PVDF-assisted pyrolysis strategy for corrugated plate oxygen electrocatalysis nanoreactor:Simultaneously realizing efficient active sites and rapid mass transfer

Though Zn-air batteries(ZABs)are one of the most promising system for energy storage and conversion,challenge still persists in its commercial application due to the sluggish kinetics of oxygen reduction/evolution reaction(ORR/OER).Hereby,a polyvinylidene fluoride(PVDF)-assisted pyrolysis strategy is proposed to develop a novel corrugated plate-like bifunctional electrocatalyst using two-dimensional zeolitic imidazolate frameworks(2D ZIF-67)as the precursor.The employed PVDF plays an important role in inheriting the original 2D structure of ZIF-67 and modulating the composition of the final products.As a result,a corrugated plate-like electrocatalyst,high-density Co nanoparticles decorated 2D Co,N,and F tri-doped carbon nanosheets,can be obtained.The acquired electrocatalyst enables efficient active sites and rapid mass transfer simultaneously,thus showing appreciable electrocatalytic performance for rechargeable Zn-air batteries.Undoubtedly,our proposed strategy offers a new perspective to the design of advanced oxygen electrocatalysts.

Boric Acid-Assisted Pyrolysis for High-Loading Single-Atom Catalysts to Boost Oxygen Reduction Reaction in Zn-Air Batteries

The emerging of single-atom catalysts(SACs)offers a great opportunity for the development of advanced energy storage and conversion devices due to their excellent activity and durability,but the actual mass production of high-loading SACs is still challenging.Herein,a facile and green boron acid(H_(3)BO_(3))-assisted pyrolysis strategy is put forward to synthesize SACs by only using chitosan,cobalt salt and H_(3)BO_(3)as precursor,and the effect of H_(3)BO_(3)is deeply investigated.The results show that molten boron oxide derived from H_(3)BO_(3)as ideal high-temperature carbonization media and blocking media play important role in the synthesis process.As a result,the acquired Co/N/B tri-doped porous carbon framework(Co-N-B-C)not only presents hierarchical porous structure,large specific surface area and abundant carbon edges but also possesses high-loading single Co atom(4.2 wt.%),thus giving rise to outstanding oxygen catalytic performance.When employed as a catalyst for air cathode in Zn-air batteries,the resultant Co-N-B-C catalyst shows remarkable power density and long-term stability.Clearly,our work gains deep insight into the role of H_(3)BO_(3)and provides a new avenue to synthesis of high-performance SACs.

Enhancing long-term stability of bio-photoelectrochemical cell by defect engineering of a WO_(3-x) photoanode

Bio-photoelectrochemical cells(BPECs)can further expand the use of conventional biofuel cells for renewable energy,but the poor stability of the photoelectrode still hinders their practical application.Herein,a BPEC capable of long-term operating in a fuel-free model is fabricated by WO3-xphotoanode with oxygen vacancy(Ov)and bilirubin oxidase catalyzed biocathode.The construction of Ov on the WO3surface significantly suppresses the dissolution of W species into the electrolyte,and improves the charge separation efficiency and the reaction kinetics during the photoelectrochemical oxygen evolution process,thus enhancing the stability and power output performance of the BPEC.As a result,the assembled BPEC can output an open circuit voltage of 0.81 V and deliver a maximum output power of up to 283μW cm^(-2).Impressively,the BPECs maintain 97%of their original power after 36000 s of consecutive discharge under an enclosed environment.This fuel-free BPEC based on a robust WO3-xphotoanode shows excellent promise for accurate application.

新工科背景下湖南大学应用化学专业的改革与建设

探索建立依托化学学科的"新工科"应用化学专业设置并按照"新工科"理念对现有专业进行革命性改造是十分必要的。结合我校2020应用化学专业培养计划修订及教学改革研究的实际情况,通过调整专业培养目标、课程体系、教学内容和教学模式,突出德才兼备人才培养的中心地位,以期在传承本专业腐蚀与防护的特色基础上,进一步满足新材料、新能源、高端制造、节能环保及新一代信息技术等新兴战略产业对人才的需求。还提出了应用化学新工科专业发展的方向。

