Crystal Structure and Electrochemical Performances of Proton

T I CS 77.160H 71Nonferrous Metal IndustryStandard of the People’s Republic of ChinaYS/T 677—2016Replace the YS/T 677—2008Issued by: Ministry of Industry and Information Technology of the People's Republic of ChinaForewordSAC/TC 243 is in charge of this English translation. In case of any doubt about the contents of English translation, the Chinese original shall be considered authoritatively.This standard is drafted in accordance with the rules given in the GB/T 1.1-2009.This standard replaces the YS/T 677-2008 Lithium manganese oxide.In addition to a number of editorial changes, the following technical deviations have been made with respect to the YS/T 677-2008.—New normative references are added.—New terms and definitions are added.—The classification of the lithium manganese oxide products is added.—The performance indexes of different types of lithium manganese oxide are added.—The requirements of the magnetic impurities content are added.—The content and the requirement of the main elements in the product are modified.—The content and the requirement of the impurity elements in the product are modified.—The requirement of the mole ratio of Li to Mn in the composition of the product is deleted.—The cyclic test condition at 55℃is added.—Annex A to Annex D in the standard are deleted.This standard was prepared by SAC/TC 243 National Nonferrous Metals Standardization Technical Committee.This standard is drafted by the following organizations:This standard is mainly drafted by the following people: **，**，**The previous editions of this standard are as follows:—YS/T 677-2008.Lithium Manganese Oxide1 ScopeThis standard specifies the terms, definitions, requirements, test methods, testing rules, marking, packaging, transportation, storage, certificate of quality and contract/order content of lithium manganese oxide.This standard is applicable to spinel lithium manganese oxide, the cathode active material used in lithium-ion batteries.2 Normative ReferencesThe following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.GB/T 1717, Determination of pH value of an aqueous suspension of pigmentsGB/T 5162, Metallic powders—determination of tap densityGB/T 5314, Powders for powder metallurgical purposes—SamplingGB/T 6283, Chemical products—Determination of water Karl Fischer method (general method).GB/T 13390, Metallic powder－Determination of the specific surface area－Method of nitrogen adsorptionGB/T 19077, Particle size analysis—Laser diffraction methodsGB/T 23365, Electrochemical performance test of lithium manganese oxide—Test method for specific capacity and charge-discharge efficiency of the first cycleGB/T 23366, Electrochemical performance test of lithium manganese oxide—Test method for discharge plateau capacity ratio and cycle lifeGB/T 24533-2009, Graphite negative electrode materials for lithium ion batteriesJCPDS1)(35-0782), X - ray powder diffraction pattern of spinel lithium manganese oxide3 Terms and definitionsFor the purposes of this document, the terms and definitions given in GB/T 20252-2014 apply.4 Requirements1) Joint Committee on Powder Diffraction Standards4.1 Product classificationLithium manganese oxide is divided into 2 types according to their properties and applications: the high capacity lithium manganese oxide, and the high power lithium manganese oxide.4.2 Chemical compositionThe Chemical composition of the product shall meet the requirements in Table 1.Table 1Chemical composition4.3 MoistureThe moisture content of the high capacity lithium manganese oxide shall not be more than 0.07%. The moisture content of the high power lithium manganese oxide shall not be more than 0.05%.4.4 pH ValueThe pH value of the product shall be in the range of 7.0 to 11.0.4.5 Magnetic ImpuritiesThe magnetic impurities content of the product for which the buyer side requires, shall be determined by both the supplier and the buyer and specified in the contract.4.6 Particle Size DistributionThe characteristic value of the particle size distribution shall meet the requirements in Table 2.Table 2 Particle size distribution4.7 Tap densityThe tap density of the product shall meet the requirements in Table 3.Table 3 Tap density4.8 Specific surface areaThe specific surface of the product shall meet the requirements in Table 4.Table 4 Specific surface area4.9 AppearanceThe product shall be uniform black powder and agglomeration is not allowed.4.10 Crystal structureThe crystal structure of the product shall be in accordance with the JCPDS standard (35-0782), and the impurity phase shall not be detected compared with the standard pattern.4.11 Specific discharge capacityThe initial specific discharge capacity of the product under specified conditions shall meet the requirements in Table 5.Table 5 Initial specific discharge capacity4.12 Charge/discharge efficiencyThe first charge/discharge efficiency of the product under specified conditions shall not be less than 90%.4.13 Plateau capacity ratioThe plateau capacity ratio of the product under specified conditions shall not be less than 90% after 10 cycles, and 85% after 100 cycles.4.14 Cycle LifeThe cycle life of the product shall meet the requirements in Table 6, when the discharge capacity reaches 80% of the discharge capacity of the first cycle.Table 6 Cycle life4.15 High temperature cycle lifeThe cycle life of the high power lithium manganese oxide tested at 55℃shall not be less than 300 cycles, when the discharge capacity reaches 80% of the discharge capacity of the first cycle.5 Test methods5.1 Chemical CompositionThe test on the chemical composition is carried out according to the methods agreed by both suppliers and buyers.5.2 MoistureThe determination of the moisture content is carried out according to GB/T 6283.5.3 pH valueThe determination of pH value of the product is carried out according to GB/T 1717.5.4 Magnetic impuritiesThe determination of the magnetic impurities content of the product is carried out according to the provisions in Annex K of GB/T 24533-2009.5.5 Particle size distributionThe determination of the size distribution of the product is carried out according to GB/T 19077.5.6 Tap densityThe determination of the tap density of the product is carried out according to GB/T 5162.5.7 Specific surface areaMeasurement of the specific surface area of the product is carried out according to GB/T 13390.5.8 AppearanceVisual inspection of the product’s appearance.5.9 Crystal structureThe crystal structure of the product is detected by X-ray diffractometer.5.10 Specific discharge capacityThe determination of the first discharge specific discharge capacity of the product is carried out according to GB/T 23365. The charging and discharging voltage range is 3.00-4.30V, and the other conditions remain unchanged.5.11 EfficiencyThe determination of the first charge discharge efficiency of the product is carried out according to GB/T 23365. The charging and discharging voltage range is 3.00-4.30V, and the other conditions remain unchanged.5.12 Plateau capacity ratioThe measurement of the capacity ratio of the product platform is carried out according to the provisions of GB/T 23366. The charging and discharging voltage range is 3.00-4.20V, and the other conditions remain unchanged.5.13 Cycle lifeThe determination of the cycle life of the product is carried out according to GB/T 23366. The charging and discharging voltage range is 3.00-4.20V, and the other conditions are unchanged.5.14 High temperature cycle lifeThe determination of the high temperature cycle life of the product is carried out according to GB/T 23366. The test temperature is at 55℃and the charging and discharging voltage range is 3.00-4.20V, and the other conditions are unchanged.6 Inspection provisions6.1Inspection and acceptance6.1.1 The supplier shall check the product and fill in the quality certificate to insure that the quality of the product is in accordance with this standard and the contract (or order).6.1.2 The buyer shall check the received product according to this standard, and negotiate with the supplier within 3 months after receiving the product, in the case that the check result doesn’t accord to this standard or the contract (or order). If any arbitration is needed, samples shall be obtained from both sides.6.2 BatchesThe product shall be submitted for the acceptance in batches and each batch is composed of the same mixture, with weight of not more than 5 000 kg. If the buyer has special requirement, it shall be settled based on the negotiation between both sides.6.3 Product inspection6.3.1 Inspection classificationsThe inspection in this standard is classified into: inspection by batch, and periodic inspection.6.3.2 Inspection by batchEach batch of the product shall be tested.6.3.3 Periodic InspectionThe item of the periodic inspection is determined according to their difficulty degree and stability. In the case of the normal production, the inspection shall be carried out once a month. The periodic inspection shall be carried out when the raw materials or production processes significantly changes or the production is restored after long terms. It shall be indicated in the contract if there are special requirements of the periodic inspection from the buyer.6.3.4 Inspection items and samplingProduct inspection items and sampling are shown in Table 7.Table 7 Inspection items and sampling6.4 Judgment on inspection results6.4.1 One batch of the product is judged as unqualified, if any of the chemical composition, the moisture content, the pH value, the magnetic impurities content, the particle size distribution, the tap density, the specific surface area and the crystal structure is tested to be unqualified.6.4.2 The disqualification of the product’s appearance will disqualify the whole barrel (bag) of the product.6.4.3 Make six test batteries according to the method in GB / T 23365. Three batteries are picked randomly to do the specific capacity and the first cycle coulombic efficiency test. If two batteries can’t reach the requirement of this standard, this batch of the product is judged as unqualified. However, repeated test is allowed for the other three batteries, and if two of them can reach the requirement of this standard, this batch of the product is judged as qualified.6.4.4 Make six test batteries according to the method in GB / T 23366. Three batteries are picked randomly to do the plateau capacity ratio, the cycle life and the high temperature cycle life test. If two batteries can’t reach the requirement of this standard, this batch of the product is judged as unqualified. However, repeated test is allowed for the other three batteries, and if two of them can reach the requirement of this standard, this batch of the product is judged as qualified.7 Marks, packaging, transportation, storage and quality certificate7.1 MarksOn the outer package, the followings shall be marked:a)product name;b)supplier name, address;c)batch number, type;d)net weight;e)test date;f)damp proof mark;g)standard number, YS/T 677-2016.7.2 PackagingProducts are packed using plastic bag, and put into the barrel after thermoplastic sealing. A barrel of the product has a net weight of 25.00 kg. The packaging can also be settled by negotiation to satisfy the buyer’s requirement.7.3 Transportation and storage7.3.1 Damage to the packaging shall be avoided during transportation process.7.3.2 Products shall be avoided of damp during storage. Guarantee period is one years, starting at the date of the production.7.4 Quality certificateQuality certificate shall be attached to each batch of the products, which indicates:a)supplier name, address, telephone and fax;b)product name and model;c)batch number, type;d)net weight and number;e)partition test result; Seal from the technical supervision department;f)standard number, YS/T 677-2016;g)released date.8 Contract (or order) contentsThe contract (or order) for the product listed in this standard shall include the following contents:a)product name;b)type and quantity;c)standard number, YS/T 677-2016;d)others.。

