A Designed Durable Electrolyte for High-Voltage Lithium-Ion Batteries and Mechanism Analysis.

Rechargeable lithium-ion batteries (LIBs) dominate the energy market, from electronic devices to electric vehicles, but pursuing greater energy density remains challenging owing to the limited electrode capacity. Although increasing the cut-off voltage of LIBs (>4.4 V vs. Li/Li+ ) can enhance the energy density, the aggravated electrolyte decomposition always leads to a severe capacity fading and/or expiry of the battery. Herein, a new durable electrolyte is reported for high-voltage LIBs. The designed electrolyte is composed of mixed linear alkyl carbonate solvent with certain cyclic carbonate additives, in which use of the ethylene carbonate (EC) co-solvent was successfully avoided to suppress the electrolyte decomposition. As a result, an extremely high cycling stability, rate capability, and high-temperature storage performance were demonstrated in the case of a graphite|LiNi0.6 Co0.2 Mn0.2 O2 (NCM622) battery at 4.45 V when this electrolyte was used. The good compatibility of the electrolyte with the graphite anode and the mitigated structural degradation of the NCM622 cathode are responsible for the high performance at high potentials above 4.4 V. This work presents a promising application of high-voltage electrolytes for pursuing high energy LIBs and provides a straightforward guide to study the electrodes/electrolyte interface for higher stability.

A multifunctional dual cation doping strategy to stabilize high-voltage medium-nickel low-cobalt lithium layered oxide cathode.

High-voltage medium-nickel low-cobalt lithium layered oxide cathode materials are intriguing for lithium-ion batteries (LIBs) applications because of their relatively low cost and high capacity. Unfortunately, high charging voltage induces bulk layered structure decline and interface environment deterioration, low cobalt content reduces lithium diffusion kinetics, severely limiting the performance liberation of this kind of cathode. Here, a multifunctional Al/Zr dual cation doping strategy is employed to enhance the electrochemical performance of LiNi0.6Co0.05Mn0.35O2 (NCM) cathode at a high charging cut-off voltage of 4.5 V. On the one hand, Al/Zr co-doping weakens the Li+/Ni2+ mixing through magnetic interactions due to the inexistence of unpaired electrons for Al3+ and Zr4+, thereby increasing the lithium diffusion rate and suppressing the harmful coexistence of H1 and H2 phases. On the other hand, they enhance the lattice oxygen framework stability due to strong Al-O and Zr-O bonds, inhibiting the undesired H2 to H3 phase transition and interface lattice oxygen loss, thereby enhancing the stability of the bulk structure and cathode-electrolyte interface. As a result, Al/Zr co-doped NCM (NCMAZ) shows a 94.2 % capacity retention rate after 100 cycles, while that of NCM is only 79.4 %. NCMAZ also exhibits better rate performance than NCM, with output capacities of 92 mAh/g and 59 mAh/g at a high current density of 5C, respectively. The modification strategy will make the high-voltage medium-nickel low-cobalt cathode closer to practical applications.

Copper(II)-based metal-organic framework delivery of calcium ascorbate for enhanced chemodynamic therapy via H2O2 self-supply and glutathione depletion.

Chemodynamic therapy (CDT) is a promising cancer treatment strategy. However, mild acidic pH, insufficient H2O2 content, and overexpressed glutathione (GSH) in the tumor microenvironment (TME) severely impair CDT efficiency. In this study, a novel therapeutic nanosystem (Cu/ZIF-8/Vc-Ca/HA) was constructed for H2O2 self-supply and GSH depletion co-enhanced CDT. Typically, calcium ascorbate (Vc-Ca) loaded on the surface of Cu2+-doped ZIF-8 (Cu/ZIF-8) was designed as an original source for H2O2 generation, and a hyaluronic acid (HA) shell was subsequently coated to act as a tumor-targeted "guide" and protective layer. Along with the HA shell disintegrated in the TME, exposed Cu/ZIF-8/Vc-Ca dissociated in the tumor acidic microenvironment, thus triggering the release of Vc-Ca and Cu2+. Vc-Ca selectively produced H2O2 in tumor cells, which provided abundant H2O2 for boosting Fenton-like reactions. Meanwhile, the released Cu2+ could get converted into Cu+ by consuming excess intracellular GSH, which could reduce the tumor antioxidant capability of the nanosystem. Moreover, byproduct Cu+ reacted with abundant H2O2 by a highly efficient Fenton-like reaction to generate toxic ˙OH. Biological assays indicated that the Cu/ZIF-8/HA@Vc-Ca nanosystem showed significant anticancer activity by enhancing the CDT process. This study may provide a new strategy for improving the effectiveness of CDT.

