MnO2 机理

Charge Storage Mechanism of MnO2Electrode Used in Aqueous Electrochemical Capacitor

Mathieu Toupin,?Thierry Brousse,*,?,?and Daniel Be′langer*,?De′partement de Chimie,Universite′du Que′bec a`Montre′al,Case Postale8888, succursale Centre-Ville,Montre′al,Que′bec H3C3P8,Canada,and Laboratoire de Ge′nie des Mate′riaux,Ecole Polytechnique de l’Universite′de Nantes,La Chantrerie,

rue Christian Pauc,BP50609,44306Nantes Cedex3,France

Received March2,2004.Revised Manuscript Received June2,2004

The charge storage mechanism in MnO2electrode,used in aqueous electrolyte,was investigated by cyclic voltammetry and X-ray photoelectron spectroscopy.Thin MnO2films deposited on a platinum substrate and thick MnO2composite electrodes were used.First, the cyclic voltammetry data established that only a thin layer of MnO2is involved in the redox process and electrochemically active.Second,the X-ray photoelectron spectroscopy data revealed that the manganese oxidation state was varying from III to IV for the reduced and oxidized forms of thin film electrodes,respectively,during the charge/discharge process. The X-ray photoelectron spectroscopy data also show that Na+cations from the electrolyte were involved in the charge storage process of MnO2thin film electrodes.However,the Na/ Mn ratio for the reduced electrode was much lower than what was anticipated for charge compensation dominated by Na+,thus suggesting the involvement of protons in the pseudofaradaic mechanism.An important finding of this work is that,unlike thin film electrodes,no change of the manganese oxidation state was detected for a thicker composite electrode because only a very thin layer is involved in the charge storage process.

Introduction

Electrochemical supercapacitors are currently inves-tigated in various academic and industrial laboratories because they can be used as complementary charge storage devices to conventional batteries in various applications that require peak power pulses.1,2In these electrochemical supercapacitors,the energy being stored is either capacitive or pseudocapacitive in nature.The capacitive or nonfaradaic process is based on charge separation at the electrode/solution interface,whereas the pseudocapacitive process consists of faradaic redox reactions that occur within the active electrode materi-als.The most widely used active electrode materials are carbon,3,4conducting polymers,5,6and both noble7-9and transition-metal oxides.10-29

The main motivation for the use of transition-metal oxides lies in their low cost compared to noble metal oxides such as ruthenium7,8and iridium9oxides.The initial studies were performed on nickel oxide10and cobalt oxide11but more recently iron12-15and manga-nese oxides14,16-29were investigated.The research ef-forts focused on compounds providing high cyclability and capacitance.On the other hand,the charge storage mechanism of MnO2has not been investigated in detail. Until now,two mechanisms were proposed to explain the MnO2charge storage behavior.The first one implies the intercalation of protons(H+)or alkali metal cations (C+)such as Li+in the bulk of the material upon reduction followed by deintercalation upon oxidation.17

or

The second mechanism is based on the surface adsorption of electrolyte cations(C+)on MnO216 where C+)Na+,K+,Li+.This mechanism was proposed following the observation of significant difference of the cyclic voltammogram and the capacitance of MnO2in the presence of various metal alkali cations in the electrolyte.16It should be noticed that both proposed

*To whom correspondence should be addressed.E-mail: thierry.brousse@polytech.univ-nantes.fr(T.B.)and belanger.daniel@ uqam.ca(D.B.).

?Universite′du Que′bec a`Montre′al.

?Ecole Polytechnique de l’Universite′de Nantes.

(1)Conway,B.E.Electrochemical Supercapacitors,Scientific Fun-damentals and Technological applications;Kluwer Academic/Plenum Press:New York,1999.

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MnO

2

+H++e-S MnOOH(1)

MnO

2

+C++e-S MnOOC(2)

(MnO

2

)

surface

+C++e-S(MnO

2

-C+)

surface

(3)

3184Chem.Mater.2004,16,3184-3190

10.1021/cm049649j CCC:$27.50?2004American Chemical Society

Published on Web07/16/2004

mechanisms involved a redox reaction between the III and IV oxidation states of Mn.

The mechanism based on the solid-state diffusion of protons in the bulk of the material is similar to that proposed for RuO2.7However,only a limited fraction of the MnO2composite is electrochemically active,thus suggesting that the protonic diffusion in the bulk of the MnO2compound might not be as fast as in the case of RuO2.21Subsequently,the charge storage might only involved the surface atoms of the MnO2crystallites or a very thin layer.Then it might be plausible to assume that ions from the electrolyte would participate in the charge compensation process.On the other hand,the reported capacitance ranging between150and200F/g for composite electrode cannot be only associated to the formation of the classical double layer.21Hence,the nature of the charge storage mechanism must be pseudocapacitive.

This work aimed at getting a better understanding of the charge storage mechanism in manganese dioxide electrodes when cycled in aqueous electrolyte.The electrodes were characterized by cyclic voltammetry and X-ray photoelectron spectroscopy in order to determine a change of the manganese valence upon charge/ discharge.Additionally,the experimental results were used to determine whether the charge storage process was limited to the surface of the oxide or if it occurred inside the bulk of the material.