Preparation and Characterization of Thin Film Li4Ti5O12Electrodes by Magnetron SputteringC.-L.Wang,a,b Y.C.Liao,a,c,z F.C.Hsu,a,b N.H.Tai,b and M.K.Wu a,c,da Materials Science Center,b Department of Materials Science and Engineering,andc Department ofPhysics,National Tsing Hua University,Hsinchu,Taiwand Institute of Physics,Academia Sinica,Nankang,Taipei,TaiwanThis paper reports that spinel-phase Li4Ti5O12thinfilms were successfully grown by radio frequency͑rf͒magnetron sputtering on an Au/Ti/SiO2/Si substrate.In this process,the buffer layer of gold serves as a template for the texture growth of Li4Ti5O12film. The growth temperature affects the microstructure and electrochemical characteristics of the depositedfilms.In our study,the spinel phase of Li4Ti5O12appears at deposition temperatures above500°C.The redox peaks in the cyclic voltammetry of the Li/Li4Ti5O12cell approach the typical value of1.55V as raising the deposition temperature.Moreover,the influences of the surface morphology of thefilm on the capacity were studied.They show that a columnar structure with high porosity was obtained in thefilm deposited above650°C.The columnar grains with good crystallinity of the deposited Li4Ti5O12enhance the capacity of the electrode.In this work,the capacity of53␮Ah/cm2␮m can be attained for thefilm with a thickness of230nm deposited at700°C.This study sheds light on the realization of a solid-state thinfilm battery and provides a possible solution of electrical power for a mobile integrated circuit chip.©2005The Electrochemical Society.͓DOI:10.1149/1.1861193͔All rights reserved.Manuscript submitted May17,2004;revised manuscript received September25,2004.Available electronically February10,2005.Solid-state thin-film rechargeable batteries have great advantages over other types of batteries due to theirflexibility,safety,and min-iaturization.There are many potential applications,such as smart cards,complementary metal oxide semiconductor͑CMOS͒-based integrated circuits,and microelectromechanical system͑MEMS͒de-vices.Lithium-transition-metal-oxide thinfilms have long been recognized as good candidates for battery electrode materials. For example,layered-phase LiCoO2,1LiNiO2,2and spinel-phase LiMn2O43with high voltage and stability were successfully used as the positive electrode in lithium ion batteries.Thackeray et al.4pro-posed that the ionic conductor Li4Ti5O12can also be a good elec-trode material for rechargeable lithium ion batteries.This material can be used as the negative electrode in the cell combined with other high voltage materials,such as LiCoO2and LiMn2O4.5,6The theo-retical capacity of Li4Ti5O12is175mAh/g͑60␮Ah/cm2␮m͒ac-cording to the following reaction suggested by Ohzuku et al.7͑Li͒8a͑Li1/3,Ti5/3͒16d O4+e−+Li+→͑Li2͒16c͑Li1/3,Ti5/3͒16d O4 Based on this equation,during the insertion process,lithium ions are in the tetrahedral͑8a͒sites and the guest lithium ions move to the octahedral͑16c͒sites,thus the total insertion capacity is determined by the number of free octahedral sites.The merits of adopting spinel Li4Ti5O12include itsflat electrical potential,nearly zero volume change,and excellent reversibility during the insertion/extraction process of Li ions.Li4Ti5O12thinfilm prepared by the sol-gel process for lithium battery electrodes has been reported in the past.8-10The sol-gel growth method is known to be difficult to incorporate into the con-ventional semiconductor process.This article reports the successful growth of spinel Li4Ti5O12thinfilms using a radio frequency͑RF͒magnetron sputtering technique.Through a series of examinations of the crystallinity,surface morphology,and electrochemical properties of the high quality Li4Ti5O12thinfilm,this paper demonstrates the great potential of Li4Ti5O12used as the material of the electrodes of solid-state thin-film batteries.ExperimentalLi4Ti5O12thinfilms were deposited by rf magnetron sputtering from a2in.diameter target onto Au͑100nm͒/ Ti͑10nm͒/SiO2/Si substrate maintained at various temperatures in the range of500-700°C.The substrate was adhered to the surface of the heater by a silver paste,and the temperature was determined bythe thermocouple in the heater.All substrates were cleaned in anorganic solvent͑acetone,methanol,isopropanol͒using a ultrasoniccleaner.The background pressure of the chamber before the heating of the substrate was less than10−5Torr.Aufilm functions as acurrent collector,while the Ti layer is the buffer layer that improves the adhesion between Au and SiO2.These two metal layers were deposited by standard dc magnetron sputtering.The Li4Ti5O12target was prepared by the solid-state reaction of TiO2and Li2CO3pow-ders.The mixed powder was calcined at800°C.Then it was re-ground,cold pelletized,and sintered at950°C in the ambient air.The X-ray diffraction͑XRD͒patterns showed a pure spinel phase with the space group Fd3¯m.Before the deposition,the target was presputtered for about20min.Thefilms were deposited at the pres-sure of30mTorr with the mixed Ar/O2͑3:2͒gas,and the power density was estimated to beϳ4W/cm2.Allfilms have a thickness around230nm.The crystal structure was examined by an X-ray diffractometer͑MAC Science͒employing Cu K␣line.The surface morphologies of Li4Ti5O12films deposited at various temperatureswere observed with a JEOL6500F scanning electron microscope ͑SEM͒.The electrochemical properties of the oxidefilms were measuredin a two-electrode cell at room temperature.The cell uses an oxidefilm as the working electrode combined with a lithium metal foil asthe counter electrode.In the cell,the electrolyte was prepared by adopting1M LiPF6dissolved in a solution of ethylene carbonate ͑EC͒and ethylmethyl carbonate͑EMC͒with the volume ratio of 1:1.All cells were assembled inside the argon-filled glove box.For galvanostatic cycling testing,cells were discharged and charged at the constant current density of10␮A/cm2between1.0and2.0V. Cyclic voltammetry͑CV͒was performed at a sweep rate of 0.5mV/s for the characterization of thefilm electrode.ResultsTexture and crystallinity of the as-deposited thinfilms.—Figure 1shows the X-ray diffraction͑XRD͒patterns of the Li4Ti5O12thin films grown on the Au/Ti/SiO2/Si substrate at different deposition temperatures.The well-crystallized thinfilm can be obtained at the deposition temperatures above500°C,and it exhibits a texture growth in the͑111͒plane.The texture growth along certain direc-tions is beneficial to the performance of the thin-film electrode.11 These thinfilms are colorless insulators,as expected.As the sub-strate temperature is increased,the crystallinity of thefilms is sub-z E-mail:ycliao@.tw Journal of The Electrochemical Society,152͑4͒A653-A657͑2005͒0013-4651/2005/152͑4͒/A653/5/$7.00©The Electrochemical Society,Inc.A653stantially improved,and it shows a highly preferred orientation along the ͓111͔,which is the major diffusion channel of Li ion.As mentioned earlier,the Au layer functions as the current col-lector for the electrode.Surprisingly,we find that this Au layer en-hances the crystallinity of the as-grown thin films,thus gold acts as a buffer layer between the substrate and the Li 4Ti 5O 12film as well.As shown in Fig.1,the Au layer also exhibits the preferred ͑111͒orientation at the deposition temperature.The preferred orientation of the Au buffer layer provides a better template to grow ͑111͒-oriented Li 4Ti 5O 12films.This statement is proved by comparing the XRD patterns between the Li 4Ti 5O 12films deposited on the sub-strates Au/Ti/SiO 2/Si and SiO 2/Si ͑Fig.2͒.The ͑111͒peak of Li 4Ti 5O 12film grown at 700°C is enhanced by using the Au/Ti/SiO 2/Si substrate,while the amorphous SiO 2layer did not act as a good template to deposit Li 4Ti 5O 12film.The preferred orientation along ͓111͔in the Au layer also plays an important role here.Our experimental results indicate that there is no preferred orientation in the Li 4Ti 5O 12film deposited on a gold foil without a specific texture.This gives further support to the above statement.The lattice constant of Li 4Ti 5O 12film deposited on Au/Ti/SiO 2/Si,calculated from the XRD data,does not show any specific trend with the deposition temperature.The average of cubic lattice constants of the four samples is 8.291Åwith a standard deviationof 0.006Å.This value is only 0.81%less than the bulk value ͑8.358Å͒of Li 4Ti 5O 12.Perhaps it is the strain of gold ͑2a 0=8.158Å,a 0is the cubic lattice constant of gold ͒that leads to this result.To conclude the discussion on the XRD data,the gold layer on the substrate can promote the texture growth of Li 4Ti 5O 12along ͓111͔.The evolvement of surface morphology of Li 4Ti 5O 12film with the deposition temperature is shown in Fig.3.There exists a transi-tion of surface morphology around the growth temperature of 650°C.At the deposition temperature of 600°C,the Li 4Ti 5O 12film is smooth and shows densely packed grains ͑Figs.3a and 4a ͒.Above 650°C,more dispersed island-like grains emerge in the film,as shown in the cross-sectional SEM image of the sample deposited at 700°C ͑Fig.4b ͒,and the film exhibits a rougher surface.The length scale of this porous structure is around 0.1-0.2␮m.This kind of structure does not exist in the Li 4Ti 5O 12film grown on the SiO 2/Si substrate at the same growth temperature,which is demonstrated in Fig.4c.The formation of these grain structures should be attributed to the presence of islands on the Au layer.These islands,which form preferentially along the ͓111͔plane,serve as the nucleation sites for the depositing Li 4Ti 5O 12materials.Consequently,the preferred ori-ented Li 4Ti 5O 12grains with good crystallinity and the island-like structure appear only on the Au-buffered substrate.This is consistent with our XRD results.Electrochemical measurement of the as-deposited thin films .—Figure 5shows the CVs obtained from the Li 4Ti 5O 12films grown at various substrate temperatures.All cyclic voltammogram measurements were operated in the potential range between 1.0and 2.0V at a scan rate of 0.5mV/s.The measurement results indicate that the primary insertion and extraction potential of Li ion are in a range between 1.5and 1.6V,which have been suggested resulting from the coexistence of the spinel phase and the rock-salt phase during the extraction and insertion processes of Li +ions.12The CV diagrams clearly show that the shape and peak current density of redox peaks depend on the growth temperature.As increasing the deposition temperature,the difference in the peak potential and the width of the redox peak reduce gradually.This reveals the better crystallinity of the film grown at a higher temperature.The value of the potential,which is 1.54and 1.59V in Li insertion and extraction of the film deposited at 700°C respectively,agrees with the typical value of Li 4Ti 5O 12.13This result indicates that the insertion and extraction of lithium ions are easier to accomplish in the film syn-thesized under higher deposition temperature.The observation is consistent with the previous data that the films grown at higher temperature exhibits better crystallinity and preferred orientation.These films provide more reversible channels for Li ions to diffuse in the three-dimensional framework of Li 4Ti 5O 12.14Figure 6shows the discharge behaviors between 1.0and 2.0V of the films deposited at various temperatures at the constant current density of 10␮A/cm 2.All these as-grown films show the potential plateau around 1.55V,which is the typical redox value of spinel-phase Li 4Ti 5O 12.The discharge capacity for the films deposited at 700°C is about 53␮Ah/cm 2␮m,and it is much greater than the films deposited at 600°C.These observations are consistent with the results of cyclic voltammograms,where the peak current density relating to the capacity is enhanced significantly from the deposition temperature of 600to 650°C.The capacity of the deposited thin film increases substantially as the deposition temperature over 650°C.However,the crystallinity does not change drastically above 650°C.This suggests that the crystallinity of the as-grown film is not the sole reason responsible for the large energy capacity.The plot of both ⌬2␪of ͑111͒diffraction peak and the discharge capacity confirms this suggestion further.In the left axis of Fig.7,it shows that the crystallinity of Li 4Ti 5O 12film improves gradually with rais-ing the growth temperature while there is a significant enhancement of discharge capacity above 650°C,as shown in the right axis.The transitions of electrochemical properties coincide with the transition of surface morphology ͑Fig.3and 4͒.It is apparent that thesurfaceFigure 1.XRD patterns of the Li 4Ti 5O 12films deposited on Au/Ti/SiO 2/Si at various deposition temperatures.It shows that both Li 4Ti 5O 12film and the gold layer have the preferred orientation ͑111͒.Figure 2.XRD patterns of the Li 4Ti 5O 12films on the two substrates Au/Ti/SiO 2/Si and SiO 2/Si grown at 700°C.The film on Au/Ti/SiO 2/Si has a much better crystallinity than the film on SiO 2/Si.A654Journal of The Electrochemical Society ,152͑4͒A653-A657͑2005͒morphology of the film also plays an important role on the capacity.Owing to the finite diffusion length of Li ions in Li 4Ti 5O 12,Li ions cannot fully penetrate into the grains.Those island-like grains that exist in the films deposited at higher temperatures provide much more effective area for the insertion of Li ions.This statement is inagreement with the previous study on the relationship between the charge capability and the particle size of Li 4Ti 5O 12.15In that paper,Kavan et al.showed that the charge capacity is proportional to the surface area of Li 4Ti 5O 12powder before the particle size reaches to few tens of nanometers.Therefore,the high capacity of Li 4Ti 5O 12film deposited on Au/Ti/SiO 2/Si at 700°C results from both the rougher island-like grains and the good crystallinity,and conse-quently,it has sharp redox peaks and a large capacity.ConclusionsSpinel-phase Li 4Ti 5O 12thin films are successfully grown by rf magnetron sputtering on Au/Ti/SiO 2/Si substrate.Thedeposi-Figure 3.SEM images of the surface morphology of Li 4Ti 5O 12thin films deposited on Au/Ti/SiO 2/Si at ͑a ͒600,͑b ͒650,and ͑c ͒700°C.The surface morphology transits to a rougher one at the deposition temperature above650°C.Figure 4.SEM image of the cross-sectional structure of Li 4Ti 5O 12thin films deposited at ͑a ͒600and ͑b ͒700on Au/Ti/SiO 2/Si and ͑c ͒700°C on SiO 2/Si.The film on Au/Ti/SiO 2/Si grown at 700°C has a disperse-like grain structure while the same one deposited at 600°C shows the close-packed grains.This is attributed to the effect of the gold layer because the film grown on SiO 2/Si at 700°C did not have a columnar structure.A655Journal of The Electrochemical Society ,152͑4͒A653-A657͑2005͒tion temperature influences the physical and electrochemical characteristics of the films profoundly.Li 4Ti 5O 12films grown on Au/Ti/SiO 2/Si can possess good crystallinity and proper surface morphology for the application in an electrode of a thin film ing the optimized Li 4Ti 5O 12thin film,the test cell of Li/Li 4Ti 5O 12exhibits sharp redox peaks and a large capacity.The capacity of this film estimated by the discharge curve is 53␮Ah/cm 2␮m,and this value is comparable to those elec-trodes prepared by other methods.Both CV diagrams and dis-charge curves show that thin film Li 4Ti 5O 12/Au/Ti/SiO 2/Si depos-ited by sputtering can be used as an excellent negative electrode in a lithium thin-film battery.The results of this study demonstrate the potential for the realization of lithium-based solid-state thin-film batteries.AcknowledgmentsThe authors thank Chen-En Wu for help taking the SEM images.We also thank Phillip Wu for help editing the English writing.This work is supported by the Taiwan National Science Council grant no.NSC91-2112-M-007-056.Figure 5.Cyclic voltammograms of Li 4Ti 5O 12thin films deposited on Au/Ti/SiO 2/Si at various deposition temperatures ͑a ͒600,͑b ͒650,and ͑c ͒700°C in 1M in LiPF 6/EC +EMC at 0.5mV/s.The peak current density is significantly enhanced above 650°C.The potentials of reduction peak ͑Li +insertion ͒and oxidization peak ͑Li +extraction ͒agree with otherstudies.Figure 6.Initial discharge curves of Li 4Ti 5O 12thin films deposited on Au/Ti/SiO 2/Si at various temperatures.The substantial increase of charge capacity indicates that there should be some transition around the deposition temperature of 650°C.The capacity of the film grown at 700°C reaches to nearly 90%of the theoretical value ͑60␮Ah/cm 2␮m ͒.Figure 7.The plot of both ⌬2␪of ͑111͒diffraction peak ͑left axis ͒and the discharge capacity ͑right axis ͒.It indicates that the enhancement of capacity of Li 4Ti 5O 12thin film does not totally result from the improvement of crys-tallinity.Because the discharge curve of the film deposited at 500°C did not have any observable plateau,the discharge capacity of this film is nominally zero in our measurement.A656Journal of The Electrochemical Society ,152͑4͒A653-A657͑2005͒National Tsing Hua University assisted in meeting the publication costs of this article.References1. C.N.Polo da Fonseca,J.Davalos,M.Kleinke,M.C.A.Fantini,and A.Gorenstein,J.Power Sources,81-82,575͑1999͒.2.M.Yoshimura,K.S.Han,and S.Tsurimoto,Solid State Ionics,106,39͑1998͒.3. F.K.Shokoohi,J.M.Tarascon,B.J.Wolkens,D.Guyomard,and C.C.Chang,J.Electrochem.Soc.,137,1845͑1992͒.4. E.Ferg,R.J.Gummow,A.de Kock,and M.M.Thackeray,J.Electrochem.Soc.,141,L147͑1994͒.5.N.Koshiba,K.Takada,M.Nakanishi,K.Chikayama,and Z.Takehara,DenkiKagaku oyobi Kogyo Butsuri Kagaku,62,970͑1994͒.6.G.X.Wang,D.H.Bradhurst,S.X.Dou,and H.K.Liu,J.Power Sources,83,156͑1999͒.7.T.Ohzuku,A.Ueda,and N.Yamamoto,J.Electrochem.Soc.,142,1431͑1995͒.8.Y.H.Rho,K.Kanamura,M.Fujisaki,J.Hamagami,S.Suda,and T.Umegaki,SolidState Ionics,151,151͑2002͒.9.L.Kavan and M.Grätzel,Electrochem.Solid-State Lett.,5,A39͑2002͒.10.Y.H.Rho,K.Kanamura,and T.Umegaki,Chem.Lett.,2001,1322.11.K.-F.Chiu,F.C.Hsu,G.S.Chen,and M.K.Wu,J.Electrochem.Soc.,150,503͑2003͒.12.S.Scharner,W.Weppner,and P.Schmid-Beurmann,J.Electrochem.Soc.,146,857͑1999͒.13. D.Peramunage and K.M.Abraham,J.Electrochem.Soc.,145,2609͑1998͒.14. C.-M.Shen,X.-G.Zhang,Y.-K.Zhou,and H.-L.Li,Mater.Chem.Phys.,78,437͑2002͒.15.L.Kavan,G.Procházka,T.M.Spitler,M.Kalbáč,M.Zakalová,T.Drezen,and M.Grätzel,J.Electrochem.Soc.,150,1000͑2003͒.A657Journal of The Electrochemical Society,152͑4͒A653-A657͑2005͒。

