Poly(siloxane imide) Binder for Silicon‐Based Lithium‐Ion Battery Anodes via Rigidness/Softness Coupling

Binders play a crucial role in maintaining mechanical integrity of electrodes in lithium‐ion batteries. However, the conventional binders lack proper elasticity, and they are not suitable for high‐performance silicon anodes featuring huge volume change during cycling. Herein, a poly(siloxane imide) copolymer (PSI) has been designed, synthesized, and utilized as a binder for silicon‐based anodes. A rigidness/softness coupling mechanism is demonstrated by the PSI binder, which can accommodate volume expansion of the silicon anode upon lithiation. The electrochemical performance in terms of cyclic stability and rate capability can be effectively improved with the PSI binder as demonstrated by a silicon nanoparticle anode.     

Crosslinked carboxymethyl cellulose-sodium borate hybrid binder for advanced silicon anodes in lithium-ion batteries

Hybrid gel binder with deformable network and strong adhesive capability on silicon particles can effectively accommodate the large volume change of silicon anodes upon cycling, leading to an excellent cycling stability and high Coulombic efficiency.     

Role of Low Molecular Weight Polymers on the Dynamics of Silicon Anodes During Casting

This work probes the slurry architecture of a high silicon content electrode slurry with and without low molecular weight polymeric dispersants as a function of shear rate to mimic electrode casting conditions for poly(acrylic acid) (PAA) and lithium neutralized poly(acrylic acid) (LiPAA) based electrodes. Rheology coupled ultra-small angle neutron scattering (rheo-USANS) was used to examine the aggregation and agglomeration behavior of each slurry as well as the overall shape of the aggregates. The addition of dispersant has opposing effects on slurries made with PAA or LiPAA binder. With a dispersant, there are fewer aggregates and agglomerates in the PAA based silicon slurries, while LiPAA based silicon slurries become orders of magnitude more aggregated and agglomerated at all shear rates. The reorganization of the PAA and LiPAA binder in the presence of dispersant leads to a more homogeneous slurry and a more heterogeneous slurry, respectively. This reorganization ripples through to the cast electrode architecture and is reflected in the electrochemical cycling of these electrodes.     

Effect of high adhesive polyvinyl alcohol binder on the anodes of lithium ion batteries

High molecular weight (MW) polyvinyl alcohol (PVA) was synthesized by two-step polymerizations and employed as an anodic binder of lithium ion batteries (LIBs). Numerous hydroxyl groups in PVA formed strong hydrogen bonds with both active materials and the current collector. These strong hydrogen bonds led to an increase in the amount of binder covering the surface of active materials and significantly enhanced the adhesion strength of electrodes. The high MW PVA binder showed much better cyclic performance for silicon/carbon anodes than polyvinylidene fluoride (PVDF) and polyacrylic acid (PAA) binders.     

