Co-Al/Ni-Al二元水滑石及其复合氧化物的电化学性能研究
|
摘要
本文采用水热法合成了金属原子的物质的量比为3:1的镍铝、钴铝水滑石,并通过一定条件下的热处理制备了相应的复合金属氧化物。采用XRD、FT-IR、TG-DSC及TEM等测试手段对样品的组成和结构进行了表征。XRD研究表明水热法合成的样品均具有水滑石的层状结构,晶形良好,纯度很高。
为了研究水滑石材料的电化学性能,本文采用循环伏安、交流阻抗和恒流充放电测试技术考察了水滑石修饰电极在0.5 mol/L NaOH电解液和K_3[Fe(CN)_6]电解液中的电化学行为。研究表明,Ni/Al-CO_3水滑石和Ni/Al-Cl水滑石修饰电极在NaOH溶液中的具有相似的电化学行为,它们的电化学响应都是由水滑石晶格中的二价金属离子与导电物质间的电荷转移引起的。Co/Al-CO_3水滑石电极在0.5 mol/L NaOH溶液中表现为典型的赝电容性能,其单电极比容量达到163.1 F/g。Ni/Al-CO_3水滑石在0.5 mol/L K_3[Fe(CN)_6]溶液的电化学行为表现出电化学电容性能。水滑石修饰电极在NaOH和K_3[Fe(CN)_6]溶液中的反应是半无限扩散控制的电极反应,分别受OH~-和[Fe(CN)_6]~(3-)离子的扩散控制。
本文对Ni/Al、Co/Al水滑石复合金属氧化物的电化学性能进行了详细的研究。结果表明,所有氧化物电极在工作范围内(0.15～0.50 V)均具有良好的赝电容特性,法拉第准电容主要来源于电极材料自身可逆的氧化还原反应过程。Ni/Al-Cl水滑石在450℃温度焙烧时的比容量最大,电流密度为50mA/cm~2时单电极比容量达到419.0 F/g。该样品在大电流密度下经过400次连续循环后比容量大约只有4.3%的损失,表现出良好的稳定性。Co/Al-CO_3水滑石在300℃温度焙烧时的比容量最大,为265.5 F/g。
A series of Ni/Al and Co/Al hydrotalcite which M~(2+)/M~(3+) molar rations are 3 were synthesized by hydrothermal method. The layered double oxides (LDOs) were prepared through the thermal treatment of hydrotalcite. The structure and morphology of the samples were characterized by XRD, FT-IR, TG-DSC and TEM. XRD result showed that the obtained samples had nice crystal forms and high purity.
The electrochemical performance of hydrotalcite modified electrode in 0.5 mol/L NaOH and K_3[Fe(CN)_6] media was investigated by cyclic voltammetry, impedance and constant current charge/discharge measurements. The analysis results indicated that the electrochemical performances of Ni/Al-Cl hydrotalcite and Ni/Al-CO_3 hydrotalcite in NaOH solution were similiar. The mechanism to explain the redox behavior of the electrode system was the electron transfer between the oxidative M~(2+) and anion located in the interlayer spacing. Furthermore, the Co/Al hydroxide modified electrode exhibited a pseudo-capacitive behaviour in 0.5 mol/L NaOH media. Such materials had good long-term capacitive performance with the highest specific capacitance value of 163.1 F/g. The Ni/Al-CO_3 hydroxide modified electrode exhibited a pseudo-capacitive behaviour in 0.5 mol/L K_3[Fe(CN)_6] media. Cyclic voltammetry results demonstrated that electrochemical reaction occured under semi-infinite linear diffusion conditions and the electrode reaction was controlled by the diffusion of OH~- and [Fe(CN)_6]~(3-).
In addition, the electrochemical performance of LDOs was examined by cyclic voltammetry, impedance and constant current charge/discharge measurements. It was found that the clear faradaic pseudocapacitance behavior existed in all the samples. NiAl-Cl hydrotalcite calcined at 450℃displayed excellent capacitive properties within the potential range of 0.15～0.50 V in 0.5 mol/L NaOH electrolyte. Charge/discharge behaviors were observed with the highest specific capacitance value of 419.0 F/g at the large current density of 50 mA/cm~2 and approximately 4.3 % loss of specific capacitance after 400 cycles. Moreover, the highest septic capacitance values of 265.5 F/g could be achieved with Co/Al hydrotalcite calcined at 300℃.