Experimental Section

Preparation of the MnO2Powder.The MnO2powder was synthesized by coprecipitation.21Briefly,KMnO4and MnSO4?H2O were mixed in a2:3molar ratio,leading to a dark brown precipitate.The amorphous nature of the as-synthesized MnO2powder was confirmed by the X-ray diffraction(XRD) spectrum(Figure SI1),which shows broad peaks related to a poorly crystallized compound.From chemical analysis,the stoichiometry for the powder was determined to be K0.02-MnO2H0.33,0.53H2O.Thereafter,the compound will be named “MnO2”despite that it does not reflect the exact composition of the sample.

Scanning electron micrographs revealed that the as-synthesized R-MnO2powder is made of spherical grains (Figure SI2).The length scale is systematically indicated as a white bar on the bottom left corner of the micrographs.A statistical analysis of the grain diameter performed over more than100particles yielded a Gaussian distribution centered at420nm with a standard deviation of190nm.Each grain seems to result from the agglomeration of smaller particles (Figure SI3).Using the geometric surface of spherical grains (420nm diameter assuming a density of4.8g/cm3)the specific surface was estimated to a value close to3m2/g.The specific surface area determined from BET measurements(160(3 m2/g)is larger than this value thus indicating that pores and voids exist inside the grains examined by scanning electron microscopy.

Preparation of the Electrodes.To investigate the influ-ence of both the thickness and the composition of the elec-trodes,thick film(≈100μm)and thin film(<5μm)electrodes were prepared.For the thick film samples,a composite was typically prepared by mixing80%of active powder,7.5%of graphite(Alfa Aesar),7.5%of acetylene black(Alfa Aesar),and 5%of PTFE(poly(tetrafluoroethylene),Dupont)in ethanol (Fisher).Then,cold rolling of the obtained paste resulted in a black shiny film,which was pressed in a ply of a stainless steel mesh(Alfa Aesar,200mesh)current collector under a pressure of9metric tons(see Figure SI4a for a photomicrograph of these electrodes).Typically,a2mg square piece of film was used for the electrode,referred to as“composite”electrodes from now on.

Alternatively,thin films were prepared by dispersing an appropriate amount of MnO2in a solution of polyvinylidene difluoride-hexafluoropropylene(copolymer PVdF-HFP,Ky-narflex)in N-methyl pyrolydinone(NMP,Fisher)to obtain a final concentration of1mg(MnO2)/mL with10%w/w of polymer.The dispersion was left in a ultrasonic bath for30 min.A platinum foil(1.5×0.5cm;thickness0.1mm;Alfa Aesar)was used as the substrate(and current collector)and coated with the MnO2slurry by adding5μL drops of the dispersion with a micropipet(Eppendorf)(see Figure SI4b for a photomicrograph of these electrodes).The electrode was dried in a oven at65°C for30min between each drop.Typically the area of platinum covered with the slurry was0.75cm×0.5cm.The mass of the deposited material was deduced by weighing the electrode before and after the coating.Thereafter, these electrodes will be referred to as“thin film”electrodes. However,this denomination is not totally correct since the “film”is most likely seen as aggregates of MnO2particles (thickness is less than2μm)on the platinum substrate(see Figure SI4b).

Electrochemical Measurements.The cyclic voltammetry and polarization experiments were carried out with a1470 multipotentiostat(Solartron,Mobrey)using the Corrware software(Scribner Associates,version2.6).A beaker type cell containing a0.1M Na2SO4electrolyte solution was used for all the electrochemical measurements.The cyclic voltammetry experiments were performed between0and0.9V vs Ag/AgCl (3M NaCl)at a scan rate of5mV/s.

The specific capacitance,C cv,was calculated using the voltammetric charge integrated from the cyclic voltammogram according to the following equation

where C cv is the specific capacitance(in F/g),Q is the charge (in C),?E is the potential window(in V),and m is the mass of active material(in g).

Surface Characterization of the Electrodes.After polarization,the electrodes were dried out in a vacuum oven at ambient temperature for1hour.The XPS studies were conducted with a VG Escalab220i-XL instrument equipped with a hemispherical analyzer and using an aluminum anode (monochromatic K R X-rays at1486.6eV)as a source(at12-14kV and10-20mA).The XPS spectra were analyzed and fitted using CasaXPS software(version2.2.27).The C1s region

(11)Lin,C.;Ritter,J.A.;Popov,B.N.J.Electrochem.Soc.1998, 145,4097.

(12)Wu,N.-L.;Wang,S.-Y.;Han,C.-Y.;Wu,D.-S.;Shiue,L.-R.J. Power Sources2003,113,173.

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(14)Brousse,T.;Be′langer,D.Electrochem.Solid-State Lett.2003, 6,A244.

(15)Brousse,T.;Delahaye,T.;Be′langer,D.In preparation.

(16)Lee,H.Y.;Goodenough,J.B.J.Solid State Chem.1999,144, 220.See also a more detailed version of this study in the following: Lee,H.Y.;Manivannan,V.;Goodenough,J.B.C.R.Acad.Sci.Paris 1999,t.2,Se′rie II c,565.

(17)Pang,S.C.;Anderson,M.A.;Chapman,T.W.J.Electrochem. Soc.2000,147,444.

(18)Lee,H.Y.;Kim,S.W.;Lee,H.Y.Electrochem.Solid-State Lett.

2001,4,A19.

(19)Hu,C.C.;Tsou,https://www.wendangku.net/doc/278773351.html,m.2002,4,105.

