铅酸蓄电池正极容量的提高

用电化学和扫描电镜方法,对铅酸蓄电池中含有复合添加剂的正极进行了研究.结果表明:这种添加剂能促进β-PbO_2的产生和活性物质的细化,因而提高了正极容量10%～20%.这种添加剂还有利于活性物质粒子和板栅的结合,使充放电循环寿命延长.

锂离子电容器负极/正极容量比的调控与性能

以商业化活性炭(AC)为正极材料,钛酸锂(LTO)为负极材料,通过“Z”型叠片方式制得LTO-AC锂离子电容器。考察负极/正极容量比(N/P比)对电容器电化学性能的影响。当N/P=0.95时,正、负极材料的利用率最好,电容器的比能量和比功率分别可达43.7 Wh/kg和2.2 kW/kg。化成曲线和dQ/dU曲线显示,此时锂离子电容器没有出现明显的电压平台,主要表现为电容特性。

添加剂对正极循环容量影响的初步研究

随着电动车辆的开发研究,迫切需要延长蓄电池的循环寿命,通常认为电池寿命决定于正极板,蓄电池正极板损坏的主要原因是板栅腐蚀和活性物质脱落。

锂离子电池正极材料合成及改性

电动汽车续航里程的提升主要依赖于锂离子电池的能量密度,其中发展高容量的正极材料成为关键。富锂锰基层状氧化物(LLOs)和高镍三元层状氧化物(NCM,Ni≥80%)等高容量正极材料成为了研究热点,其前体的开发对正极材料电化学性能的发挥有重要的影响。本文从工业化的角度对共沉淀法制备LLOs和NCM正极材料前体的反应过程和影响因素进行了介绍,分析了球形团聚体、单晶和浓度梯度等正极材料的结构和性能,并详细阐述了正极材料中晶面取向调控、掺杂及表界面处理等改性策略的原理及优缺点。文章指出,综合来看单晶材料表现出较好的循环稳定性和热稳定性,但倍率性能有待进一步提升。浓度梯度正极材料不仅保持了高容量特性,还兼顾良好的结构稳定性和热稳定性,有望突破高容量正极材料进一步发展的技术瓶颈。最后,基于本文作者课题组在高容量正极材料方面的研究,对正极材料的未来发展趋势给出了一些建议。

新一代高比能量锂离子电池富锂氧化物正极材料的研究进展

富锂氧化物xLi_2MnO_3·(1-x)LiMO_2(M为Co、Ni、Mn等)的比容量可达250~300mAh/g,是高比能量锂离子电池正极材料的首选之一。介绍了材料的晶体结构、嵌/脱锂机制和充放电过程中发生的结构相变,分析讨论了材料出现首次不可逆容量大、电压和容量衰减快、倍率性能和低温性能较差等问题的原因,阐述了材料的合成方法及改性技术,如表面包覆、离子掺杂、形貌和晶面调控以及合成层状相-尖晶石相共生结构的异质材料等。最后从基础研究和应用研究两个方面展望了富锂氧化物材料的发展前景。

Influence of synthesis temperature on electrochemical performance of polyoxomolybdate as cathode material of lithium ion battery

In order to improve the electrochemical performance of polyoxomolybdate Na3[AlMo6O24H6]（NAM） as the cathode material of lithium ion battery, the NAM materials with small particle size were synthesized by elevatingthe synthesistemperaturein the solution.The as-prepared NAM materials were investigated by FT-IR, XRD, SEM and EIS. Their discharge-charge and cycle performance were also tested. The resultsshowthat the particle size decreasesto less than10μm at the temperature ofhigher than 40℃.When synthesized at 80℃,the NAMwiththe smallest particle size （-3μm）exhibitsthe best electrochemical performance such ashigh initial discharge capacity of 409 mA·h/gandcoulombic efficiency of 95% in the first cycle at 0.04C.

