323

Index

a – electronic and geometric effects 96 aluminum anodizing models 126 centralized energy system 284 anodic oxide films 107 chemical etching 21 anodic porous alumina combined MR read/inductive write head 24 – applications 165, 166 computational energy science – crystallinity 164 – design-time energy system 266 – duplex structure 152 – extended Reference Energy System – electrochemical anodization 145–147, 149 – – containers 272 – geometry control – – graphical representation 271 – – hard anodization 156 – – process and commodity 272 – – mild anodization 154 ––USES,see Universal Scheme for modeling – improved ordering 162, 163 Energy Systems (USES) – morphology 153, 154 – Reference Energy System 269, 270 – nanomaterials fabrication – run-time energy system 266 – – electrodeposition 166 – smart grid, virtual power stations 266–268 ––metaloxides 168 – virtual autonomous networks, hierarchy ––metals 167 – – extended hierarchical organization 278, ––polymers 168 280, 281 – – semiconductors 168 – – flat organization 278–281 – self-organization 149, 152 – – goal and control strategy 276 – template materials 146 – – structure 277 aprotic Li–air batteries 5 conventional core–shell structures aqueous Li–air batteries 5 – continuum DIS models ARPA-E program 229 – – boundary conditions 205 AZ-1350 resist 43, 47, 49 – – concentration induced deformation 207 – – displacement equations 205 b – – jump stress 208 batch-fabricated thin-film heads 15 – – solute diffusion 199, 200 “bleed and feed” procedures 33 – – stress–strain relations 201–203, 205 bottom-up process 264, 282, 315 – – thermodynamics 198 Bruckenstein–Swathirajan (BS) isotherm 63 – displacement and stress Butler–Volmer electrochemical kinetic – – initial behavior of 209–214 expression 127 – – transient behavior of 212, 215–218 – schematic diagram 194 c core–shell structures catalysis, UPCD – ab initio simulations 195, 197 – atomic surface configuration 96, 97 –conventional,see conventional core–shell – binary and ternary Pt-based alloys 97 structures

Electrochemical Engineering Across Scales: From Molecules to Processes, First Edition. Edited by Richard C. Alkire, Phil N. Bartlett, and Jacek Lipkowski. © 2015 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2015 by Wiley-VCH Verlag GmbH & Co. KGaA. 324 Index