粘结剂对形貌各异的石墨负极电化学性能的影响

As an important component in electrodes, the choice of an appropriate binder is significant when fabricating lithium-ion batteries (LIBs) with good cycle stability and rate capability, which are used in numerous applications, especially portable electronics and eco-friendly electric vehicles (EVs). Semi-crystalline poly(vinylidene fluoride) (PVDF), which is a traditional and widely used binder, cannot efficiently accommodate the volume changes observed in the anode during the charge-discharge process while binding all the components in the electrode together, which results in increased internal cell resistance, detachment of the electrode components, and capacity fading. Herein, we have investigated a highly polar and elastomeric polyacrylonitrile-butadiene (NBR) rubber for use as a binder in LIBs, which can accommodate graphite particles of different shapes compared to semi-crystalline PVDF. Prior to our electrochemical tests, NBR was analyzed using thermogravimetric analysis (TGA) and X-ray diffraction (XRD), showing good thermal stability and an amorphous morphology. NBR is more conformable to irregular surfaces, which results in the formation of a homogeneous passivation layer on both spherical and flaky graphite particles to effectively suppress any electrolyte side reactions, further allowing more uniform and fast Li ion diffusion at the electrolyte/electrolyte interface. As a result, the electrochemical performance of both spherical and flaky shape graphite electrodes was significantly improved in terms of their first cycle Coulombic efficiency (CE) and cycle stability. With comparative specific capacity, the first cycle CE of the NBR-based spherical and flaky graphite electrodes were 87.0% and 85.5%, compared to 85.3% and 82.6% observed for their corresponding PVDF-based electrodes, respectively. After 1000 discharge-charge cycles at 1C, the capacity retention of the NBR-based graphite electrodes was significantly higher than that of PVDF-based electrodes. This was attributed to the good stability of the solid electrolyte interphase (SEI) formed on the graphite electrodes and the high stretching ability of the elastomeric NBR binder, which help to accommodate the repeated volume fluctuation of graphite observed during long-term charge-discharge cycling. Electrochemical impedance spectroscopy (EIS) and microscopic analysis (SEM and TEM) were carried out to investigate the formation and evolution of the SEI layers formed on the spherical and flaky graphite electrodes. The results show that thin, homogeneous, and stable SEI layers are formed on the surface of both spherical and flaky graphite electrodes prepared using the NBR binder. When compared to the PVDF-based graphite electrodes, the graphite electrodes constructed using NBR showed decreased resistance in the SEI layer and faster charge transfer, thus enhancing the electrode kinetics for Li ion intercalation/deintercalation. Our study shows that the electrochemical performance of spherical and flaky graphite electrodes prepared using the NBR binder is significantly improved, demonstrating that NBR is a promising binder for these electrodes in LIBs.     

Transformation of Rusty Stainless‐Steel Meshes into Stable,Low‐Cost,and Binder‐Free Cathodes for High‐Performance Potassium‐Ion Batteries

To recycle rusty stainless‐steel meshes (RSSM) and meet the urgent requirement of developing high‐performance cathodes for potassium‐ion batteries (KIB), we demonstrate a new strategy to fabricate flexible binder‐free KIB electrodes via transformation of the corrosion layer of RSSM into compact stack‐layers of Prussian blue (PB) nanocubes (PB@SSM). When further coated with reduced graphite oxide (RGO) to enhance electric conductivity and structural stability, the low‐cost, stable, and binder‐free RGO@PB@SSM cathode exhibits excellent electrochemical performances for KIB, including high capacity (96.8 mAh g⁻¹), high discharge voltage (3.3 V), high rate capability (1000 mA g⁻¹; 42 % capacity retention), and outstanding cycle stability (305 cycles; 75.1 % capacity retention).     

锂离子电池硅基负极材料的最新研究进展

硅基材料因具有目前最高的理论比容量、合适的嵌锂平台、大储量等优点,引起了众多研究者的关注,成为最具潜力的下一代锂离子电池的负极材料. 但是硅在嵌锂过程中巨大的体积变化,容易破坏电极结构的稳定性,使电极循环性能迅速衰减,这对硅基材料的应用造成了很大的阻碍. 本文主要针对近年来在硅电极自身的结构（包括：多孔硅基复合材料的合成、硅粘结剂的选择,无粘结剂的纳米硅电极的制备）以及电解液添加剂的选择两大方面的最新研究进展进行总结与评述.     

果胶粘结剂在锂硫电池中的应用研究

锂硫电池由于其超高理论能量密度(2567 Wh·kg^?1),较低的成本,以及环境友好性,被视为下一代储能设备的有力竞争者之一.鉴于粘结剂在稳定硫正极结构和抑制多硫化物穿梭方面可发挥重要作用,发展高性能硫正极粘结剂是改善锂硫电池性能的有效途径之一.本文研究了以果胶作为锂硫电池正极粘结剂的可行性.研究表明,采用果胶作为粘结剂的锂硫电池在电化学循环测试中首次放电比容量可达1210.6 mAh·g^?1,并且在200次循环后仍有837.4 mAh·g^?1的放电比容量,明显优于羧甲基纤维素钠-丁苯橡胶复合粘结剂的电池性能.经研究证实果胶粘结剂性能优良的原因在于其可以有效确保多壁碳纳米管/硫复合正极的结构稳定性并抑制多硫化物的穿梭.     

