Rational Design of High-Performance PEO/Ceramic Composite Solid Electrolytes for Lithium Metal Batteries

Composite solid electrolytes(CSEs)with poly(ethylene oxide)(PEO)have become fairly prevalent for fabricating high-performance solid-state lithium metal batteries due to their high Li~+solvating capability,flexible processability and low cost.However,unsatisfactory room-temperature ionic conductivity,weak interfacial compatibility and uncontrollable Li dendrite growth seriously hinder their progress.Enormous efforts have been devoted to combining PEO with ceramics either as fillers or major matrix with the rational design of two-phase architecture,spatial distribution and content,which is anticipated to hold the key to increasing ionic conductivity and resolving interfacial compatibility within CSEs and between CSEs/electrodes.Unfortunately,a comprehensive review exclusively discussing the design,preparation and application of PEO/ceramic-based CSEs is largely lacking,in spite of tremendous reviews dealing with a broad spectrum of polymers and ceramics.Consequently,this review targets recent advances in PEO/ceramicbased CSEs,starting with a brief introduction,followed by their ionic conduction mechanism,preparation methods,and then an emphasis on resolving ionic conductivity and interfacial compatibility.Afterward,their applications in solid-state lithium metal batteries with transition metal oxides and sulfur cathodes are summarized.Finally,a summary and outlook on existing challenges and future research directions are proposed.

One-step electrochemical in-situ Li doping and LiF coating enable ultra-stable cathode for sodium ion batteries

Despite of the higher energy density and inexpensive characteristics,commercialization of layered oxide cathodes for sodium ion batteries(SIBs)is limited due to the lack of structural stability at the high voltage.Herein,the one-step electrochemical in-situ Li doping and LiF coating are successfully achieved to obtain an advanced Na0.79Lix[Li_(0.13)Ni_(0.20)Mn_(0.67)]O_(2)@LiF(NaLi-LNM@LiF)cathode with superlattice structure.The results demonstrate that the Li^(+)doped into the alkali metal layer by electrochemical cycling act as"pillars"in the form of Li-Li dimers to stabilize the layered structure.The supplementation of Li to the superlattice structure inhibits the dissolution of transition metal ions and lattice mismatch.Furthermore,the in-situ LiF coating restrains side reactions,reduces surface cracks,and greatly improves the cycling stability.The electrochemical in-situ modification strategy significantly enhances the electrochemical performance of the half-cell.The NaLi-LNM@LiF exhibits high reversible specific capacity(170.6 m A h g^(-1)at 0.05 C),outstanding capacity retention(92.65%after 200 cycles at 0.5 C)and excellent rate performance(80 mA h g^(-1)at 7 C)in a wide voltage range of 1.5-4.5 V.This novel method of in-situ modification by electrochemical process will provide a guidance for the rational design of cathode materials for SIBs.

Effect of Mn-doping on performance of Li_3V_2(PO_4)_3/C cathode material for lithium ion batteries

Li3V2-2/3xMnx（PO4）3（0≤x≤0.12） powders were synthesized by sol-gel method. The effect of Mn2＋-doping on the structure and electrochemical performances of Li3V2（PO4）3/C was characterized by XRD, SEM, XPS, galvanostatic charge /discharge and electrochemical impedance spectroscopy（EIS）. The XRD study shows that a small amount of Mn2＋-doped does not alter the structure of Li3V2（PO4）3/C materials, and all Mn2＋-doped samples are of pure single phase with a monoclinic structure （space group P21/n）. The XPS analysis indicates that valences state of V and Mn are ＋3 and ＋2 in Li3V1.94Mn0.09（PO4）3/C, respectively, and the citric acid in raw materials was decomposed into carbon during calcination, and residual carbon exists in Li3V1.94Mn0.09（PO4）/C. The results of electrochemical measurements show that Mn2＋-doping can improve the cyclic stability and rate performance of these cathode materials. The Li3V1.94Mn0.09（PO4）3/C cathode material shows the best cyclic stability and rate performance. For example, at the discharge current density of 40 mA/g, after 100 cycles, the discharge capacity of Li3V1.94Mn0.09（PO4）3/C declines from initial 158.8 mA·h/g to 120.5 mA·h/g with a capacity retention of 75.9%; however, that of the Mn-undoed sample declines from 164.2 mA·h/g to 72.6 mA·h/g with a capacity retention of 44.2%. When the discharge current is increased up to 1C, the intial discharge capacity of Li3V1.94Mn0.09（PO4）3/C still reaches 146.4 mA·h/g, and the discharge capacity maintains at 107.5 mA·h/g after 100 cycles. The EIS measurement indicates that Mn2＋-doping with a appropriate amount of Mn2＋ decreases the charge transfer resistance, which is favorable for the insertion/extraction of Li＋.