前沿讲座 Seminar专业英语 Professional English现代分析化学 Modern analytical che mistry生物分析技术 Bioanalytical techniques高分子进展 Advances in polymers功能高分子进展 Advances in function al polymers有机硅高分子研究进展 Progresses in organosilicon polymers高分子科学实验方法 Scientific experimental methods of polymers 高分子设计与合成 The design and sy nthesis of polymers反应性高分子专论 Instructions to re active polymers网络化学与化工信息检索 Internet Se arching for Chemistry & Chemical E ngineeringinformation有序分子组合体概论 Introduction to Organized Molecular Assembilies两亲分子聚集体化学 Chemistry of am phiphilic aggregates表面活性剂体系研究新方法 New Meth od for studying Surfactant System 微纳米材料化学 Chemistry of Micro-NanoMaterials分散体系研究新方法 New Method for studying dispersion分散体系相行为 The Phase Behavior of Aqueous Dispersions 溶液-凝胶材料 Sol-Gel Materials高等量子化学 Advanced Quantum Chemistry分子反应动力学 Molecular Reaction Dynamic计算量子化学 Computational QuantumChemistry群论 Group Theory分子模拟理论及软件应用 Theory andSoftware of Molecular Modelling &Application价键理论方法 Valence Bond Theory量子化学软件及其应用Software of Quantum Chemistry & its Application分子光谱学 Molecular Spectrum算法语言 Computational Languange高分子化学 Polymer Chemistry高分子物理 Polymer Physics药物化学 Medicinal Chemistry统计热力学 Statistic Thermodynamics液-液体系专论 Discussion on Liquid-Liquid System配位化学进展 Progress in Coordination Chemistry无机材料及物理性质 Inorganic Materials and Their Physical Properties物理无机化学 Physical Inorganic Chemistry相平衡 Phase Equilibrium现代无机化学 Today's Inorganic Chemistry无机化学前沿领域导论 Introduction to Forward Field in Inorganic Chemistry量子化学 Quantum Chemistry分子材料 Molecular Material固体酸碱理论 Solid Acid-Base Theory萃取过程物理化学 Physical Chemistryin Extraction表面电化学 Surface Electrochemistry电化学进展 Advances on Electrochemistry现代电化学实验技术 Modern Experimental Techniques of Electrochemistry金属-碳多重键化合物及其应用 Compounds with Metal-Carbon multiple bonds and Their Applications叶立德化学:理论和应用 Ylides Chemistry: Theory and Application立体化学与手性合成 Stereochemistryand Chiral Synthesis杂环化学 Heterocyclic Chemistry有机硅化学 Organosilicon Chemistry药物设计及合成 Pharmaceutical Design and Synthesis超分子化学 Supramolecular Chemistry分子设计与组合化学 Molecular Designand Combinatorial Chemistry纳米材料化学前沿领域导论 Introduction to Nano-materials Chemistry纳米材料控制合成与自组装 Controlled-synthesis and Self-assembly of Nan o-materials前沿讲座 Leading Front Forum专业英语 Professional English超分子化学基础 Basics of Supramolec ular Chemistry液晶材料基础 Basics of Liquid Crysta l Materials现代实验技术 Modern analytical testi ng techniques色谱及联用技术 Chromatography and Technology of tandem发光分析及其研究法 Luminescence an alysis and Research methods胶束酶学 Micellar Enzymology分析化学中的配位化合物 Complex in Analytical Chemistry电分析化学 Electroanalytical chemist ry生物分析化学 Bioanalytical chemistry分析化学 Analytical chemistry仪器分析 Instrument analysis高分子合成化学 Polymers synthetic c hemistry高聚物结构与性能 Structures and pr operties of polymers有机硅化学 Organosilicon chemistry 功能高分子Functional polymers有机硅高分子 Organosilicon polymers 高分子现代实验技术 Advanced experimental technology of polymers高分子合成新方法 New synthetic methods of polymers液晶与液晶高分子 Liquid crystals andliquid crystal polymers大分子反应 Macromolecules reaction水溶性高分子 Water-soluble polymers聚合物加工基础 The basic process ofpolymers聚合物复合材料 Composite materials高等化工与热力学 Advanced ChemicalEngineering and Thermodynamics高等反应工程学 Advanced Reaction Engineering高等有机化学 Advanced Organic Chemistry高等有机合成 Advanced Organic synthesis有机化学中光谱分析 Spectrum Analysis in Organic Chemistry催化作用原理 Principle of Catalysis染料化学 Dye Chemistry中间体化学与工艺学 Intermediate Chemistry and Technology化学动力学 Chemical Kinetics表面活性剂合成与工艺 Synthesis andTechnology of Surfactants环境化学 Environmental Chemistry化工企业清洁生产 Chemical Enterprise Clean Production化工污染及防治 Chemical Pollution and Control动量热量质量传递 Momentum, Heat and Mass Transmission化工分离工程专题 Separation Engineering耐蚀材料 Corrosion Resisting Material网络化学与化工信息检索 Internet Searching for Chemistry & Chemical Engineering information新型功能材料的模板组装 Templated Assembly of Novel Advanced Materials胶体与界面 Colloid and Interface纳米材料的胶体化学制备方法 Colloid Chemical Methods for Preparing Nano-materials脂质体化学 Chemistry of liposome表面活性剂物理化学 Physico-chemistry of surfactants高分子溶液与微乳液 Polymer Solutions and Microemulsions两亲分子的溶液化学 Chemistry of Amphiphilic Molecules in solution介孔材料化学 Mesoporous Chemistry超细颗粒化学 Chemistry of ultrafinepowder分散体系流变学 The Rheolgy of Aqueous Dispersions量子化学 Quantum Chemistry统计热力学 Statistic Thermodynamics群论 Group Theory分子模拟 Molecular Modelling高等量子化学 Advanced Quantum Ch emistry价键理论方法 Valence Bond Theory 量子化学软件及其应用Software of Q uantum Chemistry & its Application计算量子化学 Computational Quantum Chemistry分子模拟软件及其应用Software of M olecular Modelling & its Application分子反应动力学 Molecular Reaction D ynamic分子光谱学 Molecular Spectrum算法语言 Computational Languange 高分子化学 Polymer Chemistry高分子物理 Polymer Physics腐蚀电化学 Corrosion Electrochemist ry物理化学 Physical Chemistry结构化学 structural Chemistry现代分析与测试技术(试验为主） Moder n Analysis and Testing Technology（e xperimetally)高等无机化学 Advanced Inorganic Ch emistry近代无机物研究方法 Modern Research Methods for Inorganic Compounds 萃取化学研究方法 Research Methods for Extraction Chemistry单晶培养 Crystal Culture 固态化学 Chemistry of Solid Substance液-液体系专论 Discussion on Liquid-Liquid System配位化学进展 Progress in Coordination Chemistry卟啉酞箐化学 Chemistry of Porphyrine and Phthalocyanine无机材料及物理性质 Inorganic Materials and Their Physical Properties物理无机化学 Physical Inorganic Chemistry相平衡 Phase Equilibrium生物化学的应用 Application of Biologic Chemistry生物无机化学 Bio-Inorganic Chemistry绿色化学 Green Chemistry金属有机化合物在均相催化中的应用 Applied Homogeneous Catalysis with Organometallic Compounds功能性食品化学 Functionalized FoodChemistry无机药物化学 Inorganic Pharmaceutical Chemistry电极过程动力学 Kinetics on ElectrodeProcess电化学研究方法 Electrochemical Research Methods生物物理化学 Biological Physical Chemistry波谱与现代检测技术 Spectroscopy and Modern Testing Technology理论有机化学 theoretical Organic Chemistry合成化学 Synthesis Chemistry有机合成新方法 New Methods for Organic Synthesis生物有机化学 Bio-organic Chemistry药物化学 Pharmaceutical Chemistry金属有机化学 Organometallic Chemistry金属-碳多重键化合物及其应用 Compounds with Metal-Carbon multiple bonds and Their Applications分子构效与模拟 Molecular Structure-Activity and Simulation过程装置数值计算 Data Calculation ofProcess Devices石油化工典型设备 Common Equipmentof Petrochemical Industry化工流态化工程 Fluidization in Chemical Industry化工装置模拟与优化 Analogue and Optimization of Chemical Devices化工分离工程 Separation Engineering化工系统与优化 Chemical System andOptimization高等化工热力学 Advanced Chemical Engineering and Thermodynamics超临界流体技术及应用 Super CraticalLiguid Technegues and Applications膜分离技术 Membrane Separation T echnegues溶剂萃取原理和应用 Theory and Appli cation of Solvent Extraction树脂吸附理论 Theory of Resin Adso rption中药材化学 Chemistry of Chinese Me dicine生物资源有效成分分析与鉴定 Analysis and Detection of Bio-materials相平衡理论与应用 Theory and Applic ation of Phase Equilibrium计算机在化学工程中的应用 Application of Computer in Chemical Engineerin g微乳液和高分子溶液 Micro-emulsion a nd High Molecular Solution传递过程 Transmision Process反应工程分析 Reaction Engineering A nalysis腐蚀电化学原理与应用 Principle and A pplication of Corrosion Electrochem istry腐蚀电化学测试方法与应用 Measureme nt Method and Application of Corro sion Electrochemistry耐蚀表面工程 Surface Techniques of Anti-corrosion缓蚀剂技术 Inhabitor Techniques 腐蚀失效分析 Analysis of Corrosion Destroy材料表面研究方法 Method of Studyin g Material Surfacc分离与纯化技术 Separation and Purification Technology现代精细有机合成 Modern Fine Organic Synthesis化学工艺与设备 Chemical Technologyand Apparatuas功能材料概论 Functional Materials Conspectus油田化学 Oilfield Chemistry精细化学品研究 Study of Fine Chemicals催化剂合成与应用 Synthesis and Application of Catalyzer低维材料制备 Preparation of Low-Dimension Materials手性药物化学 Symmetrical Pharmaceutical Chemistry光敏高分子材料化学 Photosensitive Polymer Materials Chemistry纳米材料制备与表征 Preparation andCharacterization of Nanostructuredmaterials溶胶凝胶化学 Sol-gel Chemistry纳米材料化学进展 Proceeding of Nano-materials Chemistry●化学常用词汇汉英对照表1●氨ammonia氨基酸amino acid铵盐ammonium salt饱和链烃saturated aliphatichydrocarbon苯benzene变性denaturation不饱和烃unsaturatedhydrocarbon超导材料superconductivematerial臭氧ozone醇alcohol次氯酸钾potassiumhypochlorite醋酸钠sodium acetate蛋白质protein氮族元素nitrogen groupelement碘化钾potassium iodide碘化钠sodium iodide电化学腐蚀electrochemicalcorrosion电解质electrolyte电离平衡ionizationequilibrium电子云electron cloud淀粉starch淀粉碘化钾试纸starchpotassium iodide paper二氧化氮nitrogen dioxide二氧化硅silicon dioxide二氧化硫sulphur dioxide二氧化锰manganese dioxide芳香烃arene放热反应exothermic reaction非极性分子non-polar molecule非极性键non-polar bond肥皂soap分馏fractional distillation酚phenol复合材料composite干电池dry cell干馏dry distillation甘油glycerol高分子化合物polymer共价键covalent bond官能团functional group光化学烟雾photochemical fog过氧化氢hydrogen peroxide合成材料synthetic material合成纤维synthetic fiber合成橡胶synthetic rubber核电荷数nuclear charge number核素nuclide化学电源chemical powersource化学反应速率chemical reactionrate化学键chemical bond化学平衡chemical equilibrium 还原剂reducing agent磺化反应sulfonation reaction 霍尔槽 Hull Cell极性分子polar molecule极性键polar bond加成反应addition reaction加聚反应addition polymerization甲烷methane碱金属alkali metal碱石灰soda lime结构式structural formula聚合反应po1ymerization可逆反应reversible reaction空气污染指数air pollution index勒夏特列原理Le Chatelier's principle离子反应ionic reaction离子方程式ionic equation离子键ionic bond锂电池lithium cell两性氢氧化物amphoteric hydroxide两性氧化物amphoteric oxide裂化cracking裂解pyrolysis硫氰化钾potassium thiocyanate硫酸钠sodium sulphide氯化铵ammonium chloride氯化钡barium chloride氯化钾potassium chloride氯化铝aluminium chloride氯化镁magnesium chloride氯化氢hydrogen chloride氯化铁iron (III) chloride氯水chlorine water麦芽糖maltose煤coal酶enzyme摩尔mole摩尔质量molar mass品红magenta或fuchsine葡萄糖glucose气体摩尔体积molar volume of gas铅蓄电池lead storage battery强电解质strong electrolyte氢氟酸hydrogen chloride氢氧化铝aluminium hydroxide取代反应substitutionreaction醛aldehyde炔烃alkyne燃料电池fuel cell弱电解质weak electrolyte石油Petroleum水解反应hydrolysis reaction四氯化碳carbontetrachloride塑料plastic塑料的降解plasticdegradation塑料的老化plastic ageing酸碱中和滴定acid-baseneutralization titration酸雨acid rain羧酸carboxylic acid碳酸钠 sodium carbonate碳酸氢铵 ammonium bicarbonate碳酸氢钠 sodium bicarbonate糖类 carbohydrate烃 hydrocarbon烃的衍生物 derivative ofhydrocarbon烃基 hydrocarbonyl同分异构体 isomer同素异形体 allotrope同位素 isotope同系物 homo1og涂料 coating烷烃 alkane物质的量amount of substance物质的量浓度 amount-of-substanceconcentration of B烯烃 alkene洗涤剂 detergent纤维素 cellulose相对分子质量 relative molecularmass相对原子质量relative atomic mass消去反应 elimination reaction硝化反应 nitratlon reaction硝酸钡 barium nitrate硝酸银silver nitrate溴的四氯化碳溶液 solution ofbromine in carbon tetrachloride溴化钠 sodium bromide溴水bromine water溴水 bromine water盐类的水解hydrolysis of salts盐析salting-out焰色反应 flame test氧化剂oxidizing agent氧化铝 aluminium oxide氧化铁iron (III) oxide乙醇ethanol乙醛 ethana1乙炔 ethyne乙酸ethanoic acid乙酸乙酯 ethyl acetate乙烯ethene银镜反应silver mirror reaction硬脂酸stearic acid油脂oils and fats有机化合物 organic compound元素周期表 periodic table ofelements元素周期律 periodic law ofelements原电池 primary battery原子序数 atomic number皂化反应 saponification粘合剂 adhesive蔗糖 sucrose指示剂 Indicator酯 ester酯化反应 esterification周期period族group（主族：main group）Bunsen burner 本生灯product 化学反应产物flask 烧瓶apparatus 设备PH indicator PH值指示剂,氢离子(浓度的)负指数指示剂matrass 卵形瓶litmus 石蕊litmus paper 石蕊试纸graduate, graduated flask 量筒,量杯reagent 试剂test tube 试管burette 滴定管retort 曲颈甑still 蒸馏釜cupel 烤钵crucible pot, melting pot 坩埚pipette 吸液管filter 滤管stirring rod 搅拌棒element 元素body 物体compound 化合物atom 原子gram atom 克原子atomic weight 原子量atomic number 原子数atomic mass 原子质量molecule 分子electrolyte 电解质ion 离子anion 阴离子cation 阳离子electron 电子isotope 同位素isomer 同分异物现象polymer 聚合物symbol 复合radical 基structural formula 分子式valence, valency 价monovalent 单价bivalent 二价halogen 成盐元素bond 原子的聚合mixture 混合combination 合成作用compound 合成物alloy 合金organic chemistry 有机化学inorganic chemistry 无机化学derivative 衍生物series 系列acid 酸hydrochloric acid 盐酸sulphuric acid 硫酸nitric acid 硝酸aqua fortis 王水fatty acid 脂肪酸organic acid 有机酸 hydrosulphuric acid 氢硫酸hydrogen sulfide 氢化硫alkali 碱,强碱ammonia 氨base 碱hydrate 水合物hydroxide 氢氧化物,羟化物hydracid 氢酸hydrocarbon 碳氢化合物,羟anhydride 酐alkaloid 生物碱aldehyde 醛oxide 氧化物phosphate 磷酸盐acetate 醋酸盐methane 甲烷,沼气butane 丁烷salt 盐potassium carbonate 碳酸钾soda 苏打sodium carbonate 碳酸钠caustic potash 苛性钾caustic soda 苛性钠ester 酯gel 凝胶体analysis 分解fractionation 分馏endothermic reaction 吸热反应exothermic reaction 放热反应precipitation 沉淀to precipitate 沉淀to distil, to distill 蒸馏distillation 蒸馏to calcine 煅烧to oxidize 氧化alkalinization 碱化to oxygenate, to oxidize 脱氧,氧化to neutralize 中和to hydrogenate 氢化to hydrate 水合,水化to dehydrate 脱水fermentation 发酵solution 溶解combustion 燃烧fusion, melting 熔解alkalinity 碱性isomerism, isomery 同分异物现象hydrolysis 水解electrolysis 电解electrode 电极anode 阳极,正极cathode 阴极,负极catalyst 催化剂catalysis 催化作用oxidization, oxidation 氧化reducer 还原剂dissolution 分解synthesis 合成reversible 可逆的1. The Ideal-Gas Equation 理想气体状态方程2. Partial Pressures 分压3. Real Gases: Deviation from IdealBehavior 真实气体：对理想气体行为的偏离4. The van der Waals Equation 范德华方程5. System and Surroundings 系统与环境6. State and State Functions 状态与状态函数7. Process 过程8. Phase 相9. The First Law of Thermodynamics热力学第一定律10. Heat and Work 热与功11. Endothermic and ExothermicProcesses 吸热与发热过程12. Enthalpies of Reactions 反应热13. Hess’s Law 盖斯定律14. Enthalpies of Formation 生成焓15. Reaction Rates 反应速率16. Reaction Order 反应级数17. Rate Constants 速率常数18. Activation Energy 活化能19. The Arrhenius Equation 阿累尼乌斯方程20. Reaction Mechanisms 反应机理21. Homogeneous Catalysis 均相催化剂22. Heterogeneous Catalysis 非均相催化剂23. Enzymes 酶24. The Equilibrium Constant 平衡常数25. the Direction of Reaction 反应方向26. Le Chatelier’s Principle 列·沙特列原理27. Effects of Volume, Pressure, Temperature Changes and Catalysts i. 