Quantitative lithium substitution of carboxyl hydrogens in polyacrylic acid binder enables robust SiO electrodes with durable lithium storage stability

The design of advanced binders plays a critical role in stabilizing the cycling performance of large-volume-effect silicon monoxide(SiO)anodes.For the classic polyacrylic acid(PAA)binder,the self-association of-COOH groups in PAA leads to the formation of intramolecular and intermolecular hydrogen bonds,greatly weakening the bonding force of the binder to SiO surface.However,strengthening the binder-material interaction from the perspective of binder molecular regulation poses a significant challenge.Herein,a modified PAA-Li_(x)(0.25≤x≤1)binder with prominent mechanical properties and adhesion strength is specifically synthesized for SiO anodes by quantitatively substituting the carboxylic hydrogen with lithium.The appropriate lithium substitution(x=0.25)not only effectively increases the number of hydrogen bonds between the PAA binder and SiO surface owing to charge repulsion effect between ions,but also guarantees moderate entanglement between PAA-Li_x molecular chains through the ion-dipole interaction.As such,the PAA-Li_(0.25)/SiO electrode exhibits exceptional mechanical properties and the lowest volume change,as well as the optimum cycling(1237.3 mA h g^(-1)after 100cycles at 0.1 C)and rate performance(1000.6 mA h g^(-1)at 1 C),significantly outperforming the electrode using pristine PAA binder.This work paves the way for quantitative regulation of binders at the molecular level.

Construction of strong built-in electric field in binary metal sulfide heterojunction to propel high-loading lithium-sulfur batteries

The practical application of lithium-sulfur(Li-S)batteries is greatly hindered by soluble polysulfides shuttling and sluggish sulfur redox kinetics.Rational design of multifunctional hybrid materials with superior electronic conductivity and high electrocatalytic activity,e.g.,heterostructures,is a promising strategy to solve the above obstacles.Herein,a binary metal sulfide MnS-MoS_(2) heterojunction electrocatalyst is first designed for the construction of high-sulfur-loaded and durable Li-S batteries.The MnS-MoS_(2) p-n heterojunction shows a unique structure of MoS_(2) nanosheets decorated with ample MnS nanodots,which contributes to the formation of a strong built-in electric field at the two-phase interface.The MnS-MoS_(2) hybrid host shows strong soluble polysulfide affinity,enhanced electronic conductivity,and exceptional catalytic effect on sulfur reduction.Benefiting from the synergistic effect,the as-derived S/MnS-MoS_(2) cathode delivers a superb rate capability(643 m A h g^(-1)at 6 C)and a durable cyclability(0.048%decay per cycle over 1000 cycles).More impressively,an areal capacity of 9.9 m A h cm^(-2)can be achieved even under an extremely high sulfur loading of 14.7 mg cm^(-2)and a low electrolyte to sulfur ratio of 2.9μL mg^(-1).This work provides an in-depth understanding of the interfacial catalytic effect of binary metal compound heterojunctions on sulfur reaction kinetics.

A robust interphase via in-situ pre-reconfiguring lithium anode surface for long-term lithium-oxygen batteries

Lithium-oxygen(Li-O) battery is considered as one of the most promising alternatives because of its ultrahigh theoretical energy density. However, their cycling stability is severely restricted by the uncontrollable dendrite growth and serious oxygen corrosion issue on Li surface. Herein, a sulfur-modified Li surface can be successfully constructed via chemical reaction of guanylthiourea(GTU) molecule on Li,which can induce the selectively fast decomposition of lithium bis(trifluoromethanesulfonyl)imide(LiTFSI) to form a smooth and stable inorganics-rich solid-electrolyte interphase(IR-SEI) during the subsequent electrochemical process. Such an IR-SEI cannot only offer a highly reversible and stable Li plating/stripping chemistry with dendrite-free property(10 mA cm^(-2)-10 mAh cm^(-2), > 0.5 years;3 mA cm^(-2)-3 m Ah cm^(-2), > 1 year) but also endows the Li metal an anti-oxygen corrosion function, thereby significantly improving the cycling stability of Li-Obatteries. This work provides a new idea for constructing functional solid-electrolyte interphase(SEI) to achieve highly stable Li metal anode.

Ruthenium(Ⅱ)-cored supramolecular organic framework-mediated recyclable visible light photoreduction of azides to amines and cascade formation of lactams

Ru(bpy)3]2+-cored supramolecular organic framework SMOF-1, assembled from a [Ru(bpy)3]2+-derived hexaarmed molecule and cucurbit[8]uril, has been demonstrated to heterogeneously catalyze visible light-induced reduction of phenyl, benzyl, 2-phenylethyl and 3-phenylpropyl azides in acetonitrile to produce the corresponding amines in good to high yields. For the last two kinds of azides that bear a CO2Me group at the para-position of the benzene ring, cascade reactions take place to generate the corresponding lactams in high yields. Compared with homogeneous control [Ru(bpy)3]Cl2, SMOF-1 exhibits remarkably increased photocatalysis activity as a result of synergistic effect of the [Ru(bpy)3]2+ units that form cubic cages to host the azide molecules and related intermediates. Moreover, SMOF-1 displays high recyclability and considerable photocatalysis activity after 3 to 12 runs.