Insight into the Coprecipitation-Controlled Crystallization Reaction for Preparing Lithium-Layered Oxide Cathodes.

The nucleation and growth of spherical Ni0.6Co0.2Mn0.2(OH)2 agglomerates using the hydroxide coprecipitation (HCP) method in the presence of ammonia is investigated through chemical equilibrium calculations and experiments. In the nucleation stage, the transition metal ions in the salt solution gradually complete the nucleation reaction in the diffusion process from pH 5.4 to 11 after dropping into the continuously stirred tank reactor, and then Me(NH3)n2+ and Me(OH)2(s) (Me: Ni, Co, and Mn) reach a dynamic precipitation dissolution equilibrium. In the growth stage, the concentration ratio of Me(NH3)n2+ and OH- (complexation and precipitation, Rc/p) in the solution has an important influence on obtaining high-quality materials, which is further confirmed using the first principles density functional theory calculations on surface energy and adsorption energy. Then, the HCP reaction could be divided into three parts through experiments: incomplete precipitation area (Rc/p > 10.1); time-dependent area (Rc/p = 0.1-10.1); and hard-to-control area (Rc/p <0.1). According to the optimal ratio (Rc/p = 3.4), a prediction formula for the optimal synthesis conditions of the materials is proposed (y = 0.7731 × ln(x + 0.0312) + 11.6708, the optimal pH value (y) corresponds to different ammonia concentrations (x)). The results obtained for the growth reaction mechanism and the prediction scheme would help the modification research of the materials and obtain the desired lithium-layered transition metal oxide cathode material with excellent performance in the shortest time.

A highly promising high-nickel low-cobalt lithium layered oxide cathode material for high-performance lithium-ion batteries.

Reducing cobalt dependency has attracted great interest for lithium batteries manufacturing due to limited cobalt resources and high prices. A highly promising LiNi0.6Co0.05Mn0.35O2 (NCM60535) high-nickel low cobalt lithium layered oxide cathode material is successfully prepared by systematically examining the two key synthesis conditions of pH and annealing temperature. The obtained materials exhibit a uniform size distribution, good spherical morphology, clear structure, and homogeneous element distribution. NCM60535 shows competitive electrochemical properties: when compared with the LiNi1/3Co1/3Mn1/3O2, with a higher output specific capacity and cycling stability at 4.3 V low voltage; when compared with the LiNi0.8Co0.1Mn0.1O2, with a comparable discharge capacity but relatively poor cycling stability at 4.5 V high voltage. A new type of electrolyte that combines high lithium salt concentration, EC-free solvent system, and VC and LiPO2F2 functional additives is designed and greatly improves the electrochemical properties of the material under high voltage. Moreover, it also delivers superior electrochemical properties in high voltage lithium full battery (270 Wh Kg-1). And we suggest that NCM60535 is expected to become a substitute for the currently widely commercialized LiNi1/3Co1/3Mn1/3O2 (NCM333), LiNi0.5Co0.2Mn0.3O2 (NCM523), LiNi0.6Co0.2Mn0.2O2 (NCM622), and LiNi0.8Co0.1Mn0.1O2 (NCM811) due to its relatively low production cost and competitive electrochemical properties.

Unraveling the New Role of Metal-Organic Frameworks in Designing Silicon Hollow Nanocages for High-Energy Lithium-Ion Batteries.

