V: 1C, from 69.46% to 81.92%; 5C from 57.73% to 81.35%). We systematically summarized the rate-dependent failure mechanism and the corresponding integrated interface reconstruction principle. These key findings offer valuable insights for the development of high-energy–density and long-life lithium-ion batteries in commercial applications.

Long-life lithium-ion batteries realized by low-Ni, Co-free cathode chemistry

Long-life lithium-ion batteries realized by low-Ni, Co-free cathode chemistry

Research on the utilization of ultra-long carbon nanotubes in lithium-ion batteries based on an environment-friendly society.

To build an environment-friendly society, clean transportation systems, and renewable energy sources play essential roles. It is critical to improve the lifetime mileage of electric vehicles' batteries for reducing the cycle life cost and carbon footprint in green transportation. In this paper, a long-life lithium-ion battery is achieved by using ultra-long carbon nanotubes (UCNTs) as a conductive agent with relatively low content (up to 0.2% wt.%) in the electrode. Ultra-long CNT could realize longer conductive path crossing active material bulks in the electrode. Meanwhile, the low content of UCNTs can help to minimize conductive agent content in electrodes and obtain higher energy density. The film resistance and electrochemical impedance spectroscopy (EIS) confirmed that the use of UCNTs could markedly enhance electronic conductivity in the battery. The battery's life and life mileage can be prolonged by almost half due to the superior electronic conductivity of UCNTs. The life cycle cost and carbon footprint are also significantly reduced, which could markedly increase economic and environmental performance.

Fabrication of a LiNi0.5Mn0.4Ti0.03Mg0.03Nb0.01Mo0.03O2 cathode for low-cost long-life lithium-ion batteries.

The high price of Co and Ni restricts the development of the lithium-ion battery industry. Reducing the Ni content and eliminating Co is an effective way to lower the cost. In this work, we eliminate the Co in NCM523 cathodes by using a complex concentrated doping strategy. LiNi0.5Mn0.4Ti0.03Mg0.03Nb0.01Mo0.03O2 shows an unparalleled cost advantage with relatively high specific energy (>720 W h kg-1) and significantly improved overall performance (96% capacity retained after 1000 cycles). This report offers an important pathway to fabricate cathode materials for low-cost and long-life LIBs.

Suppressing the Mn dissolution in LiMn2O4 positive materials toward long-life lithium ion battery through Gd2O3 surface modification

Suppressing the Mn dissolution in LiMn2O4 positive materials toward long-life lithium ion battery through Gd2O3 surface modification

Integrated Modification Strategy Enables Remarkable Cyclability and Thermal Stability of Ni-Rich Cathode Materials for Lithium-Ion Batteries

Structural degradation and surface chemical instability are dominant issues of Ni-rich layered cathodes, which trigger capacity fading and safety concerns, hindering the extensive application of Ni-rich cathodes toward high-energy, long-life lithium-ion batteries. Here, by combining trace Ta doping and an ultrathin Zr-Y mixed oxide coating, an integrated modification strategy significantly improves the cycling and thermal stability of Ni-rich LiNi0.88Co0.10Al0.02O2 (NCA) cathodes. The integrated modified Ni-rich cathode provides an unprecedented comprehensive performance with a high discharge capacity of 212.2 mA h g-1 at 0.1 C, an 88.6% cycling retention after 500 cycles at 1 C, and a high exothermic peak temperature of 261 °C compared with the pristine NCA cathode (67.4% capacity retention for 500 cycles and 221 °C for the exothermic peak). Further mechanism studies illustrate that a dual-structural surface constructed of a rock salt surface induced by Ta doping and ultrathin Zr-Y mixed oxide coating jointly suppresses surface side reactions between cathodes and electrolytes. Moreover, trace Ta doping in the bulk stabilizes the bulk structure and prevents mechanical cracks. This study highlights the importance of comprehensive modification of the bulk and surface for improving the electrochemical performance and provides a potential optimizing strategy for the commercialization of high-capacity Ni-rich cathode materials.

