Electrodeposition (eBook)

Preface 6
Contributors 15
Chapter 1 Hydrogen Co-deposition Effects on the Structure of Electrodeposited Copper 18
I. Introduction 18
II. The Concept of ``The Effective Overpotential' 21
1. The Definition of the Concept and Mathematical Model 21
2. The Concept of ``Effective Overpotential' Applied for Metal Electrodeposition Under an Imposed Magnetic Field 31
III. Phenomenology of a Formation of a Honeycomb-Like Structure During Copper Electrodeposition 34
IV. The Effect of Deposition Conditions on Copper Deposits Morphology 41
1. The Surface Preparation 41
2. The Effect of Concentration of Cu(II) Ions 43
(i) Morphologies of Copper Deposits Obtained at Overpotentials up to 800mV 49
(ii) Morphologies of Copper Deposits Obtained at an Overpotential of 1,000mV 52
3. The Effect of Concentration of H2SO4 58
(i) Morphologies of Copper Deposits Obtained at Overpotentials up to 800mV 61
(ii) Morphologies of Copper Deposits Obtained at an Overpotential of 1,000mV 65
4. The Effect of Temperature on Electrodeposition of Disperse Copper Deposits 66
5. Analysis of Deposition Conditions with the Aspect of the Honeycomb-like Structure Formation 72
V. Influence of Ionic Equilibrium in the CuSO4--H2SO4--H2O System on the Formation of Irregular Electrodeposits of Copper 76
VI. The Shape of Electrochemically Formed Copper Powder Particles and their Dependence on the Quantity of Evolved Hydrogen 79
Acknowledgment 83
References 84
Chapter 2 Noble Metal Nanoislands Decoration of Au(111) and Pt(111) Single Crystal Surfaces 88
I. Introduction 88
II. Preparation and Characterization of Me/Au(111) and Me/Pt(111) Surfaces 90
1. Au(111) and Pt(111) Single Crystal Preparation for In Situ STM Measurements 90
2. In Situ STM Imaging of the Au(111) and Pt(111) Single Crystals Decorated with Metal Nanoislands 93
III. Electrochemical Deposition of Ru on Au(111) 94
1. The Electrodeposition of Ru on Au(111) Observed by Cyclic Voltammetry 94
2. The Electrodeposition of Ru on Au(111) Observed by In Situ STM 97
IV. Spontaneous Deposition of Ru on Au(111) 101
V. Spontaneous Deposition of Os on Au(111) 107
VI. Spontaneous Deposition of Ru on Pt(111) 113
VII. Spontaneous Deposition of Os on Pt(111) 115
VIII. Applications of Selected Bimetallic Surfaces for the Electrocatalytic Purposes 118
1. CO Oxidation on Ru/Au(111) Prepared by Electrochemical Ru Deposition 118
2. CO Oxidation on Ru/Au(111) Prepared by Spontaneous Ru Deposition 120
3. Formaldehyde Oxidation on Ru/Au(111) Prepared by Spontaneous Ru Deposition 121
4. CO Oxidation on Os/Au(111) Prepared by Spontaneous Os Deposition 124
5. CO Oxidation on Ru/Pt(111) Prepared by Spontaneous Ru Deposition 124
6. Methanol Oxidation on Pt(111) Modified by Spontaneously Deposited Ru 126
7. CO Oxidation on Os/Pt(111) Prepared by Spontaneous Os Deposition 128
IX. Conclusions 129
Acknowledgments 129
References 131
Chapter 3 Electrodeposition for Electrochemical Energy Conversion and Storage Devices 134
I. Introduction 134
II. Proton Exchange Membrane Fuel Cells 135
1. Membrane Electrode Assembly 135
2. Electrodeposition of Pt Electrocatalystsfor MEAs 136
3. Electrodeposition of Carbon Monoxide Tolerant Electrocatalysts 140
III. Solid Oxide Fuel Cells 142
1. Ferritic Stainless Steel Interconnects for SOFCs 143
2. Conductive/Protective Coatings for Ferritic Stainless Steel Interconnects 143
3. Spinel Coating via Electrodeposition/HeatTreatment 144
