Hierarchically Micro/Nanostructured Current Collectors Induced by Ultrafast Femtosecond Laser Strategy for High-Performance Lithium-ion Batteries

Commercial Cu and Al current collectors for lithium-ion batteries(LIBs)possess high electrical conductivity,suitable chemical and electrochemical stability.However,the relatively flat surface of traditional current collectors causes weak bonding strength and poor electrochemical contact between current collectors and electrode materials,resulting in potential detachment of active materials and rapid capacity degradation during extended cycling.Here,we report an ultrafast femtosecond laser strategy to manufacture hierarchical micro/nanostructures on commercial Al and Cu foils as current collectors for high-performance LIBs.The hierarchically micro/nanostructured current collectors(HMNCCs)with high surface area and roughness offer strong adhesion to active materials,fast electronic delivery of entire electrodes,significantly improving reversible capacities and cyclic stability of HMNCCs based LIBs.Consequently,LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(NCM523)cathode with Al HMNCC generated a high reversible capacity after 200 cycles(25%higher than that of cathode with Al CC).Besides,graphite anode with Cu HMNCC also maintained prominent reversible capacity even after 600 cycles.Moreover,the full cell assembled by graphite anode with Cu HMNCC and NCM523 cathode with Al HMNCC achieved high reversible capacity and remarkable cycling stability under industrial-grade mass loading.This study provides promising candidate for achieving high-performance LIBs current collectors.

Bismuth nanorods confined in hollow carbon structures for high performance sodium-and potassium-ion batteries

Bismuth has drawn widespread attention as a prospective alloying-type anode for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its large volumetric capacity.However,such material encounters drastic particle pulverization and overgrowth of solid-electrolyte interphase(SEI)upon repeated(de)alloying,thus causing poor rate and cycling degradation.Herein,we report a unique structure design with bismuth nanorods confined in hollow N,S-codoped carbon nanotubes(Bi@NS-C)fabricated by a solvothermal method and in-situ thermal reduction.Ex-situ SEM observations confirm that such a design can significantly suppress the size fining of Bi nanorods,thus inhibiting the particle pulverization and repeated SEI growth upon charging/discharging.The as achieved Bi@NS-C demonstrates outstanding rate capability for SIBs(96.5%capacity retention at 30 A g^(-1) vs.1 A g^(-1)),and a record high rate performance for PIBs(399.5 m Ah g^(-1)@20 A g^(-1)).Notably,the as constructed full cell(Na_(3)V_(2)(PO_(4))_(3)@C|Bi@NS-C)demonstrates impressive performance with a high energy density of 219.8 W h kg^(-1) and a high-power density of 6443.3 W kg^(-1)(based on the total mass of active materials on both electrodes),outperforming the state-of-the-art literature.

Controllable synthesis of high loading LiFePO_4/C nanocomposites using bimodal mesoporous carbon as support for high power Li-ion battery cathodes

Mesoporous LiFePO4/C composites containing 80 wt% of highly dispersed LiFePO4 nanoparticles(4-6 nm) were fabricated using bimodal mesoporous carbon(BMC) as continuous conductive networks. The unique pore structure of BMC not only promises good particle connectivity for LiFePO4, but also acts as a rigid nano-confinement support that controls the particle size. Furthermore, the capacities were investigated respectively based on the weight of LiFePO4 and the whole composite. When calculated based on the weight of the whole composite, it is 120 mAh·g-1at 0.1 C of the high loading electrode and 42 mAh·g-1at 10 C of the low loading electrode. The electrochemical performance shows that high LiFePO4 loading benefits large tap density and contributes to the energy storage at low rates, while the electrode with low content of LiFePO4 displays superior high rate performance, which can mainly be due to the small particle size, good dispersion and high utilization of the active material, thus leading to a fast ion and electron diffusion.

A Li-rich layered-spinel cathode material for high capacity and high rate lithium-ion batteries fabricated via a gas-solid reaction

Lithium-rich layered oxide(LLO)cathode materials have drawn extensive attention due to their ultrahigh specific capacity and energy density.However,their commercialization is still restricted by their low initial coulombic efficiency,slow intrinsic kinetics and structural instability.Herein,a facile surface treatment strategy via gaseous phosphine was designed to improve the rate performance and capacity stability of LLOs.During the solid-gas reaction,phosphine reacted with active oxygen at the surface of LLOs due to its reductivity,forming oxygen vacancies and spinel phase at the surface region.As a result,Li ion conductivity and structural stability were greatly enhanced.The phosphinetreated LLOs(LLO@P)showed a layered-spinel hybrid structure and delivered an outstanding rate performance of156.7 mA h g^-1 at 10 C and a high capacity retention of 74%after 300 cycles at 5 C.

Engineering layered/spinel heterostructure via molybdenum doping towards highly stable Li-rich cathodes

Li-rich layered oxide(LLO),e.g.,Li_(1.12)[Mn_(0.56)Ni_(0.16)Co_(0.08)]O_(2)(LRMO),is considered as a promising cathode material due to its superior Li-storage capability.However,the poor cycling stability and large voltage decay,which are related to the phase transition,limit its industrialization process.Herein,a Mo-doped LRMO(Li_(1.12)[Mn_(0.56)Ni_(0.16)Co_(0.08)]_(0.98)Mo_(0.02)O_(2),LRMO-Mo2.0%)was successfully synthesized via a simple combination of co-precipitation with high-temperature calcination for solving the mentioned above-disadvantages.Compared with the pristine counterpart,the as-prepared LRMO-Mo2.0%shows more excellent electrochemical performance in terms of rate capability(reversible capacity of 118 mA·h·g^(−1) at 5 C),cyclic ability(94.3%capacity retention after 100 cycles at 0.2 C)and discharge midpoint voltage decay(0.11 V after 100 cycles).Systematic investigation of structural evolution and electrochemical kinetics elucidate that the synergic effect of robust oxygen framework and layered/spinel heterostructure is the key to its performance improvement.Such synergy helps to stabilize the layered structure by curbing the structural transformation and oxygen escaping during the electrochemical cycling.This work paved the way for the simple and efficient preparation of highly stable LLO cathode materials.

