Analysis_and_Design_of_Monolithic,_High_PSR,_Linear_Regulators_for_SoC_Applications

A review of advanced and practical lithium battery materialsRotem Marom,*S.Francis Amalraj,Nicole Leifer,David Jacob and Doron AurbachReceived 3rd December 2010,Accepted 31st January 2011DOI:10.1039/c0jm04225kPresented herein is a discussion of the forefront in research and development of advanced electrode materials and electrolyte solutions for the next generation of lithium ion batteries.The main challenge of the field today is in meeting the demands necessary to make the electric vehicle fully commercially viable.This requires high energy and power densities with no compromise in safety.Three families of advanced cathode materials (the limiting factor for energy density in the Li battery systems)are discussed in detail:LiMn 1.5Ni 0.5O 4high voltage spinel compounds,Li 2MnO 3–LiMO 2high capacity composite layered compounds,and LiMPO 4,where M ¼Fe,Mn.Graphite,Si,Li x TO y ,and MO (conversion reactions)are discussed as anode materials.The electrolyte is a key component that determines the ability to use high voltage cathodes and low voltage anodes in the same system.Electrode–solution interactions and passivation phenomena on both electrodes in Li-ion batteries also play significant roles in determining stability,cycle life and safety features.This presentation is aimed at providing an overall picture of the road map necessary for the future development of advanced high energy density Li-ion batteries for EV applications.IntroductionOne of the greatest challenges of modern society is to stabilize a consistent energy supply that will meet our growing energy demands.A consideration of the facts at hand related to the energy sources on earth reveals that we are not encountering an energy crisis related to a shortage in total resources.For instancethe earth’s crust contains enough coal for the production of electricity for hundreds of years.1However the continued unbridled usage of this resource as it is currently employed may potentially bring about catastrophic climatological effects.As far as the availability of crude oil,however,it in fact appears that we are already beyond ‘peak’production.2As a result,increasing oil shortages in the near future seem inevitable.Therefore it is of critical importance to considerably decrease our use of oil for propulsion by developing effective electric vehicles (EVs).EV applications require high energy density energy storage devices that can enable a reasonable driving range betweenDepartment of Chemistry,Bar-Ilan University,Ramat-Gan,52900,Israel;Web:http://www.ch.biu.ac.il/people/aurbach.E-mail:rotem.marom@live.biu.ac.il;aurbach@mail.biu.ac.ilRotem MaromRotem Marom received her BS degree in organic chemistry (2005)and MS degree in poly-mer chemistry (2007)from Bar-Ilan University,Ramat Gan,Israel.She started a PhD in electrochemistry under the supervision of Prof.D.Aurbach in 2010.She is currently con-ducting research on a variety of lithium ion battery materials for electric vehicles,with a focus on electrolyte solutions,salts andadditives.S :Francis AmalrajFrancis Amalraj hails from Tamil Nadu,India.He received his MSc in Applied Chemistry from Anna University.He then carried out his doctoral studies at National Chemical Laboratory,Pune and obtained his PhD in Chemistry from Pune University (2008).He is currently a postdoctoral fellow in Prof.Doron Aurbach’s group at Bar-Ilan University,Israel.His current research interest focuses on the synthesis,electrochemical and transport properties of high ener-getic electrode materials for energy conversion and storage systems.Dynamic Article Links CJournal ofMaterials ChemistryCite this:DOI:10.1039/c0jm04225k /materialsFEATURE ARTICLED o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 24 F e b r u a r y 2011P u b l i s h e d o n 23 F e b r u a r y 2011 o n h t t p ://p u b s .r s c .o r g | d o i :10.1039/C 0J M 04225KView Onlinecharges and maintain acceptable speeds.3Other important requirements are high power density and acceptable safety features.The energy storage field faces a second critical chal-lenge:namely,the development of rechargeable systems for load leveling applications (e.g.storing solar and wind energy,and reducing the massive wasted electricity from conventional fossil fuel combustion plants).4Here the main requirements are a very prolonged cycle life,components (i.e.,relevant elements)abun-dant in high quantities in the earth’s crust,and environmentally friendly systems.Since it is not clear whether Li-ion battery technology can contribute significantly to this application,battery-centered solutions for this application are