锂硫电池的实用化挑战

本文针对锂硫电池产业化进展缓慢的现状,从实用化层面分析了制约锂硫电池发展的基本问题:正极面容量低,电解液用量高,电池倍率性能差及锂负极的不稳定性,并结合自身工作,提出了解决方案。

Synthesis and electrochemical performance of Li_2Mg_(0.15)Mn_(0.4)Co_(0.45)SiO_4/C cathode material for lithium ion batteries

The synthesis, structure and performance of Li2Mg0.15Mn0.4Co0.45SiO4/C cathode material were studied. The Li2Mg0.15Mn0.4Co0.45SiO4/C solid solution with orthorhombic unit cell （space group Pmn21） was synthesized successfully by combination of wet process and solid-state reaction at high temperature, and its electrochemical performance was investigated primarily. Li2Mg0.15Mn0.4Co0.45SiO4/C composite materials deliver a charge capacity of 302 mA-h/g and a discharge capacity of 171 mA.h/g in the first cycle. The discharge capacity is stabilized at about 100 mA-h/g after 10 cycles at a current density of 10 mA/g in the voltage of 1.5-4.8 V vs Li/Li^＋. The results show that Mg-substitution for the Co ions in Li2Mn0.4Co0.6SiO4 improves the stabilization of initial structure and the electrochemical nerformance.

Multifunctional V3S4-nanowire/graphene composites for high performance Li-S batteries

Lithium sulfur(Li-S)batteries have been regarded as a promising next-generation energy storage system with high theoretical specific capacity and energy density,but still facing challenges.In order to make Li-S batteries more competitive,combination of trapping sites and electrocatalytic properties for polysulfides is an effective way to improve the battery performance.In this study,we prepare a type of multifunctional V3S4-nanowire/graphene composites(V3S4-G)by uniformly dispersing V3S4 nanowires on the graphene substrate.This structure contributes to the sufficient exposure of multifunctional V3S4 active sites which can anchor polysulfides and accelerate reaction kinetics.Thus,the Li-S batteries based on the multifunctional V3S4-G sulfur cathode deliver a stable cycling performance and good rate capability.Even at sulfur loading of 3 mg cm^−2,the V3S4-G sulfur cathode possesses a low capacity decay rate of 0.186%per cycle at 0.5 C.

Self-assembled α-MnO2 urchin-like microspheres as a high-performance cathode for aqueous Zn-ion batteries

Aqueous Zn-ion batteries(AZIBs)are one of the promising battery technologies for the green energy storage and electric vehicles.As one attractive cathode material for AZIBs,α-MnO2 materials exhibit superior electrochemical properties.However,their long-term reversibility is still in great suspense.Considering the decisive effect of the structure and morphology on theα-MnO2 materials,hierarchicalα-MnO2 materials would be promising to improve the cycle performance of AZIB.Here,we synthesized theα-MnO2 urchin-like microspheres(AUM)via a self-assembled method.The porous microspheres composed of one-dimensionalα-MnO2 nanofibers with high crystallinity,which improved the surface area and active sites for Zn2+intercalation.The AUM-based AZIB realized a high initial capacity of 308.0 mA hg-1,and the highest energy density was 396.7 W hkg-1.The kinetics investigation confirmed the high capacitive contribution and fast ion diffusion of the AUM.Ex-situ XRD measurement further verified the synergistic insertion/extraction of H+and Zn2+ions during the charge/discharge process.The superiority of the AUM guaranteed good electrochemical performance and reversible phase evolution,and this application would promote the follow-up research on the advanced AZIB.

Plum pudding model inspired KVPO4F@3DC as high-voltage and hyperstable cathode for potassium ion batteries