(20)Chin,S.F.;Pang,S.C.;Anderson,M.A.J.Electrochem.Soc. 2002,149,A379.

(21)Toupin,M.;Brousse,T.;Be′langer,D.Chem.Mater.2002,14, 3946.

(22)Brousse,T.;Toupin,M.;Be′langer,D.J.Electrochem.Soc.2004, 151,A614.

(23)Jiang,J.;Kucernak,A.Electrochim.Acta2002,47,2381.

(24)Hu,C.C.;Tsou,T.W.Electrochim.Acta2002,47,3523.

(25)Jeong,Y.U.;Manthiram,A.J.Electrochem.Soc.2002,149, A1419.

(26)Broughton,J.N.;Brett,M.J.Electrochem.Solid-State Lett. 2002,5,A279.

(27)Kim,H.;Popov,B.N.J.Electrochem.Soc.2003,150,D56.

(28)Hu,C.-C.;Wang,C.-C.J.Electrochem.Soc.2003,150,A1079.

(29)Chang,J.-K.;Tsai,W.-T.J.Electrochem.Soc.2003,150,A1333.C

cv

)

Q

?E×m

(4)

Charge Storage Mechanism of MnO2Electrode Chem.Mater.,Vol.16,No.16,20043185

was used as a reference for surface charging and was set at 284.9eV.A mixture of Gaussian (70%)and Lorentzian (30%)functions was used for the least-squares curve fitting proce-dure.

The manganese oxidation state was determined from the Mn 3s and O 1s core level spectra.The procedure used to analyze the Mn 3s spectra has been described previously.21,30,31In the case of the O 1s data,the average manganese oxidation state for the three electrodes can be computed from the intensities of the Mn -O -Mn and Mn -OH components ac-cording to

where S stands for signal of the different components of the O 1s spectra.Since all manganese atoms are bonded to an oxygen atom,the Mn -O -Mn signal should represent the contribution of two species:MnOOH and MnO 2.Hence,the XPS signal related to the Mn(IV)species can be computed by subtracting the contribution of the hydroxyl group (Mn -OH)from the Mn -O -Mn signal.Binding energies and manganese oxidation states of authentic samples can be found in Table 1of ref 30.

Results and Discussion

Electrochemical Behavior of the MnO 2Compos-ite Electrode.Figure 1A shows a typical cyclic volta-mmogram for a composite film electrode in 0.1M Na 2SO 4at a scan rate of 5mV/s.The cyclic voltammetry response when the negative and positive potential limits are restricted to 0and 0.9V,respectively,is character-istic of a pseudocapacitive electrode material,but it is not perfectly rectangular due to polarization resistance.This effect is noticeably more significant at the less positive potential limit compared to the positive limit,and this specific point will be discussed later.The cyclic voltammogram is similar to that previously reported for MnO 2-based composite electrode,and a capacitance of 150F/g can be computed for this electrode.14,21,22

XPS Surface Analysis of the Composite Elec-trodes.To observe the change in oxidation state of manganese when the electrode is cycled between 0and 0.9V and if ionic species are involved in the charge storage mechanism,the composite electrodes were characterized by X-ray photoelectron spectroscopy (XPS).Prior to the XPS measurements,the composite elec-trodes were polarized at 0or 0.9V until the charge passed was equal to the charge integrated from the cyclic voltammogram.The survey spectra presented in Figure 2for oxidized and reduced MnO 2-based compos-ite electrodes show Mn 2p (642eV),Mn 3s (84eV),and O 1s (530eV)peaks attributed to manganese dioxide.The C 1s (285and 293eV)peaks and F 1s (685eV)are associated with the presence of acetylene black,graph-ite,and PTFE.The two spectra are almost identical with the exception of the Na 1s peak that is almost absent for the oxidized composite electrodes (vide infra).

The Mn 3s,Mn 2p,and O 1s core level spectra can be used to assess the change in oxidation state of manga-nese for the oxidized and reduced MnO 2electrodes (see Experimental Section).The Mn 3s core level spectra should usually show a peak splitting and a doublet due to the parallel spin coupling of the 3s electron with the 3d electron during the photoelectron ejection.30,33,34The energy separation between the two peaks is related to the mean manganese oxidation state.Since a lower valence implies more electrons in the 3d orbital,more interaction can occur upon photoelectron ejection.Con-sequently,the energy separation between the two components of the Mn 3s multiplet will increase.30The inverse trend will be observed when the manganese valency increases.

The Mn 3s core level spectra were recorded (Figure SI5)for oxidized and reduced MnO 2-based composite electrodes,and the relevant data are included in Table 1.The data of Table 1revealed that the peak splitting of the doublet of the Mn 3s core level spectra is almost

(30)Chigane,M.;Ishikawa,M.J.Electrochem.Soc.2000,147,2246.(31)Chigane,M.;Ishikawa,M.;Izaki,M.J.Electrochem.Soc.2001,148,D96.

(32)Long,J.W.;Young,A.L.;Rolison D.R.J.Electrochem.Soc.2003,150,A1161.

(33)Moulder,J.F.;Strickle,W.F.,Sobol,P.E.;Bomben,K.D.Handbook of X-ray Photoelectron Spectroscopy ;Perkin-Elmer Corpora-tion:Physical Electronics Division:Eden Prairie,MN,1992.