Metal-organic framework (MOF)-derived materials are attracting considerable attention because of the moldability in compositions and structures, enabling greater performances in diverse applications. However, the nanostructural control of multicomponent MOF-based complexes remains challenging due to the complexity of reaction mechanisms. Herein, we present a surface-induced self-nucleation-growth mechanism for the zeolitic imidazolate framework (ZIF) to prepare a new type of ZIF-8@SiO2 polyhedral nanoparticles. We discover that the Zn hydroxide moieties (Zn-OH) within ZIF-8 can trigger the hydrolysis of tetraethyl orthosilicate effectively on the ZIF-8 surface precisely, avoiding the formation of free orthosilicic acid (Si(OH)4) successfully. This is a pioneering work to elucidate the importance of MOF surface properties for preparing multicomponent materials. Then, a novel well-dispersed silicon hollow nanocage (H-Si@C) modified by the carbon was prepared after removal of the ZIF-8 and magnesiothermic reduction. The as-prepared H-Si@C demonstrates an overwhelmingly high lithium storage capability and extraordinary stability in lithium-ion batteries (LIBs), particularly the impressive performances when it was matched with the LiNi0.6Co0.2Mn0.2O2 cathode in a full cell. The MOF surface-induced self-nucleation-growth strategy is useful for preparing more multifunctional materials, while the study of lithium storage performances of the H-Si@C material is practical for LIB applications.

An SiOx anode strengthened by the self-catalytic growth of carbon nanotubes.

Modification using carbon nanotubes (CNTs) is one of the most important strategies to boost the performance of materials in various applications, among which the CNT-modified silicon-based anodes have gained considerable attention in lithium-ion batteries (LIBs) due to their improved conductivity and cycle stability. However, the realization of a close-knit CNT coating on silicon (Si) through an efficient and cost-effective approach remains challenging. Herein, a new in situ self-catalytic method by acetylene treatment is presented, in which, CNTs can be directly grown and knitted on the SiOx particles to construct a conductive additive-free SiOx@CNT anode. The in situ grown CNTs can not only enhance electric conductivity and alleviate the volume effect of SiOx effectively, but also mitigate the electrolyte decomposition with improved coulombic efficiency. As a result, an extremely high capacity of 1012 mA h g-1, long lifespan over 500 cycles at a current density of 2 A g-1 as well as a good performance in full LIBs with a working potential of about 3.4 V (vs. nickel-rich cathode) were obtained. The rationally constructed SiOx@CNTs with easy synthesis and high throughput will hopefully promote LIBs with energy density above 300 W h kg-1. This study opens a new avenue to prepare CNT-decorated functional materials and brings the SiOx-based anode one step closer to practical applications.

In Situ Growth of Lithiophilic MOF Layer Enabling Dendrite-free Lithium Deposition.

Lithium metal batteries have recently emerged as alternative energy storage systems beyond lithium-ion batteries. However, before this kind of batteries can become a viable technology, the critical issues of the Li anodes, like dendrites growth and low Coulombic efficiency (CE), need to be conquered. Herein, lithiophilic Cu-metal-organic framework thin layer (Cu-MOF TL) is in situ grown on the surface of Cu foil by a facile immersion strategy to construct a multifunctional current collector. Profiting from the high electrical conductivity and unique porous structure, the Cu-MOF TL with high affinity to electrolyte can provide uniform nucleation sites and promote homogeneous Li+ flux, as a result, radically restrain the Li dendrite growth, leading to stable Li plating/striping behaviors. The modified current collector enables Li plating/stripping with a prominent CE (∼97.1%) and a stable lifetime (∼2500 h). Importantly, the synthesis method can be easily large-scale production in a series of organic solvents.

Crystal reconstruction of binary oxide hexagonal nanoplates: monocrystalline formation mechanism and high rate lithium-ion battery applications.

Structural design and/or carbon modification are the most important strategies to improve the performance of materials in many applications, where metal (oxide)-based anode design attracts great attention in metal ion batteries due to their high capacities. However, achieving these two goals within one-step remains challenging due to the lower cost and higher efficiency needed to satisfy the demand in practical application. Herein, we report a new approach for the crystal reconstruction of metal oxides by acetylene treatment, in which a hierarchical binary oxide decorated with carbon (i.e., Mn2Mo3O8@C) is introduced. The mechanism of constructing unique monocrystalline hexagonal nanoplates and uniform carbon coating is discussed in detail. Benefiting from the uniqueness of structure and composition, the Mn2Mo3O8@C demonstrates an extremely high lithium storage capacity of 890 mA h g-1 and good rate capacities at 20 A g-1 over 1000 cycles. In addition, the high rate capabilities and long cycle lifespan are further confirmed when the Mn2Mo3O8@C anode is matched with the nickel-rich layered oxide cathode. This study not only introduces a new binary oxide anode with high performances in lithium (ion) batteries but also presents a convenient methodology to design more advanced functional materials.