Silicon-containing anodes with low accumulated irreversible capacity for lithium-ion batteries

Within the framework of the novel strategy of the arrangement of silicon particles in a rigid matrix framework, hybrid electrodes were fabricated from mixtures of synthetic graphite with small additions of nanosilicon/solid carbon and microsilicon, natural graphite/solid carbon composites. The electrode cycling parameters achieved (high loading capacity and low accumulated irreversible capacity) are due to high density of the electrodes and formation of stable electrode|electrolyte interface.     

Effects of alloying elements and binder on the electrochemical behavior of metal hydride electrodes in potassium hydroxide electrolyte

This investigation examines the effect of alloying elements on the charge–discharge performance of LaNi_3.6(Co+Mn+Al)_1.4 electrodes in 7 M KOH electrolyte. The activation behavior and the effect of binder content were also examined. Both half-cell and full-cell systems were employed to evaluate the electrochemical performance. Experimental results indicated that a few cycles of charge–discharge at a rate of 150 mA/g in 7 M KOH electrolyte were sufficient to activate the freshly prepared LaNi_3.6(Co+Mn+Al)_1.4 electrodes. The amount of binder affected the activation behavior, the overvoltage for hydrogen ions reduction and the discharge capacity of the MmNi_3.55Co_0.75Mn_0.4Al_0.3 electrode. In the alloy of the LaNi_3.6(Co+Mn+Al)_1.4 electrodes, a high Co content helped to promote both the capacity at a relatively low discharging rate and the cyclic life. An increase of the Al content raised the discharge voltage and improved the high rate discharge capacity, but reduced the cyclic stability. The alloy with a high Mn content required the least cathodic polarization during charging but had the lowest discharge capacity at a rather high discharging rate.     

Electrostatic Interactions Leading to Hierarchical Interpenetrating Electroconductive Networks in Silicon Anodes for Fast Lithium Storage

Recently, the frequency of combining MXene, which has unique properties such as metal-level conductivity and large specific surface area, with silicon to achieve excellent electrochemical performance has increased considerably. There is no doubt that the introduction of MXene can improve the conductivity of silicon and the cycling stability of electrodes after elaborate structure design. However, most exhaustive contacts can only improve the electrode conductivity on the plane. Herein, a MXene@Si/CNTs (HIEN-MSC) composite with hierarchical interpenetrating electroconductive networks has been synthesized by electrostatic self-assembly. In this process, the CNTs are first combined with silicon nanoparticles and then assembled with MXene nanosheets. Inserting CNTs into silicon nanoparticles can not only reduce the latter‘s agglomeration, but also immobilizes them on the three-dimensional conductive framework composed of CNTs and MXene nanosheets. Therefore, the HIEN-MSC electrode shows superior rate performance (high reversible capacity of 280 mA h⁻¹ even tested at 10 A g⁻¹), cycling stability (stable reversible capacity of 547 mA h g⁻¹ after 200 cycles at 1 A g⁻¹) and applicability (a high reversible capacity of 101 mA h g⁻¹ after 50 cycles when assembled with NCM622 into a full cell). These results may provide new insights for other electrodes with excellent rate performance and long-cycle stability.     

Novel binding material for supercapacitor electrodes

Environmentally friendly water-based composite material has been investigated as a novel binder for manufacturing supercapacitor electrodes. The performance of these electrodes and those with the conventional polyvinylidene fluoride (PVDF) binder were studied. Results obtained from cyclic voltammetry, electrochemical impedance spectrometry, and charge/discharge measurements showed that the electrodes with the new binder performed significantly better than the electrodes with the conventional PVDF binder; the specific capacitance increased by 51 % in an aqueous electrolyte while in an organic electrolyte, it increased by 15 %. This increase in capacitance was attributed to the electrophilic and hydrophilic nature of the new binding composite. The main reason for the improvement in capacitance was ascribed to reduction of equivalent series resistance (ESR). The presence of highly amorphous polyvinylpyrrolidone (PVP), a polymeric component of the new composite binder, was responsible for the reduction in ESR.     