体积，压力，温度变化以及催化剂的影响28. Spontaneous Processes 自发过程29. Entropy (Standard Entropy) 熵（标准熵）30. The Second Law of Thermodynamics 热力学第二定律31. Entropy Changes 熵变32. Standard Free-Energy Changes 标准自由能变33. Acid-Bases 酸碱34. The Dissociation of Water 水离解35. The Proton in Water 水合质子36. The pH Scales pH值37. Bronsted-Lowry Acids and Bases Bronsted-Lowry 酸和碱38. Proton-Transfer Reactions 质子转移反应39. Conjugate Acid-Base Pairs 共轭酸碱对40. Relative Strength of Acids and Bases 酸碱的相对强度41. Lewis Acids and Bases 路易斯酸碱42. Hydrolysis of Metal Ions 金属离子的水解43. Buffer Solutions 缓冲溶液44. The Common-Ion Effects 同离子效应45. Buffer Capacity 缓冲容量46. Formation of Complex Ions 配离子的形成47. Solubility 溶解度48. The Solubility-Product ConstantKsp 溶度积常数49. Precipitation and separation ofIons 离子的沉淀与分离50. Selective Precipitation of Ions 离子的选择沉淀51. Oxidation-Reduction Reactions 氧化还原反应52. Oxidation Number 氧化数53. Balancing Oxidation-ReductionEquations 氧化还原反应方程的配平54. Half-Reaction 半反应55. Galvani Cell 原电池56. Voltaic Cell 伏特电池57. Cell EMF 电池电动势58. Standard Electrode Potentials 标准电极电势59. Oxidizing and Reducing Agents 氧化剂和还原剂60. The Nernst Equation 能斯特方程61. Electrolysis 电解62. The Wave Behavior of Electrons电子的波动性63. Bohr’s Model of The HydrogenAtom 氢原子的波尔模型64. Line Spectra 线光谱65. Quantum Numbers 量子数66. Electron Spin 电子自旋67. Atomic Orbital 原子轨道68. The s (p, d, f) Orbital s（p，d，f）轨道69. Many-Electron Atoms 多电子原子70. Energies of Orbital 轨道能量71. The Pauli Exclusion Principle 泡林不相容原理72. Electron Configurations 电子构型73. The Periodic Table 周期表74. Row 行75. Group 族76. Isotopes, Atomic Numbers, andMass Numbers 同位素，原子数，质量数77. Periodic Properties of theElements 元素的周期律78. Radius of Atoms 原子半径79. Ionization Energy 电离能80. Electronegativity 电负性81. Effective Nuclear Charge 有效核电荷82. Electron Affinities 亲电性83. Metals 金属84. Nonmetals 非金属85. Valence Bond Theory 价键理论86. Covalence Bond 共价键87. Orbital Overlap 轨道重叠88. Multiple Bonds 重键89. Hybrid Orbital 杂化轨道90. The VSEPR Model 价层电子对互斥理论91. Molecular Geometries 分子空间构型92. Molecular Orbital 分子轨道93. Diatomic Molecules 双原子分子94. Bond Length 键长95. Bond Order 键级96. Bond Angles 键角97. Bond Enthalpies 键能98. Bond Polarity 键矩99. Dipole Moments 偶极矩100. Polarity Molecules 极性分子101. Polyatomic Molecules 多原子分子102. Crystal Structure 晶体结构103. Non-Crystal 非晶体104. Close Packing of Spheres 球密堆积105. Metallic Solids 金属晶体106. Metallic Bond 金属键107. Alloys 合金108. Ionic Solids 离子晶体109. Ion-Dipole Forces 离子偶极力110. Molecular Forces 分子间力111. Intermolecular Forces 分子间作用力112. Hydrogen Bonding 氢键113. Covalent-Network Solids 原子晶体114. Compounds 化合物115. The Nomenclature, Composition and Structure of Complexes 配合物的命名，组成和结构116. Charges, Coordination Numbers,and Geometries 电荷数、配位数、及几何构型117. Chelates 螯合物118. Isomerism 异构现象119. Structural Isomerism 结构异构120. Stereoisomerism 立体异构121. Magnetism 磁性122. Electron Configurations inOctahedral Complexes 八面体构型配合物的电子分布123. Tetrahedral and Square-planarComplexes 四面体和平面四边形配合物124. General Characteristics 共性125. s-Block Elements s区元素126. Alkali Metals 碱金属127. Alkaline Earth Metals 碱土金属128. Hydrides 氢化物129. Oxides 氧化物130. Peroxides and Superoxides 过氧化物和超氧化物131. Hydroxides 氢氧化物132. Salts 盐133. p-Block Elements p区元素134. Boron Group (Boron, Aluminium,Gallium, Indium, Thallium) 硼族（硼，铝，镓，铟，铊）135. Borane 硼烷136. Carbon Group (Carbon, Silicon,Germanium, Tin, Lead) 碳族（碳，硅，锗，锡，铅）137. Graphite, Carbon Monoxide,Carbon Dioxide 石墨，一氧化碳，二氧化碳138. Carbonic Acid, Carbonates andCarbides 碳酸，碳酸盐，碳化物139. Occurrence and Preparation ofSilicon 硅的存在和制备140. Silicic Acid，Silicates 硅酸，硅酸盐141. Nitrogen Group (Phosphorus,Arsenic, Antimony, and Bismuth) 氮族（磷，砷，锑，铋）142. Ammonia, Nitric Acid, PhosphoricAcid 氨，硝酸，磷酸143. Phosphorates, phosphorusHalides 磷酸盐，卤化磷144. Oxygen Group (Oxygen, Sulfur,Selenium, and Tellurium) 氧族元素（氧，硫，硒，碲）145. Ozone, Hydrogen Peroxide 臭氧，过氧化氢146. Sulfides 硫化物147. Halogens (Fluorine, Chlorine,Bromine, Iodine) 卤素（氟，氯，溴，碘）148. Halides, Chloride 卤化物，氯化物149. The Noble Gases 稀有气体150. Noble-Gas Compounds 稀有气体化合物151. d-Block elements d区元素152. Transition Metals 过渡金属153. Potassium Dichromate 重铬酸钾154. Potassium Permanganate 高锰酸钾155. Iron Copper Zinc Mercury 铁，铜，锌，汞156. f-Block Elements f区元素157. Lanthanides 镧系元素158. Radioactivity 放射性159. Nuclear Chemistry 核化学160. Nuclear Fission 核裂变161. Nuclear Fusion 核聚变162. analytical chemistry 分析化学163. qualitative analysis 定性分析164. quantitative analysis 定量分析165. chemical analysis 化学分析166. instrumental analysis 仪器分析167. titrimetry 滴定分析168. gravimetric analysis 重量分析法169. regent 试剂170. chromatographic analysis 色谱分析171. product 产物172. electrochemical analysis 电化学分析173. on-line analysis 在线分析174. macro analysis 常量分析175. characteristic 表征176. micro analysis 微量分析177. deformation analysis 形态分析178. semimicro analysis 半微量分析179. systematical error 系统误差180. routine analysis 常规分析181. random error 偶然误差182. arbitration analysis 仲裁分析183. gross error 过失误差184. normal distribution 正态分布185. accuracy 准确度186. deviation 偏差187. precision精密度188. relative standard deviation相对标准偏差（RSD）189. coefficient variation变异系数（CV）190. confidence level置信水平191. confidence interval置信区间192. significant test显著性检验193. significant figure有效数字194. standard solution标准溶液195. titration滴定196. stoichiometric point化学计量点197. end point滴定终点198. titration error滴定误差199. primary standard基准物质200. amount of substance物质的量201. standardization标定202. chemical reaction化学反应203. concentration浓度204. chemical equilibrium化学平衡205. titer滴定度206. general equation for a chemicalreaction化学反应的通式207. proton theory of acid-base酸碱质子理论208. acid-base titration酸碱滴定法209. dissociation constant解离常数210. conjugate acid-base pair共轭酸碱对211. acetic acid乙酸212. hydronium ion水合氢离子213. electrolyte电解质214. ion-product constant of water水的离子积215. ionization电离216. proton condition质子平衡217. zero level零水准218. buffer solution缓冲溶液219. methyl orange甲基橙220. acid-base indicator酸碱指示剂221. phenolphthalein酚酞222. coordination compound配位化合物223. center ion中心离子224. cumulative stability constant累积稳定常数225. alpha coefficient酸效应系数226. overall stability constant总稳定常数227. ligand配位体228. ethylenediamine tetraacetic acid 乙二胺四乙酸229. side reaction coefficient副反应系数230. coordination atom配位原子231. coordination number配位数232. lone pair electron孤对电子233. chelate compound螯合物234. metal indicator金属指示剂235. chelating agent螯合剂236. masking 掩蔽237. demasking解蔽238. electron电子239. catalysis催化240. oxidation氧化241. catalyst催化剂242. reduction还原243. catalytic reaction催化反应244. reaction rate反应速率245. electrode potential电极电势246. activation energy 反应的活化能247. redox couple 氧化还原电对248. potassium permanganate 高锰酸钾249. iodimetry碘量法250. potassium dichromate 重铬酸钾251. cerimetry 铈量法252. redox indicator 氧化还原指示253. oxygen consuming 耗氧量（OC）254. chemical oxygen demanded 化学需氧量(COD)255. dissolved oxygen 溶解氧(DO)256. precipitation 沉淀反应257. argentimetry 银量法258. heterogeneous equilibrium of ions多相离子平衡259. aging 陈化260. postprecipitation 继沉淀261. coprecipitation 共沉淀262. ignition 灼烧263. fitration 过滤264. decantation 倾泻法265. chemical factor 化学因数266. spectrophotometry 分光光度法267. colorimetry 比色分析268. transmittance 透光率269. absorptivity 吸光率270. calibration curve 校正曲线271. standard curve 标准曲线272. monochromator 单色器273. source 光源274. wavelength dispersion 色散275. absorption cell吸收池276. detector 检测系统277. bathochromic shift 红移278. Molar absorptivity 摩尔吸光系数279. hypochromic shift 紫移280. acetylene 乙炔281. ethylene 乙烯282. acetylating agent 乙酰化剂283. acetic acid 乙酸284. adiethyl ether 乙醚285. ethyl alcohol 乙醇286. acetaldehtde 乙醛287. β-dicarbontl compound β–二羰基化合物288. bimolecular elimination 双分子消除反应289. bimolecular nucleophilic substitution 双分子亲核取代反应290. open chain compound 开链族化合物291. molecular orbital theory 分子轨道理论292. chiral molecule 手性分子293. tautomerism 互变异构现象294. reaction mechanism 反应历程295. chemical shift 化学位移296. Walden inversio 瓦尔登反转n 297. Enantiomorph 对映体298. addition rea ction 加成反应299. dextro- 右旋300. levo- 左旋301. stereochemistry 立体化学302. stereo isomer 立体异构体303. Lucas reagent 卢卡斯试剂304. covalent bond 共价键305. conjugated diene 共轭二烯烃306. conjugated double bond 共轭双键307. conjugated system 共轭体系308. conjugated effect 共轭效应309. isomer 同分异构体310. isomerism 同分异构现象311. organic chemistry 有机化学312. hybridization 杂化313. hybrid orbital 杂化轨道314. heterocyclic compound 杂环化合物315. peroxide effect 过氧化物效应t316. valence bond theory 价键理论317. sequence rule 次序规则318. electron-attracting grou p 吸电子基319. Huckel rule 休克尔规则320. Hinsberg test 兴斯堡试验321. infrared spectrum 红外光谱322. Michael reacton 麦克尔反应323. halogenated hydrocarbon 卤代烃324. haloform reaction 卤仿反应325. systematic nomenclatur 系统命名法e326. Newman projection 纽曼投影式327. aromatic compound 芳香族化合物328. aromatic character 芳香性r329. Claisen condensation reaction克莱森酯缩合反应330. Claisen rearrangement 克莱森重排331. Diels-Alder reation 狄尔斯-阿尔得反应332. Clemmensen reduction 克莱门森还原333. Cannizzaro reaction 坎尼扎罗反应334. positional isomers 位置异构体335. unimolecular elimination reaction单分子消除反应336. unimolecular nucleophilicsubstitution 单分子亲核取代反应337. benzene 苯338. functional grou 官能团p339. configuration 构型340. conformation 构象341. confomational isome 构象异构体342. electrophilic addition 亲电加成343. electrophilic reagent 亲电试剂344. nucleophilic addition 亲核加成345. nucleophilic reagent 亲核试剂346. nucleophilic substitution reaction亲核取代反应347. active intermediate 活性中间体348. Saytzeff rule 查依采夫规则349. cis-trans isomerism 顺反异构350. inductive effect 诱导效应 t351. Fehling’s reagent 费林试剂352. phase transfer catalysis 相转移催化作用353. aliphatic compound 脂肪族化合物354. elimination reaction 消除反应355. Grignard reagent 格利雅试剂 356. nuclear magnetic resonance 核磁共振357. alkene 烯烃358. allyl cation 烯丙基正离子359. leaving group 离去基团360. optical activity 旋光性361. boat confomation 船型构象 362. silver mirror reaction 银镜反应363. Fischer projection 菲舍尔投影式 364. Kekule structure 凯库勒结构式365. Friedel-Crafts reaction 傅列德尔-克拉夫茨反应366. Ketone 酮367. carboxylic acid 羧酸368. carboxylic acid derivative 羧酸衍生物369. hydroboration 硼氢化反应 370. bond oength 键长371. bond energy 键能372. bond angle 键角373. carbohydrate 碳水化合物374. carbocation 碳正离子375. carbanion 碳负离子376. alcohol 醇377. Gofmann rule 霍夫曼规则 378. Aldehyde 醛379. Ether 醚380. Polymer 聚合物ace- 乙（酰基）acet- 醋；醋酸；乙酸acetamido- 乙酰胺基acetenyl- 乙炔基acetoxy- 醋酸基；乙酰氧基acetyl- 乙酰（基）aetio- 初allo- 别allyl- 烯丙（基）；CH2=CH-CH2-amido- 酰胺（基）amino- 氨基amyl- ①淀粉②戊（基）amylo- 淀粉andr- 雄andro- 雄anilino- 苯胺基anisoyl- 茴香酰；甲氧苯酰anti- 抗apo- 阿朴；去水aryl- 芳（香）基aspartyl- 门冬氨酰auri- 金（基）；（三价）金基aza- 氮（杂）azido- 叠氮azo- 偶氮basi- 碱baso- 碱benxoyl- 苯酰；苯甲酰benzyl- 苄（基）；苯甲酰bi- 二；双；重biphenyl- 联苯基biphenylyl- 联苯基bis- 双；二bor- 硼boro- 硼bromo- 溴butenyl- 丁烯基（有1、2、3位三种）butoxyl- 丁氧基butyl- 丁基butyryl- 丁酰caprinoyl- 癸酰caproyl- 己酰calc- 钙calci- 钙calco- 钙capryl- 癸酰capryloyl- 辛酰caprylyl- 辛酰cef- 头孢（头孢菌素族抗生素词首）chlor- ①氯②绿chloro- ①氯②绿ciclo- 环cis- 顺clo- 氯crypto- 隐cycl- 环cyclo- 环de- 去；脱dec- 十；癸deca- 十；癸dehydro- 去氢；去水demethoxy- 去甲氧（基）demethyl- 去甲（基）deoxy- 去氧des- 去；脱desmethyl- 去甲（基）desoxy- 去氧dex- 右旋dextro- 右旋di- 二diamino- 二氨基diazo- 重氮dihydro- 二氢；双氢endo- 桥epi- 表；差向epoxy- 环氧erythro- 红；赤estr- 雌ethinyl- 乙炔（基）ethoxyl- 乙氧（基）ethyl- 乙基etio- 初eu- 优fluor- ①氟②荧光fluoro- ①氟②荧光formyl- 甲酰（基）guanyl- 脒基hepta- 七；庚hetero- 杂hexa- 六；己homo- 高(比原化合物多一个-CH2-)hypo- 次io- 碘indo- 碘iso- 异keto- 酮laevo- 左旋leuco- 白levo- 左旋。

