On the homotopy type of the spectrum representing elliptic cohomology
A_review_of_advanced_and_practical_lithium_battery_materials

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。
Preface 兰氏化学手册

PREFACE TOFIFTEENTH EDITIONThis new edition,thefifth under the aegis of the present editor,remains the one-volume source of factual information for chemists,both professionals and students—thefirst place in which to“look it up”on the spot.The aim is to provide sufficient data to satisfy all one’s general needs without recourse to other reference sources.A user willfind this volume of value as a time-saverbecause of the many tables of numer ical data which have been especially compiled.Descriptive properties for a basic group of approximately4300organic compounds are compiled in Section1,an increase of300entries.All entries are listed alphabetically according to the senior prefix of the name.The data for each organic compound include (where available)name,structural formula,formula weight,Beilstein reference(or if un-available,the entry to the Merck Index,12th ed.),density,refractive index,melting point, boiling point,flash point,and solubility(citing numerical values if known)in water andvarious common organic solvents.Structural formulas either too complex or too ambig-uous to be rendered as line formulas are grouped at the bottom of each facing double page on which the entries appear.Alternative names,as well as trivial names of long-standing usage,are listed in their respective alphabetical order at the bottom of each double page in the regular alphabetical sequence.Another feature that assists the user in locating a desired entry is the empirical formula index.Section2on General Information,Conversion Tables,and Mathematics has had the table on general conversion factors thoroughly reworked.Similarly the material on Statis-tics in Chemical Analysis has had its contents more than doubled.Descriptive properties for a basic group of inorganic compounds are compiled in Section 3,which has undergone a small increase in the number of entries.Many entries under the column“Solubility”supply the reader with precise quantities dissolved in a stated solvent and at a given temperature.Several portions of Section4,Properties of Atoms,Radicals,and Bonds,have been significantly enlarged.For example,the entries under“Ionization Energy of Molecular and Radical Species”now number740and have an additional column with the enthalpy of formation of the ions.Likewise,the table on“Electron Affinities of the Elements, Molecules,and Radicals”now contains about225entries.The Table of Nuclides has material on additional radionuclides,their radiations,and the neutron capture cross sec-tions.Revised material for Section5includes the material on surface tension,viscosity,di-electric constant,and dipole moment for organic compounds.In order to include more data at several temperatures,the material has been divided into two separate tables.Ma-terial on surface tension and viscosity constitute thefirst table with715entries;included is the temperature range of the liquid phase.Material on dielectric constant and dipoleviiviii PREFACE TO FIFTEENTH EDITIONmoment constitute another table of1220entries.The additional data at two or more tem-peratures permit interpolation for intermediate temperatures and also permit limited ex-trapolation of the data.The Properties of Combustible Mixtures in Air has been revised and expanded to include over450compounds.Flash points ar e to be found in Section1. Completely revised are the tables on Thermal Conductivity for gases,liquids,and solids. Van derWaals’constants forgases has been br ought up to date and expanded to over500 substances.Section6,which includes Enthalpies and Gibbs Energies of Formation,Entropies,and Heat Capacities of Organic and Inorganic Compounds,and Heats of Melting,Vaporization, and Sublimation and Specific Heat at Various Temperatures for organic and inorganic compounds,has expanded by11pages,but the majoradditions have involved data in columns where it previously was absent.More material has also been included for critical temperature,critical pressure,and critical volume.The section on Spectroscopy has been retained but with some revisions and expansion. The section includes ultraviolet-visible spectroscopy,fluorescence,infrared and Raman spectroscopy,and X-ray spectrometry.Detection limits are listed for the elements when usingflame emission,flame atomic absorption,electrothermal atomic absorption,argon induction coupled plasma,andflame atomicfluorescence.Nuclear magnetic resonance embraces tables for the nuclear properties of the elements,proton chemical shifts and coupling constants,and similar material for carbon-13,boron-11,nitrogen-15,fluorine-19,silicon-19,and phosphorus-31.In Section8,the material on solubility constants has been doubled to550entries. Sections on proton transfer reactions,including some at various temperatures,formation constants of metal complexes with organic and inorganic ligands,buffer solutions of all types,reference electrodes,indicators,and electrode potentials are retained with some revisions.The material on conductances has been revised and expanded,particularly in the table on limiting equivalent ionic conductances.Everything in Sections9and10on physiochemical relationships,and on polymers, rubbers,fats,oils,and waxes,respectively,has been retained.Section11,Practical Laboratory Information,has undergone significant changes and expansion.Entries in the table on“Molecular Elevation of the Boiling Point”have been increased.McReynolds’constants for stationary phases in gas chromatography have been reorganized and expanded.The guide to ion-exchange resins and discussion is new and embraces all types of column packings and membrane materials.Gravimetric factors have been altered to reflect the changes in atomic weights for several elements.Newly added are tables listing elements precipitated by general analytical reagents,and giving equations for the redox determination of the elements with their equivalent weights.Discussion on the topics of precipitation and complexometric titrations include primary standards and indicators for each analytical technique.A new topic of masking and demasking agents includes discussion and tables of masking agents forvar ious elements,foranions and neutral molecules,and common demasking agents.A table has been added listing the common amino acids with theirpI and p Kvalues and their3-letterand1-letterabbr evi-astly a9-page table lists the threshold limit value(TLV)for gases and vapors.As stated in earlier prefaces,every effort has been made to select the most useful and reliable information and to record it with accuracy.However,the editor’s50years ofPREFACE TO FIFTEENTH EDITION ix involvement with textbooks and handbooks bring a realization of the opportunities for gremlins to exert their inevitable mischief.It is hoped that users of this handbook will continue to offer suggestions of material that might be included in,or even excluded from, future editions and call attention to errors.These communications should be directed to the editor.The