not discussedherein.In fact,even for electrical propulsion,the non-petroleum power source with the highest energy density is the H 2/O 2fuel cell (FC).5However,despite impressive developments in recent years in the field,there are intrinsic problems related to electrocatalysis in the FCs and the storage of hydrogen 6that will need many years of R&D to solve.Hence,for the foreseeable future,rechargeable batteries appear to be the most practically viable power source for EVs.Among the available battery technologies to date,only Li-ion batteries may possess the power and energy densities necessary for EV applications.The commonly used Li-ion batteries that power almost all portable electronic equipment today are comprised of a graphite anode and a LiCoO 2cathode (3.6V system)and can reach a practical energy density of 150W h kg À1in single cells.This battery technology is not very useful for EV application due to its limited cycle life (especially at elevated temperatures)and prob-lematic safety features (especially for large,multi-cell modules).7While there are ongoing developments in the hybrid EV field,including practical ones in which only part of the propulsion of the car is driven by an electrical motor and batteries,8the main goal of the battery community is to be able to develop full EV applications.This necessitates the development of Li-ion batteries with much higher energy densities compared to the practical state-of-the-art.The biggest challenge is that Li-ion batteries are complicated devices whose components never reach thermodynamic stability.The surface chemistry that occurs within these systems is very complicated,as described briefly below,and continues to be the main factor that determines their performance.9Nicole Leifer Nicole Leifer received a BS degree in chemistry from MIT in 1998.After teaching high school chemistry and physics for several years at Stuyvesant High School in New York City,she began work towards her PhD in solid state physics from the City University of New York Grad-uate Center.Her research con-sisted primarily of employing solid state NMR in the study of lithium ion electrode materialsand electrode surfacephenomena with Prof.Green-baum at Hunter College andProf.Grey at Stony Brook University.After completing her PhD she joined Prof.Doron Aurbach for a postdoctorate at Bar-Ilan University to continue work in lithium ion battery research.There she continues her work in using NMR to study lithium materials in addition to new forays into carbon materials’research for super-capacitor applications with a focus on enhancement of electro-chemical performance through the incorporation of carbonnanotubes.David Jacob David Jacob earned a BSc from Amravati University in 1998,an MSc from Pune University in 2000,and completed his PhD at Bar-Ilan University in 2007under the tutelage of Professor Aharon Gedanken.As part of his PhD research,he developed novel methods of synthesizing metal fluoride nano-material structures in ionic liquids.Upon finishing his PhD he joined Prof.Doron Aurbach’s lithium ionbattery group at Bar-Ilan in2007as a post-doctorate and during that time developed newformulations of electrolyte solutions for Li-ion batteries.He has a great interest in nanotechnology and as of 2011,has become the CEO of IsraZion Ltd.,a company dedicated to the manufacturing of novelnano-materials.Doron Aurbach Dr Doron Aurbach is a full Professor in the Department of Chemistry at Bar-Ilan Univer-sity (BIU)in Ramat Gan,Israel and a senate member at BIU since 1996.He chaired the chemistry department there during the years 2001–2005.He is also the chairman of the Israeli Labs Accreditation Authority.He founded the elec-trochemistry group at BIU at the end of 1985.His groupconducts research in thefollowing fields:Li ion batteries for electric vehicles and for otherportable uses (new cathodes,anodes,electrolyte solutions,elec-trodes–solution interactions,practical systems),rechargeable magnesium batteries,electronically conducting polymers,super-capacitors,engineering of new carbonaceous materials,develop-ment of devices for storage and conversion of sustainable energy (solar,wind)sensors and water desalination.The group currently collaborates with several prominent research groups in Europe and the US and with several commercial companies in Israel and abroad.He is also a fellow of the ECS and ISE as well as an associate editor of Electrochemical and Solid State Letters and the Journal of Solid State Electrochemistry.Prof.Aurbach has more than 350journals publications.D o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 24 F e b r u a r y 2011P u b l i s h e d o n 23 F e b r u a r y 2011 o n