(34)Briggs,D.;Seah,M.P.Practical Surface Analysis ,2nd ed,;John Wiley &Sons:1996;Volume

1.

Figure 1.Cyclic voltamograms in 0.1M Na 2SO 4at 5mV/s of (A)a composite electrode composed of 80%MnO 2,7.5%graphite,7.5%acetylene black,and 5%Teflon and (B)a 90%MnO 2and 10%PVdF -HFP thin film electrode supported on a Pt

foil.

Figure 2.XPS survey for an oxidized and a reduced composite and thin film electrodes.

Ox ?State )

(IV*(S Mn -O -Mn -S Mn -OH ))+(III*S Mn -OH )

S Mn -O -Mn

(5)

3186Chem.Mater.,Vol.16,No.16,2004Toupin et al.

the same for all the electrodes.This value close to 5.00eV is compared to 5.79,5.50,5.41,and 4.78eV for reference sample of MnO,Mn 3O 4,Mn 2O 3,and MnO 2,respectively.30Hence,the manganese oxidation state remained at about 3.5.Similar findings were obtained for composite electrodes polarized at more positive (1.25V)and more negative (-0.65V)potential.The absence of a change of the manganese oxidation state is puzzling in light of previous reports on electrodeposited MnO 230,31and birnessite MnO x ambigel films 32in aqueous elec-trolytes.Even when the XPS measurements were performed with a takeoff angle of 30°or 45°,in condi-tions where a thinner surface layer is probed,33,34attempts to observe a change of the manganese oxida-tion state failed.Then,it was suspected that the oxidation state of the electrode changed during the drying step and exposure to air.The measurement of the open circuit potential (OCP)for both reduced or oxidized electrodes,monitored before and after the drying step,revealed a drift of the OCP to an average potential of 0.45V following the drying step.This observation suggests that only the surface MnO 2may be involved in the redox pseudocapacitive reaction.In this case,the surface of the film could be brought back very close to the oxidation state of OCP conditions by a redox reaction driven by the chemical potential between the surface and the bulk of the material.

Electrochemical Behavior of the MnO 2Thin Film Electrode.To avoid this phenomenon,thin film electrodes were used to ensure that a more significant fraction of the MnO 2film would be involved in the electrochemical reaction during the oxidation and re-duction steps.This was accomplished by using MnO 2thin film supported on platinum electrodes as described in the Experimental Section.First,experiments were performed with electrodes of different film thickness to estimate the electrochemically active fraction of the MnO 2film.The mass and thickness were controlled by adding between one and five drops of a MnO 2-PVdF -HFP mixture with a drying step between each addition (see Table 2).Figure 1B shows a representative cyclic voltammogram for the MnO 2powder supported on platinum foil,which displays the characteristic capaci-tive behavior between 0and 0.9V.The specific capaci-tance of 1380F/g obtained for this electrode is close to the theoretical value of 1370F/g expected for a redox process involving one electron per manganese atom.The larger polarization of the Pt -MnO 2electrode relative to the composite electrode (Figure 1A),demonstrated by the more pronounced curvature of the cyclic volta-mmogram near the potential limits,is due to the absence of the conductive carbon in the thin film electrode.Table 2shows the variation of the voltam-metric charge measured for each electrode as a function of the MnO 2mass.For the thinner film (electrode A),all the MnO 2material is taking part in the electro-chemical redox process,during the cyclic voltammetry experiment performed at 5mV/s,since the Coulombic efficiency is about 100%.The Coulombic efficiency is calculated from the measured voltammetric charge of the cyclic voltammogram and the theoretical calculated charge by assuming the transfer of one electron per Mn atom and that the whole MnO 2mass is electrochemi-cally active.Table 2indicates that the Coulombic

Table 1.Data Obtained from the XPS Spectra

Mn 3s (eV)Mn 2p (eV)

O 1s (eV)c

thin film E (V)peak 1peak 2?eV d 3/2?BE Mn -O a oxidation state

Mn 3s/O 1s b

BE (eV)

area %oxidized 0.90

88.8884.10 4.78642.6112.8 4.0/4.0Mn -O -Mn 529.880.6Mn -OH 531.3 2.9H -O -H 532.416.5as-prepared 88.7283.80 4.92642.4112.7 3.6/3.7Mn -O -Mn 529.764.8Mn -OH 531.020.7H -O -H 532.414.5reduced

088.98

83.65

5.33

642.3

112.4

2.9/

3.1

Mn -O -Mn 529.948.6Mn -OH 531.143.4H -O -H

532.68.0

Mn 3s (eV)Mn 2p (eV)

O 1s (eV)c

composite electrode E (V)peak 1peak 2?eV d 3/2?BE Mn -O a oxidation state

Mn 3s/O 1s b

BE (eV)

area %oxidized

1.25

88.74

83.65

5.09

642.4

112.7

3.5/3.5

Mn -O -Mn 530.250.0Mn -OH 531.024.9H -O -H 533.58.5SO 42-532.016.70.989.3984.41 4.98643.1112.7 3.5/3.5

Mn -O -Mn 530.353.2Mn -OH 531.026.9H -O -H 533.39.8SO 42-532.010.1reduced 088.5883.60 4.98643.0112.7 3.5/3.5

Mn -O -Mn 530.360.3Mn -OH 531.630.4H -O -H 533.8 6.5SO 42-532.0 2.8-0.6589.4184.39 5.02643.1112.7 3.5/3.5

Mn -O -Mn 530.249.9Mn -OH 531.025.3H -O -H 533.48.6SO 42-532.0

16.2

a

Difference in binding energy between the Mn 2p 3/2and O 1s [Mn -O -Mn]peaks.b The first entry is obtained by the Mn 3s peak shift and the second after the slash by the relative area calculation of the O 1s components.c For the composite electrode,the presence of sulfate was shown by a S 2p peak at 168.6eV).33Hence,a component at 532eV was added to fit the O 1s peak envelope in order to take into account the contribution oxygen atoms of the sulfate species when computing the Mn redox state.d Difference between the binding energies of peak 1and peak 2.