core–shell structures (contd.) – crystallinity 173 – density functional theory – doping 175, 177 – – Hohenberg and Kohn theorem 195 – single wall morphology 177 – – Kohn–Sham effective potential 195 – surface area enhancement 174–175 – diffusion-induced stress calculation 196 – tube geometry 170, 172, 173, 175 – Li diffusion mechanism 197 – lithiated graphite, see graphite-SEI e core–shell structures electric vehicles 4 –lithiatedSi,see Si-SEI core–shell structures electrical energy storage devices 285 – SEI 193 electrochemical anodization 145 coupled film memory structure 15 electrochemical atomic layer deposition (EC-ALD) 60 d electrochemical energy systems decentralized energy system 282, 284, 285 –architectures,see computational energy DEFC, see direct ethanol fuel cell (DEFC) science design-time energy system 266 – bottom-up approach 264, 282, 315 direct ethanol fuel cell (DEFC) – centralized energy system 284 –anodecatalyst – decentralized energy system 282, 284, 285 – – Pt–Ru catalysts 303, 304, 306 –DEFC,see direct ethanol fuel cell (DEFC) – – Pt–Sn/C catalysts 304–306 – PEMFCs –cathodecatalysts – – ethanol 294 – – methanol oxidation tolerance 315 – – methanol 294 – – oxygen reduction reaction (ORR) activity – – reforming process 293, 294 314 –storagedevices – cell performances 297, 298 ––lead–acidcarbattery 287 – electrocatalyst layer 300 ––Li–airbatteries 289 – electrodes 300 – – Li-ion batteries 287, 288 – elevated temperatures 299, 305, 307, 308 – – Li–S batteries 288, 289 – energy density 295 – – Munich city block, Germany 291, 292 – ethanol oxidation reaction – – parameters 285 – – acidic media 301, 302, 310, 312, 313 – – power rating and discharge time 286 – – alkaline media 305, 313, 314 ––RFBs 290 – gas diffusion layer 300 – – thermodynamic and electrical storage – vs. indirect ethanol fuel cells 296 devices 285 – MEA 301 – structure 265 – membranes 299 – top-down approach 264, 281, 315 – nanostructured model catalyst system 309, electroplating 8, 14 310 extended Reference Energy System (eRES) – reforming process 296 – containers 272 – stack hardware and design 297 – graphical representation 271 – system layout 297 – process and commodity 272 dye sensitized solar cells (DSSCs) 107 –USES,see universal Scheme for modeling – basic principle 169 Energy Systems (USES) – sandwich configuration 170 –TiO2 nanotubes, see dye-sensitized TiO2 f nanotubes field-assisted dissolution 118 dye-sensitized TiO2 nanotubes five-turn vertical thin film head 17–18 – commercialization frame plating 37, 38 – – backside vs. front-side illumination fuel cell-vehicles 3 178–180 – – flexible substrates 180 g – – long term stability 181 graphite-SEI core–shell structures – – processing speed 177, 178 – analytic parameters 218 – – scale-up 180, 181 – DFT calculations 196, 219 Index 325 grid-level storage, see liquid metal battery – – scalability 239 (LMB) ––sealingvs. temperature 237, 238 – – thermal management 239 h lithiated graphite core–shell structures, see hand-wound ferrite read/write head 12, 13 graphite-SEI core–shell structures hard anodizing 115 lithiated Si core–shell structures, see Si-SEI hard-baked photoresist 48–50 core–shell structures highly oriented pyrolytic graphite (HOPG) lithium-ion batteries 193 – core–shell structures, 193 see core–shell high performance data storage systems 11 structures – electrochemical energy systems 287, 288 i locally enhanced oxide dissolution 118 inductive read/write head 24 low-temperature sodium-based liquid metal intermittent renewables 227, 228 batteries 255 l m large scale integration (LSI) fabrication 10, magnetic film memory 10, 51 12, 17, 20, 21, 43, 51, 53 magnetic microsystems 100 Lawrence Livermore National Laboratory magnetic recording, UPCD energy flow charts 2 – patterned media design 100 lead–acid car battery 287 – perpendicular recording technology 99 levelized energy costs (LECs) 229 – recording density 100 Li–air battery 4, 289 – thin film deposition methods 100 Li ion battery technologies 4 magnetic thin film head, see thin film head Li–S batteries 289 magnetoresistive (MR) read head 24 LiC6/polymer-coating system 219–221 Margules parameters 76 light-duty vehicles, electrification of membrane electrode assembly (MEA) 301 – electric grid 4 mild anodizing 115 –naturalgas 3 molten salt-based batteries linear stability analysis – nuclear reactor development – dispersion curves 132 – – corrosion effects 246, 249–252 – limitations 133 – – molten salt properties 247, 248 – morphological stability problems 130 – – number of operable nuclear power plants – morphology evolution, 130 see also 245 morphological stability model – sodium electrodeposition – Parkhutik and Shershulsky model 130, – – Castner process 241–243 133 – – Davy process 241 – wavelength destabilizing factor 133 – – Deville process 241 liquid metal battery (LMB) – – Downs cell 242–244 – charge transfer overpotential 232 – thermally-regenerative battery ′′ – vs. competitive technologies 234, 235 ––β -Al2O3 254 – disadvantages 232 – – diagram 252 – market considerations 233 – – Li-based molten salt research 255 – mass transport overpotential 232 ––vs. secondary bimetallic devices 253 – molten salts, see molten salt-based batteries morphological stability model – ohmic overpotential 232 – Cheng and Ngan simulations 134 – overpotential losses 232 – coupled lattice map model 134 – principles of operation 230, 231 – ionic migration fluxes 138, 139 – scale-up 233 – kinetic Monte Carlo simulation 134 – strengths 232 – long-wavelength disturbances 136 – systematic down-selection methodology – mechanical and electrical forces 138 – – cell couple costs 235, 236 – oxide flow effects 137 – – corrosion rate vs. temperature 238 – oxide-solution interface kinetics 136 – – energy storage production estimates 240 – surface tension effects 136 326 Index