Self-regulation in chemical and bio-engineering materials for intelligent systems

Herein, the authors review the self-regulation system secured by well-designed hybrid materials, composites, and complex system. As a broad concept, the self-regulated material/system has been defined in a wide research field and proven to be of great interest for use in a biomedical system, mechanical system, physical system, as the fact of something such as an organisation regulating itself without intervention from external perturbation. Here, they focus on the most recent discoveries of self-regulation phenomenon and progress in utilising the self-regulation design. This paper concludes by examining various practical applications of the remarkable materials and systems including manipulation of the oil/water interface, cell out-layer structure, radical activity, electron energy level, and mechanical structure of nanomaterials. From material science to bioengineering, self-regulation proves to be not only viable, but increasingly useful in many applications. As part of intelligent engineering, self-regulatory materials are expected to be more used as integrated intelligent components.

Fe3C-N-doped carbon modified separator for high performance lithium-sulfur batteries

A new Fe3C-N-doped reduced graphene oxide(Fe3C-N-rGO)prepared by a facile method is used as a separator for high performance lithium-sulfur(Li-S)batteries.The Fe3C-N-rGO is coated on the surface of commercial polypropylene separator(Celgard 2400)close to the sulfur cathode.The special nanotubes are in-situ catalyzed by Fe3C nanoparticles.They could entrap lithium polysulfides(Li PSs)to restrain the shuttle effect and reduce the loss of active material.The battery with the modified separator and sulfur cathode shows an excellent cycle performance.It has a high rate performance,580.5 mAh/g at the high current rate of 4 C relative to 1075 mAh/g at 0.1 C.It also has an initial discharge capacity of 774.8 m Ah/g measured at 0.5 C and remains 721.8 mAh/g after 100 cycles with a high capacity retention of 93.2%.The outstanding performances are notable in recently reports with modified separator.

Facile fabrication of MoP nanodots embedded in porous carbon as excellent anode material for potassium-ion batteries

Molybdenum phosphide(MoP),owing to its abundant reserve and high theoretical capacity,is regarded as a promising anode material for potassium-ion batteries.However,it still suffers from the problems of acute volume expansion and weak diffusion kinetics.This study reports a simple method to synthesize a composite of molybdenum phosphide and porous carbon(MoP@PC)through simple mixing and annealing treatment.In the MoP@PC,lots of MoP nanodots with an average diameter of about 4 nm uniformly embedded in the petal-like porous carbon.The MoP@PC shows reversible capacities of 330 mAh g^(-1) at100 mA g^(-1) after 100 cycles,and ultra-long cycling stability with a capacity of 240 mAh g^(-1) after 1000 cycles at 1 A g^(-1) and 161 mAh g^(-1) after 1000 cycles at 5 A g^(-1).The structure of MoP@PC after charging-discharging cycles is also investigated by high resolution transmission electron microscope(HRTEM)and the result shows that MoP can still maintain the nanodot morphology without any agglomeration after 1000 cycles at 5 A g^(-1).The storage mechanism of potassium ions was studied as well,which reveals that MoP and potassium ion have a conversion reaction.

3D hierarchical microspheres constructed by ultrathin MoS2-C nanosheets as high-performance anode material for sodium-ion batteries

MoS2/C composites are considered to have great application potential in sodium-ion batteries(SIBs).It is a challenging and meaningful subject that developing high-performance anode materials via combining MoS2 and carbon effectively to give free rein to their advantages in sodium ion storage.In this work,a novel MoS2-C material was designed by using cellulose nanocrystals(CNCs)as low-cost and green carbon source.3 D hierarchical microspheres(200-250 nm)constructed by ultrathin MoS2-C nanosheets were synthesized by synchronizing the pre-carbonization of CNCs with the formation of MoS2 in hydrothermal reaction and subsequent pyrolysis process.It is found that the ultrathin MoS2-C nanosheets were composed of CNCs-derived short-range ordered carbon and few-layered MoS2.Benefiting from the unique structure and robust combination of MoS2 and CNCs-derived carbon,the ultrathin MoS2-C nanosheets composite was proved to have excellent cycling stability and superior rate performance in sodium-ion half-cell test and have high first reversible specific capacity of 397.9 m Ah/g in full-cell test.This work provides a significant and effective pathway to prepare MoS2-C materials with excellent electrochemical performance for the application in large-scale energy storage systems.