Charge Storage Mechanism of MnO 2Electrode Chem.Mater.,Vol.16,No.16,20043187

efficiency decreased when the film thickness increased and that it reached only 67%for 25μg of MnO 2.These results demonstrate clearly that a significant fraction of MnO 2was not electrochemically addressable when the film thickness increased.In contrast,in the case of a rapid protonic diffusion in the bulk of the active material,the charge would increase linearly with the mass of the electrode.17This suggests that slower ionic transport is occurring within the active material or that protons cannot diffuse freely across the thickness of the MnO 2particles (vide infra).This is supported by the relatively low diffusion coefficient (6×10-10cm 2/s)for protons in manganese dioxide.35

Some insight into the decrease of the Coulombic efficiency with an increase of the film thickness could be obtained by calculating the surface of the platinum current collector covered by MnO 2particules.By con-sidering spherical particles with a mean diameter of 420nm,the formation of a “monolayer”of these MnO 2particles will require 33μg.However,as depicted in Figure SI4b,the MnO 2particles tend to agglomerate rather than forming a monolayer.The MnO 2deposited on the platinum substrate leads to a larger number of clusters,which reduce the area of material exposed to the electrolyte.If the electrochemical process is taking place only at the surface of the MnO 2exposed to the electrolyte,the charge will decrease as the weight of MnO 2is increased.This can explain why thin films usually exhibit higher capacitance values than bulk composite electrodes.17In this study,the gravimetric charge of our composite electrodes (100μm thick)is limited to 135C/g.On the other hand,when the weight of MnO 2is much lower as for the Pt -MnO 2samples,the charge increased up to 1250C/g for very small amount of MnO 2.This Coulombic efficiency,close to 100%,implies that protons or alkali cations can diffuse through a “monolayer”of MnO 2particles.This is expected by considering the particle size (<420nm as can be seen in Figure SI3),the charge/discharge time (180s for a scan rate of 5mV/s),and the diffusion coefficient for protons in manganese dioxide.35When a larger amount is MnO 2or when a thicker film is used,the diffusion of active cations is clearly hindered.

XPS Surface Analysis of the MnO 2Thin Film Electrodes.The survey spectra for the oxidized and reduced thin film electrodes are depicted in Figure 2.These spectra differ slightly from those recorded for the corresponding composite electrode (also shown in Figure 2).These differences become more evident on the higher resolution spectra as it will be demonstrated below.

Figure 3depicts the Mn 3s core level spectra for the reduced,as-prepared,and oxidized MnO 2thin film electrodes.The separation of peak energies (?E b )of the Mn 3s components increased from 4.78eV for the oxidized film to 5.33eV for the reduced film (see also Table 1).In the case of the as-prepared thin film,an intermediate value of 4.91eV was found.The E b values are in agreement with those expected for Mn 4+and Mn 3+oxides,which should have a peak separation of about 4.7and 5.4eV,respectively.30,36In addition,it was previously shown that a linear relation exists between the energy separation of the Mn 3s peaks and the oxidation state of manganese in the oxide.21,30,31From this relationship,the mean manganese oxidation state can be established at 4.0,2.9,and 3.6for the

(35)Ruetschi,P.J.Electrochem.Soc.1984,131,2737.

(36)Audi,A.A.;Sherwood,M.A.Surf.Interface Anal.2002,33,274.

Table 2.Electrochemical and Composition Data for MnO 2Thin Film Electrodes with Different Loadings

electrode

mass (μg)amount of MnO 2(moles)voltammetric charge a (C)/(C/g)calculated charge (C)b coulombic efficiency (%)c

specific capacitance

(F/g)

A 5.0(0.3 5.75×10-80.0056/12500.00551011380

B 10.0(0.8 1.15×10-70.0106/11900.0111951320

C 15.0(1.5 1.73×10-70.0148/11000.0166891230

D 20.0(2.5 2.30×10-70.0156/8750.022270970E

25.0(3.8

2.88×10-7

0.0186/835

0.0277

67

930

a

Calculated by taking into account the mass of MnO 2in the sample (about 89.1%).The first value is in C,whereas the second is the specific voltammetric charge in C/g.b The calculated charge was obtained from the amount of MnO 2on the electrode by assuming the transfer of one electron per Mn atom.c Coulombic efficiency (%))(voltammetric charge/calculated charge)×

100.

Figure 3.Mn 3s core level spectra for reduced,as-prepared,and oxidized thin film electrodes.The peak separation between the two peaks is indicated and can be used to determine the oxidation state of manganese.The raw data are represented by the dots,and the fitted data are represented by the lines.