morphological stability model (contd.) – mechanisms – transport processes 137 – – field-assisted dissolution 118 – weakly nonlinear analysis 137 – – locally enhanced oxide dissolution 118 multi-turn, vertical thin film head 16 ––patternselection 119 – – pore initiation 118, 119 n ––self-ordering 119 natural gas 3 – metal dissolution 114 Nernst equation 76 – nanotubes 109, 110 – oxide volume expansion and tracer studies p 115, 116 Parkhutik and Shershulsky’s model – pores 109, 110 – linear stability analysis 130, 133 – porous alumina, see anodic porous alumina – oxide-solution interface motion 127, 128 – stress 115 PEMFCs, see polymer electrolyte membrane –TiO2 nanotubes, see TiO2 nanotubes fuel cells (PEMFCs) – universal scaling relations 112 permalloy plating process – vacancy-type defects 117 – electroplate NiFe alloys 29 post Li-ion batteries 288 – NiFe bath aging and steady state operation potential of zero charge (PZC) 79 32 primary energy sources, US 1, 2 – paddle cells 25 PZC, see potential of zero charge (PZC) – plating parameters 31 – real-time, on-line plating bath control 32 r photovoltaics, UPCD RAMAC 305 11, 12 – Cd–Te films 98 rechargeable Li–air batteries 5 –CuInSe2 films 98 rechargeable Li ion batteries 3 –CZTSfilms 99 Redlich–Kister expansion 76 – single crystal Si wafers 98 redox flow batteries (RFBs) 290 – vs. solar systems 97 renewable portfolio standards (RPS) 229 plate-through-mask technology, 17 see also run-time energy system 266 through-mask plating plating frame process, see frame plating s point defect models 124 Schrödinger’s equation 195 polymer electrolyte membrane fuel cells SEI, see solid electrolyte interface (SEI) (PEMFCs) selective electrodesorption based atomic layer – ethanol 294 deposition (SEBALD) 59 – methanol 294 self-organized porous anodic oxides, see – reforming process 293, 294 porous anodic oxide formation porous anodic oxides semiconductor memory 51 – electrochemical transients 110 Si-SEI core–shell structures 196, 221 – hard anodizing 115 Singapore’s electric energy system 272, 274, – mathematical models 275 – – boundary conditions 125, 126 single-turn, horizontal thin film head 15 – – bulk oxide motion 122, 123 single-turn, vertical thin film head 16 – – interface evolution equation 120, SLRR, see surface-limited redox replacement 126–128 (SLRR) – – interfacial reactions 123, 125 solid electrolyte interface (SEI) 193 – – ionic flux 121, 122 solid state memory 10 – – linear stability analysis 130–133 surface-limited redox replacement (SLRR) 59 – – morphology evolution, 110, 133 see also – deposition protocol 63, 64 morphological stability model – deposit morphology 69 – – potential field equations 120, 121 – electrochemical driving force 66–68 – – steady state porous layer growth 128, – nucleation rate 67, 68 130 – organic templates 74, 75 – – stress distributions 121 – Pt monolayer catalyst design 68, 69 Index 327