street address will change early in1999,as will the telephone number. However,the e-mail address should remain as“pd105@.”Knoxville,TN John A.DeanPREFACE TOFOURTEENTH EDITIONPerhaps it would be simplest to begin by stating the ways in which this new edition,the fourth under the aegis of the present editor,has not been changed.It remains the one-volume source of factual information for chemists,both professionals and students—thefirst place in which to“look it up”on the spot.The aim is to provide sufficient data to satisfy all one’s general needs without recourse to other reference sources.Even the worker with the facilities of a comprehensive library willfind this volume of value as a time-saverbecause of the many tables of numer ical data which have been especially compiled.The changes,however,are both numerous and significant.First of all,there is a change in the organization of the subject matter.For example,material formerly contained in the section entitled Analytical Chemistry is now grouped by operational categories:spectroscopy;electrolytes,electro-motive force,and chemical equilibrium;and practical laboratory information.Polymers,rubbers, fats,oils,and waxes constitute a large independent section.Descriptive properties for a basic group of approximately4000organic compounds are compiledin Section1.These follow a concise introduction to organic nomenclature,including the topic of stereochemistry.Nomenclature is consistent with the1979rules of the Commission on Nomencla-ture,International Union of Pure and Applied Chemistry(IUPAC).All entries are listed alphabeti-cally according to the senior prefix of the name.The data for each organic compound include(where available)name,structural formula,formula weight,Beilstein reference,density,refractive index, melting point,boiling point,flash point,and solubility(citing numerical values if known)in water and various common organic solvents.Structural formulas either too complex or too ambiguous to be rendered as line formulas are grouped at the bottom of the page on which the entries appear. Alternative names,as well as trivial names of long-standing usage,are listed in their respective alphabetical order at the bottom of each page in the regular alphabetical sequence.Another feature that assists the user in locating a desired entry is the empirical formula index.Section2combines the former separate section on Mathematics with the material involving General Information and Conversion Tables.The fundamental physical constants reflect values rec-ommended in1986.Physical and chemical symbols and definitions have undergone extensive re-vision and expansion.Presented in14categories,the entries follow recommendations published in 1988by the IUPAC.The table of abbreviations and standard letter symbols provides,in a sense,an alphabetical index to the foregoing tables.The table of conversion factors has been modified in view of recent data and inclusion of SI units;cross-entries for“archaic”or unusual entries have been curtailed.Descriptive properties for a basic group of approximately1400inorganic compounds are com-piled in Section3.These follow a concise,revised introduction to inorganic nomenclature that follows the recommendations of the IUPAC published in1990.In this section are given the exact atomic(or formula)weight of the elements accompanied,when available,by the uncertainty in the finalfigure given in parentheses.In Section4the data on bond lengths and strengths have been vastly increased so as to include not only the atomic and effective ionic radii of elements and the covalent radii for atoms,but also the bond lengths between carbon and other elements and between elements other than carbon.Allxixii PREFACE TO FOURTEENTH EDITIONlengths are given in picometers(SI unit).Effective ionic radii are tabulated as a function of ion charge and coordination number.Bond dissociation energies are given in kilojoules per mole with the uncertainty of thefinalfigure(s)given in parentheses when known.New tables include bond dipole moments,group dipole moments,work functions of the elements,and relative abundances of the naturally occurring elements.The table of nuclides has been shortened and includes only the more commonly encountered nuclides;tabulations list half-life,natural abundance,cross-section to thermal neutrons,and radiation emitted upon disintegration.Entries have been updated.Revised material in Section5includes an extensive tabulation of binary and ternary azeotropes comprising approximately850entries.Over975compounds have values listed for viscosity,di-electric constant,dipole moment,and surface tension.Whenever possible,data for viscosity and dielectric constant are provided at two temperatures to permit interpolation for intermediate tem-peratures and also to permit limited extrapolation of the data.The dipole moments are often listed for different physical states.Values for surface tension can be calculated over a range of temperatures from two constants that can befitted into a linear equation.Also extensively revised and expanded are the properties of combustible mixtures in air.A table of triple points has been added.The tables in Section6contain values of the enthalpy and Gibbs energy of formation,entropy, and heat capacity atfive temperatures for approximately2000organic compounds and1500inor-ganic compounds,many in more than one physical state.Separate tabulations have enthalpies of melting,vaporization,transition,and sublimation for organic and inorganic compounds.All values are given in SI units(joule)and have been extracted from the latest sources such as JANAF Ther-mochemical Tables,3d ed.(1986);Thermochemical Data of Organic Compounds,2d ed.(1986); and Enthalpies of Vaporization of Organic Compounds,published underthe auspices of the IUPAC (1985).Also updated is the material on critical properties of elements and compounds.The section on Spectroscopy has been expanded to include ultraviolet-visible spectroscopy,fluorescence,Raman spectroscopy,and mass spectroscopy.Retained sections have been thoroughly revised:in particular,the tables on electronic emission and atomic absorption spectroscopy,nuclear magnetic resonance,and infrared spectroscopy.Detection limits are listed for the elements when usingflame emission,flame atomic absorption,electrothermal atomic absorption,argon ICP,and flame atomicfluorescence.Nuclear magnetic resonance embraces tables for the nuclear properties of the elements,proton chemical shifts and coupling constants,and similar material for carbon-13, boron-11,nitrogen-15,fluorine-19,silicon-29,and phosphorus-31.Section8now combines all the material on electrolytes,electromotive force,and chemical equi-librium,some of which had formerly been included in the old“Analytical Chemistry”section of earlier editions.Material on the half-wave potentials of inorganic and organic materials has been thoroughly revised.The tabulation of the potentials of the elements and their compounds reflects recent IUPAC(1985)recommendations.An extensive new Section10is devoted to polymers,rubbers,fats,oils,and waxes.A discussion of polymers and rubbers is followed