Silk fibroin-based biopolymer composite binders with gradient binding energy and strong adhesion force for high-performance micro-sized silicon anodes

Micro-sized silicon anodes have shown much promise in large-scale industrial production of high-energy lithium batteries.However,large volume change(>300%)of silicon anodes causes severe particle pulverization and the formation of unstable solid electrolyte interphases during cycling,leading to rapid capacity decay and short cycle life of lithium-ion batteries.When addressing such issues,binder plays key roles in obtaining good structural integrity of silicon anodes.Herein,we report a biopolymer composite binder composed of rigid poly(acrylic acid)(PAA)and flexible silk fibroin(SF)tailored for micro-sized silicon anodes.The PAA/SF binder shows robust gradient binding energy via chemical interactions between carboxyl and amide groups,which can effectively accommodate large volume change of silicon.This PAA/SF binder also shows much stronger adhesion force and improved binding towards high-surface/defective carbon additives,resulting in better electrochemical stability and higher coulombic efficiency,than conventional PAA binder.As such,micro-sized silicon/carbon anodes fabricated with novel PAA/SF binder exhibit much better cyclability(up to 500 cycles at 0.5 C)and enhanced rate capability compared with conventional PAA-based anodes.This work provides new insights into the design of functional binders for high-capacity electrodes suffering from large volume change for the development of nextgeneration lithium batteries.

A strong and reversible adhesive fibrillar surface based on an advanced composite with high strength and strong adhesion

A material-structure integrated design method is proposed in this paper,with which micropillar and microwedge arrayed surfaces are fabricated based on a novel nanoparticlereinforced silicone rubber composite(NRSRC)with high mechanical strength and strong surface adhesion.It is found that the micropillar-arrayed surface and the microwedgearrayed surface show a normal adhesive strength of 50.9 kPa and a shear adhesive strength of 137.3 kPa,respectively,which are much higher than those of previously reported adhesive surfaces made by pure soft polymers.Furthermore,the micro-wedgearrayed surface shows not only strong and stable adhe-sion on rough and smooth substrates but also an obvious anisotropy in the adhesion property.The latter consequently leads to an easy control of the attachment/detachment switch,which is evidenced by a mechanical gripper with a microwedged surface.Therefore,firmly picking up and easily releasing a heavy glass plate can be realized.All these results demonstrate the apparent advantages of the present compo-sitebased fibrillar surfaces in achieving reliable and reversible adhesion and should have promising applications for manufac-turing advanced adhesive devices,such as mechanical fixtures,portable climbing equipment and space robots.

HYDROPHILIC NANOFILTRATION MEMBRANES WITH SELF-POLYMERIZED AND STRONGLY-ADHERED POLYDOPAMINE AS SEPARATING LAYER

Inspired by the self-polymerization and strong adhesion characteristics of dopamine in aqueous conditions, a novel hydrophilic nanofiltration （NF） membrane was fabricated by simply dipping polysulfone （PSf） ultrafiltration （UF） substrate in dopamine solution. The changes in surface chemical composition and morphology of membranes were determined by Fourier transform infrared spectroscopy （FTIR-ATR）, X-ray photoelectron spectroscopy （XPS）, scanning electron microscopy （SEM） and atomic force microscopy （AFM）. The experimental results indicated that the self-polymerized dopamine formed an ultrathin and defect-free barrier layer on the PSf UF membrane. The surface hydrophilicity of membranes was evaluated through water contact angle measurements. It was found that membrane hydrophilicity was significantly improved after coating a polydopamine （pDA） layer, especially after double coating. The dyes filtration experiments showed that the double-coated membranes were able to reject completely the dyes of brilliant blue, congo red and methyl orange with a pure water flux of 83.7 L/（mE.h） under 0.6 MPa. The zeta potential determination revealed the positively-charged characteristics of PSf/pDA composite membrane in NF process. The salt rejection of the membranes was characterized by 0.01 mmol/L of salts filtration experiment. It was demonstrated that the salts rejections followed the sequence： NaC1 〈 NaaSO4 〈 MgSO4 〈 MgC12 〈 CaCl2, and the rejection to CaC12 reached 68.7%. Moreover, the composite NF membranes showed a good stability in water-phase filtration process.