h t t p ://p u b s .r s c .o r g | d o i :10.1039/C 0J M 04225KAll electrodes,excluding 1.5V systems such as LiTiO x anodes,are surface-film controlled (SFC)systems.At the anode side,all conventional electrolyte systems can be reduced in the presence of Li ions below 1.5V,thus forming insoluble Li-ion salts that comprise a passivating surface layer of particles referred to as the solid electrolyte interphase (SEI).10The cathode side is less trivial.Alkyl carbonates can be oxidized at potentials below 4V.11These reactions are inhibited on the passivated aluminium current collectors (Al CC)and on the composite cathodes.There is a rich surface chemistry on the cathode surface as well.In their lithiated state,nucleophilic oxygen anions in the surface layer of the cathode particles attack electrophilic RO(CO)OR solvents,forming different combinations of surface components (e.g.ROCO 2Li,ROCO 2M,ROLi,ROM etc.)depending on the electrolytes used.12The polymerization of solvent molecules such as EC by cationic stimulation results in the formation of poly-carbonates.13The dissolution of transition metal cations forms surface inactive Li x MO y phases.14Their precipitation on the anode side destroys the passivation of the negative electrodes.15Red-ox reactions with solution species form inactive LiMO y with the transition metal M at a lower oxidation state.14LiMO y compounds are spontaneously delithiated in air due to reactions with CO 2.16Acid–base reactions occur in the LiPF 6solutions (trace HF,water)that are commonly used in Li-ion batteries.Finally,LiCoO 2itself has a rich surface chemistry that influences its performance:4LiCo III O 2 !Co IV O 2þCo II Co III 2O 4þ2Li 2O !4HF4LiF þ2H 2O Co III compounds oxidize alkyl carbonates;CO 2is one of the products,Co III /Co II /Co 2+dissolution.14Interestingly,this process seems to be self-limiting,as the presence of Co 2+ions in solution itself stabilizes the LiCoO 2electrodes,17However,Co metal in turn appears to deposit on the negative electrodes,destroying their passivation.Hence the performance of many types of electrodes depends on their surface chemistry.Unfortunately surface studies provide more ambiguous results than bulk studies,therefore there are still many open questions related to the surface chemistry of Li-ion battery systems.It is for these reasons that proper R&D of advanced materials for Li-ion batteries has to include bulk structural and perfor-mance studies,electrode–solution interactions,and possible reflections between the anode and cathode.These studies require the use of the most advanced electrochemical,18structural (XRD,HR microscopy),spectroscopic and surface sensitive analytical techniques (SS NMR,19FTIR,20XPS,21Raman,22X-ray based spectroscopies 23).This presentation provides a review of the forefront of the study of advanced materials—electrolyte systems,current collectors,anode materials,and finally advanced cathodes materials used in Li-ion batteries,with the emphasis on contributions from the authors’group.ExperimentalMany of the materials reviewed were studied in this laboratory,therefore the experimental details have been provided as follows.The LiMO 2compounds studied were prepared via self-combus-tion reactions (SCRs).24Li[MnNiCo]O 2and Li 2MnO 3$Li/MnNiCo]O 2materials were produced in nano-andsubmicrometric particles both produced by SCR with different annealing stages (700 C for 1hour in air,900 C or 1000 C for 22hours in air,respectively).LiMn 1.5Ni 0.5O 4spinel particles were also synthesized using SCR.Li 4T 5O 12nanoparticles were obtained from NEI Inc.,USA.Graphitic material was obtained from Superior Graphite (USA),Timcal (Switzerland),and Conoco-Philips.LiMn 0.8Fe 0.2PO 4was obtained from HPL Switzerland.Standard electrolyte solutions (alkyl carbonates/LiPF 6),ready to use,were obtained from UBE,Japan.Ionic liquids were obtained from Merck KGaA (Germany and Toyo Gosie Ltd.,(Japan)).The surface chemistry of the various electrodes was charac-terized by the following techniques:Fourier transform infrared (FTIR)spectroscopy using a Magna 860Spectrometer from Nicolet Inc.,placed in a homemade glove box purged with H 2O and CO 2(Balson Inc.air purification system)and carried out in diffuse reflectance mode;high-resolution transmission electron microscopy (HR-TEM)and scanning electron microscopy (SEM),using a JEOL-JEM-2011(200kV)and JEOL-JSM-7000F electron microscopes,respectively,both equipped with an energy dispersive X-ray microanalysis system from Oxford Inc.;X-ray photoelectron spectroscopy (XPS)using an HX Axis spectrom-eter from Kratos,Inc.