液-固相法合成LiMn_(0.6)Fe_(0.4)PO_(4)的性能

磷酸锰锂(LiMnPO_(4))材料的电导率低且充放电过程易发生Jahn-Teller效应,导致电化学性能不理想。通过液-固相法合成磷酸锰铁锂(LiMn_(0.6)Fe_(0.4)PO_(4))正极材料,并对晶体结构、放电曲线特性、循环性能等进行分析。Fe均匀地掺入Mn位形成固溶体,样品的常温电化学性能得到改善。在2.0~4.3 V循环,0.1 C倍率下的放电比容量为156.5 mAh/g;以1.0 C倍率循环2000次,容量保持率超过80%。容量衰减主要源于循环过程中正极材料颗粒产生裂纹及颗粒粉化。

Recent progress on the recycling technology of Li-ion batteries

Lithium-ion batteries(LIBs)have been widely applied in portable electronic devices and electric vehicles.With the booming of the respective markets,a huge quantity of spent LIBs that typically use either LiFePO_(4) or Li N_(x)Co_(y)Mn_(z)O_(2) cathode materials will be produced in the very near future,imposing significant pressure for the development of suitable disposal/recycling technologies,in terms of both environmental protection and resource reclaiming.In this review,we firstly do a comprehensive summary of the-state-of-art technologies to recycle Li N_(x)Co_(y)Mn_(z)O_(2) and LiFePO_(4)-based LIBs,in the aspects of pretreatment,hydrometallurgical recycling,and direct regeneration of the cathode materials.This closed-loop strategy for cycling cathode materials has been regarded as an ideal approach considering its economic benefit and environmental friendliness.Afterward,as for the exhausted anode materials,we focus on the utilization of exhausted anode materials to obtain other functional materials,such as graphene.Finally,the existing challenges in recycling the LiFePO_(4) and Li N_(x)Co_(y)Mn_(z)O_(2) cathodes and graphite anodes for industrial-scale application are discussed in detail;and the possible strategies for these issues are proposed.We expect this review can provide a roadmap towards better technologies for recycling LIBs,shed light on the future development of novel battery recycling technologies to promote the environmental benignity and economic viability of the battery industry and pave way for the large-scale application of LIBs in industrial fields in the near future.

Preparation and electrochemical properties of Y-doped Li_3V_2(PO_4)_3 cathode materials for lithium batteries

Y-doped Li3V2（PO4）3 cathode materials were prepared by a carbothermal reduction（CTR） process.The properties of the Y-doped Li3V2（PO4）3 were investigated by X-ray diffraction（XRD） and electrochemical measurements.XRD studies showed that the Y-doped Li3V2（PO4）3 had the same monoclinic structure as the undoped Li3V2（PO4）3.The Y-doped Li3V2（PO4）3 samples were investigated on the Li extraction/insertion performances through charge/discharge, cyclic voltammogram（CV）, and electrochemical impedance spectra（EIS）.The optimal doping content of Y was x=0.03 in Li3V2-xYx（PO4）3 system.The Y-doped Li3V2（PO4）3 samples showed a better cyclic ability.The electrode reaction reversibility was enhanced, and the charge transfer resistance was decreased through the Y-doping.The improved electrochemical perormances of the Y-doped Li3V2（PO4）3 cathode materials were attributed to the addition of Y3＋ ion by stabilizing the monoclinic structure.