by the formulas and key properties of plastic materials.For each member and type of the plastic families there is a tabulation of their physical,electrical, mechanical,and thermal properties and characteristics.A similar treatment is accorded the various types of rubber materials.Chemical resistance and gas permeability constants are also given for rubbers and plastics.The section concludes with various constants of fats,oils,and waxes.The practical laboratory information contained in Section11has been gathered from many of the previous sections of earlier editions.This material has been supplemented with new material under separation methods,gravimetric and volumetric analysis,and laboratory solutions.Significant new tables under separation methods include:properties of solvents for chromatography,solvents having the same refractive index and the same density,McReynolds’constants for stationary phases in gas chromatography,characteristics of selected supercriticalfluids,and typical performances in HPLC for various operating conditions.Under gravimetric and volumetric analysis,gravimetric factors,equations and equivalents for volumetric analysis,and titrimetric factors have been retainedPREFACE TO FOURTEENTH EDITION xiii along with the formation constants of EDTA metal complexes.In this age of awareness of chemical dangers,tables have been added for some common reactive and incompatible chemicals,chemicals recommended for refrigerated storage,and chemicals which polymerize or decompose on extended storage at low temperature.Updated is the information about the U.S.Standard Sieve Series.Ther-mometry data have been revised to bring them into agreement with the new International Temper-ature Scale–1990,and data for type N thermocouples are included.Every effort has been made to select the most useful and most reliable information and to record it with accuracy.However,the editor’s many years of involvement with handbooks bring a realiza-tion of the opportunities for gremlins to exert their inevitable mischief.It is hoped that users of this handbook will offer suggestions of material that might be included in,or even excluded from,future editions and call attention to errors.These communications should be directed to the editor at his home address(or by telephone).John A.DeanPREFACE TOFIRST EDITIONThis book is the result of a number of years’experience in the compiling and editing of data useful to chemists.In it an effort has been made to select material to meet the needs of chemists who cannot command the unlimited time available to the research specialist,or who lack the facilities of a large technical library which so often is not conveniently located at many manufacturing centers. If the information contained herein serves this purpose,the compiler will feel that he has accom-plished a worthy task.Even the worker with the facilities of a comprehensive library mayfind this volume of value as a time-saverbecause of the many tables of numer ical data which have been especially computed forthis pur pose.Every effort has been made to select the most reliable information and to record it with accuracy. Many years of occupation with this type of work bring a realization of the opportunities for the occurrence of errors,and while every endeavor has been made to prevent them,yet it would be remarkable if the attempts towards this end had always been successful.In this connection it is desired to express appreciation to those who in the past have called attention to errors,and it will be appreciated if this be done again with the present compilation for the publishers have giventheir assurance that no expense will be spared in making the necessary changes in subsequent printings.It has been aimed to produce a compilation complete within the limits set by the economy of available space.One difficulty always at hand to the compilerof such a book is that he must decide what data are to be excluded in order to keep the volume from becoming unwieldy because of its size.He can hardly be expected to have an expert’s knowledge of all branches of the science nor the intuition necessary to decide in all cases which particular value to record,especially when many differing values are given in the literature for the same constant.If the expert in a particularfield will judge the usefulness of this book by the data which it supplies to him fromfields other than his specialty and not by the lack of highly specialized information in which only he and his co-workers are interested(and with which he is familiar and for which he would never have occasion to consult this compilation),then an estimate of its value to him will be apparent.However,if such specialists will call attention to missing data with which they are familiar and which they believe others less specialized will also need,then works of this type can be improved in succeeding editions.Many of the gaps in this volume are caused by the lack of such information in the literature.It is hoped that to one of the most important classes of workers in chemistry,namely the teachers,the book will be of value not only as an aid in answering the most varied questions with which they are confronted by interested students,but also as an inspiration through what it suggests by the gaps and inconsistencies,challenging as they do the incentive to engage in the creative and experimental work necessary to supply the missing information.While the principal value of the book is for the professional chemist or student of chemistry,it should also be of value to many people not especially educated as chemists.Workers in the natural sciences—physicists,mineralogists,biologists,pharmacists,engineers,patent attorneys,and librar-ians—are often called upon to solve problems dealing with the properties of chemical products or materials of construction.For such needs this compilation supplies helpful information and will serve not only as an economical substitute for the costly accumulation of a large library of mono-graphs on specialized subjects,but also as a means of conserving the time required to search forxvxvi PREFACE TO FIRST EDITIONinformation so widely scattered throughout the literature.For this reason especial care has been taken in compiling a comprehensive index and in furnishing cross references with many of the tables.It is hoped that this book will be of the same usefulness to the worker in science as is the dictionary to the worker in literature,and that its resting place will be on the desk rather than on the bookshelf. Cleveland,Ohio nge May2,1934。
英文版原子物理课件

1.1 Introduction
The origins of atomic physics :quantum mechanics Bohr model of the H This introductory chapter surveys some of the early ideas: Spectrum of atomic H and Bohr Theory Einstein's treatment of interaction of atom with light the Zeeman effect Rutherford scattering And so on
Shanxi University Atomic Physics
1.2 Spectrum of atomic hydrogen_3
Wavenumbers may seem rather old-fashioned but they are very useful in atomic physics
the characteristic spectrum for atoms is composed of discrete lines that are the ‘fingerprint' of the element.