(England)with monochromic Al K a (1486.6eV)X-ray beam radiation;solid state 7Li magic angle spinning (MAS)NMR performed at 194.34MHz on a Bruker Avance 500MHz spectrometer in 3.2mm rotors at spinning speeds of 18–22kHz;single pulse and rotor synchronized Hahn echo sequences were used,and the spectra were referenced to 1M LiCl at 0ppm;MicroRaman spectroscopy with a spectrometerfrom Jobin-Yvon Inc.,France.We also used M €ossbauer spec-troscopy for studying the stability of LiMPO 4compounds (conventional constant-acceleration spectrometer,room temperature,50mC:57Co:Rh source,the absorbers were put in Perspex holders.In situ AFM measurements were carried out using the system described in ref.25.The following electrochemical measurements were posite electrodes were prepared by spreading slurries comprising the active mass,carbon powder and poly-vinylidene difluoride (PVdF)binder (ratio of 75%:15%:10%by weight,mixed into N -methyl pyrrolidone (NMP),and deposited onto aluminium foil current collectors,followed by drying in a vacuum oven.The average load was around 2.5mg active mass per cm 2.These electrodes were tested in two-electrode,coin-type cells (Model 2032from NRC Canada)with Li foil serving as the counter electrode,and various electrolyte puter-ized multi-channel battery analyzers from Maccor Inc.(USA)and Arbin Inc.were used for galvanostatic measurements (voltage vs.time/capacity,measured at constant currents).Results and discussionOur road map for materials developmentFig.1indicates a suggested road map for the direction of Li-ion research.The axes are voltage and capacity,and a variety of electrode materials are marked therein according to their respective values.As is clear,the main limiting factor is the cathode material (in voltage and capacity).The electrode mate-rials currently used in today’s practical batteries allow forD o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 24 F e b r u a r y 2011P u b l i s h e d o n 23 F e b r u a r y 2011 o n h t t p ://p u b s .r s c .o r g | d o i :10.1039/C 0J M 04225Ka nominal voltage of below 4V.The lower limit of the electro-chemical window of the currently used electrolyte solutions (alkyl carbonates/LiPF 6)is approximately 1.5V vs.Li 26(see later discussion about the passivation phenomena that allow for the operation of lower voltage electrodes,such as Li and Li–graphite).The anodic limit of the electrochemical window of the alkyl carbonate/LiPF 6solutions has not been specifically determined but practical accepted values are between 4.2and 5V vs.Li 26(see further discussion).With some systems which will be discussed later,meta-stability up to 4.9V can be achieved in these standard electrolyte solutions.Electrolyte solutionsThe anodic stability limits of electrolyte solutions for Li-ion batteries (and those of polar aprotic solutions in general)demand ongoing research in this subfield as well.It is hard to define the onset of oxidation reactions of nonaqueous electrolyte solutions because these strongly depend on the level of purity,the presence of contaminants,and the types of electrodes used.Alkyl carbonates are still the solutions of choice with little competition (except by ionic liquids,as discussed below)because of the high oxidation state of their central carbon (+4).Within this class of compounds EC and DMC have the highest anodic stability,due to their small alkyl groups.An additional benefit is that,as discussed above,all kinds of negative electrodes,Li,Li–graphite,Li–Si,etc.,develop excellent passivation in these solutions at low potentials.The potentiodynamic behavior of polar aprotic solutions based on alkyl carbonates and inert electrodes (Pt,glassy carbon,Au)shows an impressive anodic stability and an irreversible cathodic wave whose onset is $1.5vs.Li,which does not appear in consequent cycles due to passivation of the anode surface bythe SEI.The onset of these oxidation reactions is not well defined (>4/5V vs.Li).An important discovery was the fact that in the presence of Li salts,EC,one of the most reactive alkyl carbonates (in terms of reduction),forms a variety of semi-organic Li-con-taining salts that serve as passivation agents on Li,Li–carbon,Li–Si,and inert metal electrodes polarized to low potentials.Fig.2and Scheme 1indicates the most significant reduction schemes for EC,as elucidated through spectroscopic measure-ments (FTIR,XPS,NMR,Raman).27–29It is important to note (as reflected in Scheme 1)that the nature of the Li salts present greatly affects the electrode surface chemistry.When the pres-ence of the salt does not induce the formation of acidic species in solutions (e.g.,LiClO 4,LiN(SO 2CF 3)2),alkyl carbonates are reduced to ROCO 2Li and ROLi compounds,as presented in Fig. 2.In LiPF 6solutions acidic species are