Ag-modified hydrogen titanate nanowire arrays for stable lithium metal anode in a carbonate-based electrolyte

In the investigation of the next-generation battery anode,Li metal has attracted increasing attention owing to its ultrahigh specific capacity and low reduction potential.However,its low columbic efficiency,limited cycling life,and serious safety hazards have hindered the practical application of rechargeable Li metal batteries.Although several strategies have been proposed to enhance the electrochemical performance of Li metal anodes,most are centered around ether-based electrolytes,which are volatile and do not provide a sufficiently large voltage window.Therefore,we aimed to attain stable Li deposition/stripping in a commercial carbonate-based electrolyte.Herein,we have successfully synthesized hydrogen titanate(HTO)nanowire arrays decorated with homogenous Ag nanoparticles(NPs)(Ag@HTO)via simple hydrothermal and silver mirror reactions.The 3 D cross-linked array structure with Ag NPs provides preferable nucleation sites for uniform Li deposition,and most importantly,when assembled with the commercial LiNi_0.5Co0.2Mn_0.3O₂ cathode material,the Ag@HTO could maintain a capacity retention ratio of 81.2% at 1 C after 200 cycles,however the pristine Ti foil failed to do so after only 60 cycles.Our research therefore reveals a new way of designing current collectors paired with commercial high voltage cathodes that can create high energy density Li metal batteries.     

Full-chain enhanced ion transport toward stable lithium metal anodes

The dendrite growth that results from the slow electrode process kinetics prevents the lithium(Li) metal anode from being used in practical applications. Here, full-chain enhanced ion transport for stabilizing Li metal anodes is proposed. Experimental and theoretical studies confirm that full-chain enhanced ion transport(electrocrystallization, mass transport in the electrolyte and diffusion in solid electrolyte interphase) under magnetoelectrochemistry contributes to a homogeneous, dense, and d...     

Constructing nanoporous Ni foam current collectors for stable lithium metal anodes

Lithium metal,as the most ideal anode material for high energy density batteries,has been researched for several decades.However,the dendrite formation and larg...     

Regulating electrodeposition behavior through enhanced mass transfer for stable lithium metal anodes

Electrode process kinetics is a key part that determines the morphology of metal electrodeposition.However,the liquid-phase mass transfer process and its effect on lithium(Li)metal electrodeposition are still poorly understood.Herein,the effect of mass transfer on the electrodeposition behavior of Li metal is explored.Experiments and COMSOL Multiphysics simulations reveal that the enhanced mass transfer,which is induced by ultrasonic wave,can homogenize the ion flow on the surface of electrode to obtain uniform Li nucleation.Meanwhile,the rapid mass transfer of Li⁺provides sufficient cations around the germinated Li to avoid preferential growth of Li in a specific direction.Based on the simultaneous regulation of nucleation and growth behavior,a smooth and compact Li deposits can be achieved,which exhibit a small polarization voltage during repeated Li plating/striping and a considerably enhanced cyclability.This work enriches the fundamental understanding of Li electrodeposition without dendrite structure and affords fresh guidance to develop dendrite-free metal anodes for metal-based batteries.     

Inhibition of lithium dendrites and dead lithium by an ionic liquid additive toward safe and stable lithium metal anodes

The uncontrolled growth of lithium dendrites and accumulation of “dead lithium” upon cycling are among the main obstacles that hinder the widespread application of lithium metal anodes. Herein, an ionic liquid (IL) consisting of 1-methyl-1-propylpiperidinium cation (Pp₁₃⁺) and bis(fluorosulfonyl)imide anion (FSI^?), was chosen as the additive in propylene carbonate (PC)-based liquid electrolytes to circumvent the shortcoming of lithium metal anodes. The optimal 1% Pp₁₃FSI acts as the role of electrostatic shielding, lithiophobic effect and participating in the formation of solid electrolyte interface (SEI) layer with enhanced properties. The in-situ optical microscopy records that the addition of IL can effectively inhibit the growth of lithium dendrites and the corrosion of lithium anode. This study delivers an effective modification to optimize electrolytes for stable lithium metal batteries.     

A hydrophobic artificial solid-interphase-protective layer with fast self-healable capability for stable lithium metal anodes

Science China Chemistry - Lithium (Li) metal has been considered as one of the most promising anodes for high-energy-density batteries. However, the hyperactivity of metallic Li and its dendrite...     