In 1888, the Swedish professor J. Rydberg found that the spectral lines in hydrogen obey the following mathematical formula:
Shanxi University Atomic Physics
Lyman series: n’ = 2; 3; 4; … n = 1. Balmer (n = 2), Paschen series: (n = 3), Brackett (n = 4) and Pfund (n = 5)
低维拓扑简介

考研论坛»数学»低维拓扑knight51发表于2005-7-28 08:34低维拓扑<P>下面说说低维拓扑的内容:低维拓扑是微分拓扑的一部分,主要研究3,4维流形与纽结理论。
又叫几何拓扑。
主要以代数拓扑与微分拓扑为工具。
它与微分几何和动力系统关系密切。
国外搞这个方向的也几乎都搞微分几何和动力系统。
我国这个方向北大最牛,美国是伯克利和普林斯顿最牛。
比起代数几何来,它比较好入门。
初学者只需要代数拓扑,微分拓扑,黎曼几何的知识就行了。
美国这方面比较牛,几乎每个搞基础数学研究的都会低维拓扑。
</P><DIV class=postcolor>纠正一下上面的错误,美国也不是每个搞基础数的都精通低维拓扑,而是懂一些低维拓扑的知识。
如果入门后还想更加深入了解它,那还需要读一些双曲几何和拓扑动力系统的书。
</DIV><!-- THE POST --><!-- THE POST --><DIV class=postcolor>下面介绍一下这方面的牛人:Bill Thurston studied at New College, Sarasota, Florida. He received his B.S. from there in 1967 and moved to the University of California at Berkeley to undertake research under Morris Hirsch's and Stephen Smale's supervision. He was awarded his doctorate in 1972 for a thesis entitled Foliations of 3-manifolds which are circle bundles. This work showed the existence of compact leaves in foliations of 3-dimensional manifolds.After completing his Ph.D., Thurston spent the academic year 1972-73 at the Institute for Advanced Study at Princeton. Then, in 1973, he was appointed an assistant professor of mathematics at Massachusetts Institute of Technology. In 1974 he was appointed professor of mathematics at Princeton University.Throughout this period Thurston worked on foliations. Lawson ([5]) sums up this work:-It is evident that Thurston's contributions to the field of foliations are of considerable depth. However, what sets them apart is their marvellous originality. This is also true of his subsequent work on Teichmüller space and the theory of 3-manifolds.In [8] Wall describes Thurston's contributions which led to him being awarded a Fields Medal in 1982. In fact the1982 Fields Medals were announced at a meeting of the General Assembly of the International Mathematical Union in Warsaw in early August 1982. They were not presented until the International Congress in Warsaw which could not be held in 1982 as scheduled and was delayed until the following year. Lectures on the work of Thurston which led to his receiving the Medal were made at the 1983 International Congress. Wall, giving that address, said:-Thurston has fantastic geometric insight and vision: his ideas have completely revolutionised the study of topology in 2 and 3 dimensions, and brought about a new and fruitful interplaybetween analysis, topology and geometry.Wall [8] goes on to describe Thurston's work in more detail:-The central new idea is that a very large class of closed 3-manifolds should carry a hyperbolic structure - be the quotient of hyperbolic space by a discrete group of isometries, or equivalently, carry a metric of constant negative curvature. Although this is a natural analogue of the situation for 2-manifolds, where such a result is given by Riemann's uniformisation theorem, it is much less plausible - even counter-intuitive - in the 3-dimensional situation.Kleinian groups, which are discrete isometry groups of hyperbolic 3-space, were first studied by Poincaré and a fundamental finiteness theorem was proved by Ahlfors. Thurston's work on Kleinian groups yielded many new results and established a well known conjecture. Sullivan describes this geometrical work in [6], giving the following summary:-Thurston's results are surprising and beautiful. The method is a new level of geometrical analysis - in the sense of powerful geometrical estimation on the one hand, and spatial visualisation and imagination on the other, which are truly remarkable.Thurston's work is summarised by Wall [8]:-Thurston's work has had an enormous influence on 3-dimensional topology. This area has a strong tradition of 'bare hands' techniques and relatively little interaction with other subjects. Direct arguments remain essential, but 3-dimensional topology has now firmly rejoined the main stream of mathematics.Thurston has received many honours in addition to the Fields Medal. He held a Alfred P Sloan Foundation Fellowship in 1974-75. In 1976 his work on foliations led to his being awarded the Oswald Veblen Geometry Prize of the American Mathematical Society. In 1979 he was awarded the Alan T Waterman Award, being the second mathematician to receive such an award (the first being Fefferman in 1976).</DIV><!-- THE POST -->第2个牛人:Michael Freedman entered the University of California at Berkeley in 1968 and continued his studies at Princeton University in 1969. He was awarded a doctorate by Princeton in 1973 for his doctoral dissertation entitled Codimension-Two Surgery. His thesis supervisor was William Browder.After graduating Freedman was appointed a lecturer in the Department of Mathematics at the University of California at Berkeley. He held this post from 1973 until 1975 when he became a member of the Institute for Advanced Study at Princeton. In 1976 he was appointed as assistant professor in the Department of Mathematics at the University of California at San Diego.Freedman was promoted to associate professor at San Diego in 1979. He spent the year 1980/81 at the Institute for Advanced Study at Princeton returning to the University of California at San Diego where he was promoted to professor on 1982. He holds this post in addition to the Charles Lee Powell Chair of Mathematics which he was appointed to in 1985.Freedman was awarded a Fields Medal in 1986 for his work on the Poincaré conjecture. The Poincaré conjecture, one of the famous problems of 20th-century mathematics, asserts that a simply connected closed 3-dimensional manifold is a 3-dimensional sphere. The higher dimensional Poincaréconjecture claims that any closed n-manifold which is homotopy equivalent to the n-sphere must be the n-sphere. When n = 3 this is equivalent to the Poincaré conjecture. Smale proved the higher dimensional Poincaré conjecture in 1961 for n at least 5. Freedman proved the conjecture for n = 4 in 1982 but the original conjecture remains open.Milnor, describing Freedman's work which led to the award of a Fields Medal at the International Congress of Mathematicians in Berkeley in 1986, said:-Michael Freedman has not only proved the Poincaré hypothesis for 4-dimensional topological manifolds, thus characterising the sphere S4, but has also given us classification theorems, easy to state and to use but difficult to prove, for much more general 4-manifolds. The simple nature of his results in the topological case must be contrasted with the extreme complications which are now known to occur in the study of differentiable and piecewise linear 4-manifolds. ... Freedman's 1982 proof of the 4-dimensional Poincaré hypothesis was an extraordinary tour de force. His methods were so sharp as to actually provide a complete classification of all compact simply connected topological 4-manifolds, yielding many previously unknown examples of such manifolds, and many previously unknown homeomorphisms between