formed:LiPF 6decomposes thermally to LiF and PF 5.The latter moiety is a Lewis acid which further reacts with any protic contaminants (e.g.unavoidably present traces of water)to form HF.The presence of such acidic species in solution strongly affects the surface chemistry in two ways.One way is that PF 5interactswithFig.1The road map for R&D of new electrode materials,compared to today’s state-of-the-art.The y and x axes are voltage and specific capacity,respectively.Fig.2A schematic presentation of the CV behavior of inert (Pt)elec-trodes in various families of polar aprotic solvents with Li salts.26D o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 24 F e b r u a r y 2011P u b l i s h e d o n 23 F e b r u a r y 2011 o n h t t p ://p u b s .r s c .o r g | d o i :10.1039/C 0J M 04225Kthe carbonyl group and channels the reduction process of EC to form ethylene di-alkoxide species along with more complicated alkoxy compounds such as binary and tertiary ethers,rather than Li-ethylene dicarbonates (see schemes in Fig.2);the other way is that HF reacts with ROLi and ROCO 2Li to form ROH,ROCO 2H (which further decomposes to ROH and CO 2),and surface LiF.Other species formed from the reduction of EC are Li-oxalate and moieties with Li–C and C–F bonds (see Scheme 1).27–31Efforts have been made to enhance the formation of the passivation layer (on graphite electrodes in particular)in the presence of these solutions through the use of surface-active additives such as vinylene carbonate (VC)and lithium bi-oxalato borate (LiBOB).27At this point there are hundreds of publica-tions and patents on various passivating agents,particularly for graphite electrodes;their further discussion is beyond the scope of this paper.Readers may instead be referred to the excellent review by Xu 32on this subject.Ionic liquids (ILs)have excellent qualities that could render them very relevant for use in advanced Li-ion batteries,including high anodic stability,low volatility and low flammability.Their main drawbacks are their high viscosities,problems in wetting particle pores in composite structures,and low ionic conductivity at low temperatures.Recent years have seen increasing efforts to test ILs as solvents or additives in Li-ion battery systems.33Fig.3shows the cyclic voltammetric response (Pt working electrodes)of imidazolium-,piperidinium-,and pyrrolidinium-based ILs with N(SO 2CF 3)2Àanions containing LiN(SO 2CF 3)2salt.34This figure reflects the very wide electrochemical window and impressive anodic stability (>5V)of piperidium-and pyr-rolidium-based ILs.Imidazolium-based IL solutions have a much lower cathodic stability than the above cyclic quaternary ammonium cation-based IL solutions,as demonstrated in Fig.3.The cyclic voltammograms of several common electrode mate-rials measured in IL-based solutions are also included in the figure.It is clearly demonstrated that the Li,Li–Si,LiCoO 2,andLiMn 1.5Ni 0.5O 4electrodes behave reversibly in piperidium-and pyrrolidium-based ILs with N(SO 2CF 3)2Àand LiN(SO 2CF 3)2salts.This figure demonstrates the main advantage of the above IL systems:namely,the wide electrochemical window with exceptionally high anodic stability.It was demonstrated that aluminium electrodes are fully passivated in solutions based on derivatives of pyrrolidium with a N(SO 2CF 3)2Àanion and LiN(SO 2CF 3)2.35Hence,in contrast to alkyl carbonate-based solutions in which LiN(SO 2CF 3)2has limited usefulness as a salt due to the poor passivation of aluminium in its solutions in the above IL-based systems,the use of N(SO 2CF 3)2Àas the anion doesn’t limit their anodic stability at all.In fact it was possible to demonstrate prototype graphite/LiMn 1.5Ni 0.5O 4and Li/L-iMn 1.5Ni 0.5O 4cells operating even at 60 C insolutionsScheme 1A reaction scheme for all possible reduction paths of EC that form passivating surface species (detected by FTIR,XPS,Raman,and SSNMR 28–31,49).Fig.3Steady-state CV response of a Pt electrode in three IL solutions,as indicated.