Cathode material for sodium-ion batteries based on manganese hexacyanoferrate: the role of the binder component

Sodium manganese hexacyanoferrate (NaMnHCF) was synthesized by a hydrothermal method and investigated as a cathode material for sodium-ion batteries. The morphology and the structure of NaMnHCF were investigated by X-ray diffraction, scanning electron microscopy, and EDX analysis. New composition of NaMnHCF cathode material for sodium-ion batteries with eco-friendly water-based binder consisting of conducting polymer poly-3,4-ethylenedioxythiopene/polystyrene sulfonate (PEDOT:PSS) dispersion and carboxymethyl cellulose (СМС) was proposed. The electrochemical properties of NaMnHCF cathode material with conductive polymer binder were investigated by cyclic voltammetry and galvanostatic charge-discharge, and the results were compared with the performance of a conventional PVDF-bound material. It was shown that the initial discharge capacity of electrodes with conductive binder is 130 mAh g⁻¹, whereas the initial discharge capacity of PVDF-bound electrodes was 109 mAh g⁻¹ (both at current density 120 mA g⁻¹, values normalized by NaMnHCF mass). The material with conductive binder also has better rate capability; however, it is losing in cycling capability to the electrode composition with conventional PVDF binder.

     

Silicon nanopowder as active material for hybrid electrodes of lithium-ion batteries

Cycling parameters (reversible specific capacity, first-cycle coulombic efficiency, accumulated irreversible capacity, and reversible capacity retention) of hybrid electrodes based on mechanical mixtures of a silicon nanopowder with KS6 and MAG-20 synthetic graphites and binders of varied nature were subjected to an integrated analysis in comparison with graphite electrodes.     

Silicon-containing anodes with high capacity loading for lithium-ion batteries

Comparative analysis of cycling performance of hybrid electrodes based on the MAG synthetic graphite mechanic mixtures with silicon nanopowder and “nano-Si/SiO₂/hard carbon” ceramic frame-ordered composite in 1 M LiPF₆ solution in a monofluoroethylene carbonate-ethyl methyl carbonate mixture (30: 70, v/v), added with 3 wt % vinylene carbonate and 2 wt % ethylene sulfite, is performed. The high capacity loading (up to 6.8 mA h cm^?2 at the electrode layer thickness of 37 μm) and acceptable accumulated irreversible capacity of the composite-containing electrodes are achieved, due to the electrodes’ high density and stable silicon-containing electrode/electrolyte interface formation.     

Ionic/electronic conductivity regulation of n-type polyoxadiazole lithium sulfonate conductive polymer binders for high-performance silicon microparticle anodes

Low-cost silicon microparticles(SiMP),as a substitute for nanostructured silicon,easily suffer from cracks and fractured during the electrochemical cycle.A novel n-type conductive polymer binder with excellent electronic and ionic conductivities as well as good adhesion,has been successfully designed and applied for high-performance SiMP anodes in lithium-ion batteries to address this problem.Its unique features are attributed to the stro ng electron-withdrawing oxadiazole ring structure with sulfonate polar groups.The combination of rigid and flexible components in the polymer ensures its good mechanical strength and ductility,which is beneficial to suppress the expansion and contraction of SiMP s during the charge/discharge process.By fine-tuning the monomer ratio,the conjugation and sulfonation degrees of the polymer can be precisely controlled to regulate its ionic and electronic conductivities,which has been systematically analyzed with the help of an electrochemical test method,filling in the gap on the conductivity measurement of the polymer in the doping state.The experimental results indicate that the cell with the developed n-type polymer binder and SiMP(~0.5 μm) anodes achieves much better cycling performance than traditional non-conductive binders.It has been considered that the initial capacity of the SiMP anode is controlled by the synergetic effect of ionic and electronic conductivity of the binder,and the capacity retention mainly depends on its electronic conductivity when the ionic conductivity is sufficient.It is worth noting that the fundamental research of this wo rk is also applicable to other battery systems using conductive polymers in order to achieve high energy density,broadening their practical applications.     