known manifolds.Freedman has received many honours for his work. He was California Scientist of the Year in 1984 and, in the same year, he was made a MacArthur Foundation Fellow and also was elected to the National Academy of Sciences. In 1985 he was elected to the American Academy of Arts and Science. In addition to being awarded the Fields Medal in 1986, he also received the Veblen Prize from the American Mathematical Society in that year. The citation for the Veblen Prize reads (see [3]):-After the discovery in the early 60s of a proof for the Poincaré conjecture and other properties of simply connected manifolds of dimension greater than four, one of the biggest open problems, besides the three dimensional Poincaré conjecture, was the classification of closed simply connected four manifolds. In his paper, The topology of four-dimensional manifolds, published in the Journal of Differential Geometry (1982), Freedman solved this problem, and in particular, the four-dimensional Poincaré conjecture. The major innovation was the solution of the simply connected surgery problem by proving a homotopy theoretic condition suggested by Casson for embedding a 2-handle, i.e. a thickened disc in a four manifold with boundary.Besides these results about closed simply connected four manifolds, Freedman also proved:(a) Any four manifold properly equivalent to R4 is homeomorphic to R4; a related result holds for S3 R.(b) There is a nonsmoothable closed four manifold.© The four-dimensional Hauptvermutung is false; i.e. there are four manifolds with inequivalent combinatorial triangulations.Finally, we note that the results of the above mentioned paper, together with Donaldson's work, produced the startling example of an exotic smoothing of R4.In his reply Freedman thanked his teachers (who he said included his students) and also gave some fascinating views on mathematics [3]:-My primary interest in geometry is for the light it sheds on the topology of manifolds. Here it seems important to be open to the entire spectrum of geometry, from formal to concrete. By spectrum, I mean the variety of ways in which we can think about mathematical structures. At one extreme the intuition for problems arises almost entirely from mental pictures. At the other extreme the geometric burden is shifted to symbolic and algebraic thinking. Of course this extreme is only a middle ground from the viewpoint of algebra, which is prepared to go much further in the direction of formal operations and abandon geometric intuition altogether.In the same reply Freedman also talks about the influence mathematics can have on the world and the way that mathematicians should express their ideas:-In the nineteenth century there was a movement, of which Steiner was a principal exponent, to keep geometry pure and ward off the depredations of algebra. Today I think we feel that much of the power of mathematics comes from combining insights from seemingly distant branches of the discipline. Mathematics is not so much a collection of different subjects as a way of thinking. As such, it may be applied to any branch of knowledge. I want to applaud the efforts now being made by mathematicians to publish ideas on education, energy, economics, defence, and world peace. Experience inside mathematics shows that it isn't necessary to be an old hand in an area to make a contribution. Outside mathematics the situation is less clear, but I cannot help feeling that there, too, it is a mistake to leave important issues entirely to experts.In June 1987 Freedman was presented with the National Medal of Science at the White House by President Ronald Reagan. The following year he received the Humboldt Award and, in 1994, he received the Guggenheim Fellowship Award.<DIV class=postcolor>介绍第3个牛人:Simon Donaldson's secondary school education was at Sevenoaks School in Kent which he attended from 1970 to 1975. He then entered Pembroke College, Cambridge where he studied until 1980, receiving his B.A. in 1979. One of his tutors at Cambridge described him as a very good student but certainly not the top student in his year. Apparently he would always come to his tutorials carrying a violin case.In 1980 Donaldson began postgraduate work at Worcester College, Oxford, first under Nigel Hitchen's supervision and later under Atiyah's supervision. Atiyah writes in [2]:-In 1982, when he was a second-year graduate student, Simon Donaldson proved a result that stunned the mathematical world.This result was published by Donaldson in a paper Self-dual connections and the topology of smooth 4-manifolds which appeared in the Bulletin of the American Mathematical Society in 1983. Atiyah continues his description of Donaldson's work [2]:-Together with the important work of Michael Freedman ..., Donaldson's result implied that there are "exotic" 4-spaces, i.e. 4-dimensional differentiable manifolds which are topologically but not differentiably equivalent to the standard Euclidean 4-space R4. What makes this result so surprising is that n = 4 is the only value for which such exotic n-spaces exist. These exotic 4-spaces have the remarkable property that (unlike R4) they contain compact sets which cannot be contained inside any differentiably embedded 3-sphere !After being awarded his doctorate from Oxford in 1983, Donaldson was appointed a Junior Research Fellow at All Souls College, Oxford. He spent the academic year 1983-84 at the Institute for Advanced Study at Princeton, After returning to Oxford he was appointed Wallis Professor of Mathematics in 1985, a position he continues to hold.Donaldson has received many honours for his work. He received the Junior Whitehead Prize from the London Mathematical Society in 1985. In the following year he was elected a Fellow of the Royal Society and, also in 1986, he received a Fields Medal at the International Congress at Berkeley. In 1991 Donaldson received the Sir William Hopkins Prize from the Cambridge Philosophical Society. Then, the following year, he received the Royal Medal from the Royal Society. He also received the Crafoord Prize from the Royal Swedish Academy of Sciences in 1994:-... for his fundamental investigations in four-dimensional geometry through application of instantons, in particular his discovery of new differential invariants ...Atiyah describes the contribution which led to Donaldson's award of a Fields Medal in [2]. He sums up Donaldson's contribution:-When Donaldson produced his first few results on 4-manifolds, the ideas were so new and foreign to geometers and topologists that they merely gazed in bewildered admiration.Slowly the message has gotten across and now Donaldson's ideas are beginning to be used by others in a variety of ways. ... Donaldson has opened up an entirely new area; unexpected and mysterious phenomena about the geometry of 4-dimensions have been discovered. Moreover the methods are new and extremely subtle, using difficult nonlinear partial differential equations. On the other hand, this theory is firmly in the mainstream of mathematics, having intimate links with the past, incorporating ideas from theoretical physics, and tying in beautifully with algebraic geometry.The article [3] is very interesting and provides both a collection of reminiscences by Donaldson on how he came to make his major discoveries while a graduate student at Oxford and also a survey of areas which he has worked on in recent years. Donaldson writes in [3] that nearly all his work has all come under the headings:-(1) Differential geometry of holomorphic vector bundles.