Polyaniline spaced MoS_(2)nanosheets with increased interlayer distances for constructing high-rate dual-ion batteries

Dual-ion batteries(DIBs)have attracted great attention due to their affordable prices,environmentalfriendliness,and high operating voltage.However,the conventional graphite anode in DIBs has draw-backs such as unsatisfactory capacity and worrying safety.MoS_(2)is considered to be a competitive anodematerial that exhibits large capacity due to its unique layered structure for cation insertion/extraction.Nevertheless,the sluggish reaction kinetics of MoS_(2)does not match the cathode side,which makes theconstructed full DIBs show poor rate ability.Here,a flower-like MoS_(2)/polyaniline composite electrode(MoS_(2)-PANI)where PANI was grown in situ between layers of MoS_(2)nanosheets was designed.In thisdesign,the inserted PANI can broaden the layer distance of MoS_(2)to facilitate cation diffusion and pre-vent the restacking of nanosheets.Furthermore,PANI is also expected to increase the conductivity andrelieve the volume changes during repeated charge/discharge cycles.Benefiting from that,the MoS_(2)-PANIelectrode delivered a reversible capacity of 561.91 mA h g^(-1) at 5 A g^(-1) in half-cell test.Moreover,whencoupled with a mildly expanded graphite(MEG)cathode,the obtained MEG//MoS_(2)-PANI DIB shows ex-cellent rate ability with a reversible discharge capacity of 86.62 mA h g^(-1) and a desirable energy densityof 308.83 W h kg-1 at 20 C.These results provide some inspiration for the design of high-rate DIBs.

Ultrafine RuO_(2) nanoparticles/MWCNTs cathodes for rechargeable Na-CO_(2) batteries with accelerated kinetics of Na_(2)CO_(3) decomposition

Na-CO_(2) batteries have attracted extensive attention due to their high theoretical energy density(1125 Wh/kg),efficient utilization of CO_(2),and abundant sodium resources.However,they are trapped by the sluggish decomposition kinetic of discharge products (mainly Na_(2)CO_(3)) on cathode side during the charging process.Here we prepared a series of nano-composites composed of RuO_(2) nanoparticles in situ loaded on activated multi-walled carbon nanotubes (RuO_(2)@a-MWCNTs) through hydrolyzing reaction followed by calcination method and used them as cathode catalysts to accelerate the decomposition of Na_(2)CO_(3).Among all catalysts,the RuO_(2)@a-MWCNTs with appropriate ratio of RuO_(2)(49.7 wt%) demonstrated best stability and rate performance in Na-CO_(2) batteries,benefiting from both high specific surface area (160.3 m^(2)/g) and highly dispersed RuO_(2) with ultrafine nanostructures (~2 nm).At a limited capacity of 500 mAh/g,Na-CO_(2) batteries could afford the operation of over 120 cycles at 100 mA/g,and even at the current density to 500 mA/g,the charge voltage was still lower than 4.0 V after 40 cycles.Further theoretical calculations proved that RuO_(2) was the catalytically active center and contributed to the decomposition of Na_(2)CO_(3) by weakening the C=O bond.The synergetic functions of high specific surface(CNTs) and high catalytic activity (RuO_(2)) will inspire more progress on metal-CO_(2) batteries.

温度调控制备锡或二氧化锡@中空多孔碳纳米纤维电极用于个性化定制锂离子电池

锂离子电池广泛应用于电动汽车、混合动力汽车、便携式电子设备等储能系统,但由于电荷在活性材料中传输缓慢以及活性材料易粉碎等缺点,开发同时具有高容量以及快充性能的电极材料仍然是一个极大的挑战.针对这一问题,本文通过温度调控将SnO_(2)量子点或Sn纳米团簇均匀负载在中空多孔碳纳米纤维(HPCNFs)的内部,用于制备个性化定制锂离子电池.一方面,高度互联的碳纳米纤维形成三维网络,加快了电子传输,提高了电子导电性.另一方面,中空多孔结构缩短了锂离子传输路径,促进了锂离子的快速扩散,同时,抑制了Sn和SnO_(2)的体积膨胀.由于具有较高的锂离子吸附性能以及快的离子扩散速率,低碳化温度下(450℃)合成的SnO_(2)@HPCNFs复合电极在0.1 A g^(-1)的小电流密度下具有较高的放电比容量(899.3 mA h g~(-1)).此外,由于在大的电流密度下,Sn的大孔结构能够储存更多的锂离子,以及具有较高的电子电导率,因此,高碳化温度下(850℃)制备的Sn@HPCNFs复合电极展现出优异的快充性能,同时,在5 A g^(-1)(~10 C)的高电流密度下具有238.8 mA h g^(-1)的放电容量.本文通过调控碳化温度来研究SnO_(2)和Sn电极之间的电化学行为,为构建高性能储能器件提供了新的思路.