Bio-template synthesis of LiVO3 anode material for high-rate and long-life lithium-ion batteries

Bio-template synthesis of LiVO3 anode material for high-rate and long-life lithium-ion batteries

Composite of Ge and α-MnSe in carbon nanofibers as a high- performance anode material for LIBs

Improving the performance of anode materials is of great importance for lithium-ion batteries (LIBs). Transition metal selenides compositing carbon and germanium (Ge) have attracted extensive attention. In this work, an anode material that integrates Ge and α-MnSe in carbon nanofibers (CNFs) was first synthesized by heat treatment after electrospinning. The coupling of Ge with α-MnSe and carbon can cause the growth process of α-MnSe to occur inside the CNFs, which can buffer the volume change, refine the grains and avoid particles protruding from the surface of CNFs. In addition, the interconnected conductive network of Ge/α-MnSe@CNFs can provide fast diffusion channels for Li ions and improve the electrical conductivity. Importantly, there is a synergistic effect of Ge, α-MnSe, and CNFs on the anode material for LIBs. As expected, Ge/α-MnSe@CNFs exhibited an excellent performance with a capacity of 1514.7 mAh g −1 after 200 cycles at 0.1 A g −1 and 1030 mAh g −1 after 1000 cycles even at 1 A g −1 . Therefore, this new preparation strategy of Ge/α-MnSe@CNFs offers novel ideas to develop high-performance and long-life LIBs. • Ge/α-MnSe carbon nanofibers were first synthesized for lithium-ion batteries. • Coupling Ge with α-MnSe can help to limit the in-situ growth of α-MnSe inside CNFs rather than at the surface. • Ge/α-MnSe@CNFs showed a high capacity and long-time cycles life for LIBs.

Atomic Short-Range Order in a Cation-Deficient Perovskite Anode for Fast-Charging and Long-Life Lithium-Ion Batteries.

Perovskite-type oxides are widely used for energy conversion and storage, but their rate-inhibiting phase transition and large volume change hinder the applications of most perovskite-type oxides for high-rate electrochemical energy storage. Here, it is shown that a cation-deficient perovskite CeNb3 O9 (CNO) can store a sufficient amount of lithium at a high charge/discharge rate, even when the sizes of the synthesized particles are on the order of micrometers. At 60 C (15 A g-1 ), corresponding to a 1 min charge, the CNO anode delivers over 52.8% of its capacity. In addition, the CNO anode material exhibits 96.6% capacity retention after 2000 charge-discharge cycles at 50 C (12.5 A g-1 ), indicating exceptional long-term cycling stability at high rates. The excellent cycling performance is attributed to the formation of atomic short-range order, which significantly prevents local and long-range structural rearrangements, stabilizing the host structure and being responsible for the small volume evolution. Moreover, the extremely high rate capacity can be explained by the intrinsically large interstitial sites in multiple directions, intercalation pseudocapacitance, atomic short-range order, and cation-vacancy-enhanced 3D-conduction networks for lithium ions. These structural characteristics and mechanisms can be used to design advanced perovskite electrode materials for fast-charging and long-life lithium-ion batteries.

SnO2 Anchored in S and N Co-Doped Carbon as the Anode for Long-Life Lithium-Ion Batteries.

Tin dioxide (SnO2) has been the focus of attention in recent years owing to its high theoretical capacity (1494 mAh g−1). However, the application of SnO2 has been greatly restricted because of the huge volume change during charge/discharge process and poor electrical conductivity. In this paper, a composite material composed of SnO2 and S, N co-doped carbon (SnO2@SNC) was prepared by a simple solid-state reaction. The as-prepared SnO2@SNC composite structures show enhanced lithium storage capacity as compared to pristine SnO2. Even after cycling for 1000 times, the as-synthesized SnO2@SNC can still deliver a discharge capacity of 600 mAh g−1 (current density: 2 A g−1). The improved electrochemical performance could be attributed to the enhanced electric conductivity of the electrode. The introduction of carbon could effectively improve the reversibility of the reaction, which will suppress the capacity fading resulting from the conversion process.

Scalable Synthesis of Pore-Rich Si/C@C Core-Shell-Structured Microspheres for Practical Long-Life Lithium-Ion Battery Anodes.