(See structure formulae presented therein.)The CV presentations include insets of steady-state CVs of four electrodes,as indicated:Li,Li–Si,LiCoO 2,and LiMn 1.5Ni 0.5O 4.34D o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 24 F e b r u a r y 2011P u b l i s h e d o n 23 F e b r u a r y 2011 o n h t t p ://p u b s .r s c .o r g | d o i :10.1039/C 0J M 04225Kcomprising alkyl piperidium-N(SO2CF3)2as the IL solvent and Li(SO2CF3)2as the electrolyte.34Challenges remain in as far as the use of these IL-based solutions with graphite electrodes.22Fig.4shows the typical steady state of the CV of graphite electrodes in the IL without Li salts.The response in this graph reflects the reversible behavior of these electrodes which involves the insertion of the IL cations into the graphite lattice and their subsequent reduction at very low potentials.However when the IL contains Li salt,the nature of the reduction processes drastically changes.It was recently found that in the presence of Li ions the N(SO2CF3)2Àanion is reduced to insoluble ionic compounds such as LiF,LiCF3, LiSO2CF3,Li2S2O4etc.,which passivate graphite electrodes to different extents,depending on their morphology(Fig.4).22 Fig.4b shows a typical SEM image of a natural graphite(NG) particle with a schematic view of its edge planes.Fig.4c shows thefirst CVs of composite electrodes comprising NG particles in the Li(SO2CF3)2/IL solution.These voltammograms reflect an irreversible cathodic wave at thefirst cycle that belongs to the reduction and passivation processes and their highly reversible repeated Li insertion into the electrodes comprising NG. Reversible capacities close to the theoretical ones have been measured.Fig.4d and e reflect the structure and behavior of synthetic graphiteflakes.The edge planes of these particles are assumed to be much rougher than those of the NG particles,and so their passivation in the same IL solutions is not reached easily. Their voltammetric response reflects the co-insertion of the IL cations(peaks at0.5V vs.Li)together with Li insertion at the lower potentials(<0.3V vs.Li).Passivation of this type of graphite is obtained gradually upon repeated cycling(Fig.4e), and the steady-state capacity that can be obtained is much lower than the theoretical one(372mA h gÀ1).Hence it seems that using graphite particles with suitable morphologies can enable their highly reversible and stable operation in cyclic ammonium-based ILs.This would make it possible to operate high voltage Li-ion batteries even at elevated temperatures(e.g. 4.7–4.8V graphite/LiMn1.5Ni0.5O4cells).34 The main challenge in thisfield is to demonstrate the reasonable performance of cells with IL-based electrolytes at high rates and low temperatures.To this end,the use of different blends of ILs may lead to future breakthroughs.Current collectorsThe current collectors used in Li-ion systems for the cathodes can also affect the anodic stability of the electrolyte solutions.Many common metals will dissolve in aprotic solutions in the potential ranges used with advanced cathode materials(up to5V vs.Li). Inert metals such as Pt and Au are also irrelevant due to cost considerations.Aluminium,however,is both abundantand Fig.4A collection of data related to the behavior of graphite electrodes in butyl,methyl piperidinium IL solutions.22(a)The behavior of natural graphite electrodes in pure IL without Li salt(steady-state CV is presented).(b)The schematic morphology and a SEM image of natural graphite(NG)flakes.(c)The CV response(3first consecutive cycles)of NG electrodes in IL/0.5lithium trifluoromethanesulfonimide(LiTFSI)solution.(d and e)Same as(b and c)but for synthetic graphiteflakes.DownloadedbyBeijingUniversityofChemicalTechnologyon24February211Publishedon23February211onhttp://pubs.rsc.org|doi:1.139/CJM4225Kcheap and functions very well as a current collector due to its excellent passivation properties which allow it a high anodic stability.The question remains as to what extent Al surfaces can maintain the stability required for advanced cathode materials (up to 5V vs.Li),especially at elevated temperatures.Fig.5presents the potentiodynamic response of Al electrodes in various EC–DMC solutions,considered the alkyl carbonate solvent mixture with the highest anodic stability,at 30and 60 C.37The inset to this picture shows several images in which it is demonstrated that Al surfaces are indeed active and develop unique morphologies in the various solutions due to their obvious anodic processes in solutions,some of which lead to their effective passivation.The electrolyte used has a critical impact on the anodic stability of the Al.In general,LiPF 6solutions demonstrate the highest stability even at elevated temperatures due to the formation of surface AlF 3and even Al(PF 6)3.Al CCs in EC–DMC/LiPF 6solutions provide the highest anodic stability possible for conventional electrode/solution systems.This was demonstrated for Li/LiMn 1.5Ni 0.5O 4spinel (4.8V)cells,even at 60 C.36This was also confirmed using bare Al electrodes polarized up to 5V at 60 C;the anodic currents were seen to decay to negligible values due to passivation,mostly by surface AlF 3.37Passivation can also be reached in Li(SO 2CF 3),LiClO 4and LiBOB solutions (Fig.5).Above 4V (vs.Li),the formation of a successful passivation layer on Al CCs is highly dependent on the electrolyte