3188Chem.Mater.,Vol.16,No.16,2004Toupin et al.

oxidized,reduced,and as-prepared electrodes,respec-tively.Thus,in contrast to the thicker composite electrode,a change of the oxidation state of manganese can be observed for the thinner film electrode on platinum substrate.This change is also accompanied by a color change upon redox switching.

The O 1s core level spectra were also used to confirm the change of manganese oxidation state during redox switching.Figure 4shows a significant difference of the O 1s envelope between the reduced,as-prepared,and oxidized thin film electrodes.Indeed,the reduced film shows a distinct high-intensity shoulder on the higher binding side of the main peak.To get some insight into the chemical modification that are occurring upon redox switching,the O 1s spectra were analyzed by curve fitting.Figure 4(see also Table 1)shows that the spectra can be fitted with three components which are related to the Mn -O -Mn bond (529.8(0.1eV)for the tetravalent oxide,the Mn -OH bond (531.1(0.2eV)for an hydrated trivalent oxide,and finally to a H -O -H bond (532.5(0.1eV)for residual structure water.28,37,38So,the change of the shape of the O 1s envelope is caused by the variation of the Mn -O -Mn and Mn -OH contributions (Table 1).For the oxidized electrode,the Mn -O -Mn component contributes to about 81%of the O 1s peak,whereas for the reduced electrode,the intensity of the Mn -O -Mn and Mn -OH signals is almost identical.The variation of the relative intensity of the O1s components indicates a change of the manganese oxide oxidation state between the oxidized

and reduced states.Table 1indicates that the mean manganese oxidation state,obtained from eq 5,is equal to 4for the oxidized electrode,whereas,for the reduced electrode,an oxidation level of 3.1is found.In the case of the as-prepared electrode,an intermediate oxidation state of 3.7is determined.These values are in excellent agreement with those computed from the Mn 3s data (vide supra).

Figure 5shows Mn 2p spectra of thin film samples.Such Mn 2p core level spectra have been recently used to determine the contribution of various Mn species.28However,the evaluation of the Mn(II),Mn(III),and Mn-(IV)contributions rely on a curve fitting procedure,which can be arbitrary since the shape of the spectra of the electrodes does not appear to change drastically (Figure 5).Nevertheless,the binding energy separation (?E Mn -O )between the Mn 2p 3/2and O 1s [Mn -O -Mn]peaks has been found to change slightly when the electrode is oxidized or reduced.30,33As shown in Table 1,the ?E Mn -O values were found to be equal to 112.4and 112.8eV for the reduced and oxidized film elec-trodes,respectively.The larger ?E Mn -O for the oxidized thin film is in agreement with literature data 31despite the fact that the absolute reported value was slightly larger.Thus,all the XPS data are consistent with a change of manganese oxidation state upon switching between 0and 0.9V.The redox switching of MnO 2electrodes might involve ionic species from the electro-lyte solution (0.1M Na 2SO 4),and the appropriate XPS core level spectra (Na 1s and S 2p)were measured to further characterize the charge storage mechanism.Figure 6shows that the intensity of the Na 1s peak is larger for the reduced thin film (thin film,0V)in comparison to the oxidized electrode (thin film,0.9V).This is consistent with a charge compensation of MnOO -by Na +for the reduced film (eq 3).In addition,Figure 6demonstrates that the sulfate anions are not involved in the redox process,since the S 2p spectra are feature-less.This is to be contrasted with the significant

(37)Banerjee,D.;Nesbitt,H.W.Geochim.Cosmochim.Acta 1999,63,3025.

(38)Banerjee,D.;Nesbitt,H.W.Geochim.Cosmochim.Acta 2001,65,

1703.

Figure 4.O 1s core level spectra for reduced,as-prepared,and oxidized thin film electrodes.The raw data are represented by the dots,and the fitted data are represented by the

lines.

Figure 5.Mn 2p core level spectra for reduced,as-prepared and oxidized thin film electrodes.The raw data are represented by the dots,and the fitted data are represented by the lines.

Charge Storage Mechanism of MnO 2Electrode Chem.Mater.,Vol.16,No.16,20043189

difference in the variation of the Na 1s and S 2p spectra for the composite electrode.When the composite elec-trode is switched from 0to 0.9V,the Na 1s signal decreased,whereas the S 2p signal increased.Obviously,some salt seems to be trapped since both Na +and SO 42-are found in the electrodes.The oxidized composite electrode contains an excess of sulfate (ratio S/Mn )0.064),whereas the reduced electrode has an excess of Na +(ratio Na/Mn )0.105).The variation of the Na +and SO 42-concentrations for the composite electrode may appear puzzling considering that the valence of manganese does not appear to change between the oxidized and reduced states.The excess of Na +and SO 42-for the reduced and oxidized electrodes,respec-tively,can be attributed to the presence of carbon in the composite electrodes.Thus,this behavior is consis-tent with that expected for a classical double layer charge storage process.1The invariance of the manga-nese oxidation state for the composite electrodes which contrasts with the change observed for the thin film electrodes suggests that only a thin layer of MnO 2on the electrode is involved in the redox interconversion.This is also confirmed by the high capacitance recorded for the thinner films,which almost reached the theo-retical values (vide supra).