The investigation on the cathode material of potassium ion batteries(PIBs),one of the most promising alternatives to lithium ion batteries,is of great significance.Potassium vanadium fluorophosphate(KVPO4F)with a high working voltage is an appealing cathode candidate for PIBs,while the poor cycling performance and low electronic conductivity dramatically hinder the application.Herein,a plum pudding model inspired three-dimensional amorphous carbon network modified KVPO4F composite(KVPO4F@3DC)is successfully designed in this study to tackle these problems.In the composite,KVPO4F particles are homogeneously wrapped by a layer of amorphous carbon and bridged by crosslinked large area carbon sheets.As the cathode for PIBs,the KVPO4F@3DC composite exhibits a high average operating voltage about 4.10 V with a super-high discharge capacity of 102.96 mAh g^-1 at 20 mA g^-1.An excellent long cycle stability with a capacity retention of 85.4%over 550 cycles at 500 mA g^-1 is achieved.In addition,it maintains 83.6%of its initial capacity at 50 mA g^-1 after 100 cycles at 55℃.The design of KVPO4F@3DC with plum pudding structure provides facilitative electron conductive network and stable electrode/electrode interface for electrode,successfully innovating an ultra-stable and high-performance cathode material for potassium ion batteries.

High-capacity organic electrode material calix[4] quinone/CMK-3 nanocomposite for lithium batteries

Organic lithium-ion batteries（OLIBs） represent a new generation of power storage approach for their environmental benignity and high theoretical specific capacities.However, it has the disadvantage with regard to the dissolution of active materials in organic electrolyte. In this study, we encapsulated high capacity material calix[4]quinone（C4Q） in the nanochannels of ordered mesoporous carbon（OMC）CMK-3 with various mass ratios ranging from 1：3 to 3：1, and then systematically investigated their morphology and electrochemical properties. The nanocomposites characterizations confirmed that C4Q is almost entirely capsulated in the nanosized pores of the CMK-3 while the mass ratio is less than2：1. As cathodes in lithium-ion batteries, the C4Q/CMK-3（1：2） nanocomposite exhibits optimal initial discharge capacity of 427 mA h g^（-1） with 58.7% cycling retention after 100 cycles. Meanwhile, the rate performance is also optimized with a capacity of 170.4 mA h g^（-1） at 1 C. This method paves a new way to apply organic cathodes for lithium-ion batteries.

Ball-flower-like carbon microspheres via a three-dimensional replication strategy as a high-capacity cathode in lithium–oxygen batteries

The robust porous architectures of active materials are highly desired for oxygen electrodes in lithium–oxygen batteries to enable high capacities and excellent reversibility. Herein, we report a novel three-dimensional replication strategy to fabricate three-dimensional architecture of porous carbon for oxygen electrodes in lithium–oxygen batteries. As a demonstration, ball-flower-like carbon microspheres assembled with tortuous hollow carbon nanosheets are successfully prepared by completely replicating the morphology of the nanostructured zinc oxide template and utilizing the polydopamine coating layer as the carbon source.When used as the active material for oxygen electrodes, the three-dimensional porous architecture of the prepared ballflower-like carbon microspheres can accommodate the discharge product lithium peroxide and simultaneously maintain the ions and gas diffusion paths. Moreover, their high degrees of defectiveness by nitrogen doping provide sufficient active sites for oxygen reduction/evolution reaction.Thus the prepared ball-flower-like carbon microspheres demonstrate a high capacity of 9,163.7 mA h g-1 and excellent reversibility. This work presents an effective way to prepare three-dimensional architectures of porous carbon by replicating the controllable nanostructures of transition metal oxide templates for energy storage and conversion applications.

Carbon-coating-increased working voltage and energy density towards an advanced Na3V2(PO4)2F3@C cathode in sodium-ion batteries

One main challenge for phosphate cathodes in sodium-ion batteries(SIBs)is to increase the working voltage and energy density to promote its practicability.Herein,an advanced Na3V2(PO4)2F3@C cathode is prepared successfully for sodium-ion full cells.It is revealed that,carbon coating can not only enhance the electronic conductivity and electrode kinetics of Na3V2(PO4)2F3@C and inhibit the growth of particles(i.e.,shorten the Na^+-migration path),but also unexpectedly for the first time adjust the dis-/charging plateaux at different voltage ranges to increase the mean voltage(from 3.59 to 3.71 V)and energy density from 336.0 to 428.5 Wh kg^-1 of phosphate cathode material.As a result,when used as cathode for SIBs,the prepared Na3V2(PO4)2F3@C delivers much improved electrochemical properties in terms of larger specifc capacity(115.9 vs.93.5 mAh g^-1),more outstanding high-rate capability(e.g.,87.3 vs.60.5 mAh g^-1 at 10 C),higher energy density,and better cycling performance,compared to pristine Na3V2(PO4)2F3.Reasons for the enhanced electrochemical properties include ionicity enhancement of lattice induced by carbon coating,improved electrode kinetics and electronic conductivity,and high stability of lattice,which is elucidated clearly through the contrastive characterization and electrochemical studies.Moreover,excellent energy-storage performance in sodium-ion full cells further demonstrate the extremely high possibility of Na3V2(PO4)2F3@C cathode for practical applications.