formula used.The anodic stability of EC–DMC/LiPF 6solutions and Al current collectors may be further enhanced by the use of additives,but a review of additives in itself deserves an article of its own and for this readers are again referred to the review by Xu.32When discussing the topic of current collectors for Li ion battery electrodes,it is important to note the highly innovative work on (particularly anodic)current collectors by Taberna et al.on nano-architectured Cu CCs 47and Hu et al.who assembled CCs based on carbon nano-tubes for flexible paper-like batteries,38both of whom demonstrated suberb rate capabilities.39AnodesThe anode section in Fig.1indicates four of the most promising groups of materials whose Li-ion chemistry is elaborated as follows:1.Carbonaceous materials/graphite:Li ++e À+C 6#LiC 62.Sn and Si-based alloys and composites:40,41Si(Sn)+x Li ++x e À#Li x Si(Sn),X max ¼4.4.3.Metal oxides (i.e.conversion reactions):nano-MO +2Li ++2e À#nano-MO +Li 2O(in a composite structure).424.Li x TiO y electrodes (most importantly,the Li 4Ti 5O 12spinel structure).43Li 4Ti 5O 12+x Li ++x e À#Li 4+x Ti 5O 12(where x is between 2and 3).Conversion reactions,while they demonstrate capacities much higher than that of graphite,are,practically speaking,not very well-suited for use as anodes in Li-ion batteries as they generally take place below the thermodynamic limit of most developed electrolyte solutions.42In addition,as the reactions require a nanostructuring of the materials,their stability at elevated temperatures will necessarily be an issue because of the higher reactivity (due to the 1000-fold increase in surface area).As per the published research on this topic,only a limited meta-stability has been demonstrated.Practically speaking,it does not seem likely that Li batteries comprising nano-MO anodes will ever reach the prolonged cycle life and stability required for EV applications.Tin and silicon behave similarly upon alloying with Li,with similar stoichiometries and >300%volume changes upon lith-iation,44but the latter remain more popular,as Si is much more abundant than Sn,and Li–Si electrodes indicate a 4-fold higher capacity.The main approaches for attaining a workable revers-ibility in the Si(Sn)–Li alloying reactions have been through the use of both nanoparticles (e.g.,a Si–C nanocomposites 45)and composite structures (Si/Sn–M1–M2inter-metalliccompounds 44),both of which can better accommodate these huge volume changes.The type of binder used in composite electrodes containing Si particles is very important.Extensive work has been conducted to determine suitable binders for these systems that can improve the stability and cycle life of composite silicon electrodes.46As the practical usage of these systems for EV applications is far from maturity,these electrodes are not dis-cussed in depth in this paper.However it is important to note that there have been several recent demonstrations of how silica wires and carpets of Si nano-rods can act as much improved anode materials for Li battery systems in that they can serveasFig.5The potentiodynamic behavior of Al electrodes (current density measured vs.E during linear potential scanning)in various solutions at 30and 60 C,as indicated.The inset shows SEM micrographs of passivated Al surfaces by the anodic polarization to 5V in the solutions indicated therein.37D o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 24 F e b r u a r y 2011P u b l i s h e d o n 23 F e b r u a r y 2011 o n h t t p ://p u b s .r s c .o r g | d o i :10.1039/C 0J M 04225K。

⾼频PWMDC_DC转换器的设计_应建华26卷第1期2009年1⽉微电⼦学与计算机M ICROELECTRONICS&COM PUTERVol.26No.1January2009收稿⽇期:2008-02-21⾼频PWM DC/DC转换器的设计应建华,张俊,肖靖帆(华中科技⼤学电⼦科学与技术系,湖北武汉430074)摘要:设计了⼀种基于0.6L m CM OS⼯艺的⾼频PWM升压型DC/DC转换芯⽚.采⽤恒定频率、电流模式的控制结构以提供稳定的电压.本芯⽚在XFAB公司流⽚成功,测试结果表明,芯⽚的开关频率⾼达为1.2MHz,在输⼊电压分别为3.3V、5V的情况下能稳定地分别驱动4个、6个⽩光L ED,输出电压分别为12.8V、18.6V.关键词:DC/DC转换器;电流型;脉宽调制中图分类号:T N4⽂献标识码:A⽂章编号:1000-7180(2009)1-0197-04Design of High Frequency PWM DC/DC ConverterYING Jian-hua,ZHANG Jun,XIAO Jing-fan(Department of Electro nics Science and T echnology,Huazhong U niversit y of Science and Technology,Wuhan430074,China)Abstract:A hig h frequency PWM step-up DC/DC converter w ith low power dissipation w as designed by using0.6L m CM OS process.T he chip uses a constant frequency,cur rent-mode control scheme to provide steady voltag e.T he chip taped out successfully in XFA B Company.T he testing results showed that the frequency was1.2MHz,output v oltage w as12.8V and18.6V,when driving4and6white L ED in3.3V and5V input voltag e.Key words:DC/DC converter;cur rent-mode;pulse w idth modulation(PWM)1引⾔随着⼿机、mp3、PDA等便携式消费电⼦产品的⼴泛应⽤,对供电电源提出了新的要求.