Asymmetric double-layer composite electrolyte with enhanced ionic conductivity and interface stability for all-solid-state lithium metal batteries

All-solid-state Li metal battery has been regarded as a promising battery technology due to its high energy density based on the high capacity of lithium metal anode and high safety based on the all solid state electrolyte without inflammable solvent.However,challenges still exist mainly in the poor contact and unstable interface between electrolyte and electrodes.Herein,we demonstrate an asymmetric design of the composite polymer electrolyte with two different layers to overcome the interface issues at both the cathode and the anode side simultaneously.At the cathode side,the polypropylene carbonate layer has enough viscosity and flexibility to reduce the inter-facial resistance,while at the Li anode side,the polyethylene oxide layer modified with hexagonal boron nitride has high mechanical strength to suppress the Li dendrite growth.Owing to the synergetic effect between different components,the asprepared double layer composite polymer electrolyte demonstrates a large electrochemical window of5.17 V,a high ionic conductivity of 6.1×10~(-4) S/cm,and a transfe rence number of 0.56,featuring excellent ion transport kinetics and good chemical stability.All-solid-state Li metal battery assembled with LiFePO_4 cathode and Li anode delivers a high capacity of 150.9 mAh/g at 25℃ and 0.1 C-rate,showing great potential for practical applications.     

EC modified PEO/PVDF-LLZO composite electrolytes for solid state lithium metal batteries

The polymer-ceramic composite electrolytes have great application potential for next-generation solid state lithium batteries, as they have the merits to eliminate the problem of liquid organic electrolytes and enhancing chemical/electrochemical stability. However, polymer-ceramic composite electrolytes show poor ionic conductivity, which greatly hinders their practical applications. In this work, the addition of plasticizer ethylene carbonate (EC) into polymer-ceramic composite electrolyte for lithium batteries effectively promotes the ionic conductivity. A high ionic conductivity can be attained by adding 40 wt% EC to the polyethylene oxide (PEO)/polyvinylidene fluoride (PVDF)-Li₇La₃Zr₂O₁₂ (LLZO) based polymer-ceramic composite electrolytes, which is 2.64 × 10⁻⁴ S cm⁻¹ (tested at room temperature). Furthermore, the cell assembled with lithium metal anode, this composite electrolyte, and LiFePO₄ cathode can work more than 80 cycles at room temperature (tested at 0.2 C). The battery delivers a high reversible specific capacity after 89 cycles, which is 119 mAh g⁻¹.     

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.     

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.     

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...     

Novel composite anode materials for lithium ion batteries with low sensitivity towards humidity

Graphitic anode materials for lithium ion batteries processed under high humidity conditions show severe performance losses. The sensitivity of these materials towards humidity can be significantly reduced by adsorbing metal ions like silver or copper ions, with subsequent heat treatment of these composites. Results of X-ray photoelectron spectroscopy, high-resolution electron microscopy, thermogravimetry, and differential thermal analysis indicate that the deposited metals exist in metallic and carbide, M_xC (M=Cu or Ag), forms. They remove or cover (i.e. deactivate) active hydrophilic sites at the surface of the graphite. These composites absorb less water during processing. The electrochemical performance, including reversible capacity, coulombic efficiency in the first cycle, and cycling behavior, is markedly improved. This approach provides a potentially powerful method to manufacture lithium ion batteries under less demanding conditions.Presented at the 3rd International Meeting on Advanced Batteries and Accumulators, 16–20 June 2002, Brno, Czech Republic     

The recent advances in constructing designed electrode in lithium metal batteries

In this review, we focus on the design of lithium electrode and its recent advancements, which suppress the growth of lithium dendrites and improve the performance of the rechargeable batteries. To suppress the growth of lithium dendrites, the general design rules of the system require a uniform lithium ion flux, a low current density, a homogeneous nucleation process and a stable SEI layer. Improvements of the battery performance have been achieved through the delicate design of lithium electrode and here they are summarized into three groups:i) optimizing the 3D porous nanostructure of the current collector, ii) constructing rational host for lithium metal and prelithiating the 3D host matrix with molten lithium, iii) protecting the surface of lithium metal by functional layers. An outlook of the challenges and the potentials of lithium metal battery is also provided, which will facilitate the future development of lithium metal battery.     