(2) Applications of gauge theory to 4-manifold topology.and he relates his contribution to that of many others in the field.Donaldson's work in summed up by R Stern in [6]:-In 1982 Simon Donaldson began a rich geometrical journey that is leading us to an exciting conclusion to this century. He has created an entirely new and exciting area of research through which much of mathematics passes and which continues to yield mysterious and unexpected phenomena about the topology and geometry of smooth 4-manifolds</DIV><DIV class=postcolor>下面continue介绍第4个牛人:Robion Kirby。
蛋白质的三维结构之二

speciation in geographically答案

speciation in geographically答案【1】Evolutionary biologists believe that speciation,th e formation of a new species,often begins when some kind of physical barrier arises and divides a population of a sing le species into separate subpopulations.Physical separation between subpopulations promotes the formation of new speci es because once the members of one subpopulation can no lon ger mate with members of another subpopulation,they cannot exchange variant genes that arise in one of the subpopulati ons.In the absences of gene flow between the subpopulations, genetic differences between the groups begin to accumulate. Eventually the subpopulations become so genetically distinc t that they cannot interbreed even if the physical barriers between them were removed.At this point the subpopulations have evolved into distinct species.This route to speciatio n is known as allopatry(“alio-”means“different”,and“p atria”means“homeland”).【2】Allopatric speciation may be the main speciation r oute.This should not be surprising,since allopatry is prett y common.In general,the subpopulations of most species are separated from each other by some measurable distance.So ev en under normal situations the gene flow among the subpopulations is more of an intermittent trickle than a steady str eam.In addition,barriers can rapidly arise and shut off the trickle.For example,in the 1800s a monstrous earthquake ch anged the course of the Mississippi River,a large river flo wing in the central part of the United States of America.Th e change separated populations of insects now living along opposite shore,completely cutting off gene flow between the m.【3】Geographic isolation also can proceed slowly,over great spans of time.We find evidence of such extended event s in the fossil record,which affords glimpses into the brea kup of formerly continuous environments.For example,during past ice ages,glaciers advanced down through North America and Europe and gradually cut off parts of populations from one another.When the glacier retreated,the separated popula tions of plants and animals came into contact again.Some gr oups that had descended from the same parent population wer e no longer reproductively compatible—they had evolved int o separate species.In other groups,however,genetic divergen ces had not proceeded so far,and the descendants could stil l interbreed—for them,reproductive isolation was not compl eted,and so speciation had not occurred.【4】Allopatric speciation can also be brought by the i mperceptibly slow but colossal movements of the tectonic pl ates that make up Earth’s surface.About 5 million years ag o such geologic movements created the land bridge between N orth America and South America that we call the Isthmus of Panama.The formation of the isthmus had important consequen ces for global patterns of ocean water flow.While previousl y the gap between the continents had allowed a free flow of water,now the isthmus presented a barrier that divided the Atlantic Ocean from the Pacific Ocean.This division set th e stage for allopatric speciation among populations of fish es and other marine species.【5】In the 1980s,John Graves studied two populations o f closely related fishes,one population from the Atlantic s ide of isthmus,the other from the Pacific side.He compared four enzymes found in the muscles of each population.Graves found that all four Pacific enzymes function better at low er temperatures than the four Atlantic versions of the same enzymes.This is significant because Pacific seawater is ty pically 2 to 3 degrees cooler than seawater on the Atlantic side of isthmus.Analysis by gel electrophoresis revealed s light differences in amino acid sequence of the enzymes oftwo of the four pairs.This is significant because the amino acid sequence of an enzyme is determined by genes.【6】Graves drew two conclusions from these observation s.First,at least some of the observed differences between t he enzymes of the Atlantic and Pacific fish populations wer e not random but were the result of evolutionary adaption.S econd,it appears that closely related populations of fishes on both sides of the isthmus are starting to genetically d iverge from each other.Because Graves’s study of geographi cally isolated populations of isthmus fishes offers a glimp se of the beginning of a process of gradual accumulation of mutations that are neutral or adaptive,divergences here mi ght be evidence of allopatric speciation in process.托福阅读试题1.The word"promotes"in the passage is closest in meaning toA.describes.B.encourages.C.delays.D.requires.2.According to paragraph 1,allopatric speciation involv es which of the following?A.The division of a population into subspecies.B.The reuniting of separated populations after they hav e become distinct species.C.The movement of a population to a new homeland.D.The absence of gene flow between subpopulations.3.Why does the author provide the information that"the subpopulations of most species are separated from each othe r by some measurable distance"?A.To indicate how scientists are able to determine whet her subpopulations of a species are allopatric.B.To define what it means for a group of animals or pla nts to be a subpopulation.C.To suggest that allopatric speciation is not the only route to subpopulation.D.To help explain why allopatric speciation is a common way for new species to come about.4.The word"accumulate"in the passage is closest in mean ing toA.Become more significant.B.Occur randomly.C.Gradually increase in number.D.Cause changes.5.In paragraph 2,why does the author mention that some insect populations were separated from each other by a chan ge in the course of Mississippi River caused by an earthqua ke?A.To make the point that some kind of physical barrier separates the subpopulations of most species.B.To support the claim that the condition of allopatry can sometimes arise in a short time.C.To provide an example