为了研究水滑石材料的电化学性能,本文采用循环伏安、交流阻抗和恒流充放电测试技术考察了水滑石修饰电极在0.5 mol/L NaOH电解液和K_3[Fe(CN)_6]电解液中的电化学行为。研究表明,Ni/Al-CO_3水滑石和Ni/Al-Cl水滑石修饰电极在NaOH溶液中的具有相似的电化学行为,它们的电化学响应都是由水滑石晶格中的二价金属离子与导电物质间的电荷转移引起的。Co/Al-CO_3水滑石电极在0.5 mol/L NaOH溶液中表现为典型的赝电容性能,其单电极比容量达到163.1 F/g。Ni/Al-CO_3水滑石在0.5 mol/L K_3[Fe(CN)_6]溶液的电化学行为表现出电化学电容性能。水滑石修饰电极在NaOH和K_3[Fe(CN)_6]溶液中的反应是半无限扩散控制的电极反应,分别受OH~-和[Fe(CN)_6]~(3-)离子的扩散控制。
本文对Ni/Al、Co/Al水滑石复合金属氧化物的电化学性能进行了详细的研究。结果表明,所有氧化物电极在工作范围内(0.15～0.50 V)均具有良好的赝电容特性,法拉第准电容主要来源于电极材料自身可逆的氧化还原反应过程。Ni/Al-Cl水滑石在450℃温度焙烧时的比容量最大,电流密度为50mA/cm~2时单电极比容量达到419.0 F/g。该样品在大电流密度下经过400次连续循环后比容量大约只有4.3%的损失,表现出良好的稳定性。Co/Al-CO_3水滑石在300℃温度焙烧时的比容量最大,为265.5 F/g。
A series of Ni/Al and Co/Al hydrotalcite which M~(2+)/M~(3+) molar rations are 3 were synthesized by hydrothermal method. The layered double oxides (LDOs) were prepared through the thermal treatment of hydrotalcite. The structure and morphology of the samples were characterized by XRD, FT-IR, TG-DSC and TEM. XRD result showed that the obtained samples had nice crystal forms and high purity.
The electrochemical performance of hydrotalcite modified electrode in 0.5 mol/L NaOH and K_3[Fe(CN)_6] media was investigated by cyclic voltammetry, impedance and constant current charge/discharge measurements. The analysis results indicated that the electrochemical performances of Ni/Al-Cl hydrotalcite and Ni/Al-CO_3 hydrotalcite in NaOH solution were similiar. The mechanism to explain the redox behavior of the electrode system was the electron transfer between the oxidative M~(2+) and anion located in the interlayer spacing. Furthermore, the Co/Al hydroxide modified electrode exhibited a pseudo-capacitive behaviour in 0.5 mol/L NaOH media. Such materials had good long-term capacitive performance with the highest specific capacitance value of 163.1 F/g. The Ni/Al-CO_3 hydroxide modified electrode exhibited a pseudo-capacitive behaviour in 0.5 mol/L K_3[Fe(CN)_6] media. Cyclic voltammetry results demonstrated that electrochemical reaction occured under semi-infinite linear diffusion conditions and the electrode reaction was controlled by the diffusion of OH~- and [Fe(CN)_6]~(3-).
In addition, the electrochemical performance of LDOs was examined by cyclic voltammetry, impedance and constant current charge/discharge measurements. It was found that the clear faradaic pseudocapacitance behavior existed in all the samples. NiAl-Cl hydrotalcite calcined at 450℃displayed excellent capacitive properties within the potential range of 0.15～0.50 V in 0.5 mol/L NaOH electrolyte. Charge/discharge behaviors were observed with the highest specific capacitance value of 419.0 F/g at the large current density of 50 mA/cm~2 and approximately 4.3 % loss of specific capacitance after 400 cycles. Moreover, the highest septic capacitance values of 265.5 F/g could be achieved with Co/Al hydrotalcite calcined at 300℃.
引文
[1] R. Roto, G. Villemure. Electrochemical impedance spectroscopy of electrodes modified with thin films of Mg-Mn-CO_3 layered double hydroxides[J]. Electrochimica Acta, 2006, 51: 2539-2546P
[2] J. Qiu, G. Villemure. Anionic clay modified electrodes: electron transfer mediated by electroactive nickel, cobalt or manganese sites in layered double hydroxide films[J]. Journal of Electroanalytical Chemistry, 1997, 428:165-172P
[3] E. Scavetta, M. Berrettoni, M. Giorgetti, et al. Electrochemical characterisation of Ni/Al-X hydrotalcites and their electrocatalytic behaviour[J].Electrochimica Acta, 2002,47: 2451-2461P
[4] B. Ballarin, M. Berrettoni, I. Carpani, et al. Electrodes modified with an electrosynthesised Ni/Al hydrotalcite as amperometric sensors in flow systems[J]. Analytica Chimica Acta, 2005, 538: 219-224P