Improved electrochemical performances of yttrium oxyfluoride-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 for lithium ion batteries

The Li-rich layered oxides show a higher discharge capacity over 250 mAh/g and have been developed into a promising positive material for lithium ion batteries. A rare earth metal oxyfluoride YOF-coated Li[Lio.2Mno.54Ni0.13Co0.13]O2 composites have been synthesized by a simple wet chem- ical method. Crystal structure, micro-morphology and element valence of the pristine and YOF-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 materials are characterized by XRD, SEM, TEM, and XPS. The results indicate that all materials exhibit a typical layered structure, and are made up of small and homogenous parti- cles ranging from 100 nm to 200 nm. In addition, YOF layer with a thickness of approximately 3-8 nm is precisely coated on the surface of the Li[Li0.2Mn0.54Ni0.13Co0.13]02. Constant current charge/discharge tests at various current densities show that the electrochemical performance of 2 wt% YOF-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 has been improved significantly. 2 wt% YOF-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 delivers the highest discharge capacity of 250.4 mAh/g at 20 mA/g among all the samples, and capacity retention of 87% after 100 charge/discharge cycles at 200 mA/g while that of the pristine one is only 81.6%. The superior electrochemical performance of 2wt% YOF-coated sample is ascribed to YOF coating layer, which could not only reduce side reactions between the electrode and liquid electrolyte, but also promote lithium ion migration.

Growth of SnO_2 Nanoflowers on N-doped Carbon Nanofibers as Anode for Li-and Na-ion Batteries

It is urgent to solve the problems of the dramatic volume expansion and pulverization of SnO_2 anodes during cycling process in battery systems. To address this issue, we design a hybrid structure of N-doped carbon fibers@SnO_2 nanoflowers(NC@SnO_2) to overcome it in this work. The hybrid NC@SnO_2 is synthesized through the hydrothermal growth of SnO_2 nanoflowers on the surface of N-doped carbon fibers obtained by electrospinning. The NC is introduced not only to provide a support framework in guiding the growth of the SnO_2 nanoflowers and prevent the flower-like structures from agglomeration, but also serve as a conductive network to accelerate electronic transmission along one-dimensional structure effectively. When the hybrid NC@SnO_2 was served as anode, it exhibits a high discharge capacity of 750 Ah g^(-1) at 1 A g^(-1) after 100 cycles in Li-ion battery and 270 mAh g^(-1) at 100 mA g^(-1) for 100 cycles in Na-ion battery, respectively.

Microwave synthesis of Li_2FeSiO_4 cathode materials for lithium-ion batteries

A novel synthetic method of microwave processing to prepare Li2FeSiO4 cathode materials is adopted. The Li2FeSiO4 cathode material is prepared by mechanical ball-milling and subsequent microwave processing. Olivin-type Li2FeSiO4 sample with uniform and fine particle sizes is successfully and fast synthesized by microwave heating at 700 ℃ in 12 rain. And the obtained Li2FeSiO4 materials show better electrochemical performance and microstructure than those of Li2FeSiO4 sample by the conventional solidstate reaction. ？2009 Yan Bing Cao. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Si-Based Anode Materials for Li-Ion Batteries:A Mini Review

Si has been considered as one of the most attractive anode materials for Li-ion batteries(LIBs) because of its high gravimetric and volumetric capacity. Importantly, it is also abundant, cheap, and environmentally benign. In this review, we summarized the recent progress in developments of Si anode materials. First, the electrochemical reaction and failure are outlined, and then, we summarized various methods for improving the battery performance, including those of nanostructuring, alloying, forming hierarchic structures, and using suitable binders. We hope that this review can be of benefit to more intensive investigation of Si-based anode materials.

Recycle and synthesis of LiCoO_2 from incisors bound of Li-ion batteries

A new LiCoO2 recovery technology of Li-ion battery was studied. LiCoO2 was initially separated from the Al foil with dimethyl acetamide(DMAC), and then the polyvinylidene fluoride(PVDF) and carbon powders in the active material were eliminated by high temperature calcining. The content of the elements in the recovered powder was analyzed. The structure and morphology of the resulted samples were observed by XRD and SEM. Then the Li2CO3 was added in the recycled powder to adjust the Li/Co molar ratio to 1. The new LiCoO2 was synthesized by calcining at 850 ℃ for 12 h in air. The well-crystallized single phase LiCoO2 without Co3O4 phase was obtained. The recycle-synthesized LiCoO2 powders have good characteristics as a cathode active material in terms of charge-discharge capacity and cycling performance.