PIM-1 as an artificial solid electrolyte interphase for stable lithium metal anode in high-performance batteries

Lithium metal anode is a promising electrode with high theoretical specific capacity and low electrode potential.However,its unstable interface and low Coulombic efficiency,resulting from the dendritic growth of lithium,limits its commercial application.PIM-1(PIM:polymer of intrinsic microporosity),which is a polymer with abundant micropores,exhibits high rigidity and flexibility with contorted spirocenters in the backbone,and is an ideal candidate for artificial solid electrolyte interphases(SEI).In this work,a PIM-1 membrane was synthesized and fabricated as a protective membrane on the surface of an electrode to facilitate the uniform flux of Li ions and act as a stable interface for the lithium plating/stripping process.Nodule-like lithium with rounded edges was observed under the PIM-1 membrane.The Li@PIM-1 electrode delivered a high average Coulombic efficiency(99.7%),excellent cyclability(80%capacity retention rate after 600 cycles at 1 C),and superior rate capability(125.3 m Ah g~(-1) at 10 C).Electrochemical impedance spectrum(EIS)showed that the PIM-1 membrane could lower the diffusion rate of Li~+ significantly and change the rate-determining step from charge transfer to Li~+diffusion.Thus,the PIM-1 membrane is proven to act as an artificial SEI to facilitate uniform and stable deposition of lithium,in favor of obtaining a compact and dense Li-plating pattern.This work extends the application of PIMs in the field of lithium batteries and provides ideas for the construction of artificial SEI.     

Recent advances in nanostructured composite solid electrolyte

Solid-state lithium batteries (SSLBs) potentially offer safer and higher energy density batteries than traditional Li-ion batteries, but many challenges remain in the development of high-performance SSLBs. For example, solid-state electrolytes with high ionic conductivity are still critically needed. Composite solid electrolytes (CSEs), which are constituted of ceramic fillers dispersed in polymer matrices, may potentially combine the advantages of ceramic and polymer electrolytes and thus have been intensively investigated. Recent works have found that the size, geometry, and dispersion of ceramic ?llers strongly influence the conductivity of CSEs. This review aims at giving a summary of the recent progresses in CSE including the developments in materials as well as mechanistic characterizations. We believe the latest scientific insights will help the researchers in the field to better design CSEs toward the development of high-performance SSLBs.     

Recent progress in lithium-ion and lithium metal batteries

Moving towards carbon-free energy and global commercialization of electric vehicles stimulated extensive development in the field of lithium-ion batteries (LIBs), and to date, many scientific and technological advances have been achieved. The number of research works devoted to developing high-capacity and stable materials for lithium- ion and lithium metal batteries (LMBs) is constantly rising. This review covers the main progress in the development of LIBs and LMBs based on research works published in 2021. One of the main goals in the recent publications is to solve the problem of instability of layered nickel-rich lithium– nickel–cobalt–manganese oxides (Ni-rich NMC) cathodes, as well as silicon anodes. Improving the stability of NMC cathodes can be achieved by doping them with cations as well as by coating the oxides’ surfaces with protective layers (organic polymers and inorganic materials). The most effective strategies for dampening volumetric changes in silicon anodes include using porous silicon structures, obtaining composites with carbon, coating silicon-containing particles with inorganic or polymeric materials, and replacing standard binder materials. Much work has been devoted to suppressing dendrite formation in LMBs by forming stable coating layers on the surface of lithium metal, preparing composite anodes and alloys, and changing the composition of electrolytes. At the same time, in the field of electrolyte development, many research works have been devoted to the search for new hybrid polymer electrolytes containing lithium-conducting inorganic materials.     

甘氨酸电解液添加剂对水系锌离子电池电化学性能的影响

水系锌离子电池因其高安全性、高容量、低价格等优点,有望成为下一代规模储能设备。然而,副反应、锌枝晶和有限的使用寿命阻碍了其实际应用。我们将电解质添加剂甘氨酸(Gly)引入到常规水系ZnSO₄电解质中。Gly中的极性基团(—COOH和—NH₂)可以调节Zn²⁺的溶剂化结构,从而重新分配Zn²⁺的沉积以避免枝晶和副反应发生。结果表明,在ZnSO₄电解质中添加50 mmol·L^-1的Gly后(ZnSO₄-Gly),Zn||Zn对称电池在1 mA·cm^-2和1 mAh·cm^-2下,表现出良好的循环寿命(3 000 h),明显高于使用ZnSO₄电解质的性能(300 h)。以ZnSO₄-Gly为电解液的Zn||MnO₂全电池,在比电容和倍率性能方面比无添加剂器件表现得更好。     