(i) Drawbacks of Spinel Coatings via Electrodeposition/oxidation 146
4. Anodic Deposition of Co--Mn Spinels 149
IV. Electrochemical Supercapacitors 150
1. Faradic and Non-Faradic Supercapacitors 150
2. Metal Oxide Electrodes 151
3. Electrodeposition of Manganese Oxides 152
4. Conductive Polymer Electrodes 155
5. Electrodeposition of Conductive Polymers 155
6. Composite Electrodeposition of Metal Oxides/Polymers 161
V. Lithium Ion Batteries 163
1. Tin-Oxide-Based Anodes 164
2. Tin and Tin Intermetallic Anodes 168
VI. Conclusions 171
Acknowledgments 171
References 172
Chapter 4 The Effect of Morphology of Activated Electrodes on Their Electrochemical Activity 180
I. Introduction 180
II. Micro- and Macroelectrodes 182
III. Inert Macroelectrode Partially Covered With Hemispherical Active Microelectrodes 188
1. Mathematical Model 188
2. Polarization Curves 193
(i) Calculated Polarization Curves Without Included Ohmic Potential Drop 193
(ii) Calculated Polarization Curves With Included Ohmic Potential Drop 197
3. Experimental Verification 200
4. The Required Quantity of Active Substance 205
IV. Inert Electrodes Activated With Dendrites 207
1. Large Level of Coarseness 207
2. Low Level of Coarseness 215
V. Applied Aspects 225
VI. Conclusions 226
Acknowledgments 226
References 227
Chapter 5 Electrochemical Micromachining and Microstructuring of Aluminum and Anodic Alumina 231
I. Introduction 231
II. Electrochemical Micromachining and Localized Anodization 233
1. Electrochemical Methods for 3D Microstructure Fabrication: Additive Plating and Wet Subtractive Etching 233
2. Fabrication of 3D Metallic and 3D Ceramic Microstructures Based on Electrochemical Micromachining of Al 234
3. Undermask Anodization During Localized Anodization of Al and Fidelity of the MaskTransfer 235
4. Technological Limitations and Economical Benefits of Electrochemical Micromachining of Al 237
III. Technological Aspects of Localized Anodization of Aluminum Substrates 238
1. Mask Reliability During Localized Anodization 238
2. Etch Factor as a Function of Process Conditions 240
3. Current Density Distribution at the Pattern Scale During Localized Anodization 244
IV. Localized Anodization and Electrochemical Micromachining: Applications and Devices 247
1. Metallization Applications in the Microelectronics and Solar Cells Industry, and Fabrication of Passive Components 248
2. Surface Microstructuring 251
3. Freestanding Porous Al2O3 Substrates and Devices 255
4. Multilevel Alumina Ceramics and Its Applications 258
V. Conclusions 261
Acknowledgments 261
References 262
Chapter 6 Electroless Deposition: Theory and Applications 266
I. Introduction 266
II. General Considerations of Electroless Deposition 267
1. Displacement Deposition 268
2. Autocatalytic Deposition 271
3. Electroless Oxidation of Metals 276
III. Mechanistic Aspects Of Electroless Deposition 277
IV. Recent Developments and Applications of Electroless Deposition 281
1. Electroless Deposition in Electronics Applications 281
2. Electroless Deposition for Electromagnetic Shielding 287
3. Electroless Deposition of Magnetic Materials 288
4. Electroless Deposition for Energy Conversion and Catalytic Purposes 290
5. Electroless Deposition for the Biomedical Applications 293
6. Electroless Deposition and Anticorrosion Applications 296
7. Electroless Deposition and Nanotechnology 298
V. Conclusions 300
Acknowledgments 300
References 301
Index 305