[5] E. Scavetta, B. Ballarin, M. Berrettoni, et al. Electrochemical sensors based on electrodes modified with synthetic hydrotalcites[J]. Electrochimica Acta,2006, 51: 2129-2134P
[6] D. Shan, S. Cosnier, C. Mousty. Layered Double Hydroxides: An Attractive Material for Electrochemical Biosensor Design[J]. Analalytical Chemistry,2003, 75: 3872-3879P
[7] K.X. He, X.G. Zhang, J. Li. Preparation and electrochemical capacitance of Me double hydroxides (Me=Co and Ni)/TiO_2 nanotube composites electrode[J]. Electrochimica Acta, 2006, 51: 1289-1292P
[8] X.M. Liu, Y.H. Zhang, X.G. Zhang, et al. Studies on Me/Al-layered double hydroxides (Me=Ni and Co) as electrode materials for electrochemical capacitors[J]. Electrochimica Acta, 2004,49: 3137-3141P
[9]Y.Wang,W.S.Yang,S.C.Zhang,et al.Synthesis and Electrochemical Characterization of Co-Al Layered Double Hydroxides[J].Journal of The Electrochemical Society,2005,152:A2130-A2137P
[10]P.Beaudot,M.E.De Roy,J.R Besse.Intercalation of noble metal complexes in LDH compounds[J].Journal of Solid State Chemistry,2004,177:2691-2698P
[11]H.Schaper,J.J.Berg-slot,W.H.J.Stork.Stabiilized Magnesia:a novel catalyst(Support) material[J].Applied Catalysis B,1996,7:397-406P
[12]郑崇辉,王君,孙炜岩等.二维层状磁性镁铝水滑石的制备与表征[J].功能材料,2006,37:1712-1715页
[13]T.R.Walter.Cryatal structures of some double hydroxide minerals[J].Jouranl of Catalysis,1985,94:547-557P
[14]K.Chibwe,W.Jones.Intercalation of organic and inorganic anions into layered double hydroxides[J].Journal of Chemical Society,Chemical Communications,1989,18:926-927P
[15]F.Cavani,F.Trifiro,A.Vaccari.Hydrotalcite-type anionic clays:preparation,properties and applications[J].Catalysis Today,1991,11:173-301P
[16]黄小葳,李殿卿,段雪.利用人工神经网络建立水滑石晶化过程的关联方程[J].北京联合大学学报(自然科学版),2006,20(1):40-44页
[17]J.Shen,B.Guang,M.Tu,et al.Preparation and characterization if Fe-MgO catalysts obtained from hydrotalcite-like compounds[J].Catalysis Today,1996,30:77-82P
[18]F.Millange,R.I.Walton,D.O'Hare.Time-resolved in site X-ray diffraction study of the liquid-phase reconstruction of Mg/Al-carbonate hydrotalcite-like compounds[J].Journal of Materials Chemistry,2002,10:1713-1720P
[19]F.Kovanda,D.Kolousek,Z.Cilova,et al.Crystallization of synthetic hydrotalcite under hydrothermal conditions[J].Applied Clay Science,2005,28:101-109P
[20]赵芸,矫庆泽.介孔镁铝复合氧化物的成孔机理及其结构特征[J].中国科学B辑,2002,32(1):67-73页
[21]M.A.Drezdzon.Synthesis of isopolymetalate-pillared hydrotalcite via organic-anion-pillared precursors[J].Inorganic Chemistry,1988,27:4628-4632P
[22]S.Tetsuya,Y.Shinsuke,T.Katsuhiko.Photopolymerization of 4-vinyl-benzoate and m-and p-phenylenediacrylates in hydrotalcite interlayers[J].Superamolecular Science,1998,5:303-308P
[23]杨飘萍,宿美平,杨青微等.尿素法合成高结晶度类水滑石[J].无机化学学报,2003,19(5):485-489页
[24]B.M.Choudary,M.L.Kantam,B.Kavita,et al.Catalytic C-C Bond Formation Promoted by Mg-Al-O-t-Bu Hydrotalcite[J].Tetrahedron,2000,56(47):9357-9364P
[25]徐芳.碳酸型水滑石的合成及其修饰电极的电化学行为[D].武汉:华中师范大学,2006.
[26]R.S.Maxwell,R.K.Kukkadapu,J.E.Amonette,et al.,~2H Solid-State NMR Investigation of Terephthalate Dynamics and Orientation in Mixed-Anion Hydrotalcite-Like Compounds[J].Journal of Physical Chemistry B,1999,103(25):5197-5203P
[27]A.M.Aicken,I.S.Bell,P.V.Coveney,et al.Simulation of layered double hydroxide intercalates[J].Advanced Materials,1997,9(6):496-500P
[28]S.P.Newman,S.J.Williams,P.V.Coveney,et al.Interlayer Arrangement of Hydrated MgAl Layered Double Hydroxides Containing Guest Terephthalate Anions:Comparison of Simulation and Measurement[J].Joumal of Physical Chemistry B,1998,102(34):6710-6719P