Design of advanced porous silver powder with high-sintering activity to improve silicon solar cells

Silver(Ag)paste is widely used in semiconductor metallization,especially in silicon solar cells.Ag powder is the material with the highest proportion in Ag paste.The morphology and structure of Ag powder are crucial which determine its characteristics,especially for the sintering activity.In this work,a simple method was developed to synthesize a type of microcrystalline spherical Ag particles(SP-A)with internal pores and the structural changes and sintering behavior were thoroughly studied by combining ultra-small-angle X-ray scattering(USAXS),small-angle X-ray scattering(SAXS),in-situ heating X-ray diffraction(XRD),focused ion beam(FIB),and thermal analysis measurement.Due to the unique internal pores,the grain size of SP-A is smaller,and the coefficient of thermal expansion(CTE)is higher than that of traditional solid Ag particles.As a result,the sintering activity of SP-A is excellent,which can form a denser sintered body and form silver nanoparticles at the Ag–Si interface to improve silver silicon contact.Polycrystalline silicon solar cell built with SP-A obtained a low series resistance(Rs)and a high photoelectric conversion efficiency(PCE)of 19.26%.These fill a gap in Ag particle structure research,which is significant for the development of high-performance electronic Ag particles and efficient semiconductor devices.

Low cost and low density chloride solid electrolyte for all solid state cathode with high active material ratio

Chloride solid electrolytes(SEs)have attracted widespread attention due to their high room-temperature ionic conductivity and excellent cathode compatibility.However,the conventionally selected central metal elements(e.g.,In,Y and Ta)are usually rare and heavy,inevitably causing the high cost and high density of the obtained chloride SEs.Here,by choosing abundant and light Mg and Al as central metal elements,we develop a cheap and low density Li_(1.2)Mg_(0.95)Al_(0.3)Cl_(4)SE for high active material ratio in all solid state cathode.Partial replacement of Mg^(2+)by Al^(3+)in the framework yields vacancies and lowers the non-lithium metal ions occupancy at Mg/Li co-occupied 16d site,effectively relieving the blocking effects by Mg^(2+)in the pristine spinel Li_(2-2x)Mg_(1+x)Cl_(4).Thus,a significantly improved room-temperature conductivity of 3.08×10^(-4)S·cm^(-1)is achieved,two orders of magnitude higher than that of Li_(1.2)Mg_(1.4)Cl_(4).More attractively,its low density of only 1.98 g·cm-3 enables low SE mass ratio in cathodes(only 16 wt.%)with still effective electrolyte/cathode contact and lithium-ion conduction inside.When charged to potential of 4.30 V,the asfabricated Li_(1.2)Mg_(0.95)Al_(0.3)Cl_(4)-based solid lithium battery with uncoated NCM523 cathode can be cycled for over 100 cycles with a capacity retention of 86.68%at room temperature.

Fe-Co-Ni ternary single-atom electrocatalyst and stable quasi-solidelectrolyte enabling high-efficiency zinc-air batteries

The non-noble metal(Fe,Co,Ni,etc.)catalysts possess promising potential to replace noble metals(e.g.,Pt,Ru,Ir,etc.)as catalysts for oxygen electrocatalysis.Up to now,various mono-and dual-single-atom catalysts have been fabricated,though it is still challenging to synthesise ternary single-atom catalysts due to the difference of interaction forces between different metal ions(Fe,Co,Ni,etc.)and ligands.Here,we report a Fe-Co-Ni ternary single-atom catalyst(FeCoNi-Nx)derived from a zeolitic imidazolate frameworks(ZIF)precursor as an efficient oxygen electrocatalyst,and an optimised flexible casting-drying polyvinyl alcohol(CD-PVA)film as a quasi-solid electrolyte host,for high-efficiency solid-state Zn-air batteries.The aberration-corrected HAADF-STEM and EELS spectrum confirm the co-existence of Fe,Co and Ni single atoms in the FeCoNi-Nx catalyst,and the electrochemical,mechanical,and durability tests prove the superiority of the CD-PVA film.As a result,the FeCoNi-Nx-based rechargeable Zn-air battery delivers superior specific capacity(846.8 mAh·gZn-1)and power density(135 mW·cm^(-2))in aqueous electrolyte,as well as an over 60 mW·cm^(-2)power density in quasi-solid electrolyte.As a result,the quasi-solid-state Zn-air battery with a small area of only 2 cm2 is able to charge a mobile phone,which outperforms all the reported devices to date.