Nonflammable nonaqueous electrolytes for lithium batteries

As the energy density of state-of-the-art lithium (Li)-ion batteries (LIBs) increases, the safety concern of LIBs using liquid electrolytes is drawing increasing attention. Flammability of electrolytes is a critical link of the overall safety performance of LIBs and Li metal batteries. For this reason, intensive efforts have been devoted to suppressing the flammability of liquid electrolytes. In this short review, the common approaches to reduce the flammability of the nonaqueous liquid electrolytes will be summarized. The advantages and limitations of these approaches will also be discussed.     

Protection of Li metal anode by surface-coating of PVDF thin film to enhance the cycling performance of Li batteries

The PVDF thin film on the surface of the lithium metal can highly suppress the lithium dendrites.     

Directly conversion the biomass-waste to Si/C composite anode materials for advanced lithium ion batteries

The necessity to explore high-efficiency and high-value utilization strategy for biomass-waste is desirable.Herein,the strategy for direct conversion biomass-waste(rice husks) to Si/C composite structure anode was built.The Si/C composite materials were successfully obtained via the typical thermal reduction with magnesium,and the Si nanopa rticle was uniformly embedded in carbon frame,as revealed by Raman,X-ray diffraction(XRD) and transmission electron microscope(TEM) measurement.The carbon structure among rice husks was effectively used as a protective layer to accommodate the volume variation of Si anode during the repeated lithiation/delithiation process.Benefitting from the structure design,the batteries show a superior electrochemical stability with the capacity retention rate above 90% after 150 cycles at the charge/discha rge rate of 0.5 C(1 C=600 mAh/g),and hold a high charge capacity of 420.7 mAh/g at the rate of 3 C.Therefore,our finding not only provides a promising design strategy for directly conversion biomass-waste to electrochemical storage materials but broadens the high-efficiency utilization method for other biomass by-products.     

Electrolyte additive maintains high performance for dendrite-free lithium metal anode

Because of their high capacity and low potential, lithium metal anodes are considered to be promising candidates for next generation electrode materials. However, the safety concerns and limited cycling life associated with uncontrollable dendrite growth hamper practical applications. In this work, the acidified cellulose ester, which is a mixed fiber microporous membrane film, was used as a novel electrolyte additive that effectively improves the cycle stability of the lithium metal anode and inhibits dendrite growth. The focus of this paper is on inhibiting the formation and growth of lithium dendrites. The coulombic efficiency of a Li|Cu battery with this acidified cellulose ester additive remains stable at 99% after 500 cycles under a current density of 1 mA/cm². Symmetric batteries also remain stable after 500 cycles (1000 h) under a current density of 1 mA/cm². These superior properties can be ascribed to the induced nucleation and the uniform distribution of lithium ion flux. This study uncovers an approach for effectively enabling stable cycling of dendrite-free lithium metal anodes.     

A novel PEO-based composite solid-state polymer electrolyte with methyl group-functionalized SBA-15 filler for rechargeable lithium batteries

Functionalized molecular sieve SBA-15 with trimethylchlorosilane was used as an inorganic filler in a poly(ethyleneoxide) (PEO) polymer matrix to synthesize a composite solid-state polymer electrolyte (CSPE) using LiClO₄ as the doping salts, which is designated to be used for rechargeable lithium batteries. The methyl group-functionalized SBA-15 (^fSBA-15) powder possesses more hydrophobic characters than SBA-15, which improves the miscibility between the ^fSBA-15 filler and the PEO matrix. The interaction between the ^fSBA-15 and PEO polymer matrix was investigated by scanning electron microscopy, X-ray diffraction, and differential scanning calorimetry. Linear sweep voltammetry and electrochemical impedance spectroscopy were employed to study the electrochemical stability windows, ionic conductivity, and interfacial stability of the CSPE. The temperature dependence of the change of the PEO polymer matrix in the CSPE from crystallization to amorphous phase was surveyed, for the first time, at different temperature by Fourier transform infrared emission spectroscopy. It has demonstrated that the addition of the ^fSBA-15 filler has improved significantly the electrochemical compatibility of the CSPE with a lithium metal electrode and enhanced effectively the ion conductivity of the CSPE. Dedicated to Professor Oleg Petrii on the occasion of his 70th birthday on August 24th, 2007.     