[29]K.Itaya,H.C.Chang,I.Uchida.Anion-exchanged clay(hydrotalcite-like compounds) modified electrodes[J].Inorganic Chemistry,1987,26:624-626P
[30]董绍俊.化学修饰电极[M].北京:科学出版社,1995:8页
[31]D.Ege,P.K.Gosh,J.R.White,et al.Clay modified electrodes.3.Electrochemical and electron spin resonance study of montmorillonite layers[J].Journal of American Chemical Society,1985,107(20):5644-5652P
[32]M.Yuasa,T.Naigaiwa,M.Kato,et al.Electrochemical Properties of Metalloporphyrin-Clay Complex-modified Electrode Systems:Investigation as Oxygen Sensors[J].Journal of the Electrochemical Society,1995,142(8):2612-2617P
[33]S.A.Lee,A.Fitch.Conductivity of clay-modified electrodes:alkali metal cation hydration and film preparation effects[J].Journal of Physical Chemistry,1990,94:4998-5004P
[34]K.Itaya,A.J.Bard.Preparation and electrochemical characterization of pillared clay-modified electrodes and membranes[J].Journal of Physical Chemistry,1985,89:5565-5568P
[35]W.E.Rudzinski,A.J.Bard.Clay modified electrodes:Part VI.Aluminum and silicon pillared clay-modified electrodes[J].Journal of Electroanalytical Chemistry,1986,199(2):323-340P
[36]D.Petridis,P.S.Kaviratna,T.J.Pinnavaia.Electrochemistry of alumina pillared clay modified electrodes[J].Journal of Electroanalytical Chemistry,1996,410:93-99P
[37]吕少仿.化学修饰电极及其在环境分析中的应用[J].阜阳师范学院学报(自然科学版),2003,12:117-120页
[38]B.Ballarin.T.J.Pinnavaia.Nanostructuring electrodes with carbon nanotubes:A review on electrochemistry and applications for sensing[J].Electrochemistry,1997,111(5):223-229P
[39]L.Qiu,G.Villemure.Anionic clay modified electrodes:electron transfer mediated by electroactive nickel,cobalt or manganese sites in layered double hydroxide films[J].Chemistry & Industry Magazine,1990,94:4998-5003P
[40]张校刚,刘献明,包淑娟等.Ni离子掺杂对CoAl双氢氧化物电化学电容的影响[J].无机化学学报,2004,20(1):94-98页
[41]K.Yao,M.Taniguchi,M.Nakata,et al.Electrochemical Scanning Tunneling Microscopy Observation of Ordered Surface Layers on an Anionic Clay-Modified Electrode[J].Langrnuir,1998,14:2890-2895P
[42]徐芳,王军涛,费锡明.水滑石的合成及修饰电极的电化学行为[J].合成化学,2006,14:175-177页
[43]E.Scavetta,M.Berrettoni,F.Nobili,et al.Electrochemical characterisation of electrodes modified with a Co/Al hydrotalcite-like compound[J].Electrochimica Acta,2005,50:3305-3311P
[44]R.Roto,L.Yu,G.Villemure.Effect of potential cycling in basic solutions.on the structure of Ni-Al layered double hydroxide films[J].Journal of Electroanalytical Chemistry,2006,587:263-268P
[45]B.Ballarin,M.Gazzano,R.Seeber.Electrodes coated by hydrotalcite-like clays.Effect of the metals and the intercalated anions on ion accumulation and retention capacibility[J].Journal of Electroanalytical Chemistry,1998,445:27-37P
[46]E.Scavetta,M.Berrettoni,R.Seeber,et al.[Ni/Al-Cl]-based hydrotalcite electrodes as amperometric sensors:preparation and electrochemical study[J].Electrochimica Acta,2001,46:2681-2692P
[47]B.Ballarin,M.Morigi,E.Scavetta,et al.Hydrotalcite-like compounds as ionophores for the development of anion potentiometric sensors[J].Journal of Electroanalytical Chemistry,2000,492:7-14P
[48]L.H.Su,X.G.Zhang.Effect of carbon entrapped in Co-Al double oxides on structural restacking and electrochemical performances[J].Journal of Power Sources,2007,172:999-1006P
[49]刘献明,张校刚.水热处理对Co-Al双氢氧化物电容性能的影响[J].应用化学,2003,20(6):524-527页
[50]黄可龙,曾雯雯,杨幼平等.溶剂热法合成纳米立方状CO_3O_4及其电容特性研究[J].无机化学学报,2007,23(9):1555-1560页
[51]H.KuanXin,Z.Xiaogang,L.Juan.Preparation and electrochemical capacitance of Me double hydroxides(Me=Co and Ni)/TiO_2 nanotube composites electrode[J].Electrochimica Acta,2006,51:1289-1292P