The variation of the Na/Mn ratio,for the thin film electrode,upon potential switching deserves some com-ments.As mentioned above,the higher Na/Mn ratio for the reduced electrode in comparison to the oxidized electrode is consistent with a charge compensation of MnOO -by Na +.On the other hand,the Na/Mn is much lower than that expected for a complete compensation by Na +.These results clearly demonstrate that protons are involved in the redox process of MnO 2.Despite these experimental XPS results,the exact mechanism for the uptake of Na +is unclear.Recent electrochemical mea-surements of the intercalation of alkali metal ions into birnessite manganese dioxide in aqueous media sug-gested that protons are directly intercalated but not the alkali metal cations.39The presence of the alkali metal

cations in the oxide matrix was explained by an ion-exchange reaction between the cations and H +.Accord-ingly,a similar mechanism cannot be ruled out com-pletely for our electrodes.

Conclusion

In this work,the charge storage mechanism in MnO 2electrode,used in aqueous electrolyte,was investigated by cyclic voltammetry and X-ray photoelectron spec-troscopy.The main objective was to determine whether the manganese oxidation state changed during potential switching between 0and 0.9V vs Ag/AgCl.To this end,thin MnO 2films deposited on a platinum substrate and thicker MnO 2composite electrodes were used.X-ray photoelectron spectroscopy (XPS)measurements (Mn 3s and O 1s)with the thick composite electrodes did not reveal any change that could be assigned to a variation of the manganese valency,and,at this point,the charge storage mechanism could be based on electrostatic effects only.In fact,the charge storage would be similar to that observed for carbon electrodes.1On the other hand,a completely different XPS behavior was noticed for the thin film electrodes.Both the Mn 3s and O 1s spectra were consistent with manganese oxidation states of +3and +4for the reduced and oxidized forms,respectively.The XPS data also show that Na +cations from the electrolyte are involved in the charge storage process of MnO 2thin film electrodes.The Na/Mn ratio for the reduced electrode is much lower than what is anticipated for charge compensation dominated by Na +and suggests the involvement of protons.The apparent discrepancy between the XPS data (Mn 3s and O 1s spectra)can be explained by the cyclic voltammetry data of the thin film electrodes which established that only a thin layer of MnO 2is involved in the redox process and is electrochemically active.Presumably,this thin surface layer cannot be probed for the composite elec-trode because this region is brought back to the chemical (oxidation)state of the bulk by internal redox intercon-version.

Acknowledgment.The financial support of the Natural Science and Engineering Research Council (NSERC)and the Canadian Foundation for Innovation (CFI)is acknowledged.One of the authors (T.B.)would like to thank “l’Universite ′de Nantes”for giving him the opportunity to work in UQAM and UQAM for welcom-ing him as a visiting professor.The “Ministe `re Franc ?ais des Affaires Etrange `res”and the “Ministe `re des Rela-tions Internationales du Que ′bec”are also greatly ac-knowledged for supporting this work within the frame-work of the “Commission Permanente de Coope ′ration Franco-Que ′be ′coise”(project #59-102).

Supporting Information Available:X-ray diffraction pattern of the as-synthesized MnO 2powder (Figure SI1),scanning electron micrograph of the as-synthesized MnO 2powder (Figures SI2and SI3),scanning electron micrographs of a MnO 2composite electrode (Figure SI4a),scanning electron micrograph of MnO 2powder -PVdF -HFP coated on Pt (Figure SI4b),and Mn 3s core level spectra (Figure SI5).This material is available free of charge via the Internet at https://www.wendangku.net/doc/278773351.html,.CM049649J

(39)Kanoh,H.;Tang,W.;Makita,Y.;Ooi,https://www.wendangku.net/doc/278773351.html,ngmuir 1997,13,

6845.

Figure 6.Na 1s and S 2p core level spectra for composite and thin film electrodes.

3190Chem.Mater.,Vol.16,No.16,2004Toupin et al.

地黄的研究综述

课程报告 学院：生命科学与技术学院 专业年级：2012级生物工程 题目：我国中药资源利用的文献综述 姓名：任泽文 学号： 20120479 指导教师：张少冰 2015年 1 月 9 日