Research on cathode material of Li-ion battery by yttrium doping

Modification of LiFePO4, LiMn2O4 and Li1＋xV3O8 by doping yttrium was investigated. The influences of doping Y on structure, morphology and electrochemical performance of cathode materials were investigated systematically. The results indicated that the mechanisms of Y doping in three cathode materials were different, so the influences on the material performance were different. The crystal structure of the three materials was not changed by Y doping. However, the crystal parameters were influenced. The crystal parameters of LiMn2O4 became smaller, and the interlayer distance of （100） crystal plane of Li1-xV3O8 was lengthened after Y doping. The grain size of Y-doped LiFePO4 became smaller and grain morphology became more regular than that of undoped LiFePO4. It indicated that Y doping had no influence on crystal particle and morphology of LiMn2O4. The morphology of Li1＋xV3O8 became irregular and its size became larger with the increase of Y. For LiFePOaand Li1＋xV3O8, both the initial discharge capacities and the cyclic performance were improved by Y doping. For LiMn2O4, the cyclic performance became better and the initial discharge capacities declined with increasing Y doping.

Influence of Ti^(4+) doping on electrochemical properties of LiFePO_4/C cathode material for lithium-ion batteries

To improve the performance of LiFePO4, single phase Li1-4xTixFePO4/C (x=0, 0.005, 0.010, 0.015) cathodes were synthesized by solid-state method. A certain content of glucose was used as carbon precursor and content of carbon in every final product was about 3.5%. The samples were characterized by X-ray diffraction(XRD), scanning electron microscopy observations(SEM), charge/discharge test, carbon analysis and electrochemical impedance spectroscopy(EIS). The results indicate that the prepared samples have ordered olivine structure and doping of the low concentration Ti^(4+) does not affect the structure of the samples. The electrochemical capabilities evaluated by charge-discharge test show that the sample with 1% Ti^(4+) (molar fraction) has good electrochemical performance delivering about an initial specific capacity of 146.7 mA·h/g at 0.3C rate. Electrochemical impedance spectroscopy measurement results show that the charge transfer resistance of the sample could be decreased greatly by doping an appropriate amount Ti^(4+).

Synthesis and electrochemical performances of LiCoO_2 recycled from the incisors bound of Li-ion batteries

A new LiCoO2 recovery technology for Li-ion batteries was studied in this paper. LiCoO2 was peeled from the Al foil with dimethyl acetamide （DMAC）, and then polyvinylidene fluoride （PVDF） and carbon powders in the active material were eliminated by high temperature calcining. Subsequently, Li2CO3, LiOH-H20 and LiAc-2H2O were added into the recycled powders to adjust the Li/Co molar ratio to 1.00. The new LiCoO2 was obtained by calcining the mixture at 850℃ for 12 h in air. The structure and morphology of the recycled powders and resulting samples were studied by XRD and SEM techniques, respectively. The layered structure of LiCoO2 synthesized by adding Li2CO3 is the best, and it is found to have the best characteristics as a cathode material in terms of charge-discharge capacity and cycling performance. The first discharge capacity is 160 mAh·g^-1 between 3.0-4.3 V. The discharge capacity after cycling for 50 times is still 145.2 mAh·g^-1.

The development in aqueous lithium-ion batteries

To meet the growing energy demands, it is urgent for us to construct grid-scale energy storage systemthan can connect sustainable energy resources. Aqueous Li-ion batteries （ALIBs） have been widely in-vestigated to become the most promising stationary power sources for sustainable energy such as windand solar power. It is believed that advantages of ALIBs will overcome the limitations of the traditionalorganic lithium battery in virtue of the safety and environmentally friendly aqueous electrolyte. In thepast decades, plentiful works have been devoted to enhance the performance of different types of ALIBs.In this review, we discuss the development of cathode, anode and electrolyte for acquiring the desiredelectrochemical performance of ALIBs. Also. the main challenges and outlook in this field are briefly dis-cussed.