[52]R.S.Jayashree,P.Vishnu Kamath.Layered double hydroxides of Ni with Cr and Mn as candidate electrode materials for alkaline secondary cells[J].Journal of Power Sources,2002,107:120-124P
[53]W.K.Hu,D.Noréus.Alpha Nickel Hydroxides as Lightweight Nickel Electrode Materials for Alkaline Rechargeable Cells[J].Chemistry of Materials,2003,15:974-978P
[54]冯桃,李殿卿,Evans D.G等.水滑石晶体厚度比及晶粒尺寸控制方法研究[J].无机化学报,2002,18(11):78-82页
[55]刘媛.层状双金属氢氧化物的合成与应用[J].化工时刊.2005,19(12):59-62页
[56]B.Zapata,P.Bosch,G.Fetter.Co(Ⅱ)-Co(Ⅲ) hydrotalcite-like compounds[J].International Journal of Inorganic Materials,2001,3:23-29P
[57]肖铁,马俊,任韶玲,杨锡尧.碳酸根离子柱钴铝水滑石的合成与表征[J].催化学报,1999,20:63-66页
[58]温斌,何鸣元,宋家庆等.铈镁铝混合氧化物催化剂的脱NO_x性能[J].催化学报,2000,21(1):31-34页
[59] H. Bode, K. Dehmelt, J. Witte. Zur kenntnis der nickelhydroxidelektrode-I.Uber das nickel (II)-hydroxidhydrat[J]. Electrochimica Acta, 1966, 11:1079-1087P
[60] B. Ballarin, R. Seeber, D. Tonelli, et al. Electrocatalytic properties of nickel(II) hydrotalcite-type anionic clay: application to methanol and ethanol oxidation[J]. Journal of Electroanalytical Chemistry, 1999,463: 123-127P
[61] A. Walcarius, S. Rozanska, J. Bessiere, et al. Screen-printed zeolite-modified carbon electrodes[J]. The Analyst, 1999,124: 1185-1190P
[62] G. Barral, S. Maximovitch, F. Njanjo-Eyoke. Study of electrochemically formed Ni(OH)_2 layers by EIS[J]. Electrochimica Acta, 1996, 41:1305-1311P
[63] T. Pajkossy, L. Nyikos. Scaling-law analysis to describe the impedance behavior of fractal electrodes[J]. Physical Review B, 1990,42: 709-719P
[64] J. Bisquert, G. Garcia-Belmonte, F. Fabregat-Santiago, et al. Doubling Exponent Models for the Analysis of Porous Film Electrodes by Impedance.Relaxation of TiO_2 Nanoporous in Aqueous Solution[J]. Journal of Physical Chemistry B. 2000,104: 2287-2298P
[65] E. Scavetta, D. Tonelli, M. Giorgetti, et al. AC impedance study of a synthetic hydrotalcite-like compound modified electrode in aqueous solution[J]. Electrochimica Acta, 2003,48: 1347-1355P
[66] J. Qiu, G. Villemure. Anionic clay modified electrodes: electron transfer mediated by electroactive nickel, cobalt or manganese sites in layered double hydroxide films[J]. Journal of Electroanalytical Chemistry, 1997, 428(1-2):165-172P
[67] R. Roto, G. Villemure. Electrochemical impedance spectroscopy of electrodes modified with thin films of Ni-Al-Cl layered double hydroxides[J].Journal of Electroanalytical Chemistry, 2002, 527: 123-130P
[68]F.Svegl,B.Orel,M.G.Hutchins,et al.Structural and Spectroelectrochemical Investigations of Journal of Sol-Gel Derived Electrochromic Spinel Co_3O_4 Films[J].The Electrochemical Society,1996,143(5):1532-1537P
[69]D.D.Zhao,S.J.Bao,W.J.Zhou,et al.Preparation of hexagonal nanoporous nickel hydroxide film and its application for electrochemical capacitor[J].Electrochemistry Communications,2007,9:869-874P
[70]S.Venkat,W.W.John.Studies on the capacitance of nickel oxide films:effect of heating temperature and electrolyte concentration[J].Journal of The Electrochemical Society,2000,147(3):880-885P
[71]Q.Huang,X.Wang,J.Li,et al.Nickel hydroxide/activated carbon composite electrodes for electrochemical capacitors[J].Journal of Power Sources,2007,164:425-429P
[72]T.C.Girija,M.V.Sangaranarayanan.Investigation of polyaniline-coated stainless steel electrodes for electrochemical supercapacitors[J].Synthetic Matels,2006,156(2-4):244-250P
[73]郑明波,曹洁明,陈勇平等.快速沉淀法制备多孔纳米NiO及其电容性质研究[J].高等学校化学学报,2006,27(6):1138-1140页
[74]邓梅根,杨邦朝,胡永达.纳米NiO的制备及其赝电容特性研究[J].材料工程,2005,5:19-26页
[75]韩丹丹,陈野,张密林等.纳米NiO的制备及其性能研究[J].电池,2006,36(4):283-285页
[76]C.Lin,J.A.Ritter,B.N.Popov.Characterization of Sol-Gel-Derived Cobalt Oxide Xerogels as Electrochemical Capacitors[J].Journal of The Electrochemical Society,1998,145(12):4097-4103P
