12-锡电极材料综述.pdf

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1、Contents lists available at ScienceDirectEnergy Storage Materialsjournal homepage: progress in phosphorus based anode materials for lithium/sodiumion batteriesWeili Liu,Hanqian Zhi,Xuebin YuDepartment of Materials Science,Fudan University,Shanghai 200433,ChinaA R T I C L E I N F OKeywords:Lithium io

2、n batteriesSodium ion batteriesPhosphorus carbon compositesMetal phosphidesAnodeA B S T R A C TPhosphorus has aroused growing concern as a promising anode material for both lithium and sodium ionbatteries,owning to its high theoretical capacity and appropriately low redox potential.However,the poore

3、lectronic conductivity and large volume expansion of phosphorus during cycling lead to low electrochemicalactivity and unstable cyclability,which limits its practical application.Recently,various nanostructuredphosphorus based anodes,which efficiently restrained the pulverization and supplied faster

4、 reaction kinetics,have been developed to solve these issues.This review aims to summarize the major progress of nanostructuredphosphorus based electrode materials for lithium/sodium ion batteries.We first examine the most widely-useddesign strategy of compositing phosphorus with various carbon mate

5、rials,ranging from 0D particles,1D tubesor fibers,2D sheets to 3D frameworks.And then,the progress of various metal phosphides and their compositesis discussed,which mainly include Sn-P phosphides,Ni-P phosphides,Cu-P phosphides,Fe-P phosphides,Co-Pphosphides,etc.,and their composites.This is follow

6、ed by a comparison of different compositing methods,which involve in preparing phosphorus-carbon composites and nanostructured metal phosphides or theircomposites.Finally,the challenges and perspectives regarding the phosphorus based anode materials areproposed.1.IntroductionEnergy issues have attra

7、cted great attentions during the past decadedue to growing energy demand,exhausting refined fossil fuels andserious environmental issues caused by their usage.Various new andclean energy sources,i.e.,solar,wind,hydro,tidal,and geothermalenergies,are emerging rapidly.Therefore,a large-scale energy st

8、oragesystem is urgently required to store these renewable energies into theelectrical grid to realize the peak shift.Lithium ion batteries(LIBs)have been presenting great promise,due to their fascinating character-istics,such as high energy conversion efficiency,stable cyclability,simple maintenance

9、,adaptable power and energy features for differentgrid functions 1.LIBs have been extensively used as the common power sources inthe market of portable electronics since Sony realized their firstcommercial launch in early 1990s 24.LIB technology has beenexperiencing great progress and commercializat

10、ion in mid-size appli-cations such as hybrid electric vehicles(HEVs)and electric vehicles(EVs)applications.Moreover,lots of grid-scale LIBs prototypes(approximately tens of megawatt-hours),used for storing renewableenergy sources,have emerged on the market 57.However,thegrowing cost of LIBs due to t

11、he finite lithium resources(0.0065%asshown in Fig.1a)would ultimately fail to satisfy the ever-increasingindustrial demand,especially for HEVs,EVs,and large-scale renewableenergy storage 810.Alternatively,sodium ion batteries(NIBs)have attracted greatattentions with the ever-growing demand for advan

12、ced rechargeablebatteries,assigned to the abundance of sodium resources(2.74%asshown in Fig.1a).Theoretically speaking,Na is heavier than Li,andNIBs may have a lower energy density than LIBs.However,the energypenalty is small because sodium has a suitable potential of 2.71 V(vsSHE).Therefore NIBs ar

13、e much more suitable to a large grid stationaryapplication,where the low cost and long cycle life of the batteries aremore important for a whole system 11.The electrochemical properties of the electrode materials are vital tothe important performance characteristics of battery such as specificcapaci

14、ty and operation voltage.Therefore,the major challenge inadvancing LIB and NIB technology lies in finding good electrodematerials.However,the specific capacities of most cathode materialsare low and it is difficult to greatly increase their specific capacities.Theapplication of cathode materials wit

15、h high redox potentials is alsolimited by the electrolyte which decomposes at high potentials.https:/doi.org/10.1016/j.ensm.2018.05.020Received 10 April 2018;Received in revised form 20 May 2018;Accepted 21 May 2018Corresponding author.E-mail address:(X.Yu).Energy Storage Materials 16(2019)290322Ava

16、ilable online 24 May 20182405-8297/2018 Published by Elsevier B.V.MARKTherefore,it is a desiring approach to develop anode materials whichown high specific capacities and relatively low redox potentials.Usingconversion chemistry such as alloying materials is one of most usedstrategy for storing a la

17、rge number of ions.Si-based material is therepresentative example,for which 4.4 Li can react with one Si to formLi-Si alloy,providing the highest theoretical specific capacity of 4200mAh/g among LIB anode materials(Fig.1b)1215.However,forNIBs,it can store only one Na per Si,delivering a theoretical

18、specificcapacity of 954mAh/g 1618.While phosphorus can not only reactelectrochemically with lithium to form Li3P,but also store three Na atattractive potentials with a high theoretical specific capacity of 2596mAh/g,which significantly exceeds that of any other NIB anodepresently available(Fig.1c)19