锂离子电池氧化物固态电解质研究进展
姚忠冉;孙强;顾骁勇;邹晔;李吉;何祺
【期刊名称】《新能源进展》
【年(卷),期】2023(11)1
【摘要】可充电锂离子电池(LIB)是移动和固定存储系统中最具潜力的电池体系。

然而,传统锂离子电池中不稳定的电沉积和不可控的界面反应会在液体电解质中发生,导致电池存在安全隐患。

采用固态电解质(SSE)的全固态锂离子电池因具有高安全性、高可靠性和高能量密度可满足许多方面对储能的要求。

但要实现商业化,SSE 依然面临诸多挑战,如室温离子电导率较低(1×10^(-5)~1×10^(-3)S/cm)以及电极和电解质之间的界面稳定性差等。

为加快SSE的研究与开发,分别对无机钙钛矿(LLTO)型、石榴石(LLZO)型和钠快离子导体(NASICON)型固态电解质的结构和电导率改性进行了综述,特别强调了电解质与电极界面的重要性及其对电池性能的影响。

【总页数】9页(P76-84)
【作者】姚忠冉;孙强;顾骁勇;邹晔;李吉;何祺
【作者单位】无锡职业技术学院;华晨新日新能源汽车有限公司
【正文语种】中文
【中图分类】TK02
【相关文献】
1.无机固态锂离子电池电解质的研究进展
2.锂离子电池用PEO改性聚合物固态电解质的研究进展
3.全固态锂离子电池固态电解质的研究进展
4.无机固态电解质及其电极-电解质界面优化对全固态锂离子电池性能提高的研究进展
5.基于硫化物电解质的全固态锂离子电池负极研究进展
因版权原因，仅展示原文概要，查看原文内容请购买。

子技术分册部分单词子技术分册部分单词缩略词：BJT 双极结型晶体管 Bipolar Junction TransistorLED 发光二极管 Light Emitting DiodeMOS 金属氧化物半导体场效应晶体管 Metal Oxide SemiconductorFET 场效应晶体管 Filed Effect Transistorbcc 体心立方 Body-centered cubicfcc 面心立方 Face-centered cubicSOI Silicon-On-Insulator绝缘层上硅结构CVD Chemical Vapor Deposition化学气相淀积+ plus/positive - negative * minus / negativeX2 X square the square root of X3 x cube the cubic root of X y X to the yth单词：Semiconductor半导体transition 跃迁Conductivit电导率diffusivity piecewise 分段扩散率 resistivity 电阻率diffusivity 扩散系数Bipolar transistor 双极型晶体管 step junction 突变结Rectifie整流器 metallurgical junction 合金结Photodiode 光电二极管 fermi level 费米能级Leakage current 漏电流exponential 指数的Silicon dioxide 二氧化硅 dopant 掺杂Lattice 晶格dielectric 电解质 dislodge 移出Unit cell 晶胞 Facet 晶面bonding 键合phonon 声子Lattice constant 晶格常数 tetrahedral 四面体的 Diamond lattice 金刚石晶格Level energy 能级 Miller indices 弥勒指数 acoustic 声学的Hole 空穴lifetime 寿命Permittivity 介电常数continuity equation连续方程Covalent bonding 共价键 impurity 杂质Conduct/valence band 导带，价带device 装置，器件Effective density of states 有效态密度 magnetic 有磁性的Intrinsic 本征的 illumination 照明 silicon ，gallium，germanium，gallium arsenideExtrinsic 非本征的 reciprocal 倒数，相反的Carrier 载流子 agitation 激动，搅拌Bandgap 能带间隙 incremental 增加的Mass action law 质量作用定律excitation 激发Donor acceptor 施主受主Injection 注入collision 冲突，抵触impact ionization 碰撞电离superimposed 叠加sufficient 充分的Scatter 散射Drift 漂移 succession 连续的 drift velocity 漂移速度Mean free time /path 平均自由时间/程Mobility 迁移率saturation 饱和Recombination 复合 spatial 空间overwhelm vt.压倒；淹没；受打击 Decay 衰减Abrupt 突变 derivative 衍生物bias 偏见 gradient 梯度；magnitude 量级 Direct Recombination 直接复合Photoconductivity 光电导 potential barrier [物] 势垒；[电子] 位垒;voltmeter 电压计quantitative 定量的amplification 放大（率steady state 恒稳态;transient state 瞬态；过渡状态; qualitative .定性的rectification n. [电] 整流 equilibrium condition 平衡态endeavor 努力 conceive 设想；考虑 ; postulate.假定 unfolding 演变; Prime n. 初期； Primitive 原始的，简单的，粗糙的; artistic adj. 艺术的；supervisor n. 监督人，管理人；检查员;Instinct n. 本能，直觉 analog n.模拟；类似物analytical adj. 分析的 genuine adj. 真实的，真正的 inferior n. 下级；次品 acronym n. 首字母缩略词; insofar as 在…的范围内；到…程度; embodimentn. 体现；化身；具体化 ;proliferate vi. 增殖；扩散；激增vt.使激增;constantly adv. 不断地；时常地; complementary adj. 补足的，补充的; dissipation n.浪费；消散；[物] 损耗; vehicle n. [车辆] 车辆；工具；交通工具；传播媒介Parallelepiped n. 平行六面体; metallurgical adj. 冶金的；冶金学的; Pedestal n. 基架，基座； analogous adj. 类似的；可比拟的; Ambiguity n.含糊；不明确； retain vt.保持；雇；记住; Resemblance n. 相似；相似之处prototypical adj. 原型的；典型的; Parasitic adj. 寄生的（等于parasitical）;Vestigial adj. 退化的；残余的；发育不全的;parallel n. 平行线平行的 Grooves n. 细槽，凹槽simultaneously同时发生地 remnant n. 剩余adj. 剩余的;Mount n. 山峰；底座； Acknowledge 承认; disturbance 干扰; inevitable 不可避免的;inherent 固有的; subsume 把。