地黄的研究综述 摘录 本文清楚的介绍了玄参科地黄属多年生草本植物地黄的形态特征，地理分布，有效成分，药用机理以及古代临床上的一些处方，向我们介绍了地黄的详细信息。地黄按照不同的炮制方法在中药学上分为不同的中药，有鲜地黄和熟地黄之分。 关键词地黄理化性质药理作用 1、植物形态特征 地黄（拉丁学名：Rehmannia glutinosa (Gaetn.) Libosch. ex Fisch. et Mey.），玄参科地黄属多年生草本植物，体高10-30厘米，密被灰白色多细胞长柔毛和腺毛。根茎肉质，鲜时黄色，在栽培条件下，直径可达5.5厘米，茎紫红色。叶通常在茎基部集成莲座状，向上则强烈缩小成苞片，或逐渐缩小而在茎上互生；叶片卵形至长椭圆形，上面绿色，下面略带紫色或成紫红色，长2-13厘米，宽1-6厘米，边缘具不规则圆齿或钝锯齿以至牙齿；基部渐狭成柄，叶脉在上面凹陷，下面隆起。花具长0.5-3厘米之梗，梗细弱，弯曲而后上升，在茎顶部略排列成总状花序，或几全部单生叶腋而分散在茎上；萼长1-1.5厘米，密被多细胞长柔毛和白色长毛，具10条隆起的脉；萼齿5枚，矩圆状披针形或卵状披针形抑或多少三角形，长0.5-0.6厘米，宽0.2-0.3厘米，稀前方2枚各又开裂而使萼齿总数达7枚之多；花冠长3-4.5厘米；花冠筒多少弓曲，外面紫红色，被多细胞长柔毛；花冠裂片，5枚，先端钝或微凹，内面黄紫色，外面紫红色，两面均被多细胞长柔毛，长5-7毫米，宽4-10毫米；雄蕊4枚；药室矩圆形，长2.5毫米，宽1.5毫米，基部叉开，而使两药室常排成一直线，子房幼时2室，老时因隔膜撕裂而成一室，无毛；花柱顶部扩大成2枚片状柱头。蒴果卵形至长卵形，长1-1.5厘米。花果期4-7月。 2、地理分布 分布于辽宁、河北、河南、山东、山西、陕西、甘肃、内蒙古、江苏、湖北等省区。生于海拔50-1100米之砂质壤土、荒山坡、山脚、墙边、路旁等处。此外，国内各地及国外均有栽培。 3、有效成分 到目前为止，已经明确地黄的主要成分为苷类、糖类及氨基酸，并以苷类为主，在苷类中又以环烯醚萜苷为主。目前已从地黄中分离出32种环烯醚萜类化合物，其中一梓醇含量最高。

光学作图类型注意事项及相关知识点

光学作图类型注意事项及相关知识点 光学作图的考查形式主要有以下五种： 1、光的反射 2、光的折射 3、平面镜成像 4、透镜的特殊光线 5、凸透镜成像 ★光学作图需注意以下几点： 1、要借助工具（铅笔和直尺），作图要规范； 2、实际光线画实线，不是实际光线（如法线、光线的反向延长线、平面镜所成的像、像与物之间的连线）要画虚线； 3、光线要标箭头，同时注意箭头的方向； 4、如光源、物点、像点有对应符号、字母的要标上； 5、法线与镜面或界面垂直，像与物之间的连线与镜面垂直，垂直要画垂足符号； 6、务必记住凸透镜的三条特殊光线，利用特殊光线可以画出凸透镜成像光路图。 相关知识点： ▲光线：用一条带箭头的直线表示（箭头代表传播方向；直线代表光沿直线传播） 光的传播：光在同种均匀介质中沿直线传播。 实像：是一个明亮的区域，因为实像是由实际光线汇聚而成的；影子：是一个阴暗的区域，因为光线透不过去，在不透明物体后面形成

的。 ▲实像与虚像 区别：1、能不能用光屏承接。实像能，虚像不能。 2、是不是由实际光线汇聚而成。实像是，虚像不是。（虚像只能用肉眼看到，它是由实际光线的反向延长线交汇而成） 3、像的特点是不是一定是倒立的。实像是，虚像不是。 ▲光的反射 反射现象中的术语： 一点：入射点O（是指光线射到反射面上的一点）两角：入射角（指入射光线与法线之间的夹角）反射角（指反射光线与法线之间的夹角）三线：入射光线（指射到物体表面的光线） 反射光线（指被物体反射出的光线）法线（指垂直于镜面的虚线） ★反射定律：三线同面，法线居中，两角相等。即：1.反射光线、入射光线和法线在同一平面上； 2.反射光线、入射光线分居法线的两侧； 3.反射角等于入射角。（注意因果关系，入射决定了反射，应把反射叙述在前面） ★关于光的反射定律，应掌握以下几点： 1）一条反射光射只对应一条入射光线 2）入射光线垂直于反射面时，入射角为0°，反射角为0°，三线重合，但方向相反。

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目的：规范批生产记录管理，使生产记录能全面地、准确地反映某批产品的生产历史及与质量有关的情况。 适用范围：批生产记录的管理。 责任：岗位操作人员、班组长负责执行，生产部负责人、QA质监员、质保部负责人负责监督本制度的实施。 内容： 1.批生产记录定义： 1.1批生产记录是为一个批次的产品生产所有完成的活动和达到的结果提供客观证据的文件。 它记录了一个批次的待包装品或成品的所有生产过程，提供该批产品的生产历史、以及与质量有关的情况。具有以下作用： 1.1.1为质量保证部进行批次质量审计，确定是否放行，提供真实、客观的依据，以便质量保 证部门做出正确判断； 1.1.2提供对有缺陷的产品或用户投拆产品进行调查与追溯的证据和信息，以便做出正确的处 理决定，确认是否应该迅速召回产品； 1.1.3用于对产品的回顾性评价。它以批记录为依据，以数理统计为手段，可以发现潜在的质 量问题以及批生产指令和批包装指令的不完善处，为标准的修订提供信息和依据； 1.1.4用于回顾性验证，提供设备与工艺管理改进的信息。 2.技术依据： 2.1产品工艺规程、岗位标准操作规程； 2.2原辅料质量标准、中间产品质量标准、成品质量标准、包材质量标准； 2.3相关药品法规要求。 3.批生产记录的制定： 3.1批生产记录由工艺员制定，生产部负责人审核，质保部负责人批准后执行。批生产记录的 制定、审核、批准、修改、收回、保存等，应遵循《GMP文件的制定、审批、颁发管理规

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地黄的炮制与应用

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