Silicon/carbon (Si/C) composites have rightfully earned the attention as anode candidates for high-energy-density lithium-ion batteries (LIBs) owing to their advantageous capacity and superior cycling stability, yet their practical application remains a significant challenge. In this study, we report the large-scale synthesis of an intriguing micro/nanostructured pore-rich Si/C microsphere consisting of Si nanoparticles tightly immobilized onto a micron-sized cross-linked C matrix that is coated by a thin C layer (denoted P-Si/C@C) using a low-cost spray-drying approach and a chemical vapor deposition process with inorganic salts as pore-forming agents. The as-obtained P-Si/C@C composite has high porosity that provides sufficient inner voids to alleviate the huge volume expansion of Si. The outer smooth and robust C shells strengthen the stability of the entire structure and the solid-electrolyte interphase. Si nanoparticles embedded in a microsized cross-linked C matrix show excellent electrical conductivity and superior structural stability. By virtue of structural advantages, the as-fabricated P-Si/C@C anode displays a high initial Coulombic efficiency of 89.8%, a high reversible capacity of 1269.6 mAh g-1 at 100 mA g-1, and excellent cycle performance with a capacity of 708.6 mAh g-1 and 87.1% capacity retention after 820 cycles at 1000 mA g-1, outperforming the reported results of Si/C composite anodes. Furthermore, a low electrode swelling of 18.1% at a high areal capacity of 3.8 mAh cm-2 can be obtained. When assembled into a practical 3.2 Ah cylindrical cell, extraordinary long cycling life with a capacity retention of 81.4% even after 1200 cycles at 1C (3.2 A) and excellent rate performance are achieved, indicating significant advantages for long-life power batteries in electric vehicles.

One polymer with three charge states for two types of lithium-ion batteries with different characteristics as needed

Organic batteries materials exhibit merits of diverse structures, high capacities, less pollution and abundant sources, therefore, developing high-performance organic electrode materials is promising for the next generation of rechargeable batteries. Various advanced organic cathode materials have been reported but most of them possess only two charge states and can be used for one kind of battery. Thus, it is challenging to design organic material with three charge states for two types of high-performance organic batteries with different characteristics as needed. Herein, we designed and synthesized a polymer named P-BQPZ, which integrates maximum n-type and p-type redox-active moieties into one stable polymer with minimum redox-inactive moieties, and thus it can be used for two types of long-life lithium-ion batteries with different features (e.g. high capacity or output potential) by using different redox-active sites. The cathode half-cell based on n-type redox-active reaction exhibits a high capacity of 431.3 mA h g−1 (2.4 V vs Li/Li+) at 50 mA g−1 and a high retention of 99.95% per cycle up to 500 cycles at 1,000 mA g−1. Furthermore, the cathode half-cell based on p-type redox-active reaction displays relatively high output voltage of 3.1 V (vs Li/Li+, 176.6 mA h g−1 at 50 mA g−1) and superior retention of 99.97% per cycle at 500 mA g−1 for 1,000 cycles. More importantly, two kinds of all-organic batteries by using P-BQPZ cathode also operate well.

Regulation of morphology evolution and Mn dissolution for ultra-long cycled spinel LiMn2O4 cathode materials by B-doping

Electrochemical properties of spinel LiMn2O4 cathode material have been always suffered from Mn dissolution and Jahn-Teller distortion. Herein, various Ni/B dual-doped LiNi0.08BxMn1.92-xO4 (x = 0–0.15) with a truncated octahedral morphology are synthesized via a facile solid-state combustion. The effects of Ni/B co-doping on the morphology, crystal structure, Mn dissolution, Li+ diffusion coefficient and activation energy are investigated. Due to the relatively high Ni–O and B–O bond energy than that of Mn–O bond, the structure stability of the LiMn2O4 is enhanced, whilst restraining the Jahn-Teller distortion. The LiNi0.08Mn1.92O4 shows (111), (110) and (100) facets. In comparison, the B-doping endows the LiNi0.08BxMn1.92-xO4 (x ≥ 0.02) with (111) and (100) facets. This morphology evolution without (110) facets effectively inhibits the Mn dissolution. Owing to the synergistic merits of Ni/B dual-doping and unique truncated octahedron, the optimized LiNi0.08B0.06Mn1.86O4 delivers an initial discharge capacity of 113.9 mAh∙g−1 at 1C and maintains a durable cycling life up to 2000 cycles at 5C. Even at 20C, a capacity retention of 86.3% is still obtained after 2000 cycles. Furthermore, a capacity retention of 70.6% can be retained after 500 cycles at 5C and 55 °C. The truncated octahedral LiNi0.08BxMn1.92-xO4 with excellent electrochemical performance will be a good candidate for developing long-life lithium-ion batteries.

Ultrafine ZnO particles anchored on hollow porous carbon nanocubes for high-rate and long-life lithium-ion batteries

Ultrafine ZnO particles anchored on hollow porous carbon nanocubes for high-rate and long-life lithium-ion batteries