Viscosity and binder composition effects on tyrosinase-based carbon paste electrode for detection of phenol and catechol

The systematic study of the effect of binder viscosity on the sensitivity of a tyrosinase-based carbon paste electrode (CPE) biosensor for phenol and catechol is reported. Silicon oil binders with similar (polydimethylsiloxane) chemical composition were used to represent a wide range of viscosities (10–60 000 mPa s⁻¹ at 25°C) while minimizing polarity effects. The highest response for both phenol and catechol was achieved using a silicon oil binder of intermediate viscosity (100 mPa s⁻¹). The binder viscosity showed no appreciable effect on the direct oxidation of phenol and catechol using a plain CPE, suggesting the involvement of diffusion kinetics in the binder matrix for the enzyme-based CPE. The effect of the relative binder concentration in the carbon paste was measured over the range of 30–70%. Optimal results were obtained using 40% silicon oil. For comparison of the viscosity effects observed with the carbon paste electrode (CPE) containing silicon oil, other low and high viscosity mineral oils and paraffin waxes were also examined.     

Application of Guar Gum and its Derivatives as Green Binder/Separator for Advanced Lithium-Ion Batteries

Since their first commercialization in the 1990s,lithium-ion batteries (LIBs) have become an indispensible part of our everyday life in particular for portable electronic devices. LIBs have been considered as the most promising sustainable high energy density storage device. In recent years, there is a strong demand of LIBs for hybrid electric and electric vehicles to lower carbon footprint and mitigate climate change. However, LIBs have several issues, for example, high cost and safety issues such as over discharge, intolerance to overcharge, high temperature operation etc. To address these issues several new types of electrodes are being studied. Traditional binder PVDF is costly, difficult to recyle, undergoes side reactions at high temperature and cannot stabilize high energy density electrodes. To overcome these challenges, diiferent binders have been introduced with these electrodes. This minireview is focused on the application of guar gum as a binder for different electrodes and separator. The electrochemical performance of electrodes with guar gum has been compared with other binders.     

Impregnation of Acetylene Black Electrodes with a Polytetrafluoroethylene Binder with an Aqueous Solution and Evaluation of Its Specific Double Layer Capacity

The effect of (0.05 M) tetraalkylammonium salt additions in aqueous 0.5 M KOH on the rate of impregnation of carbon black electrodes with a polytetrafluoroethylene binder (5–20 wt % PTFE) at hydrogen evolution potentials was studied. It was shown that tetraalkylammonium salts facilitate the fast filling of electrodes with electrolyte, and their effect increases with the molecular mass of the cation. Tetramethylammonium bromide showed the weakest effect. In solutions with tetrabutylammonium bromide, the electrodes were completely flooded with 5 wt % PTFE within 15 min. Diethyldibenzylammonium bromide had a similar effect. The influence of the PTFE concentration in the electrodes on their capacity was studied. The specific capacity of acetylene black in acid and alkaline aqueous solutions was evaluated from the electrode surface area determined by low-temperature nitrogen adsorption (BET).     

The effect of the binder morphology on the cycling stability of Li–alloy composite electrodes

It is demonstrated that the design of the composite electrode, or more precisely the morphology and distribution of the binder poly(vinylidine fluoride) (PVdF) within the composite electrode, has a significant impact on the cycling performance of Li storage alloy (Sn/SnSb) electrodes. Different binder morphologies and distributions have been obtained by using different solvents for the slurry preparation, such as 1-methyl-2-pyrrolidinone (NMP), in which PVdF is dissolved, yielding electrodes with a homogeneously and finely distributed binder, or decane, in which PVdF is only dispersed, yielding electrodes in which the original particle morphology of the binder powder is preserved. In constant current cycling tests carried out in an excess of electrolyte, the electrodes with the ‘dispersed’ binder show far better cycling capacities and stabilities than those with the ‘dissolved’ binder. This is explained by the different binding strengths, swelling behaviour in the electrolyte, electrode porosities, and possible ‘buffer’ effects of the compact and the finely distributed binders.