of a situation in which gene fl ow among the subpopulations of a species happens at a slow rate.D.To explain why insects living along opposite shores of the Mississippi River are very different from each other.6.According to paragraph 3,separation of subpopulation s by glaciers resulted in speciation in those groups of pla nts and animals thatA.were reproductively isolated even after the glaciers disappeared.B.had adjusted to the old conditions caused by the glac iers.C.were able to survive being separated from their paren t population.D.had experienced some genetic divergences from their p arent population.7.The word"colossal"in the passage is closet in meaning toA.consistent.B.gradual.C.enormous.D.effective.8.According to paragraph 4,which of the following is tr ue of the geologic movements that brought about the Isthmus of Panama?A.The movements brought populations of certain fishes a nd marine organisms into contact with one another for the f irst time.B.The movements transferred populations of fishes and o ther marine animals between the Pacific and Atlantic Ocean s.C.The movements created conditions that allowed water t o flow more freely between the Pacific and Atlantic Oceans.D.The movements created conditions for the formation of new species of fishes and other marine animals.9.The word"sequence"in the passage is closet in meaning toA.quality.B.order.C.function.D.number.10.According to paragraph 5,by comparing the enzymes fr om two related groups of fishes on opposite sides of the is thmus,Graves found evidence thatA.there were slight genetic divergences between the two groups.B.the Atlantic group of fishes were descended from the Pacific group of fishes.C.the temperature of water on either side of the isthmu s had changed.D.genetic changes in the Atlantic group of fishes were more rapid and frequent than in the Pacific group of fishe s.11.It can be inferred from paragraph 5 and 6 that the r eason Graves concluded that some of the differences between the Pacific and Atlantic enzymes were not random was thatA.each of the Pacific enzymes works better in cooler wa ters.B.the Enzymes of the Atlantic fish populations had not changed since the formation of the Isthmus of Panama.C.gel electrophoresis showed that the changes benefited both the Atlantic and the Pacific fish populations.D.the differences between the enzymes disappeared when the two fish populations were experimentally switched to ot her side of the isthmus.12.Which of the sentence below best expresses the essen tial information in the highlighted sentence in the passage? Incorrect choices change the meaning in important ways or l eave out essential information.A.Graves's study provides evidence that isthmus fishes are in the process of becoming geographically isolated.B.Graves's study of mutating isthmus fishes yields resu lts that differ from results of other studies involving all opatric speciation.C.Graves's study of isolated populations of isthmus fis hes provides some evidence that allopatric speciation might be beginningD.Grave's study indicates that when isolated,population s of isthmus fished register neutral or adaptive mutations.13.Look at the four squares[]that indicate where the fo llowing sentence can be added to the passage.Where would th e sentence best fit?The formation of the isthmus had import ant consequences for global patterns of ocean water flow.【A】About 5 million years ago such geologic movements created the land bridge between North America and South Ame rica that we call the Isthmus of Panama.The formation of th e isthmus had important consequences for global patterns of ocean water flow.【B】While previously the gap between the continents ha d allowed a free flow of water,now the isthmus presented a barrier that divided the Atlantic Ocean from the Pacific Oc ean.【C】This division set the stage for allopatric speciat ion among populations of fishes and other marine species.【D】Allopatric speciation can also be brought by the i mperceptibly slow but colossal movements of the tectonic pl ates that make up Earth's surface.14.Directions:An introductory sentence for a brief summ ary of the passage is provided plete the summary by selecting the THREE answer choices that express the most important ideas in the passage.Some sentences do not belong in the summary because they express ideas that are not pre sented in the passages or are minor ideas in the passage.Th is question is worth 2 points.Allopatric speciation takes place when physically separ ated populations of a single species gradually diverge gene tically to the point of becoming unable to interbreedA.Allopatric speciation is common because the gene flow between subpopulations is generally limited and the barrie rs that completely separate subpopulations can arise in a v ariety of ways.B.During past ice ages,some,but not all,subpopulations separated by glaciers evolved into distinct species.C.Speciation does not need to take place through allopa try because subpopulations will form distinct species whene ver there are adaptive advantages or notD.Physical barriers from glaciers and the movement of t ectonic plates form so slowly that the subpopulations on ei ther side of the barriers usually do not form distinct spec ies.E.Graves's study of fish populations separated by the I sthmus of Panama may well provide a picture of the beginning stages of speciation.F.Graves's study of physically separated fish populatio ns show that there must be large differences between the en vironments of the isolated populations if allopatric specia tion is to take place.托福阅读答案1.promote本身是促进的意思。
A Tutorial on Spectral Clustering

Ulrike von Luxburg Max Planck Institute for Biological Cybernetics Spemannstr. 38, 72076 T¨ ubingen, Germany ulrike.luxburg@tuebingen.mpg.de
2
Similarity graphs
Given a set of data points x1 , . . . xn and some notion of similarity sij ≥ 0 between all pairs of data points xi and xj , the intuitive goal of clustering is to divide the data points into several groups such that points in the same group are similar and points in different groups are dissimilar to each other. If we do not have more information than similarities between data points, a nice way of representing the data is in form of the similarity graph G = (V, E ). Each vertex vi in this graph represents a data point xi . Two vertices are connected if the similarity sij between the corresponding data points xi and xj is positive or larger than a certain threshold, and the edge is weighted by sij . The problem of clustering can now be reformulated using the similarity graph: we want to find a partition of the graph such that the edges between different groups have very low weights (which means that points in different clusters are dissimilar from each other) and the edges within a group have high weights (which means that points within the same cluster are similar to each other). To be able to formalize this intuition we first want to introduce some basic graph notation and briefly discuss the kind of graphs we are going to study.