Exploring the structural properties of cathode and anode materials in Li-ion battery via neutron diffraction technique

As a unique microprobe for structure and dynamics of materials,neutron possesses superior ability in penetration as well as sensitivity for light and magnetic elements in comparison with X-ray and electron.As for the research and development of lithium-ion batteries(LIBs),neutron diffraction techniques play an indispensable role in exploring the structural properties of various electrode materials,especially the detailed structural evolution of cathode and anode materials during electrochemical cycling.Moreover,based on thorough analysis of neutron diffraction results,an in-depth and systematic understanding of some fundamental mechanisms,such as the formation mechanism of defects and migration mechanism of lithium ions,could also be established,which is essential for the development of high-performance electrode materials for the next-generation LIBs.Nevertheless,that technique would not seem to be widely applied yet in comparison with the application of X-ray diffraction and more attention should be paid.To demonstrate the advantages of neutron diffraction technique in research of LIBs materials,this work systematically summarizes representative neutron diffraction studies on exploring structural details hidden in electrode materials and on probing structural evolution of electrode materials during charge/discharge processes.Prospects for further applications of neutron diffraction techniques in research of LIBs are also put forward.

共掺杂策略协同激活阴离子氧化还原构建高容量钠离子电池层状氧化物阴极材料

作为锂离子电池的潜在替代品,钠离子电池由于成本、安全性等方面的优势吸引了广泛关注.但如何进一步提高其正极材料的能量密度仍是挑战,而通过激活阴离子氧化还原提供额外容量是一种可行的策略.本文报告了一种高性能锰基氧化物正极材料,Na_(0.67)Mg_(0.1)Zn_(0.1)Mn_(0.8)O_(2)(NMZMO).通过共掺杂策略协同激活阴离子氧化还原,此材料首圈可以放出~233 mAh g^(-1)的超高容量,明显高于Mg或Zn单掺杂的同类材料.综合多种光谱技术,作者证明了更高的容量源于更强的阴离子氧化还原活性.结合中子全散射以及共振非弹性X射线散射发现,Mg与Zn在高电压下会向面外迁移至四面体位点,诱导面内重排形成空位团簇,将氧阴离子以分子O_(2)的形式困于其中.Mg/Zn共存时,刺激了彼此更多的向面外迁移,为形成更多晶内分子O_(2)提供先决条件.本文提出了关于阴离子氧化还原的新见解,并为高容量钠电正极材料的开发提供了理论依据.

Structural insights into lithium-deficient type Li-rich layered oxide for high-performance cathode

As one of the promising candidate cathode materials for the high-performance lithium-ion batteries,Li-rich layered oxides still suffer from a series of critical drawbacks,such as voltage decay,oxygen release,irrevers-ible migration of transition metal ions,etc.In this work,Li-deficient method has been confirmed as an effective approach to improve the overall electrochemical performances of Li-rich cathode.The optimized lithium-deficient Li-rich layered cathode exhibits splendid discharge capacity of~297 mAh/g at 0.1 C and prominent rate per-formance of-143 mAh/g at 5 C.Subsequently,neutron diffraction in combination with Raman spectroscopy is applied to explore and clarify the underlying mechanism for improved performances.It was found that the lithium-deficient induced nickel migration and oxygen vacancy play an significant role in improving electro-chemical performances,because migration of nickel into Li layer is able to expand the Li layer spacing and reduce the Li/Ni antisite,leading to facilitated diffusion of lithium ions.Moreover,the formation of oxygen vacancy is able to promote anionic redox processes and suppress the gas release,thus leading to higher capacity.The results present valuable structural insights into the influence of lithium deficiency and provide guidance for the devel-opment of Li-rich cathode materials.