19、30.In addition,phosphorus hasthe advantages of low cost,abundance(0.118%in Fig.1a)and easyavailability,which provide great potential for its practical applicationsfor LIBs and NIBs.In this review,we will present the recent advances in phosphorusbased anodes for LIBs/NIBs,with a focus on phosphorus c

20、arboncomposites and metal phosphides or their composites.This articlecovers the development of new promising phosphorus based anodes forLIBs/NIBs,lithium-storage mechanisms of metal phosphides andmany efforts to enhance the electrochemical performance of phos-phorus based anodes.In addition,methods

21、for the synthesis ofphosphorus-carbon composites and metal phosphides or their compo-sites are summarized.Finally,the challenges and opportunities for thephosphorus based anodes of LIBs/NIBs are suggested.2.Phosphorus based anodes for LIBs/NIBsAs an element of the fifth group in the periodic table,p

22、hosphoruspossesses four main allotropes:white phosphorus,red phosphorus,violet phosphorus and black phosphorus(Fig.2a)31.White phos-phorus is volatile and toxic,and it bursts into flames if exposed to thenatural atmosphere,enabling it unsuitable for electrode materials.Violet phosphorus has been rar

23、ely investigated in the past decades.However,its 2D layered violet phosphorene has drawn increasingresearch interest recently 32,33.Alternatively,red phosphorus andblack phosphorus have been studied commonly as the anode materialsbecause they are chemically stable at room temperature and atmo-sphere

24、.Red phosphorus is commercially available with ease,but its lowconductivity(1014S/cm)results in poor reversibility of electro-chemical reaction.Crystalline black phosphorus as anode materialsshows substantially improved reversibility relative to red phosphorus(Fig.2b)19.However,due to the nature of

25、poor electronicconductivity of phosphorus,there is a far way between its experimentalcapacity and theoretical value.It has been demonstrated that theconductivity of phosphorus based electrode can be improved by dopingred phosphorus with iodine,and the electrodes for LIBs exhibitedmuch higher specifi

26、c capacity(1868 mAh/g at the second cycle)andmuch longer cycling life(1562mAh/g at 520mA/g after 150 cycles)than that of red phosphorus,even than black phosphorus Fig.2c)34.However,the electrochemical performance of most phosphorus basedelectrodes has been improved by forming different type of phosp

27、horuscarbon composites and metal phosphides or their composites asdiscussed in the following sections.2.1.Phosphorus carbon compositesThe intrinsic outstanding conductivity and diversity in architectureof carbon material make it the most popular material preferred forphosphorus based anodes.Various

28、strategies have been developed torealize a perfect compositing between phosphorus and carbon materi-als.Carbon materials can be summed as particles,e.g.,carbon blackand graphite 19,25,31,3541;one-dimensional materials,e.g.,nano-tubes and nanofibers 4249;two-dimensional materials,e.g.,gra-phene and r

29、educed graphene oxide 5364;and three-dimensionalmaterials,e.g.,aerogels and mesoporous carbon 6570,74.In thissection we will give a summary of the recent progress in phosphoruscarbon composites.2.1.1.Lithium/sodium-storage mechanismThe general reactions of phosphorus carbon composites withlithium/so

30、dium are summarized as follows:P+xLi+/Na+xe-LixP/NaxP(1)Li P/Na P+3xLi/Na+3xe Li P/Na Pxx+33(2)Duringlithiation/sodiationprocess,phosphorusreactswithlithium/sodium to form the compounds of LixP/NaxP,with the finalproducts of Li3P/Na3P.The delithiation/desodiation process involves astepwise lithium/s

31、odium ion extraction from the fully lithiated/sodia-tied Li3P/Na3P,corresponding to several plateaus in voltage profile,aswell as the several cathodic peaks in the cyclic voltammogram.Fig.1.(a)Elemental abundance in the earths crust.(b)Theoretical specific capacity ofthe C,Si,Ge,Sn,P,As and Sb eleme

32、nts for LIBs;(c)Theoretical specific capacity of theSi,Ge,Sn,P,As and Sb elements for NIBs.W.Liu et al.Energy Storage Materials 16(2019)2903222912.1.2.Particle carbon materialsPark and Sohn first composited black phosphorus with carbon black(Super P),used as an anode material for LIBs in 2007 throug

33、h a high-energy mechanical milling method 19.The composite displayedenhanced electrochemical discharge/charge performance with a highinitial Coulombic efficiency(90%)(Fig.2b)and good cycle perfor-mance(600mAh/g after 100 cycles between 0.78 and 2.0V).Tofurther improve the electrochemical performance

34、 of phosphorus,Qian et al.prepared an amorphous phosphorus/carbon nanocomposite(a-P/C)through ball-milling red phosphorus with conductive carbonblack powders and found that the amorphous phosphorus can fullystore reversible 3-Li storage capacity(2355 mAh/g)with stablecyclability(2119.5mAh/g after 10