Multi-dimensional hybrid flexible films promote uniform lithium deposition and mitigate volume change as lithium metal anodes

Lithium metal is the ultimate anode material for next-generation high-energy batteries.Yet,the practical application of lithium metal anodes is limited by the formation of Li dendrites and large volume changes.Herein,an effective multi-dimensional hybrid flexible film(MD-HFF)composed of iodine ion(0 dimension),CNTs(1 dimension)and graphene(2 dimensions)is designed for regulating Li deposition and mitigating volume changes.The multi-dimensional components serve separate roles:(1)iodine ion enhances the conductivity of the electrode and provides lithiophilic sites,(2)CNTs strengthen interlaminar conductance and mechanical strength,acting as a spring in the layered structure to alleviate volume changes during Li plating and stripping and(3)graphene provides mechanical flexibility and electrical conductivity.The resulting MD-HFF material supports stable Li plating/stripping and high Coulombic efficiency(99%)over 230 cycles at 1 mA cm^-2 with a deposition capacity of 1 mAh cm^-2.Theoretical calculations indicate that LiI contributes to the lateral growth of Li on the MD-HFF surface,thereby inhibiting the formation of Li dendrites.When paired with a typical NCM811 cathode,the assembled MD-HFF‖NCM811 cell exhibit improved capability and stable cycling performance.This research serves to guide material design in achieving Li anode materials that do not suffer from dendrite formation and volume changes.     

Polar interaction of polymer host–solvent enables stable solid electrolyte interphase in composite lithium metal anodes

The lithium(Li) metal anode is an integral component in an emerging high-energy-density rechargeable battery.A composite Li anode with a three-dimensional(3 D) host exhibits unique advantages in suppressing Li dendrites and maintaining dimensional stability.However,the fundamental understanding and regulation of solid electrolyte interphase(SEI),which directly dictates the behavior of Li plating/stripping,are rarely researched in composite Li metal anodes.Herein,the interaction between a polar p...     

Engineering and characterization of interphases for lithium metal anodes

Lithium metal is a very promising anode material for achieving high energy density for next generation battery systems due to its low redox potential and high theoretical specific capacity of 3860 mA h g⁻¹. However, dendrite formation and low coulombic efficiency during cycling greatly hindered its practical applications. The formation of a stable solid electrolyte interphase (SEI) on the lithium metal anode (LMA) holds the key to resolving these problems. A lot of techniques such as electrolyte modification, electrolyte additive introduction, and artificial SEI layer coating have been developed to form a stable SEI with capability to facilitate fast Li⁺ transportation and to suppress Li dendrite formation and undesired side reactions. It is well accepted that the chemical and physical properties of the SEI on the LMA are closely related to the kinetics of Li⁺ transport across the electrolyte–electrode interface and Li deposition behavior, which in turn affect the overall performance of the cell. Unfortunately, the chemical and structural complexity of the SEI makes it the least understood component of the battery cell. Recently various advanced in situ and ex situ characterization techniques have been developed to study the SEI and the results are quite interesting. Therefore, an overview about these new findings and development of SEI engineering and characterization is quite valuable to the battery research community. In this perspective, different strategies of SEI engineering are summarized, including electrolyte modification, electrolyte additive application, and artificial SEI construction. In addition, various advanced characterization techniques for investigating the SEI formation mechanism are discussed, including in situ visualization of the lithium deposition behavior, the quantification of inactive lithium, and using X-rays, neutrons and electrons as probing beams for both imaging and spectroscopy techniques with typical examples.

Different strategies of SEI engineering such as modification, additive application, and artificial SEI for electrolyte are summarized. Characterization techniques for SEI studies using X-ray, neutron, and electron as probing beams are discussed.     

Recent progress in liquid electrolytes for lithium metal batteries

Li metal batteries are revived as the next-generation batteries beyond Li-ion batteries. The Li metal anode can be paired with intercalation-type cathodes LiMO₂ and conversion-type cathodes such as sulfur and oxygen. Then, energy densities of Li/LiMO₂ and Li/S,O₂ batteries can reach 400 Whkg^?1 and more than 500 Whkg^?1, respectively, which surpass that of the state-of-the-art LIB (280 Whkg^?1). However, replacing the intercalation-type graphite anode with the Li metal anode suffers from low coulombic efficiency during repeated Li plating/stripping processes, which leads to short cycle lifetime and potential safety problems. The key solution is to construct a stable and uniform solid electrolyte interphase with high Li⁺ transport and high elastic strength on the Li metal anode. This review summarizes recent progress in improving the solid electrolyte interphase by tailoring liquid electrolytes, a classical but the most convenient and cost-effective strategy.     

Gamma ray irradiation for sludge solubilization and biological nitrogen removal

This study was conducted to investigate the effects of gamma ray irradiation on the solubilization of waste sewage sludge. The recovery of an organic carbon source from sewage sludge by gamma ray irradiation was also studied. The gamma ray irradiation showed effective sludge solubilization efficiencies. Both soluble chemical oxygen demand (SCOD) and biochemical oxygen demand (BOD₅) increased by gamma ray irradiation. The feasibility of the solubilized sludge carbon source for a biological nitrogen removal was also investigated. A modified continuous bioreactor (MLE process) for a denitrification was operated for 20 days by using synthetic wastewater. It can be concluded that the gamma ray irradiation was useful for the solubilization of sludge and the recovery of carbon source from the waste sewage sludge for biological nitrogen removal.     