Effect of Crystallographic Structure of MnO2on Its Electrochemical Capacitance PropertiesS.Devaraj and N.Munichandraiah*Department of Inorganic and Physical Chemistry,Indian Institute of Science,Bangalore-560012,IndiaRecei V ed:No V ember14,2007;In Final Form:January7,2008MnO2is currently under extensive investigations for its capacitance properties.MnO2crystallizes into severalcrystallographic structures,namely,R, ,γ,δ,andλstructures.Because these structures differ in the wayMnO6octahedra are interlinked,they possess tunnels or interlayers with gaps of different magnitudes.Becausecapacitance properties are due to intercalation/deintercalation of protons or cations in MnO2,only somecrystallographic structures,which possess sufficient gaps to accommodate these ions,are expected to beuseful for capacitance studies.In order to examine the dependence of capacitance on crystal structure,thepresent study involves preparation of these various crystal phases of MnO2in nanodimensions and to evaluatetheir capacitance properties.Results of R-MnO2prepared by a microemulsion route(R-MnO2(m))are alsoused for comparison.Spherical particles of about50nm,nanorods of30-50nm in diameter,or interlockedfibers of10-20nm in diameters are formed,which depend on the crystal structure and the method ofpreparation.The specific capacitance(SC)measured for MnO2is found to depend strongly on thecrystallographic structure,and it decreases in the following order:R(m)>R=δ>γ>λ> .A SC valueof297F g-1is obtained for R-MnO2(m),whereas it is9F g-1for -MnO2.A wide(∼4.6Å)tunnel size andlarge surface area of R-MnO2(m)are ascribed as favorable factors for its high SC.A large interlayer separation(∼7Å)also facilitates insertion of cations inδ-MnO2resulting in a SC close to236F g-1.A narrow tunnelsize(1.89Å)does not allow intercalation of cations into -MnO2.As a result,it provides a very small SC.1.IntroductionIn recent years,electrochemical capacitors(ECs)have received a great attention in the filed of electrochemical energy storage and conversion because of their high power capability and long cycle-life.An EC is useful as an auxiliary energy device along with a primary power source such as a battery or a fuel cell for power enhancement in short pulse applications.1-4 Charge storage mechanisms in EC capacitor materials include separation of charges at the interface between the electrode and the electrolyte and/or fast faradaic reactions occurring at the electrode.Capacitance,which arises from separation of charges, is generally called electric double-layer capacitance(EDLC). Capacitance due to a faradaic process is known as pseudoca-pacitance.Because the magnitude of capacitance of these types of capacitors is several times greater than that of conventional capacitors,ECs are also known as supercapacitors or ultraca-pacitors.Various materials investigated for ECs include(i)carboneous materials,(ii)conducting polymers,and(iii)transition-metal oxides.3Among transition-metal oxides,amorphous hydrous ruthenium oxide(RuO2‚x H2O)has specific capacitance(SC) as high as760F g-1because of the solid-state pseudofaradaic reaction.5-8However,the high cost,low porosity,and toxic nature of RuO2limit commercialization of supercapacitors employing this material.Therefore,there is a need to investigate alternate transition-metal oxides,which are cheap,available in abundance,nontoxic,and environmentally friendly.Manganese dioxide has attracted much attention9-21because it has these favorable properties and it is widely used as a cathode material in batteries.22However,the SC values reported are lower than the values obtained for RuO2‚x H2O,and studies on various ways of increasing the SC are reported.14,15Hydrous MnO2exhibits pseudocapacitance behavior in several aqueous electrolytes of alkali salts such as Li2SO4,Na2-SO4,K2SO4,and so forth.Transition of Mn4+/Mn3+involving a single electron transfer is responsible for the pseudocapacitance behavior of MnO2.10,23,24MnO2exists in several crystallographic forms,which are known as R, ,γ,δ,andλforms.22,25The R, ,andγforms possess1D tunnels in their structures,theδis a2D layered compound,and theλis a3D spinel structure. The properties of MnO2largely depend on its crystallographic nature.Because of various crystallographic structures,MnO2 is useful as a molecular sieve,26a catalyst,27and an electrode material in batteries22as well as in supercapacitors.9-21Because these structures differ in the way MnO6octahedra are inter-linked,they possess tunnels or interlayers with gaps of different magnitudes.Because capacitance properties are due to intercala-tion/deintercalation of protons or cations in MnO2,only the crystallographic structures,which possess sufficient gaps to accommodate these ions,are anticipated to be useful for capacitance studies.It is expected that the amount of alkali cations or protons intercalated/extracted into/from MnO2lattice and hence its SC largely depends on either the size of the tunnel or the interlayer separation between sheets of MnO6octahedra. MnO2with three different crystallographic forms(R, ,and γ)was prepared by the hydrothermal-electrochemical method, and lithium insertion behavior was studied.28,29R-andγ-MnO2 were prepared by the electrolysis of aqueous MnSO4solution containing various alkali and alkaline earth salts at various pH and potential values.It was found that the crystallographic structure of MnO2depends on the radius of the alkali or alkaline earth metal-ion,the pH,and the potential.30Brousse et al.studied the dependence of capacitance on surface area for various*Corresponding author.Tel:+91-80-22933183.Fax:+91-80-23600683.E-mail:muni@ipc.iisc.ernet.in.4406J.Phys.Chem.C2008,112,4406-441710.1021/jp7108785CCC:$40.75©2008American Chemical SocietyPublished on Web02/26/2008amorphous and crystalline samples of MnO 2.31On the basis of cyclic voltammetric data,SC values were calculated.The SC values obtained for δ-MnO 2were in the range of 80-110F g -1,which was slightly smaller than the values found for amorphous samples.The SC values obtained for -MnO 2(5F g -1),γ-MnO 2(30F g -1),and λ-MnO 2(70F g -1)were smaller than the values obtained for δ-MnO 2.31The present trend of research in many fields is to employ nanosize materials,which are expected to possess better properties than the micrometer-size materials.Studies on the capacitance properties of various crystallographic forms of MnO 2are scarce in the literature.31The intention of the present study is to prepare nanosize particles of R -, -,γ-,δ-,and λ-MnO 2samples and to evaluate their properties with a special interest in supercapacitor behavior.A comparison of the SC values of the various structures of MnO 2is made,and appropri-ate explanations for the variation of SC values are provided.2.Experimental SectionAll chemicals were of analytical grade,and they were used without further purification.MnSO 4‚H 2O,KMnO 4,Na 2SO 4,sodium dodecyl sulfate (SDS),and cyclohexanewere purchasedfrom Merck,n-butanol from SD Fine Chemicals,(NH 4)2S 2O 8from Ranbaxy,Mn(NO 3)2‚4H 2O from Fluka,and LiMn 2O 4from Aldrich.All solutions were prepared in doubly distilled (DD)water.Samples of MnO 2with different crystal structures were synthesized by the following procedures.2.1.Synthesis of R -MnO 2.Nanoparticles of R -MnO 2were synthesized by redox reaction between stoichiometric quantities of MnSO 4and KMnO 4in both aqueous medium 9and a microemulsion medium.15In a typical synthesis in aqueous medium,10mL of 0.1M KMnO 4solution was mixed with 10mL of 0.15M MnSO 4‚H 2O solution and stirred continuously for 6h.A dark-brown precipitate thus formed and was washed several times with DD water,centrifuged,and dried at 70°C in air for 12h.Details of the microemulsion method of synthesis of nanostructured MnO 2is reported elsewhere.15MnO 2samples obtained from aqueous and microemulsion routes are hereafter referred to as R -MnO 2and R -MnO 2(m),respectively.About 300mg of the product was synthesized in each batch.2.2.Synthesis of -MnO 2.Nanorods of -MnO 2were prepared by hydrothermal treatment of aqueous solution of Mn-(NO 3)2‚4H 2O.20Twenty-five milliliters of 0.5M Mn(NO 3)2‚4H 2O solution was loaded into a Teflon-lined stainless-steel autoclave (capacity:40mL)and heated at 190°C for 6h.The autoclave was cooled slowly to room temperature.A dark brown powder was formed.It was washed several times with DD water,centrifuged,and dried at 70°C in air for 12h.Because the amount of product obtained in a batch of synthesis (typically 20mg)was small,the synthesis was repeated several times to get sufficient quantity for the experiments.During this synthesis,it was noticed that a minor variation in temperature caused drastic variations in the properties of the product.After several experiments,the experimental conditions of hydrothermal synthesis were optimized.2.3.Synthesis of γ-MnO 2.Nanowires/nanorods of γ-MnO 2were prepared from MnSO 4using (NH 4)2S 2O 8as an oxidizing agent.21Stoichiometric amounts of MnSO 4‚H 2O and (NH 4)2S 2O 8were dissolved in DD water.They were mixed together and heated at 80°C for 4h.A dark-brown precipitate wasseparated,Figure 1.Crystal structures of R -, -,γ-,δ-,and λ-MnO 2.TABLE 1:Tunnel Size of Different Crystallographic Forms of MnO 234-36crystallographicformtunnel size/ÅR (1×1),(2×2) 1.89,4.6 (1×1)1.89γ(1×1),(1×2) 1.89,2.3δinterlayer distance7.0Figure 2.Powder XRD pattern of R -,R (m)-, -,γ-,δ-,and λ-MnO 2.The (hkl )planes are indicated.The data were recorded at a sweep rate of 0.5°min -1using Cu K R source.TABLE 2:Crystal Radius and Size of the Alkali Cation in Aqueous Solution 37alkali cationcrystal radius/Åin aqueous solution/ÅLi +0.66Na +0.954K + 1.333H +9Effect of Crystallographic Structure of MnO 2J.Phys.Chem.C,Vol.112,No.11,20084407washed,and dried at 70°C.About 3.8g of the product was synthesized in a batch.2.4.Synthesis of δ-MnO 2.Nanoplatelets of δ-MnO 2were prepared by following the same route of synthesis of R -MnO 2,but with double the stoichiometric amount of KMnO 4.The presence of excess K +ion stabilizes the 2D layered δ-structure of MnO 2.The quantity obtained was about 340mg.2.5.Synthesis of λ-MnO 2.λ-MnO 2was prepared by delithia-tion of LiMn 2O 4.32Spinel LiMn 2O 4powder was treated with 0.5M HCl at 25°C for 24h.About 500mg of the product was obtained in a batch.2.6.Characterization.Powder X-ray diffraction (PXRD)patterns of MnO 2were recorded using Philips XRD X’PERT PRO diffractometer using Cu K R radiation (λ)1.54178Å)as the source.The morphology of MnO 2was examined using an FEI scanning electron microscope (SEM)model SIRION and an FEI high-resolution transmission electron microscope (HR-TEM)model TECNAI F 30.The Brunauer -Emmett -Teller (BET)surface area and pore volume were measured by the nitrogen gas adsorption -desorption method at 77K using a Quantachrome surface area analyzer model Nova-1000.The pore size distribution was calculated by the Barrett -Jayner -Halenda (BJH)method using the desorption branch of the isotherm.Samples were heated at 120°C for 2h in air prior to surface property measurements.IR spectra were recorded using a Perkin-Elmer FT-IR spectrophotometer model Spectrum One,using KBr pellets.KBr and samples were heated at 80°C in vacuum overnight prior to measurements.Thermogravimetric analysis (TGA)was performed in the temperature range from ambient to 800°C in air at a heating rate of 10°C/min using a Perkin-Elmer thermal analyzer model Pyris Diamond TG/DTA.2.7.Electrochemical Measurements.Electrodes were pre-pared on high-purity battery-grade Ni foil (0.18mm thick)as the current collector.The Ni foil was polished with successive grades of emery,cleaned with detergent,washed copiously with DD water,rinsed with acetone,dried,and weighed.MnO 2(70wt %),acetylene black (20wt %),and polyvinylidene difluoride (10wt %)were ground in a mortar,and a few drops of 1-methyl-2-pyrrolidinone was added to form a syrup.It was coated on to the pretreated Ni foil (area of coating:2cm 2)and dried at 110°C under vacuum.Coating and drying steps were repeated to get the loading level of the active material close to 0.5mg cm -2.Finally,the electrodes were dried at 110°C under vacuum for 12h.A Sartorious balance model CP22D-OCE with 10µgFigure 3.SEM micrographs of R -,R (m)-,and -MnO 2.1and 2refer to different magnifications of a sample.4408J.Phys.Chem.C,Vol.112,No.11,2008Devaraj andMunichandraiahsensitivity was used for weighing the electrodes.A glass cell of capacity 70mL,which had provisions for introducing a MnO 2working electrode,Pt auxiliary electrodes,and a reference electrode,was employed for electrochemical studies.An aqueous solution of 0.1M Na 2SO 4was used as the electrolyte.A saturated calomel electrode (SCE)was used as the reference electrode,and potential values are reported against SCE.Electrochemical studies were carried out using a potentiostat -galvanostat EG&G model Versastat II or Solartron model SI 1287.All electrochemical experiments were carried out at 20(2°C.3.Results and DiscussionThe reactions involved in the synthesis of different crystal-lographic forms of MnO 2are listed below:We have shown recently that R -MnO 2prepared in a micro-emulsion medium (R -MnO 2(m))possesses electrochemical properties superior to those of the samples prepared in aqueous medium.15Some important results of R -MnO 2(m)are also included here for the purpose of comparison.3.1.XRD Studies.The structural frame work of MnO 2consists of basic MnO 6octahedra units,which are linked in different ways to produce different crystallographic forms.22The different ways of sharing the vertices and edges of MnO 6octahedra units lead to the building of 1D,2D,and 3D tunnel structures.33The different crystallographic forms are described by the size of the tunnel formed with the number ofoctahedraFigure 4.SEM micrographs of γ-,δ-,and λ-MnO 2.1and 2refer to different magnifications of a sample.3MnSO 4+2KMnO 4+2H 2O f 5R -MnO 2+K 2SO 4+2H 2SO 4(1)Mn(NO 3)2+1/2O 2+H 2O f -MnO 2+2HNO 3(2)MnSO 4+(NH 4)2S 2O 8+2H 2O f γ-MnO 2+(NH 4)2SO 4+2H 2SO 4(3)3MnSO 4+2KMnO 4(excess)+2H 2O f 5δ-MnO 2+K 2SO 4+2H 2SO 4(4)2LiMn 2O 4+4HCl f LiCl +3λ-MnO 2+MnCl 2+2H 2O (5)Effect of Crystallographic Structure of MnO 2J.Phys.Chem.C,Vol.112,No.11,20084409subunits (n ×m ).The structures are shown schematically in Figure 1,and the type of tunnel formed as well as the size of tunnels are presented in Table 1.34-36The structure of R -MnO 2(Figure 1R )consists of double chains of edge-sharing MnO 6octahedra,which are linked at corners to form 1D (2×2)and (1×1)tunnels that extend in a direction parallel to the c axis of the tetragonal unit cell.The size of the (2×2)tunnel is ∼4.6Å,which is suitable for insertion/extraction of alkali cations (Table 2).34,37A small amount of cations such as Li +,Na +,K +,NH 4+,Ba 2+,or H 3O +is required to stabilize the (2×2)tunnels in the formation of R -MnO 2.34 -MnO 2(Figure 1 )is composed of single strands of edge-sharing MnO6Figure 5.TEM image (R 1),HRTEM image (R 2),and bright-field (R 3)and dark-field (R 4)TEM image of R -MnO 2.SAD pattern is given as an inset in R 1.Also shown are TEM images at different magnifications (R (m)1,R (m)2,and R (m)3),HRTEM image (R (m)4)of R -MnO 2(m).SAD pattern is given as an inset in R (m)2.4410J.Phys.Chem.C,Vol.112,No.11,2008Devaraj andMunichandraiahoctahedra to form a 1D (1×1)tunnel.Because of the narrow (1×1)tunnel of size (∼1.89Å),35 -MnO 2cannot accom-modate cations.22The structure of γ-MnO 2(Figure 1γ)is random intergrowth of ramsdellite (1×2)and pyrolusite (1×1)domains.38This intergrowth structure can be described in terms of De Wolff disorder and microtwinning.38δ-MnO 2(Figure 1δ)is a 2D layered structure with an interlayer separation of ∼7Å.36It has a significant amount of water and stabilizing cations such as Na +or K +between the sheets of MnO 6octahedra.λ-MnO 2(Figure 1λ)is a 3D spinel structure.32Powder XRD patterns of MnO 2samples are shown in Figure 2.Although the pattern of samples marked R and R (m)exhibitFigure 6.TEM images ( 1, 2),HRTEM image of a single nanorod ( 3),and the corresponding FFT pattern ( 4)of -MnO 2.Also shown are TEM images at different magnifications (γ1,γ2),HRTEM image (γ3),and the corresponding FFT pattern (γ4)of γ-MnO 2.SAD pattern is given as an inset in γ2.Effect of Crystallographic Structure of MnO 2J.Phys.Chem.C,Vol.112,No.11,20084411fluorescence,broad peaks at2θ)11.6and37.3°for R and at 2θ)10.8,37.0,41.7,and65.5°for R(m)are clearly present. It is thus inferred that these samples are in a poorly crystalline state with a short-range R-crystallographic form(JCPDS no. 44-0141).The XRD patterns marked andγ(Figure2)confirm the formation of -(JCPDS no.24-0735)andγ-(JCPDS no. 14-0644)crystallographic forms of MnO2,respectively.Broad peaks at2θ)12.2,24.8,37.0,and65.4°in the pattern marked δ(Figure2)correspond toδ-MnO2(JCPDS no.18-0802),and it is also considered to be in a poorly crystalline phase.Unlikethe above patterns,the diffraction pattern markedλin Figure2 consists of clear peaks,suggesting that this sample possesses a long-range crystalline order.This pattern was indexed to cubic symmetry with space group Fd3m(no.227)using the Appleman program,and the lattice constants were calculated.The lattice constants obtained are a)b)c)8.03Å,and these values are in good agreement with the reported data for the pure phase ofλ-MnO2(JCPDS no.44-0992).323.2.SEM and TEM Studies.SEM images of R-MnO2,R-MnO2(m),and -MnO2(two magnifications for each)are shown in Figure3.R-MnO2and R-MnO2(m)are composed of spherical aggregates of nanoparticles without clear interparticle boundaries(Figure3R1,R2,R(m)1,and R(m)2).Hydrothermal treatment of the aqueous Mn(NO3)2solution yields1D nanorods of -MnO2(Figure3 1and 2),which are about50nm in diameter and several micrometers in length.Adjacent nanorods are fused to each other.SEM images ofγ-,δ-,andλ-MnO2are presented in Figure 4in two magnifications for each.The morphology ofγ-MnO2 consists of spherical brushes with straight and radially grown nanorods.Several nanorods of30-50nm in diameter and a few micrometers in length assemble together to form spherical brushes.δ-MnO2(Figure4)consists of spherical agglomerates made of interlocked short fibers of∼10-20nm in diameter. The particles ofλ-MnO2(Figure4)exhibit random shapes with sizes varying from a few tens of nanometers to a few micrometers.TEM images of R-MnO2and R-MnO2(m)are presented in Figure5.The TEM image(Figure5R1)shows that R-MnO2 consists of agglomerated particles.A selected area diffraction (SAD)pattern is shown in the inset of Figure5R1.It is seen that a couple of weak rings corresponding to the crystal planes of R-MnO2are evolved,indicating the poor crystalline nature of the sample.The HRTEM image(Figure5R2)indicates the crystalline nature of the sample.The bright-field and corre-sponding dark-field TEM images of R-MnO2(Figure5R3and R4)suggest that several nanoparticles of less than5nm are agglomerated.It seen in Figure5R(m)1,R(m)2,and R(m)3that R-MnO2-(m)has a hexagonal shape of∼50nm size.The SAD pattern is shown as the inset to Figure5R(m)2.It is seen that rings corresponding to crystal planes are absent.The spotty diffraction pattern suggests that the nanoparticles of MnO2obtained from microemulsion route possess single-crystal character.The HR-TEM image(Figure5R(m)4)shows the interplanar distance to be2.392Å,which agrees well with separation between the[211] planes of R-MnO2.Shown in Figure6 1and 2are nanorods of -MnO2,which are20-50nm in diameter and several micrometers in length. In the HRTEM(Figure6 3),lattice fringes are clearly seen. The interplanar distance is0.311nm,which agrees well with the separation between the[110]planes of -MnO2.The corresponding FFT pattern(Figure6 4)displays spot lines perpendicular to the lattice fringes of Figure6 3,suggesting the crystalline nature of -MnO2.Furthermore,the length of the nanorod extends along the[110]direction.The TEM images shown in Figure6γ1andγ2suggest that nanorods ofγ-MnO2grow in a random fashion.The SAD pattern shown as inset in Figure6γ2reveals that rings and spots corresponding to crystal planes ofγ-MnO2are better evolved compared to R-MnO2,which is in agreement with the XRD results(Figure2).It is seen in the HRTEM image(Figure6γ3) that several nanowires of less than1nm are self-assembled to form nanorods.The interplanar distance calculated from the lattice fringes of HRTEM is0.212nm,which corresponds to separation of the[200]ttice fringes are inclined at about 60°toward the self-assembled nanowires.It is also seen in the HRTEM that nanorods exhibit better crystalline character at the center of the rod than the outer part.The FFT pattern(Figure 6γ4)corresponding to the HRTEM image ofγ-MnO2shows spot lines perpendicular to lattice fringes confirming the crystalline nature and also indicating that the nanorod extends in the[200]direction.TEM images ofδ-MnO2(Figure7δ1,δ2,andδ3)show that nanofibers with thicknesses less than10nm are agglomer-ated to form interconnected spherical structures ofδ-MnO2.The SAD pattern shown as inset in Figure7δ1supports the partial crystalline nature ofδ-MnO2inferred from the powder XRD pattern.The HRTEM image(Figure7δ4)indicates the crystal-line nature of the sample.TEM images ofλ-MnO2(Figure7λ1andλ2)suggest that the particles grow in different shapes and the adjacent particles fuse to each other.Spots evolved in the FFT pattern(Figure 7λ3)are indexed,and they confirm the highly crystalline nature ofλ-MnO2.Energy-dispersive analysis of the X-ray(EDAX) spectrum shown in Figure7λ4indicates the presence of manganese and oxygen.3.3.Porosity Measurements.Nitrogen adsorption-desorp-tion isotherms for MnO2samples were measured(see Supporting Information,Figure S1).The isotherms of R-,R(m)-,γ-,and δ-MnO2belong to type IV,which indicates the mesoporous nature of the samples with an hysteresis loop.Alternatively, the isotherm ofλ-MnO2belongs to type II,which is a characteristic feature of nonporous solids.39The specific surface area,total pore volume,and average pore diameter for all crystallographic forms of MnO2are listed in Table3.Although R-MnO2and R-MnO2(m)exhibit the same type of adsorption-desorption isotherm,their surface area and pore size distribution are different.The specific surface area of123m2g-1and total pore volume of0.25cm3Å-1g-1obtained for R-MnO2(m)are greater than the specific surface area of17.3m2g-1and pore volume of0.037cm3Å-1g-1obtained for R-MnO2.These differences indicate that R-MnO2(m)is more porous thanR-MnO2,and,hence,it is anticipated that R-MnO2(m)possesses higher electrochemical activity.Lower values of specific surface area and total pore volume are observed forγ-MnO2compared to R-MnO2(m).A high average pore diameter of129Åobtained forδ-MnO2is TABLE3:Specific Surface Area and Total Pore Volume of Polymorphic MnO2crystallographicformspecificsurface area(m2g-1)totalpore volume(cc/Å/g)averagepore diameter(Å) R17.290.0367585.020R(m)123.390.2481180.431γ31.560.0600676.112δ20.930.06750129.014λ 5.210.0087867.4514412J.Phys.Chem.C,Vol.112,No.11,2008Devaraj and Munichandraiahattributed to the wide interlayer separation.The lowest values of specific surface area (5.2m 2g -1)and total pore volume (0.0088cm 3Å-1g -1)are obtained for λ-MnO 2.It is inferred from the adsorption isotherm and Table 3that λ-MnO 2is the least porous among all samples.3.4.Vibrational Spectroscopic Studies.In IR spectra of MnO 2samples (see Supporting Information,Figure S2),a broad band around 400-700cm -1observed for all crystallographic forms of MnO 2is ascribed to Mn -O bending vibration.A broad band around 3400cm -1and a weak band around 1630cm -1observed for R -,R (m)-,γ-,and δ-MnO 2are attributed to stretching and bending vibrations of H -O -H,respectively.40Bands corresponding to vibrations of water molecules are not observed for -and λ-MnO 2,suggesting that these phases do not contain water.This is in agreement with the literature report that -and λ-MnO 2do not contain lattice water.22,32Figure 7.TEM images at different magnifications (δ1,δ2,and δ3)and HRTEM image (δ4)of δ-MnO 2.SAD pattern in given as an inset in δ1.Also shown are TEM images at different magnifications (λ1,λ2),FFT pattern (λ3),and EDAX spectrum (λ4)of λ-MnO 2.Effect of Crystallographic Structure of MnO 2J.Phys.Chem.C,Vol.112,No.11,200844133.5.Thermogravimetric Analysis.TGA thermograms of different crystallographic forms of MnO 2were recorded (see Supporting Information,Figure S3).Progressive weight loss from room temperature to 500°C is observed for R -,R (m)-,γ-,and δ-MnO 2samples.This is due to removal of water.13Weight loss is not observed in the case of -and λ-MnO 2samples because of the absence of water in these phases.22,32At around 550°C,a sudden weight loss is observed for all samples except for δ-MnO 2.This weight loss corresponds to the transformation of MnO 2to Mn 2O 3.41As δ-MnO 2prepared in the presence of excess of K +ions,these ions present between the layers of δ-MnO 2prevent the conversion of MnO 2to Mn 2O 3.The weight loss corresponding to this process is sharp in the case of -MnO 2as it has very narrow (1×1)tunnel in which no stabilizing ions are present.22The weight loss is much less (<2wt %)in the case of R -MnO 2because the stabilizing cations present at low concentration in its (2×2)tunnels prevent the transformation to a large extent.Weight loss values of about 2and 6wt %are observed for R -and R -MnO 2(m),respectively.This difference is ascribed to different amounts of K +ions present in their (2×2)tunnels.All crystallographic forms of MnO 2were annealed in air for 3h at various temperatures ranging from ambient to 800°C at intervals of 200°C,and powder XRD patterns were recorded (not shown).Conversion of MnO 2to Mn 2O 3is observed for all samples annealed at g 400°C except for δ-MnO 2,thus supporting the analysis of TGA data.3.6.Electrochemical Studies.There are two mechanisms proposed for charge storage in MnO 2.The first mechanism involves intercalation/extraction of protons (H 3O +)or alkali cations such as Li +,Na +,K +,and so forth into the bulk of oxide particles with concomitant reduction/oxidation of the Mn ion.10,23The second mechanism is a surface process,which involves the adsorption/desorption of alkali cations.17Although the bulk process (reaction 6)is anticipated to occur in crystalline samples of MnO 2,the surface process (reaction 7)occurs in amorphous samples.24Electrodes,which were fabricated with different crystal-lographic forms of MnO 2,were subjected to electrochemical studies in aqueous 0.1M Na 2SO 4electrolyte.Cyclic voltam-mograms recorded between 0and 1.0V at a sweep rate of 20mV s -1for all electrodes are shown in Figure 8.All voltam-mograms are nearly rectangular in shape.The rectangular shape of the voltammogram is a fingerprint for capacitance behavior.1-3Among all samples,the highest current density is obtained for R -MnO 2(m)(Figure 8),which is attributed to the higher porosity and greater surface area in relation to the rest of the samples.The voltammograms of R -and δ-MnO 2electrodes nearly overlap,suggesting that the SC values of R -and δ-MnO 2are comparable.The voltammetric current of the γ-MnO 2electrode (Figure 8)is lower than the currents of the R -,R (m)-,and δ-MnO 2electrodes.There is an increase in current near 0and also at 1V,suggesting that the overpotentials for the hydrogen evolution reaction (HER)as well as the oxygen evolution reaction (OER)are lower for γ-MnO 2.The current values(Figure 8)for the -and λ-MnO 2electrodes are very low,suggesting that the capacitance values of these samples are very small.Thus,the SC values of MnO 2samples qualitatively decrease in the following order:R (m)>R =δ>γ>λ> .Quantitatively,the SC values were evaluated from galvanostatic charge -discharge cycling as described below.The electrodes were subjected to galvanostatic charge -discharge cycling between 0and 1.0V in aqueous 0.1M Na 2-SO 4electrolyte at several current densities.The variations of potential with time during the first few charge -discharge cycles at a current density of 0.5mA cm -2are shown in Figure 9.Linear variation of potential during both charging and discharg-ing processes are observed for all MnO 2electrodes.The linear variation of potential during charging and discharging processes is another criterion for capacitance behavior of a material in addition to exhibiting rectangular voltammograms.1The dura-tions of charging and discharging are almost equal for each electrode,implying high columbic efficiency of charge -discharge cycling.However,the durations of charge and discharge cycles are different for different crystallographic forms of MnO 2,suggesting that the SC values are different similar to the observation made from cyclic voltammograms (Figure 8).The SC values were calculated from charge -discharge cycles using the following equationwhere,I is the discharge (or charge)current,t is the discharge (or charge)time,∆E ()1.0V)is the potential window of cycling,and m is the mass of MnO 2.The discharge SC values for all electrodes are presented in Figure 10.The variation of SC values follows the order R (m)>R =δ>γ>λ> .The SC values are 240F g -1for R -MnO 2and 236F g -1for δ-MnO 2.Alternatively,they are as low as 9F g -1for -MnO 2and 21F g -1for λ-MnO 2.The SC values are generally expected to follow the trend of surface area if capacitance is due to double-layer charging or adsorption of cations on the surface of active material.In recent studies,it is shown that the surface process is dominant in the amorphous sample of MnO 2.24Because all samples of MnO 2prepared in the present study are in the crystalline or poorly crystalline state of various structures,the low values of SC obtained are not due to the amorphous nature of the samples.In fact,λ-MnO 2has greater crystallinity than the rest of the samples (Figure 2)because of its larger particle size (Figure 4),but its SC is low.It is inferred that SC values largely depend on crystal structure and not on surface area while making comparisons among various structures (within thesameFigure 8.Cyclic voltammograms of R -,R (m)-, -,γ-,δ-,and λ-MnO 2recorded between 0and 1.0V vs SCE in aqueous 0.1M Na 2SO 4at a sweep rate of 20mV s -1.SC )It /(∆Em )(8)MnO 2+M ++e -h MnOOM (M +)Li +,Na +,K +,or H 3O +)(6)(MnO 2)surface +M ++e -h (MnOOM)surface (M +)Li +,Na +,K +,or H 3O +)(7)4414J.Phys.Chem.C,Vol.112,No.11,2008Devaraj andMunichandraiah。