35、0 cycles)and high rate capability(Fig.3a&b)33.Later,Sun et al.found that phosphorus-carbon(P-C)bonds could be formed by mechanochemical reaction,and the P-Cbonds maintained stable during cycling,ensuring that phosphoruscould keep well contact with carbon(Fig.3c).Due to the stable P-Cbonds,the compos

36、ite delivered a high initial discharge capacity of2786 mAh/g at 520mA/g and an excellent cycle life(80%capacityretention over 100 cycles)(Fig.3d)31.Recently,phosphorus wasalso studied as an anode for NIBs.Qian et al.demonstrated that bycompositing amorphous phosphorus with carbon materials,a capacit

37、yof 1750 mAh/g at a current density of 250 mA/g was delivered at roomtemperature(Fig.3e)36.Simultaneously,Kim et al.estimated that acapacity of 1890mAh/g at a current density of 143mA/g could beprovided at a slightly elevated temperature of 30oC for amorphous redphosphorus-carbon composite(Fig.3f)25

38、.2.1.3.One-dimensional carbon materialsOwning to the high aspect ratios,one-dimensional carbon nano-tubes are able to form interconnected networks between phosphorusand impart long-range conductivity to phosphorus anode materials(Fig.4a).The phosphorus-carbon nanotube composite was initiallystudied

39、as lithium/sodium anode materials by Dou and co-workers,who simply hand-grinded commercial red phosphorus(P)with multi-walled carbon nanotubes(MWCNTs).The P-MWCNT compositedelivered a surprisingly high initial charge capacity of 1530 mAh/g atthe current density of 143mA/g(Fig.4b)42.However,the capac

40、ityof the P-MWCNT composite dropped quickly to 750mAh/g after only20 cycles.The unsatisfactory electrochemical performances of the P-Fig.2.(a)Schematics of white,red,violet and black phosphorus.(Reproduced with permission.Copyright 2014,American Chemical Society 31)(b)Electrochemical behaviors ofvar

41、ious types of phosphorus.(Reproduced with permission.Copyright 2007,Wiley-VCH Verlag GmbH&Co.KGaA 19)(c)Voltage profiles of Iodine doped red phosphorusnanoparticles at a rate of 0.2C between 0.01 and 2.5V.(Reproduced with permission.Copyright 2017,American Chemical Society 34).W.Liu et al.Energy Sto

42、rage Materials 16(2019)290322292MWCNT composite above are possibly due to the less contact and weakphysical interaction between phosphorus particles and carbon matrix.To create better physical interaction,red phosphorus and tangledsingle-walled carbon nanotube were heated at 600C under vacuumconditi

43、on in a sealed glass tube,where phosphorus vaporized anddiffused into the voids between and in tangled single-walled carbonnanotube bundles.Phosphorus was mainly adsorbed on the outersurface of the carbon nanotubes,with little diffused into the interspacesof the single-walled carbon nanotube bundles

44、,providing more physicalcontact between the two materials(Fig.4c).As a result,the phos-phorus-carbon nanotube anodes delivered a high discharge capacity of 300mAh/gcompositewith 80%capacity retention after 2000 cycles at2000 mA/gcomposite(Fig.4d)43.Considering these promising works,further improveme

45、nt of phosphorus-carbon nanotube(P-CNT)hybridwas conducted through chemical bonding between phosphorus,carbonnanotube,and crosslinked polymer binder formed by facile ball milling(Fig.4e),and a capacity of 1586.2 mAh/g after 100 cycles at 520mA/gcould be maintained(Fig.4f)44.One-dimensional porous ca

46、rbon nanofibers could not only forminterconnected conductivity networks between phosphorus with a free-standing characteristics,but also effectively buffer the volume changeof phosphorus anodes due to its porous structure.This was demon-strated by Li et al.,who loaded crystalline red phosphorus into

47、 free-standing porous carbon nanofibers with 3D interconnected,flexibleFig.3.(a)Charge-discharge profiles and(b)cycling performances at various current densities.(Reproduced with permission.Copyright 2012,The Royal Society of Chemistry 33)(c)The HRTEM image and schematic of black phosphorus-graphite

48、 composite;(d)The cycling performance and Coulombic efficiency of black phosphorus/graphite mixture and blackphosphorus-graphite composite electrodes at a current density of 520mA/g.(Reproduced with permission.Copyright 2014,American Chemical Society 31)(e)Initial charge/discharge curves of three ph

49、ases of phosphorus:red phosphorus,black phosphorus,and a-P/C nanocomposites.(Reproduced with permission.Copyright 2013,Wiley-VCH VerlagGmbH&Co.KGaA 36)(f)Charge-discharge voltage profile of the red phosphorus-carbon composite electrode.(Reproduced with permission.Copyright 2013,Wiley-VCH VerlagGmbH&

50、Co.KGaA 25).W.Liu et al.Energy Storage Materials 16(2019)290322293characteristics(Fig.5).When used as the additive-free flexible filmelectrodes,a reversible capacity of 2030 mAh/g and an averageCoulombic efficiency of 99.9%over 100 cycles were achieved 48.Besides the porous carbon nanofibers,N-doped