Electrospun carbon nanofibers for lithium metal anodes: Progress and perspectives

Li metal anodes(LMAs) has attracted extensive research interest because of its extremely high theoretical capacity(3860 m Ah/g) at low redox potential(-3.04 V vs. standard hydrogen electrode). However, the extremely high chemical reactivity and the intrinsic “hostless” nature of LMAs bring about serious dendritic growth and dramatic volume change during the plating/strapping process, thus resulting in poor Coulombic efficiency, short lifespan, and severe safety concerns. Of various strategies, t...     

Designing composite solid-state electrolytes for high performance lithium ion or lithium metal batteries

Solid-state electrolytes (SSEs) are capable of inhibiting the growth of lithium dendrites, demonstrating great potential in next-generation lithium-ion batteries (LIBs). However, poor room temperature ionic conductivity and the unstable interface between SSEs and the electrode block their large-scale applications in LIBs. Composite solid-state electrolytes (CSSEs) formed by mixing different ionic conductors lead to better performance than single SSEs, especially in terms of ionic conductivity and interfacial stability. Herein, we have systematically reviewed recent developments and investigations of CSSEs including inorganic composite and organic–inorganic composite materials, in order to provide a better understanding of designing CSSEs. The comparison of different types of CSSEs relative to their parental materials is deeply discussed in the context of ionic conductivity and interfacial design. Then, the proposed ion transfer pathways and models of lithium dendrite growth in composites are outlined to inspire future development of CSSEs.

Composite solid-state electrolytes (CSSEs) formed by mixing different ionic conductors lead to better performance than a single solid-state electrolytes (SSEs), demonstrating great potentials in the next-generation lithium-ion batteries (LIBs).     

Integrated lithium metal anode protected by composite solid electrolyte film enables stable quasi-solid-state lithium metal batteries

Lithium (Li) metal, possessing an extremely high theoretical specific capacity (3860 mAh/g) and the most negative electrode potential (−3.040 V vs. standard hydrogen electrode), is one the most favorable anode materials for future high-energy-density batteries. However, the poor cyclability and safety issues induced by extremely unstable interfaces of traditional liquid Li metal batteries have limited their practical applications. Herein, a quasi-solid battery is constructed to offer superior interfacial stability as well as excellent interfacial contact by the incorporation of Li@composite solid electrolyte integrated electrode and a limited amount of liquid electrolyte (7.5 μL/cm²). By combining the inorganic garnet Al-doped Li_6.75La₃Zr_1.75Ta_0.25O₁₂ (LLZO) with high mechanical strength and ionic conductivity and the organic ethylene-vinyl acetate copolymer (EVA) with good flexibility, the composite solid electrolyte film could provide sufficient ion channels, sustained interfacial contact and good mechanical stability at the anode side, which significantly alleviates the thermodynamic corrosion and safety problems induced by liquid electrolytes. This innovative and facile quasi-solid strategy is aimed to promote the intrinsic safety and stability of working Li metal anode, shedding light on the development of next-generation high-performance Li metal batteries.     

Reversing the dendrite growth direction and eliminating the concentration polarization via an internal electric field for stable lithium metal anodes

Lithium (Li) dendrite growth is a long-standing challenge leading to short cycle life and safety issues in Li metal batteries. Li dendrite growth is kinetically controlled by ion transport, the concentration gradient, and the local electric field. In this study, an internal electric field is generated between the anode and Au-modified separator to eliminate the concentration gradient of Li⁺. The Li–Au alloy is formed during the first cycle of Li plating/stripping, which causes Li⁺ deposition on the Au-modified side and lithium anode electrode, reversing the lithium dendrite growth direction. The electrically coupled Li metal electrode and Au-modified film create a uniform electric potential and Li⁺ concentration distribution, resulting in reduced concentration polarization and stable Li deposition. As a result, the Au-modified separator improves the lifespan of Li‖Li batteries; the Li‖LiFePO₄ cells show excellent capacity retention (>97.8% after 350 cycles), and Li‖LiNi_0.8Co_0.1Mn_0.1O₂ cells deliver 75.1% capacity retention for more than 300 cycles at 1C rate. This strategy offers an efficient approach for commercial application in advanced metallic Li batteries.

An internal electric field is built between the anode and the Au-modified separator to eliminate the concentration gradient of Li⁺ and reverse the dendrite growth direction.     