A stable metal-covalent-supramolecular organic framework hybrid: enrichment of catalysts for visible light-induced hydrogen production

Cubic metal-covalent-supramolecular organic framework(MCSOF-1)hybrid has been created from the reaction of two molecular components and subsequent co-assembly with cucurbit[8]uril(CB[8])in water.In the presence of CB[8],[Ru(bpy)_3]^(2+)-based acylhydrazine 1·2Cl reacted with aldehyde 2·Cl to quantitatively yield six-armed precursor 3·8Cl through the generation of MCSOF-1.MCSOF-1 combines the structural features of metal-,covalent-and supramolecular organic frameworks.Its periodicity in water and in the solid state was confirmed by synchrotron X-ray scattering and diffraction experiments.MCSOF-1could enrich discrete anionic polyoxometalates(POMs),maintain periodicity in acidic medium,and remarkably facilitate visible light-induced electron transfer from its[Ru(bpy)_3]^(2+)units to enriched POMs,leading to enhanced catalysis of the POMs for the reduction of proton to H_2in both aqueous(homogeneous)and organic(heterogeneous)media.

Aromatic Amide Polymers that Form Two Helical Conformations with Twist Sense Bias in Water

Two benzene/2,2＇-bipyridine-alternately incorporated amide polymers have been prepared, which are driven by hydrophobicity to form two different helical conformations. Both helices exhibit twist sense bias in water induced by chiral valine side chains and the coordination of the 2,2＇-bipyridine unit to the Ni2＋ ions.

The coupling effect of slow-rate mechanical motion on the confined etching process in electrochemical mechanical micromachining

By introducing the mechanical motion into the confined etchant layer technique(CELT), we have developed a promising ultraprecision machining method, termed as electrochemical mechanical micromachining(ECMM), for producing both regular and irregular three dimensional(3 D) microstructures. It was found that there was a dramatic coupling effect between the confined etching process and the slow-rate mechanical motion because of the concentration distribution of electrogenerated etchant caused by the latter. In this article, the coupling effect was investigated systemically by comparing the etchant diffusion, etching depths and profiles in the non-confined and confined machining modes. A two-dimensional(2 D) numerical simulation model was proposed to analyze the diffusion variations during the ECMM process, which is well verified by the machining experiments. The results showed that, in the confined machining mode, both the machining resolution and the perpendicularity tolerance of side faces were improved effectively. Furthermore, the theoretical modeling and numerical simulations were proved valuable to optimize the technical parameters of the ECMM process.

Local structure engineering for active sites in fuel cell electrocatalysts

In this review,we surveyed the significance of local structure engineering on electrocatalysts and electrodes for the performance of oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).Both on precious metal catalysts(PMC)and non-precious metal catalysts(NPMC),the main methods to modulate local structure of active sites have been summarized.By change of atomic coordination,modulation of bonding distortion and synergy effect from hierarchical structure,local structure engineering has influence on the intrinsic activity and stability of electrocatalysts.Moreover,we emphasized the intimate correlation between lyophobicity of electrocatalysts and membrane electrodes by local structure engineering.Our review aimed to inspire the exploration of advanced electrocatalysts and mechanism study for PEMFCs based on local structure engineering.

A non-aqueous Li/organosulfur semi-solid flow battery

Non-aqueous flow batteries have attracted extensive attention due to the advantages of wide voltagewindow, high energy density and wide operating temperature and so on. Herein, tetramethylthiuramdisulfide （TMTD） with high intrinsic capacity （223 mAh/g） and high solubility （-1 mol/L in chloroform） isinvestigated as the positive active material of the non-aqueous LiJdisulfide semi-solid flow battery. Theelectrochemical activity and reversibility are investigated by cyclic voltammetry and linear scanvoltammetry. This Li/TMTD battery with a high cell voltage of 3.36 V achieves coulombic efficiency of 99%,voltage efficiency of 73% and energy efficiency of 72% at the current density of 5 mA/cm2 with activematerial concentration of 0.1 mol/L. Moreover, the LiJTMTD battery can operate for 100 cycles withoutobvious efficiency decay, indicating good stability.

Enhancing sulfur cathode process via a functionalized complex molecule

Lithium-sulfur batteries are regarded as promising next-generation energy storage batteries for their ultra-high theoretical energy density.However,the complex sulfur electrode process with sluggish sulfur conversion reactions is a critical issue for lithiumsulfur batteries,in which catalytic interfacial reactions and accelerated lithium-ion diffusion are the key factors.Our previous work has shown that implanting functional molecules with multiple redox properties in the electrode can break through the conventional diffusion layer constraints and achieve forced convection.In this work,a functionalized complex molecule,methylene blue anthraquinone-2-sulfonate(MB-AQ),with multiple redox activities as well as abundant active sites,was synthesized and introduced into the sulfur cathode.In addition to accelerating the transport of lithium ions by reversible inhaling and exhaling lithium ions,the MB-AQ can combine polysulfides by its active sites to accelerate sulfur conversion reactions.Benefiting from two functions of accelerating ion diffusion and catalyzing interfacial reactions,MB-AQ/reduced graphene oxide(rGO)/S cathode can achieve high initial capacities of 884 and 674 mAh·g^(−1)with stable cycling of 700 and 1,000 times at 1 and 4 C,respectively.It is worth mentioning that the capacity of 462 mAh·g^(−1)can be achieved even at a high current density of 6 C.This work provides a new approach to enhancing the sulfur cathode process.