为保证系统稳定、可靠地⼯作,通常采⽤DC/DC开关变换器提供⼯作电压.⽂中设计了⼀种开关频率⾼达1.2MH z、电流控制型PWM升压DC/DC开关变换器,采⽤XFAB 公司的0.6L m CM OS⼯艺流⽚成功.测试结果表明,该转换器可稳定驱动串联的4到6个⽩光LED,满⾜系统设计要求.2PWM DC/DC转换器原理分析⽂中设计采⽤⼀种恒定频率、电流模式的控制结构[1],并把功率开关管和控制电路集成到⼀起.芯⽚结构如图1所⽰.SW为开关引脚;FB为输出电压的采样反馈端;SHDN为停机引脚.芯⽚内部主要模块包括基准电压源、误差放⼤器、PWM⽐较器、振荡器、电流采样电路、RS锁存器以及驱动.图1芯⽚电路框图该芯⽚的⼯作原理:在每个振荡周期的开始时, RS锁存器被置位,导通功率管,输出电压的采样值反馈到PWM⽐较器的正向端.当采样电压超过⽐较器的负输⼊端的⽔平时,RS锁存器被复位关闭功率管.通过开关功率管占空⽐的变化,调节输出电压使其稳定.3 主要电路模块设计分析3.1 电压基准源电路在DC -DC 转换器芯⽚中,因为芯⽚的输出功率⽐较⼤,要求带隙基准源在较宽的温度范围内参考源电压波动不⼤;同时由于⼯作电源电压的范围较宽,为了保证输出电压对⼯作电源电压的不敏感性,要设计⾼电源电压抑制⽐(PSRR)的带隙基准源.⽂中设计的带隙基准源电路如图2所⽰,由启动电路、带隙核、放⼤器A 和输出级组成.图2 带隙电路图其信号结构图如图3所⽰.图3 电压基准源信号结构图其中A 1(s )是V cc 到放⼤器A 输出的传函;A 2(s)是V cc 到电压基准源输出V re f 的传函;A 3(s )是放⼤器A 的输出到电压基准源输出V ref 的传函;A 4(s)是电压基准源的输出V re f 到放⼤器A 输⼊的传函;A 5(s)是放⼤器A 的开环传函.分析可知:V ref V cc =[A 1(s)+A 2(s )A 3(S )]@A 3(S )1+A 3(s )A 4(s )A 5(s)(1)通过参数的优化可以得到在低频范围内A 2(0)约等于0,A 3(0)约等于1,A 4(0)约等于1,A 1(0)和A 5(0)的值是与放⼤器A 结构相关的.化简式(1)可得低频电压抑制⽐为PSRR (0)=V ref V cc =1+A 5(0)A 1(0)U A 5(0)A 1(0)(2)为了获得⾼电源抑制⽐,采⽤了⼀种⾃偏置有源负载运算放⼤器A,利⽤⾃偏置电流源闭环反馈改变开环电阻的特性,实现⾼开环增益.晶体管M0、M 1、M2、M 6、M7、M 8构成⾃偏置电流源,M0由n 个(W /L )的MOS 管并联组成,M 1由1个(W /L )的MOS 管组成,M2是n -1个(W /L )的MOS 管并联组成,由电路⼩信号分析可得输出电阻R out =n @r oM0.电压基准源A 5(0)和A 1(0)的表达式分别为A 5(0)=n @g mQ4@r oM0(3)A 1(0)=r oQ4/(1/g -1mM0+r o Q4)U 1(4)电压基准源的低频电压抑制⽐:PSRR (0)U ng m Q4@r oM0(5)在XFAB 公司的X C 06⼯艺下,通过优化g m Q4和r oM 0,对基准源进⾏温度特性、电压调整率和电源抑制⽐仿真,仿真曲线如图4、图5所⽰.从图中可以看到,电压基准源的温度系数是11ppm/e ;低频电压抑制⽐达到92dB .图4 电压基准源温度系数仿真曲线图5 电压基准源PSRR 仿真曲线3.2 振荡器和斜波发⽣器振荡器产⽣恒稳的、周期性时变的输出波形,作为控制功率管开关的时钟.⽂中采⽤基本的充放电振荡器电路[3],⼜称为窗⼝⽐较式振荡器[4],提供⾼达1.2MH z 的开关频率,电路结构如图6所⽰.其⼯作原理:定时电容C 在两个门限电压V A 、V B 之间来回充放电,当定时电容上的电位达到两个门限电平中的某⼀个值时,RS 触发器输出Q 发⽣翻转;然后定时电容上的电位向相反⽅向变化,当其到达另⼀个门限电平时,Q 再次翻转.如此循环,产⽣振荡.198微电⼦学与计算机2009年图6 振荡器和斜波发⽣器电路结构图斜波发⽣器利⽤电流对定时电容的充放电,在电容C 上产⽣所需的斜波信号.产⽣斜波信号的⽬的是对电路进⾏斜波补偿,防⽌在占空⽐⼤于50%的情况下出现次谐波振荡,保证系统稳定性[2].设电容充电电流为I 1,放电电流为I 2,则电容C 的充电时间t 1=V 1-V 2I 1C,电容的放电时间t 2=V 1-V 2I 2,则振荡周期C 为t =t 1+t 2=(V 1-V 2)1I 1+1I 2C (6)由于充放电电流由电压基准源的PTAT 电流产⽣,振荡周期和斜升波的斜率基本保持不变.3.3 误差放⼤器误差放⼤器的作⽤是把反馈信号V FB 与内部基准电压进⾏⽐较,把电压之差放⼤,产⽣电压环误差信号,控制PWM ⽐较器正向输⼊端的电压信号.误差放⼤器的电路如图7所⽰.图7 误差放⼤器电路图由图7可知:M1、M2、M3、M4、M 17、M0、M 8组成误差放⼤器的第⼀放⼤级;M5、M7、M 9和M 10组成误差放⼤器第⼆级放⼤器,第⼆级电路是推挽输出结构,从⽽可以增加输⼊电压跟随能⼒.NMOS 管M 11⽤于对输出电压进⾏钳位,保证了芯⽚刚上电时不会产⽣电感上电流浪涌现象.M 3和M 4构成的交叉耦合结构,引⼊了⼀个局部正反馈,提⾼了第⼀级的放⼤增益,可以计算出从M2的漏级向下看到的等效电阻为:R eq =1/(g m2-g m4)-1,当g m 2>g m4,R eq >0,等效电阻增⼤,提⾼了开环增益:A v1=gm17/(g m2-g m4).第⼆级为推挽输出结构,可计算其增益为A v2=g m7(r 07+r o10).所以整个误差放⼤器的开环增益为A v =A v1A v2=g m17g m 7(r o7+r o10)/(g m2-g m4)(7)输出级的电阻R 1和电容C 1组成系统的补偿⽹络,⽤于保证系统环路的稳定性,其产⽣了极点和零点如下:s p1=1/2P (r o7+r o10)C 1s z1=1/2P R 1C 1其中产⽣的零点s z1⽤于补偿DC -DC 转换器输出负载电阻和滤波电容形成的极点;极点s p1⽤于对开关噪声进⾏衰减[1].误差放⼤器的频率特性的仿真曲线如图8所⽰.图8 误差放⼤器频率特性仿真曲线图8是误差放⼤器的频率特性曲线,由图可见:误差放⼤器的低频增益是48dB,⾸先经历⼀个低频极点,然后出现⼀个低频零点,零点对极点进⾏相位补偿,从⽽保证了DC -DC 转换器电路在单位增益带宽内等效只有⼀个主极点,使整个环路系统稳定.3.4 功率管由于功率管是整个驱动电路的核⼼器件,因此对于功率管的版图设计直接影响到了电路的整体性能.⽂中采⽤了蛇形栅结构的功率管,蛇形栅的结构优点是:(1)结构紧凑,等效宽度⼤,占⽤⾯积⼩;(2)由于多晶硅栅在拐弯处使⽤了135度的⾛向,有效避免了90度情况下局部雪崩击穿现象的发⽣;(3)源漏⾦属接触孔呈对⾓线分布,这使得MOS 器件的击穿特性,尤其是ESD 性能得到了提⾼.4 测试结果本电路已通过流⽚验证,对芯⽚在输⼊电压为199第1期应建华,等:⾼频PWM DC/DC 转换器的设计3.3V,驱动4个LED 和输⼊电压为5V,驱动6个LED 的情况下进⾏了测试,⽤Tektronix 公司的T DS2024B 数字存储⽰波器读取了输出电压波形和SW 开关电压波形,如图9、图10所⽰.图9 V in =3.3V,驱动4个LED图10 V in =5V ,驱动6个LED从图9、图10可以看出,芯⽚的开关频率在1.2MH z 左右,输出电压稳定.在3.3V 的输⼊电压、20~50e 的环境温度下对输出电压和开关频率的温度特性做了测试,并利⽤matlab 对测试数据进⾏了曲线拟合,如图11、图12所⽰.图11 输出电压温度特性图12 开关频率温度特性测试结果表明,当温度从21e 变化到50e 时,输出电压从12.662V 下降到12.436V,开关频率从1.211MH z 上升到1.289MH z.5 结束语⽂中设计了⼀种开关频率为1.2MHz 的DC/DC 转换器,采⽤恒定频率、电流模式的控制结构以提供稳定的电压.最终的测试结果表明,该芯⽚在输⼊电压分别为3.3V 、5V 的情况下能稳定地驱动4个、6个⽩光LED,开关频率在1.2MH z 左右,输出电压分别为12.7V 、18.6V,达到系统设计要求.参考⽂献:[1]Cheung Fai Lee,Philip K T M ok.A monolithic current-mode CM OS DC-DC converter wit h o n-chip cur rent -sensing technique[J].IEEE Journal of Solid-State Cir -cuits,2004,39(1):3-14.[2]韦枫,吴⾦.基于斜波补偿的电流模式PW M DC-DC 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The Hermeneutic MotionBy George Steiner (Excerpted from Chapter 5,pp. 312-317) The hermeneutic motion, the act of elicitation and appropriative transfer of meaning, is fourfold. There is initiative trust, an investment of belief, underwritten by previous experience but epistemologically exposed and psychologically hazardous, in the meaningfulness, in the 'seriousness' of the facing or, strictly speaking, adverse text. We venture a leap: we grant ab initio that there is 'something there' to be understood, that the transfer will not be void. All understanding, and the demonstrative statement of understanding which is translation, starts with an act of trust. This confiding will, ordinarily, be instantaneous and unexamined, but it has a complex base. It is an operative convention which derives from a sequence of phenomenological阐释学过程乔治·施泰纳（选自第五章, 312 - 317页) 阐释学过程，是引出或用于转换意义的行为，具有四重性。