The application of nanostructured transition metal sulfides as anodes for lithium ion batteries

With wide application of electric vehicles and large-scale in energy storage systems, the requirement of secondary batteries with higher power density and better safety gets urgent. Owing to the merits of high theoretical capacity, relatively low cost and suitable discharge voltage, much attention has been paid to the transition metal sulfides. Recently, a large amount of research papers have reported about the application of transition metal sulfides in lithium ion batteries. However, the practical application of transition metal sulfides is still impeded by their fast capacity fading and poor rate performance. More well-focused researches should be operated towards the commercialization of transition metal sulfides in lithium ion batteries. In this review, recent development of using transition metal sulfides such as copper sulfides,molybdenum sulfides, cobalt sulfides, and iron sulfides as electrode materials for lithium ion batteries is presented. In addition, the electrochemical reaction mechanisms and synthetic strategy of transition metal sulfides are briefly summarized. The critical issues, challenges, and perspectives providing a further understanding of the associated electrochemical processes are also discussed.     

Recent progress of composite solid polymer electrolytes for all-solid-state lithium metal batteries

In comparison with lithium-ion batteries (LIBs) with liquid electrolytes, all-solid-state lithium batteries (ASSLBs) have been considered as promising systems for future energy storage due to their safety and high energy density. As the pivotal component used in ASSLBs, composite solid polymer electrolytes (CSPEs), derived from the incorporation of inorganic fillers into solid polymer electrolytes (SPEs), exhibit higher ionic conductivity, better mechanical strength, and superior thermal/electrochemical stability compared to the single-component SPEs, which can significantly promote the electrochemical performance of ASSLBs. Herein, the recent advances of CSPEs applied in ASSLBs are presented. The effects of the category, morphology and concentration of inorganic fillers on the ionic conductivity, mechanical strength, electrochemical window, interfacial stability and possible Li⁺ transfer mechanism of CSPEs will be systematically discussed. Finally, the challenges and perspectives are proposed for the future development of high-performance CSPEs and ASSLBs.     

Amorphous silicon thin films as a high capacity anodes for Li-ion batteries in ionic liquid electrolytes

High lithiation capacity at low red-ox potentials in combination with good safety characteristics makes amorphous Si as a very promising anode material for rechargeable Li batteries.Thin film silicon electrodes were prepared by DC magnetron sputtering of silicon on stainless steel substrates. Their behavior as Li insertion/extraction electrodes was studied by voltammetry and chronopotentiometry at room temperature in the ionic liquid (IL) 1-methyl-1-propylpiperidinium bis(trifluoromethylsuphonil)imide containing 1 M Li bis(trifluoromethylsuphonil)imide. Li/Si cells containing this electrolyte showed good performance with a stable Si electrodes capacity of about 3000 mA h g⁻¹ and a relatively low irreversible capacity. Preliminary results on cycling Si–LiCoO₂ cells using this IL electrolyte are also presented.     

Synergistic effect of lithiophilic Zn nanoparticles and N-doping for stable Li metal anodes

Li metal is the most ideal anode material for next-generation high energy lithium-ion batteries.The uncontrollable growth of Li dendrites,however,hinders its practical application.Herein,we propose the adoption of Zn nanoparticles uniformly embedded in N-doped carbon polyhedra homogeneously built on carbon cloth(Zn@NC@CC)to prevent the formation of Li dendrites.Based on theoretical calculation and experimental observation,lithiophilic Zn nanoparticles and N-doping inside of the assynthesized Zn@NC play a synergistic role in enhancing the adsorption capacity with Li,thus resulting in uniform Li deposition and complete suppression of Li dendrites.Moreover,the porous N-doped carbon polyhedras uniformly distributed on carbon cloth effectively relieves the volume change of Li upon repeated Li stripping/plating process,which contributes to preserving the structural integrity of the whole electrode and hence enhancing its long-term cycling stability.Benefiting from these synergistic effects,the Li-Zn@NC@CC electrode delivers a prolonged lifespan of over 1200 h at 1 mA cm^-2 with an areal capacity of 1 mA h cm^-2 in symmetric cells and high Coulombic efficiencies of 95.4%under an ultrahigh capacity of 12 mA h cm^-2.Remarkably,Li-Zn@NC@CC//LiFePO₄ full cells deliver a high reversible capacity of 110.2 mA h g^-1 at 1 C over 200 cycles.     

In vacuo XPS investigation of surface engineering for lithium metal anodes with plasma treatment

Lithium (Li) metal is an attractive anode material with high capacity (3860 m Ah g^-1) and low potential(-3.04 V vs. standard hydrogen electrode) that shows highly promising for applications requiring high energy density. However, the low electrochemical potential of Li metal makes it extremely reactive and inevitably forming a native oxidized layer in the ambient environment and repeatedly being consumed when exposed to liquid electrolytes. It is therefore beneficial to replace the po...