High-Performance Li-ion Batteries and Super-capacitors Based on Prospective 1-D Nanomaterials

One-dimensional（1-D） nanomaterials with superior specific capacity, higher rate capability, better cycling peroperties have demonstrated significant advantages for high-performance Li-ion batteries and supercapacitors. This review describes some recent developments on the rechargeable electrodes by using 1-D nanomaterials（such as Li Mn2O4 nanowires, carbon nanofibers, Ni Mo O4 · n H2O nanorods, V2O5 nanoribbons,carbon nanotubes, etc.）. New preparation methods and superior electrochemical properties of the 1-D nanomaterials including carbon nanotube（CNT）, some oxides, transition metal compounds and polymers, and their composites are emphatically introduced. The VGCF/Li Fe PO4/C triaxial nanowire cathodes for Li-ion battery present a positive cycling performance without any degradation in almost theoretical capacity（160 m Ah/g）.The Si nanowire anodes for Li-ion battery show the highest known theoretical charge capacity（4277 m Ah/g）,that is about 11 times lager than that of the commercial graphite（372 m Ah/g）. The SWCNT/Ni foam electrodes for supercapacitor display small equivalent series resistance（ESR, 52 m?） and impressive high power density（20 k W/kg）. The advantages and challenges associated with the application of these materials for energy conversion and storage devices are highlighted.

Electrochemical performance of carbon nanotube-modified LiFePO_4 cathodes for Li-ion batteries

Carbon nanotubes (CNTs) and acetylene black (AB) were dispersed synchronously or separately between LiFePO4 (LFP) particles as conducting agents during the course of manufacture of LiFePO4 cathodes. The morphology and electrochemical performances of as-prepared LiFePO4 were evaluated by means of transmission electron microscopy (TEM), charge-discharge test, electrochemical impedance spectroscope (EIS) and cyclic voltammetry (CV). CNTs contribute to the interconnection of the isolated LiFePO4 or carbon particles. For the CNTs-modified LiFePO4, it exhibits excellent performance in terms of both specific capacity and cycle life. The initial discharge capacity is 147.9 mA·h/g at 0.2C rate and 134.2 mA·h/g at 1C rate, keeping a capacity retention ratio of 97% after 50 cycles. The results from EIS indicate that the impedance value of the solid electrolyte interface decreases. The cyclic voltammetric peak profiles is more symmetric and spiculate and there are fewer peaks. CNTs are promising conductive additives candidate for high-power Li-ion batteries.

Synthesis and Performance of LiMnO_2 as Cathodes for Li-ion Batteries

Two structure types of LiMnO 2 were synthesized by sol gel method and ion exchange method respectively.The results indicate that orthorhombic phase LiMnO 2 is more stable than layered LiMnO 2,o LiMnO 2 can be synthesized directly by sol gel methods followed by heat treated in argon,but layered LiMnO 2 was obtained only by indirect methods such as ion exchange method.In this paper,we first synthesized layered NaMnO 2 by the sol gel method,and then obtained layered LiMnO 2 by the ion exchange method.The phase constitution,chemical composition,and images of the products were tested by XRD,AAS (atomic absorption spectroscopy) and SEM.The electrochemical performances of the two structural types of LiMnO 2 are obviously different during the initial few cycles,but later they both have a good capacity retaining ability.The capacity of layered structure LiMnO 2 is higher than that of o LiMnO 2.

Synthesis and characterization of phosphate-modified LiMn_2O_4 cathode materials for Li-ion battery

LiMn2O4 spinel cathode materials were modified with 2 wt.%Li-M-PO4（M=Co,Ni,Mn） by polyol synthesis method.The phosphate surface-modified LiMn2O4 cathode materials were physically characterized by X-ray diffraction（XRD）,scanning electron microscopy（SEM） and energy dispersive X-ray spectroscopy（EDS）.The charge-discharge test showed that the cycling and rate capacities of LiMn2O4 cathode materials were significantly enhanced by stabilizing the electrode surface with phosphate.

Si-doped composite carbon as anode of lithium ion batteries

Si doped composite material was prepared by coating artificial graphite with the mixture of phenol resin and polysilicone and following with heat treatment at 1 050 ℃ in an argon gas atmosphere. The structure and characteristics of the composite carbon were determined by means of XRD, SEM, BET surface area and electrochemical measurements. The new carbon material has a disordered carbon/graphite composite structure, with silicon doped in the disordered carbon. Compared with the pristine graphite, the electrochemical performance is improved for the Si doped composite carbon with large reversible capacity of 312.6 mAh/g, high initial charge/discharge efficiency of 88.61%, and excellent cycle stability. The prototype batteries using the composite carbon as anode material have large discharge capacity of 845 mAh and high capacity retention ratio of 95.80% at the 200th cycle.