[2] J. Qiu, G. Villemure. Anionic clay modified electrodes: electron transfer mediated by electroactive nickel, cobalt or manganese sites in layered double hydroxide films[J]. Journal of Electroanalytical Chemistry, 1997, 428:165-172P
[3] E. Scavetta, M. Berrettoni, M. Giorgetti, et al. Electrochemical characterisation of Ni/Al-X hydrotalcites and their electrocatalytic behaviour[J].Electrochimica Acta, 2002,47: 2451-2461P
[4] B. Ballarin, M. Berrettoni, I. Carpani, et al. Electrodes modified with an electrosynthesised Ni/Al hydrotalcite as amperometric sensors in flow systems[J]. Analytica Chimica Acta, 2005, 538: 219-224P
[5] E. Scavetta, B. Ballarin, M. Berrettoni, et al. Electrochemical sensors based on electrodes modified with synthetic hydrotalcites[J]. Electrochimica Acta,2006, 51: 2129-2134P
[6] D. Shan, S. Cosnier, C. Mousty. Layered Double Hydroxides: An Attractive Material for Electrochemical Biosensor Design[J]. Analalytical Chemistry,2003, 75: 3872-3879P
[7] K.X. He, X.G. Zhang, J. Li. Preparation and electrochemical capacitance of Me double hydroxides (Me=Co and Ni)/TiO_2 nanotube composites electrode[J]. Electrochimica Acta, 2006, 51: 1289-1292P
[8] X.M. Liu, Y.H. Zhang, X.G. Zhang, et al. Studies on Me/Al-layered double hydroxides (Me=Ni and Co) as electrode materials for electrochemical capacitors[J]. Electrochimica Acta, 2004,49: 3137-3141P
[9]Y.Wang,W.S.Yang,S.C.Zhang,et al.Synthesis and Electrochemical Characterization of Co-Al Layered Double Hydroxides[J].Journal of The Electrochemical Society,2005,152:A2130-A2137P
[10]P.Beaudot,M.E.De Roy,J.R Besse.Intercalation of noble metal complexes in LDH compounds[J].Journal of Solid State Chemistry,2004,177:2691-2698P
[11]H.Schaper,J.J.Berg-slot,W.H.J.Stork.Stabiilized Magnesia:a novel catalyst(Support) material[J].Applied Catalysis B,1996,7:397-406P
[12]郑崇辉,王君,孙炜岩等.二维层状磁性镁铝水滑石的制备与表征[J].功能材料,2006,37:1712-1715页
[13]T.R.Walter.Cryatal structures of some double hydroxide minerals[J].Jouranl of Catalysis,1985,94:547-557P
[14]K.Chibwe,W.Jones.Intercalation of organic and inorganic anions into layered double hydroxides[J].Journal of Chemical Society,Chemical Communications,1989,18:926-927P
[15]F.Cavani,F.Trifiro,A.Vaccari.Hydrotalcite-type anionic clays:preparation,properties and applications[J].Catalysis Today,1991,11:173-301P
[16]黄小葳,李殿卿,段雪.利用人工神经网络建立水滑石晶化过程的关联方程[J].北京联合大学学报(自然科学版),2006,20(1):40-44页
[17]J.Shen,B.Guang,M.Tu,et al.Preparation and characterization if Fe-MgO catalysts obtained from hydrotalcite-like compounds[J].Catalysis Today,1996,30:77-82P
[18]F.Millange,R.I.Walton,D.O'Hare.Time-resolved in site X-ray diffraction study of the liquid-phase reconstruction of Mg/Al-carbonate hydrotalcite-like compounds[J].Journal of Materials Chemistry,2002,10:1713-1720P
[19]F.Kovanda,D.Kolousek,Z.Cilova,et al.Crystallization of synthetic hydrotalcite under hydrothermal conditions[J].Applied Clay Science,2005,28:101-109P
[20]赵芸,矫庆泽.介孔镁铝复合氧化物的成孔机理及其结构特征[J].中国科学B辑,2002,32(1):67-73页
[21]M.A.Drezdzon.Synthesis of isopolymetalate-pillared hydrotalcite via organic-anion-pillared precursors[J].Inorganic Chemistry,1988,27:4628-4632P
[22]S.Tetsuya,Y.Shinsuke,T.Katsuhiko.Photopolymerization of 4-vinyl-benzoate and m-and p-phenylenediacrylates in hydrotalcite interlayers[J].Superamolecular Science,1998,5:303-308P
[23]杨飘萍,宿美平,杨青微等.尿素法合成高结晶度类水滑石[J].无机化学学报,2003,19(5):485-489页
[24]B.M.Choudary,M.L.Kantam,B.Kavita,et al.Catalytic C-C Bond Formation Promoted by Mg-Al-O-t-Bu Hydrotalcite[J].Tetrahedron,2000,56(47):9357-9364P
[25]徐芳.碳酸型水滑石的合成及其修饰电极的电化学行为[D].武汉:华中师范大学,2006.