《固体电解质材料》课程教学大纲课程代码：ABCL0534课程中文名称:固体电解质材料课程英文名称：Solid electrolyte课程性质：专业选修课程学分数：1.5课程学时数：24授课对象：新能源材料与器件本课程的前导课程：固体物理，电化学原理一、课程简介本课程为新能源材料与器件专业选修课，主要介绍了固体电解质的理论;宏观证据液体的性质;结构模型；动力学模型；晶体结构和快速的离子导电性；间质性运动在体心立方结构；和材料与萤石和反萤石结构。

的超离子导体的衍射研究都包括在内。

以离子导电性的缺陷和障碍，重要意义进行了讨论。

描述了传输机制和晶格缺陷。

扩散和离子电导率方程的研究呈现。

二、教学基本内容和要求本课程主要包括固体电解质的定义及分类、基本物理过程及现象。

结构模型;动力学模型;晶体结构和快速的离子导电性;间质性运动在体心立方结构;和材料与萤石和反萤石结构。

固体电解质问题的计算机模拟、电池、超导、燃料电池、介电陶瓷领域的应用，了解固体电解质的制备、表征、测量、分析的基本方法。

通过教学的各个环节使学生达到各章中所提的基本要求。

第一章、晶体结构课程教学内容：晶体的宏观特征、晶体的微观结构、晶向和晶面、晶体的宏观对称性、倒易点阵、晶体衍射简介，准晶，布里渊区。

第二章、晶体的结合课程教学内容：离子键和离子晶体、共价键和共价晶体、金属键和金属晶体、分子晶体、氢键晶体和混合型晶体、晶体结合的普遍特性第三章、晶格振动课程教学内容：一维布喇菲晶格、一维双原子链、能量量子化与声子、晶体的热学性质、非谐效应第四章晶体缺陷课程教学内容：晶体缺陷的分类、点缺陷、晶体中的扩散、离子晶体的点缺陷及导电性、位错、面缺陷及其它缺陷、合金与相图第五章、金属自由电子论。

文章编号：１００１－９７３１（２０１６）０７－０７１３０－０５双钙钛矿氧化物Ｓｒ２ＦｅＭｏＯ６的微结构及磁性能＊王玉平１，２，杨新伟２，相宇博２，刘雯慧２，李金兰２，胡艳春２（１．新乡学院物理与电子工程学院，河南新乡４５３０００；２．河南师范大学物理与电子工程学院，河南新乡４５３００７）摘　要：　采用传统高温固相反应法和溶胶－凝胶法制备了样品Ｓｒ２ＦｅＭｏＯ６，分别记为１和２＃样品。

Ｘ射线衍射结果表明两种方法制备的样品均为单相，四方晶系，空间群为Ｉ４／ｍ。

在烧结温度和烧结时间等同的条件下，２＃样品的Ｆｅ／Ｍｏ有序度比１＃样品的有序度要高，溶胶－凝胶法更易影响ＦｅＯ６八面体结构，且该方法提升了ＦｅＯ６八面体的对称性。

１和２＃样品在３００Ｋ温度下的单胞磁矩分别为１．８８和２．１７μＢ，热扰动和反位缺陷是影响单胞磁矩的重要因素。

关键词：　Ｘ射线衍射；扫描电镜；晶体结构；磁性材料中图分类号：　ＴＭ２０５文献标识码：Ａ　ＤＯＩ：１０．３９６９／ｊ．ｉｓｓｎ．１００１－９７３１．２０１６．０７．０２４０　引　言钙钛矿型过渡族金属氧化物因其具有特殊的结构和多种化合价等特征在众多氧化物材料中占据重要地位。