Insoluble polyanionic anthraquinones with two strong ionic O–K bonds as stable organic cathodes for pure organic K-ion batteries

A new organic cathode namely potassium 2,6-dihydroxyanthraquinone(AQ26OK,theoretical capacity(CT)=169 mA h g^(-1))is synthesized and fully characterized for Kion batteries.AQ26OK is called polyanionic organic cathode because it has a polyanionic organic skeleton(-2 valent)and two strong ionic K-O bonds.Consequently,the polyanionic AQ26OK is hardly soluble into most organic liquid electrolytes.In half cells(0.3-3.4 V vs.K^(+)/K)using 1 mol L^(-1) KPF6 in dimethoxyethane,AQ26OK delivers a highly stable specific capacity of 201 mA h g^(-1)@50 mA g^(-1) over 450 cycles(4-month test)and realizes~106 mA h g^(-1) for 3200 cycles at 500 mA g^(-1).Using the reduced state(K4TP)of potassium terephthalate(K2TP)as the organic anode,the resulting K4TP Ⅱ AQ26OK organic potassium-ion batteries can display a highly stable average discharge capacity of 135 mA h g^(-1) cathodeover 250 cycles at 100 mA g^(-1) and~47 mA h g^(-1) for 1000 cycles at 500 mA g^(-1) during the working voltage of 0.01-3.1 V.To the best of our knowledge,AQ26OK is among the best stable cathodes reported for K-ion batteries.

Oxygen vacancies-rich cobalt-doped NiMoO4 nanosheets for high energy density and stable aqueous Ni-Zn battery

The enhancement of energy density and cycling stability is in urgent need for the widespread applications of aqueous rechargeable Ni-Zn batteries.Herein,a facile strategy has been employed to construct hierarchical Co-doped NiMoO4nanosheets as the cathode for high-performance Ni-Zn battery.Benefiting from the merits of substantially improved electrical conductivity and increased concentration of oxygen vacancies,the NiMoO4with 15%cobalt doping(denoted as CNMO-15)displays the best capacity of 361.4 m A h g-1at a current density of 3 A g-1and excellent cycle stability.Moreover,the assembled CNMO-15//Zn battery delivers a satisfactory specific capacity of 270.9 mA h g-1at 2 A g-1and a remarkable energy density of 474.1 W h kg-1at 3.5 kW kg-1,together with a maximum power density of 10.3 kW kg-1achieved at 118.8 W h kg-1.Noticeably,there is no capacity decay with a 119.8%retention observed after 5000 cycles,demonstrating its outstanding long lifespan.This work might provide valuable inspirations for the fabrication of high-performance Ni-Zn batteries with superior energy density and impressive stability.

Sulfur/nickel ferrite composite as cathode with high-volumetric-capacity for lithium-sulfur battery

Low volumetric energy density is a bottleneck for the application of lithium-sulfur (Li-S)battery.The low- density sulfur cooperated with the light-weight carbon sub- strate realizes electrochemical cycle stability,but leads to worse volumetric energy density.Here,nickel ferrite (NiFe2O4)nanofibers as novel substrate for sulfur not only anchor lithium polysulfides to enhance the cycle stability of sulfur cathode,but also contribute to the high volumetric capacity of the S/nickel ferrite composite.Specifically,the S/ nickel ferrite composite presents an initial volumetric capacity of 1,281.7mA h cm^-3-composite at 0.1C rate,1.9times higher than that of S/carbon nanotubes,due to the high tap density of the S/nickel ferrite composite.