[26]R.S.Maxwell,R.K.Kukkadapu,J.E.Amonette,et al.,~2H Solid-State NMR Investigation of Terephthalate Dynamics and Orientation in Mixed-Anion Hydrotalcite-Like Compounds[J].Journal of Physical Chemistry B,1999,103(25):5197-5203P
[27]A.M.Aicken,I.S.Bell,P.V.Coveney,et al.Simulation of layered double hydroxide intercalates[J].Advanced Materials,1997,9(6):496-500P
[28]S.P.Newman,S.J.Williams,P.V.Coveney,et al.Interlayer Arrangement of Hydrated MgAl Layered Double Hydroxides Containing Guest Terephthalate Anions:Comparison of Simulation and Measurement[J].Joumal of Physical Chemistry B,1998,102(34):6710-6719P
[29]K.Itaya,H.C.Chang,I.Uchida.Anion-exchanged clay(hydrotalcite-like compounds) modified electrodes[J].Inorganic Chemistry,1987,26:624-626P
[30]董绍俊.化学修饰电极[M].北京:科学出版社,1995:8页
[31]D.Ege,P.K.Gosh,J.R.White,et al.Clay modified electrodes.3.Electrochemical and electron spin resonance study of montmorillonite layers[J].Journal of American Chemical Society,1985,107(20):5644-5652P
[32]M.Yuasa,T.Naigaiwa,M.Kato,et al.Electrochemical Properties of Metalloporphyrin-Clay Complex-modified Electrode Systems:Investigation as Oxygen Sensors[J].Journal of the Electrochemical Society,1995,142(8):2612-2617P
[33]S.A.Lee,A.Fitch.Conductivity of clay-modified electrodes:alkali metal cation hydration and film preparation effects[J].Journal of Physical Chemistry,1990,94:4998-5004P
[34]K.Itaya,A.J.Bard.Preparation and electrochemical characterization of pillared clay-modified electrodes and membranes[J].Journal of Physical Chemistry,1985,89:5565-5568P
[35]W.E.Rudzinski,A.J.Bard.Clay modified electrodes:Part VI.Aluminum and silicon pillared clay-modified electrodes[J].Journal of Electroanalytical Chemistry,1986,199(2):323-340P
[36]D.Petridis,P.S.Kaviratna,T.J.Pinnavaia.Electrochemistry of alumina pillared clay modified electrodes[J].Journal of Electroanalytical Chemistry,1996,410:93-99P
[37]吕少仿.化学修饰电极及其在环境分析中的应用[J].阜阳师范学院学报(自然科学版),2003,12:117-120页
[38]B.Ballarin.T.J.Pinnavaia.Nanostructuring electrodes with carbon nanotubes:A review on electrochemistry and applications for sensing[J].Electrochemistry,1997,111(5):223-229P
[39]L.Qiu,G.Villemure.Anionic clay modified electrodes:electron transfer mediated by electroactive nickel,cobalt or manganese sites in layered double hydroxide films[J].Chemistry & Industry Magazine,1990,94:4998-5003P
[40]张校刚,刘献明,包淑娟等.Ni离子掺杂对CoAl双氢氧化物电化学电容的影响[J].无机化学学报,2004,20(1):94-98页
[41]K.Yao,M.Taniguchi,M.Nakata,et al.Electrochemical Scanning Tunneling Microscopy Observation of Ordered Surface Layers on an Anionic Clay-Modified Electrode[J].Langrnuir,1998,14:2890-2895P
[42]徐芳,王军涛,费锡明.水滑石的合成及修饰电极的电化学行为[J].合成化学,2006,14:175-177页
[43]E.Scavetta,M.Berrettoni,F.Nobili,et al.Electrochemical characterisation of electrodes modified with a Co/Al hydrotalcite-like compound[J].Electrochimica Acta,2005,50:3305-3311P
[44]R.Roto,L.Yu,G.Villemure.Effect of potential cycling in basic solutions.on the structure of Ni-Al layered double hydroxide films[J].Journal of Electroanalytical Chemistry,2006,587:263-268P
[45]B.Ballarin,M.Gazzano,R.Seeber.Electrodes coated by hydrotalcite-like clays.Effect of the metals and the intercalated anions on ion accumulation and retention capacibility[J].Journal of Electroanalytical Chemistry,1998,445:27-37P
[46]E.Scavetta,M.Berrettoni,R.Seeber,et al.[Ni/Al-Cl]-based hydrotalcite electrodes as amperometric sensors:preparation and electrochemical study[J].Electrochimica Acta,2001,46:2681-2692P
[47]B.Ballarin,M.Morigi,E.Scavetta,et al.Hydrotalcite-like compounds as ionophores for the development of anion potentiometric sensors[J].Journal of Electroanalytical Chemistry,2000,492:7-14P
[48]L.H.Su,X.G.Zhang.Effect of carbon entrapped in Co-Al double oxides on structural restacking and electrochemical performances[J].Journal of Power Sources,2007,172:999-1006P
[49]刘献明,张校刚.水热处理对Co-Al双氢氧化物电容性能的影响[J].应用化学,2003,20(6):524-527页
[50]黄可龙,曾雯雯,杨幼平等.溶剂热法合成纳米立方状CO_3O_4及其电容特性研究[J].无机化学学报,2007,23(9):1555-1560页