多年来，科研人员对其进行了广泛研究。

其中双钙钛矿氧化物具有独特的结构，它们的电学和磁学性质也十分奇特，使得双钙钛矿氧化物在磁传感器、磁存储器件等方面具有很好的应用前景［１－４］。

１９９８年日本科学家Ｋ．Ｋｏｂａｙａｓｈｉ等发现双钙钛矿型化合物Ｓｒ２ＦｅＭｏＯ６（ＳＦＭＯ）在３００Ｋ（７Ｔ）时高达１０％的遂穿型磁电阻效应，而且它的居里温度在室温之上（约４２０Ｋ），自发现以后受到科研工作者的广泛关注［５］。

Ｓｒ２ＦｅＭｏＯ６属于典型的双钙钛矿型Ａ２ＢＢ′Ｏ６结构。

在理想Ｓｒ２ＦｅＭｏＯ６结构中，Ｆｅ３＋、Ｍｏ５＋分别有序地占据Ｂ和Ｂ′位置，呈ＮａＣｌ型结构相间排列。

在实际Ｓｒ２ＦｅＭｏＯ６结构中，由于Ｆｅ３＋、Ｍｏ５＋的离子半径差别为０．００３５ｎｍ［６］，电荷差别等于２，因此有部分Ｆｅ３＋占据Ｂ′位置，同时有相同量的Ｍｏ５＋离子占据Ｂ位置，称之为反位缺陷。

晶面选择性生长对球形氢氧化镍形貌及电化学活性的影响唐俊杰;刘燕;田磊;张丽丽;王东兴;张廷安【摘要】在相同的物理化学条件、不同晶化时间的条件下,采用化学沉淀法制备球形氢氧化镍晶体并应用SEM技术分别考察制得样品的形貌.研究表明:在相同的物理化学条件下,随着晶化时间的增加,样品的微观形貌由不规则状晶体变为完整的球状晶体.结合XRD表征结果分析得出:(001)晶面在晶化时间达到3h时生长到了一个稳定的状态,并不随着晶化时间的增加而有明显的变化,但(100)与(101)晶面随晶化时间的增加继续生长,当晶化时间达到12h时氢氧化镍的相对结晶度最大,(100)与(101)衍射峰强度高且峰形尖锐,说明氢氧化镍晶体的结构规整性增强.本文还讨论了氢氧化镍生长结晶过程中晶面选择性生长对晶体形貌及电化学性能的影响.【期刊名称】《无机化学学报》【年(卷),期】2017(033)002【总页数】7页(P354-360)【关键词】球形氢氧化镍;晶面;衍射峰;相对结晶度【作者】唐俊杰;刘燕;田磊;张丽丽;王东兴;张廷安【作者单位】东北大学多金属共生矿生态化冶金教育部重点实验室,沈阳 110819;东北大学多金属共生矿生态化冶金教育部重点实验室,沈阳 110819;东北大学多金属共生矿生态化冶金教育部重点实验室,沈阳 110819;东北大学多金属共生矿生态化冶金教育部重点实验室,沈阳 110819;东北大学多金属共生矿生态化冶金教育部重点实验室,沈阳 110819;东北大学多金属共生矿生态化冶金教育部重点实验室,沈阳 110819【正文语种】中文【中图分类】O614.81+3Spherical Ni(OH)2is one of the most important battery material which has been widely applied in electroplating,storage battery,spaceflight and so on. Although spherical Ni(OH)2has been industrially produced in large-scale,the structures in different batches always appear different because the growthmechanism of Ni(OH)2crystal has not been researched thoroughly.Wangsummarizedthemechanismof crystal growth defect in detail.He concluded that the sub-step theory could be applied to explain the crystal growth mechanisms of both solution and sublimation processes[1-2].Ma et al.measured and estimated crystal plane growth kinetics.They presented a framework which integrated the various components to achieve the ultimate objective of model-based closed-loop control of the CShD[3-4].Huo et al.proposed a synthetic imageanalysisstrategyforin-situcrystalsize measurement and shape identification for monitoring crystallization processes,based on a real-time imaging system[5-7].X-ray diffraction plays a key role in the analysis of the crystallization process.Ramesh used XRD to determine the thermal decomposition ofNi(OH)2. Further,he concluded that the decomposition mechanism mainly depended on the preparative conditions[8]. Deschamp presented that continuing advances in all phases of a crystallographic study have expanded the ranges of samples which can be analyzed by X-raycrystallography,including larger molecules,smaller or weakly diffracting crystals,and twinned crystals[9-13]. Xu et ed X-ray diffraction to analyze the growth and phase transformation of metastable β-HgI2M[14-15].The crystallization factors of spherical Ni(OH)2on macroscopic perspective were investigated,including temperature,pH(ammonia content),reactant supersaturation,mixing intensity and paddle type as well as many other aspects[16].However,the factors of microcosmic perspective are rarely studied.Therefore,in this study the spherical Ni(OH)2was synthesized by chemical precipitation method with different aging times under the same physical and chemical conditions. The morphologies and the relative crystallinities of the spherical Ni(OH)2were characterized by SEM and XRD.It is found that the crystal growth direction selectivity has a great influence on morphologies and crystallization of spherical Ni(OH)2.This work provides the rules of the growth of crystal plane according to the crystallization of spherical Ni(OH)2.It also offers a theoretical basis and experiences for reducing the structure differences of Ni(OH)2industrial products.1.1 Preparation of spherical Ni(OH)2According to the industrial process of spherical Ni(OH)2preparation,the chemical precipitation method was applied to the preparation of spherical Ni(OH)2. The reaction temperature of the system was controlled within 50～57℃,and the pH value was controlled within 11～11.7.A certain concentration of nickel sulfatesolution,ammoniaandsodiumhydroxidesolution in a certain proportion was filled to the bottom of thereactor.Under the same physical and chemical conditions,the samples prepared with the aging times of 3,6,9 and 12 h,and then the samples were filtered out for measurement.1.2 InstrumentsThe scanning electron microscope(SEM)used in this experiment wasSU8010 produced by Japan Hitachi Company.The X-ray diffractometer used in this experiment was D8 Advance X Bruker ray analyzer produced by German Bruker Company.Light tube type was Cu target(Kα,λ=0.154 06 nm).The scan range was 10°～90°with scanning speed of 2°·min-1. The electrochemical workstation used in this experiment was Biologic vsp300 produced by France Claix Company.2.1 SEM analysisUnder the same physical and chemical conditions, when the aging time is 3 h,the Ni(OH)2particles form irregular crystals with different sizes,the surface structure of the crystals is composed of the acicular micro-crystals,as shown in Fig.1.It is because in the early reaction,theNi(OH)2particles form flocculent precipitatesandmicro-crystalsunderthestrong agglomeration.When the aging time is 6 h,the Ni(OH)2particles form many agglomerate crystals with similar sizes and shapes,the surface structure of these crystals is composed of many well-defined acicular microcrystals,as shown in Fig.2.It is because the crystalnucleuses gradually form and crystals gradually grow withtheincreaseoftheagingtimeundertheagglomeration.The flocculent precipitates gradually fill the gaps of agglomerated particles and the quasi spherical crystals are formed.Due to the growth of layers is perpendicular to the spherical surface in the crystallizationprocessofspherical Ni(OH)2,the surface of these quasi spherical crystals is formed by the well-defined acicular micro-crystals. When the aging time is 9 h,the Ni(OH)2particles form spherical crystals with similar sizes,and the surface structure of these crystals is composed of many grainy micro-crystals,as shown in Fig.3.It is because the precipitates fill the gaps of agglomerated particles and the more compact spherical crystals are formed.Due to the surface of these crystals is attached of grainy micro-crystals,the precipitates continue to adhere to the surface of the crystals and the crystals grow slowly under the agglomeration.When the aging time is 12 h,the Ni(OH)2particles form many complete spherical crystals with a uniform size,the surface structure of these crystals is composed of many micro-crystals with clear stripes,as shown in Fig.4.It is because the agglomerated particles combine more compact,and the surface structure of these crystals grows more integrated.2.2 XRD analysisThe XRD patterns of the samples with different aging times are shown in Fig.5.It can be found that the main diffraction peaks are nickel hydroxide,and other crystal items are not observed.When the aging time is 12 h,the characteristic peaks in the XRD patterns are highest,the FWHM is minimum,and the relativecrystallinityisthebest.Iftherelative crystallinity of the samples prepared at 12 h is treated as 100%,according toamorphization formula A=[1-U0Ix/(UxI0)]×100%,the calculation of each samples is plotted in a linear graph,as shown in Fig.6.Moreover, the mathe-matical relationship between aging time and amor-phization is A=-0.007 7T2+0.037 1T+0.653 2, which can be obtained according to Fig.6.It can be found that the FWHM(001)and the peak intensityon(001)diffraction peak are basically the same with the increase of the aging time from Fig.5. Which means that the growth of(001)crystal plane reaches a steady state when the aging time is 3 h. However,theFWHM(100)and FWHM(101)decrease while the peak intensities are enhanced.Which means that (100)crystal plane and(101)crystal plane continue to grow with the increase of the aging time.SEM images show that when the aging time is increased from 3 to 12 h,the morphology of Ni(OH)2crystals changes from irregular crystals to complete spherical crystals,it can be concluded that the growth of(001)crystal face has not a greater influence on the morphology of Ni(OH)2crystals,but the growths of(100)crystal plane and(101)crystal plane have a greater influence on the morphology.And the FWHM(100)and FWHM(101)of Ni(OH)2crystals with different aging times are given in Table 1.According to Table 1,the selectivity of crystal growth directionson(100)crystal plane and(101) crystal plane with differentagingtimescanbe calculated by Scherrer formula D=Kλ/(Bcosθ),and the results are given in Table 2.From Table 2 it can be seenthatthegrowthrateof(101)crystalplaneis greater than(100)crystal plane when the aging time is 6～9 h, and the growth rate of(100)crystal plane is greater than(101)crystal plane when theaging time is 9～12 h.It shows from SEM images Fig.2～Fig.3 that when the aging time is increased from 6 to 9 h,the morphologies of Ni(OH)2crystals change from agglomerate crystals to spherical crystals.This means that the growth of(101)crystal plane has a greater influence on the sphericitythan(100)crystal plane.SEM images Fig.3～Fig.4 show that when the aging time is increased from 9 to 12 h,the surface structures of Ni(OH)2crystals change from grainy micro-crystals to striped micro-crystals.This means that the growth of(100) crystal plane has a greater influence on the surface structure than(101)crystal plane.2.3 Performance characterization Theelectrochemicalactivityisthebasic indicator of Ni(OH)2.TheNi(OH)2samples prepared at different aging times were compressed with carbon black and adhesive in proportion as 7∶2∶1 into sheet electrode.CV Scan was tested at the speed of 10 mA/ s in the range of 0～0.6 V,while the Hg/HgO was selected as the reference electrode.The CV curves are shown in Fig.7.According to Fig.7,it can be seenthatwiththeincreaseoftheagingtime,the electrochemically active specific surface area also increases.When the aging time is 12 h,the electrochemically active specific surface area and peak current reach the maximum,which shows the best electrochemicalactivity.Therefore,itcanbe determined that the aging time is proportional to the electrochemical activity of Ni(OH)2crystal.According to SEM analysis and CV analysis,the aging time has a influence on the morphology and electrochemical activity.Therefore,the relationshipbetween the morphology and electrochemical activity can be determined:the higher sphericity leads to the better electrochemical activity,and the surface structure of striped micro-crystals has a better electrochemical activity than the surface structure of grainy microcrystals. Bulk density is oneofthemostimportant electrochemical indices of spherical Ni(OH)2.The bulk density of spherical Ni(OH)2determines the compactness of Ni electrode,and then affects the specific capacity.The international standard GB 1482-84 was applied in this experiment.And the bulk densities of the samples with different aging times are given in Table 3.It can be seen that the bulk density increases with the increase of the agingtime,and it suggests that the aging time is proportional to the electrochemical activity of Ni(OH)2crystal,which is in agreement with CV analysis.Moreover,Fig.8 can lead to the mathematical relationship between the bulk density and the aging time:ds=0.174T0.938.(1)Under the same physical and chemical conditions,the sophericity and the relative crystallinity of Ni(OH)2particles are proportional to the aging time. The mathematical relationship between aging time and amorphization is A=-0.007 7T2+0.037 1T+0.653 2.(2)Under the same physical and chemical conditions,the growthof(101)crystal plane has a greater influence on the sphericity ofNi(OH)2crystal than(100) crystal plane and contrary to the surface structure.(3)Under the same physical and chemical conditions,the bulk densities increase with the increase of the aging time.The mathematical relationship between the bulk density and the aging time is ds=0.174T0.938.(4)The aging time is proportional to the electrochemical activity of spherical Ni(OH)2.【相关文献】[1]WANG Ji-Yang(王继洋).Physics(物理),2001,6:332-339[2]FENG Shi-Hong(冯世宏),JIA Tai-Xuan(贾太轩),DU Hui-Ling(杜慧玲),et al.Non-Ferrous Min.Metall.(有色矿冶), 2004,20(5):48-50[3]Ma C Y,Liu J J,Wang X Z.Particuology,2016,2:1-18[4]Lee C H,Lee C H.Korean J.Chem.Eng.,2005,22:712-716[5]Huo Y,Liu T,Liu H,et al.Chem.Eng.Sci.,2016:126-139[6]Bagheri G H,Bonadonna C,Manzella I,et al.Powder Technol., 2015,270:141-153[7]Borchsert C,Sundmacher K.Chem.Eng.Technol.,2011,34: 545-556[8]Ramesh T N.J.Phys.Chem.B,2009,113:13014-13017[9]Deschamps J R.Life Sci.,2010,86:585-589[10]Deschamps J R,George C.Trends Anal.Chem.,2003,22: 561-564[11]Cachau R E,Podjarny A D.J.Mol.Recognit.,2005,18:196-202[12]Wouters J,Ooms F.Curr.Pharm.Des.,2001,7:529-545[13]Blundell T L,Jhoti H,Abell C.Nat.Rev.Drug Discovery, 2002,1:45-54[14]XU Gang(许岗),LI Ying-Jun(李英俊),GU Zhi(谷智),et al. Chinese J.Inorg.Chem.(无机化学学报),2016,32(7):1135-1140[15]Su Q F,Shi W M,Li D M,et al.Nucl.Instrum.Methods Phys.Res.Sect.A,2011,659:299-301[16]TANG Jun-Jie(唐俊杰),LIU Yan(刘燕),TIAN Lei(田磊), et al.Chinese J.Inorg.Chem.(无机化学学报),2016,32(7): 1127-1134。