Nickel foam-supported porous NiO/polyaniline film as anode for lithium ion batteries

Nickel foam-supported porous NiO film was prepared by a chemical bath deposition technique, and the NiO/polyaniline (PANI) film was obtained by depositing the PANI layer on the surface of the NiO film. The NiO film was constructed by NiO nanoflakes, and after the deposition of PANI, these nanoflakes were coated by PANI. As an anode for lithium ion batteries, the NiO/PANI film exhibits weaker polarization as compared to the NiO film. The specific capacity after 50 cycles for NiO/PANI film is 520 mAh g⁻¹ at 1 C, higher than that of NiO film (440 mAh g⁻¹). The improvement of these properties is attributed to the enhanced electrical conduction and film stability of the electrode with PANI.     

Flexible lithium metal capacitors enabled by an in situ prepared gel polymer electrolyte

The rapid development of next-generation flexible electronics stimulates the growing demand for flexible and wearable power sources with high energy density. Li metal capacitor (LMC), combining with a Li metal anode and an activated carbon cathode, exhibits extremely high energy density and high power density due to the unique energy storage mechanism, thus showing great potential for powering wearable electronic devices. Herein, a flexible LMC based on an in situ prepared PETEA-based gel polymer electrolyte (GPE) was reported for the first time. Owing to the high ionic conductivity of PETEA-based GPE (5.75 × 10⁻³ S/cm at 20 °C), the assembled flexible LMC delivers a high capacitance of 210 F/g at 0.1 A/g within the voltage range from 1.5 V to 4.3 V vs. Li/Li⁺, a high energy density of 474 Wh/kg at 0.1 A/g and a high power density of 29 kW/kg at 10 A/g. More importantly, PETEA-based GPE endows the LMC with excellent flexibility and safety, which could work normally under abuse tests, such as bending, nail penetration and cutting. The in situ prepared PETEA-based GPE simplifies the fabrication process, avoids the risk of leakage and inhibits the growth of Li dendrite, making LMC a promising flexible energy storage device for the flexible electronic field.     

Alkaline composite film as a separator for rechargeable lithium batteries

We report a new type of separator film for application in rechargeable lithium and lithium-ion batteries. The films are made of mainly alkaline calcium carbonate (CaCO₃) and a small amount of polymer binder. Owing to porosity and capillarity, the composite films show excellent wettability with non-aqueous liquid electrolytes. Typically, the composite films composed of CaCO₃ and Teflon and wetted with 1 M LiPF₆ dissolved in a solvent mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (30:70 wt%) exhibit an ionic conductivity as high as 2.5–4 mS/cm at 20 °C, in a comparable range with that (3.4 mS/cm) of the commercial Celgard membrane. In the batteries, the composite film not only serves as a physical separator but also neutralizes acidic products, such as HF formed by LiPF₆ hydrolysis, as well as those formed by solvent oxidative decomposition. A Li/LiMn₂O₄ test cell was employed to examine the electrochemical compatibility of the composite film. We observed that the composite film cell showed an improved cycling performance since the alkaline CaCO₃ neutralizes the acidic products, which otherwise promote dissolution of the electrode active materials. More importantly, the composite film cell displayed a superior performance on high-rate cycling, which was probably the result of the less resistive interface formed between the electrode and the composite film.     

Polyacrylonitrile-based gel polymer electrolyte filled with Prussian blue forhigh-performance lithium polymer batteries

Lithium polymer batteries(LPBs) rely on a high ion transport to gain improved cell performance.Thermostable and porous gel polymer electrolytes(GPEs) have attracted much attention due to their excellent properties in electrolyte wettability and ionic conductivity.In this work,iron-nickel-cobalt trimetal Prussian blue analogue(PBA) nanocubes are filled into the electro spun polyacrylonitrile(PAN)-based membranes to generate GPE composites with morphological superiority consisting of fine fibers and interconnected pores.The thus obtained PBA@PAN fibrous membrane showcases good thermal stability,high porosity and electrolyte uptake,as well as a peak io nic conductivity of 2.7 mS/cm with the addition of 10% PBA,Consequently,the assembled lithium iron phosphate(LiFePO_4) battery using PBA@PAN-10 as the GPE delivers a high capacity of 152.2 mAh/g at 0.2 C and an ultralow capacity decay of0.09% per cycle in a long-te rm cycle life of 350 cycles at 1 C,endorsing its promising applications in LPBs.