[51]H.KuanXin,Z.Xiaogang,L.Juan.Preparation and electrochemical capacitance of Me double hydroxides(Me=Co and Ni)/TiO_2 nanotube composites electrode[J].Electrochimica Acta,2006,51:1289-1292P
[52]R.S.Jayashree,P.Vishnu Kamath.Layered double hydroxides of Ni with Cr and Mn as candidate electrode materials for alkaline secondary cells[J].Journal of Power Sources,2002,107:120-124P
[53]W.K.Hu,D.Noréus.Alpha Nickel Hydroxides as Lightweight Nickel Electrode Materials for Alkaline Rechargeable Cells[J].Chemistry of Materials,2003,15:974-978P
[54]冯桃,李殿卿,Evans D.G等.水滑石晶体厚度比及晶粒尺寸控制方法研究[J].无机化学报,2002,18(11):78-82页
[55]刘媛.层状双金属氢氧化物的合成与应用[J].化工时刊.2005,19(12):59-62页
[56]B.Zapata,P.Bosch,G.Fetter.Co(Ⅱ)-Co(Ⅲ) hydrotalcite-like compounds[J].International Journal of Inorganic Materials,2001,3:23-29P
[57]肖铁,马俊,任韶玲,杨锡尧.碳酸根离子柱钴铝水滑石的合成与表征[J].催化学报,1999,20:63-66页
[58]温斌,何鸣元,宋家庆等.铈镁铝混合氧化物催化剂的脱NO_x性能[J].催化学报,2000,21(1):31-34页
[59] H. Bode, K. Dehmelt, J. Witte. Zur kenntnis der nickelhydroxidelektrode-I.Uber das nickel (II)-hydroxidhydrat[J]. Electrochimica Acta, 1966, 11:1079-1087P
[60] B. Ballarin, R. Seeber, D. Tonelli, et al. Electrocatalytic properties of nickel(II) hydrotalcite-type anionic clay: application to methanol and ethanol oxidation[J]. Journal of Electroanalytical Chemistry, 1999,463: 123-127P
[61] A. Walcarius, S. Rozanska, J. Bessiere, et al. Screen-printed zeolite-modified carbon electrodes[J]. The Analyst, 1999,124: 1185-1190P
[62] G. Barral, S. Maximovitch, F. Njanjo-Eyoke. Study of electrochemically formed Ni(OH)_2 layers by EIS[J]. Electrochimica Acta, 1996, 41:1305-1311P
[63] T. Pajkossy, L. Nyikos. Scaling-law analysis to describe the impedance behavior of fractal electrodes[J]. Physical Review B, 1990,42: 709-719P
[64] J. Bisquert, G. Garcia-Belmonte, F. Fabregat-Santiago, et al. Doubling Exponent Models for the Analysis of Porous Film Electrodes by Impedance.Relaxation of TiO_2 Nanoporous in Aqueous Solution[J]. Journal of Physical Chemistry B. 2000,104: 2287-2298P
[65] E. Scavetta, D. Tonelli, M. Giorgetti, et al. AC impedance study of a synthetic hydrotalcite-like compound modified electrode in aqueous solution[J]. Electrochimica Acta, 2003,48: 1347-1355P
[66] J. Qiu, G. Villemure. Anionic clay modified electrodes: electron transfer mediated by electroactive nickel, cobalt or manganese sites in layered double hydroxide films[J]. Journal of Electroanalytical Chemistry, 1997, 428(1-2):165-172P
[67] R. Roto, G. Villemure. Electrochemical impedance spectroscopy of electrodes modified with thin films of Ni-Al-Cl layered double hydroxides[J].Journal of Electroanalytical Chemistry, 2002, 527: 123-130P
[68]F.Svegl,B.Orel,M.G.Hutchins,et al.Structural and Spectroelectrochemical Investigations of Journal of Sol-Gel Derived Electrochromic Spinel Co_3O_4 Films[J].The Electrochemical Society,1996,143(5):1532-1537P
[69]D.D.Zhao,S.J.Bao,W.J.Zhou,et al.Preparation of hexagonal nanoporous nickel hydroxide film and its application for electrochemical capacitor[J].Electrochemistry Communications,2007,9:869-874P
[70]S.Venkat,W.W.John.Studies on the capacitance of nickel oxide films:effect of heating temperature and electrolyte concentration[J].Journal of The Electrochemical Society,2000,147(3):880-885P
[71]Q.Huang,X.Wang,J.Li,et al.Nickel hydroxide/activated carbon composite electrodes for electrochemical capacitors[J].Journal of Power Sources,2007,164:425-429P
[72]T.C.Girija,M.V.Sangaranarayanan.Investigation of polyaniline-coated stainless steel electrodes for electrochemical supercapacitors[J].Synthetic Matels,2006,156(2-4):244-250P
[73]郑明波,曹洁明,陈勇平等.快速沉淀法制备多孔纳米NiO及其电容性质研究[J].高等学校化学学报,2006,27(6):1138-1140页
[74]邓梅根,杨邦朝,胡永达.纳米NiO的制备及其赝电容特性研究[J].材料工程,2005,5:19-26页
[75]韩丹丹,陈野,张密林等.纳米NiO的制备及其性能研究[J].电池,2006,36(4):283-285页
[76]C.Lin,J.A.Ritter,B.N.Popov.Characterization of Sol-Gel-Derived Cobalt Oxide Xerogels as Electrochemical Capacitors[J].Journal of The Electrochemical Society,1998,145(12):4097-4103P