– reaction kinetics 70 – – long term stability 181 ––firstorder 70 – – processing speed 177, 178 ––Nth order 71 – – scale-up 180, 181 – – open circuit potential (OCP) transients – crucial features 146 71–73 – crystallinity 164 ––secondorder 71 –DSSCs – – zero order 70 – – crystallinity 173 – reaction stoichiometry 65, 66 – – doping 175 – – single wall morphology 177 t – – surface area enhancement 174, 175 thermodynamic energy storage devices 285 – – tube geometry 170, 172, 173 thin film head – duplex structure 153 – batch-fabricated thin film write head 14 – electrochemical anodization 147, 149 – device structures 22 – geometry control – – combined MR read/inductive write head – – diameter 158 24 – – fluoride based electrolytes 157, 158 – – inductive head 24 – – fluoride concentration 158 – – magnetoresistive (MR) read head 24 – – temperature and pH 161 –electroplating 8,14 – – tube length 158 – high performance data storage systems 8, – – water content 161 11 – improved ordering 163 – IBM’s General Products Division (GPD) 18 – morphology 153, 154 – interdisciplinary design approach 16, 52 – self-organization 149, 152 – manufacturing technology evolution, time top-down process 264, 281, 315 line of 8, 9 –materials 23 u – – hard-baked photoresist 45 U.S. Bureau of Standards Molten Salt Studies – – magnetic materials studies 44 248 – memory 8, 10 underpotential co-deposition (UPCD) 59 –patents 12 – bulk alloy thermodynamic model –patterning 22 – – activity coefficient 76 – – ancillary issues 41 – – assumption 78 ––platingframeprocess 37 – – enthalpy of mixing 77 – – through-mask plating 33 – – free energy of mixing 76 – permalloy plating process 22 – – Nernst equation 76 ––electroplateNiFealloys 29 –catalysis – – NiFe bath aging and steady state operation – – atomic surface configuration 96, 97 32 – – binary and ternary Pt-based alloys 97 ––paddlecells 25 – – electronic and geometric effects 96 ––platingparameters 31 – crystal structure, Pt–Pb alloys 92 – – real-time, on-line plating bath control 32 –energetics – processor 8, 10 – – atomistic interactions 80 – schematic drawings 12, 13 – – ion adsorption 78, 79 – 3-D structures 17, 33, 47, 51 – – PZC 79 through-mask plating 15, 21, 22, 33, 34, 36, – – surface defects and reconstruction 79 52 – – surface segregation 79, 80 – clean interface 44 – growth kinetics –resistfor 43 – – Au–Cu binary alloy 82–84 TiO2 nanotubes – – Au–Ni alloys 84, 85 – applications 166 ––Ni–Ptfilms 84 – commercialization – immiscible alloys 90–92 ––backsidevs. front-side illumination – intermetallic compounds 87–90 178–180 – magnetic microsystems 100 – – flexible substrates 180 – magnetic recording 328 Index

underpotential co-deposition (UPCD) (contd.) – Bruckenstein–Swathirajan (BS) isotherm – – hard disk drives 99 63 – – patterned media design 100 – cyclic voltammetry features 61, 62 – – perpendicular recording technology 99 –fuelcellcatalystsynthesis 61 – – recording density 100 – investigation studies 60 – – thin film deposition methods 100 –SLRR,see surface-limited redox replacement –microstructure (SLRR) – – CdTe films 94 – surface decoration 61 – – Fe–Pt films 92, 93 universal Scheme for modeling Energy Systems ––ZnOfilms 94 (USES) – phase diagram – disaggregated physical micro grids 274 – – Au–Cu alloys 86, 87 – vs. eRES 272 ––Au–Nibinarysystem 90–92 – graphical representation 273 ––Cd–Tesystem 89 – Singapore’s electric energy system 272, – – electrodeposited alloys vs. bulk 274, 275 metallurgical alloys 85, 86 UPCD, see underpotential co-deposition – – Pt–Pb binary system 87, 88 (UPCD) – photovoltaics UPD, see underpotential deposition (UPD) ––Cd–Tefilms 98 USES, see Universal Scheme for modeling ––CuInSe2 films 98 Energy Systems (USES) – – CZTS films 99 – – single crystal Si wafers 98 v ––vs. solar systems 97 vanadium redox batteries (VRB) 233 – solid solution 86, 87 – surface morphology w ––Au–Cufilms 94–96 Western Electricity Coordinating Council ––Fe–Ptfilms 96 (WECC) 229 underpotential deposition (UPD) – adsorption isotherms 62