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It is noted that your manuscript needs careful editing by someone with expertise in technical English editing paying particular attention to English grammar, spelling, and sentence structure so that the goals and results of the study are clear to the reader.2、未解释研究方法或解释不充分。
◆In general, there is a lack of explanation of replicates and statistical methods used in the study.◆Furthermore, an explanation of why the authors did these various experiments should be provided.3、对于研究设计的rationale:Also, there are few explanations of the rationale for the study design.4、夸张地陈述结论/夸大成果/不严谨:The conclusions are overstated. For example, the study did not showif the side effects from initial copper burst can be avoid with the polymer formulation.5、对hypothesis的清晰界定:A hypothesis needs to be presented。
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i
[
Σ2θ(i) K (2).
In each case the indexing i ranges over a finite set.
§0 Introduction. Recently, the subject of elliptic cohomology has become the focus of much activity amongst a wide range of mathematicians and physicists. Although the principal motivation has lain in the interface between quantum field theory, string theory, global analysis on loop spaces and equivariant bordism, it seems likely that the applications to topology itself will also prove fruitful. The principal attraction of elliptic cohomology in stable homotopy theory is perhaps that it offers the prospect of a geometric interpretation of the notion of v2 -periodicity , analogous to that of v1 -periodicity as Bott periodicity in K -theory. Unfortunately, to date there is no good geometric description of E ∗ ( ), however it seems likely that this will appear in the near future.
(E /P ) ( ) ∼ =
∗ i
K (2)2θ(i)+∗ ( ).
THE SPECTRUM REPRESENTING ELLIPTIC COHOMOLOGY
3
Associated to the latter are splittings of ring spectra E and E /P
i P i
1991 Mathematics Subject Classification. 55N22 14L05 10D05. Key words and phrases. Elliptic cohomology, v2 -periodicity, Morava K -theory. The author would like to acknowledge the support of the Science and Engineering Research Council Typeset by AMS-TEX 1
∗ )(p,Ep−1 )
∼ =
π |Ep−1 (π )∈Spec (E ∗ /(p))
E
∗ (p,π )
as topological rings. In §2 we use results of J. Igusa and P. Landweber to define formal group laws over the rings E ∗ /P and (E ∗ )P which are strictly isomorphic to the canonical one; then we use results of [BaWu] to produce a further group law on (E ∗ )P , isomorphic to the canonical one, reducing to the previous one modulo P and moreover classified by a homomorphism E (n)∗ −→ (E ∗ )P whose reduction is classified by a homomorphism K (2)∗ −→ E ∗ /P . In §3 we use results of §1 to show that there are isomorphisms of rings (E
ON THE HOMOTOPY TYPE OF THE SPECTRUM REPRESENTING ELLIPTIC COHOMOLOGY
Andrew Baker (Version 6: 8/08/1997)
Abstract.
In this paper we analyse the homotopy type at primes p > 3 of the ring spectrum E representing a version of elliptic cohomology se coefficient ring E ∗ agrees with the ring of modular forms for SL2 ( ). For any prime (=maximal) graded ideal P E ∗ containing the Eisenstein function Ep−1 as well as p, we show that there is a morphism of ring spectra b E (2) −→ E P
2
ANDREW BAKER
The purpose of the present paper is to make precise some relationships between E ∗ ( ), Morava K (2)-theory and v2 -periodicity. We use the definition of [Land 1] as modified in [Ba 1], giving a theory whose coefficient ring agrees with the full ring of modular forms for the modular group SL2 (Z). We remark that the author’s earlier work (see [Ba 1] and [Ba 2]) leads to the conclusion that there is a good set of stable operations available for use in stable homotopy theory and that together with the present results it seems reasonable to look for applications. I would like to thank the following for arousing my interest in elliptic cohomology and providing interesting discussions and encouragement: Robin Chapman, Francis Clarke, Peter Landweber, Haynes Miller, Serge Ochanine, Nigel Ray, and Bob Stong. Outline. In §1 we investigate the prime ideals P of the graded ring E ∗ containing the ideal (p, Ep−1 ); we show that these are all maximal (i.e. the ring (E ∗ )(p) has dimension 1) and have the form (p, π ) where π is an irreducible factor of Ep−1 modulo p. We deduce that the residue (graded) field has the form Fpd [Z, Z −1 ] where d ≥ 1 and |Z | = 12, 8, or 4 according as to whether E4 ∈ P , E6 ∈ P or neither of these holds. We have (E
over E ∗ together with the fact that M U∗ is identifiable with Lazard’s universal ring for formal group laws and possesses a universal group law F M U . This is described in detail in [Ba 1] and more generally in [Land 1]. We can identify the group E 2n with the group of weight n modular forms for SL2 (Z) which are meromorphic at i∞ and have q -expansions with coefficients in Z(1/6) (see [Ba 1]). The corresponding isomorphism of graded rings is effected by the pairings 1 g2 ←→ E4 12 g3 ←→ −1 E6 216
Σ2θ(i) E (2)
Σ2θ(i) K (2).
Thus we establish a precise relationship between Morava K –theory K (2)∗ ( ) and elliptic cohomology. Finally, in the Appendix we discuss the relationship of our results with the theory of supersingular elliptic curves over finite fields. §1 Supersingular reductions of the ring of modular forms. Recall from [Ba 1] that there is a multiplicative complex oriented cohomology theory defined on the category of finite CW complexes CWf by (1–1) E