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MBI-Al銀蟲(chóng) (小有名氣)
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[資源]
共享一本Energy Storage， 基本覆蓋了目前主流的能量轉(zhuǎn)換及存儲(chǔ)器件的設(shè)計(jì)
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Energy Storage Robert A. Huggins Prof. Dr. Robert A. Huggins Stanford University Department of Materials Science & Engineering 94305-4034 Stanford California USA 1 Introduction ............................................................... 1 1.1 Introduction ........................................................... 1 1.2 Storage in the Fuel Distribution System ............................. 2 1.3 Periodic Storage ...................................................... 2 1.3.1 Long-Term, or Seasonal, Storage ............................. 3 1.3.2 Daily and Weekly Storage .................................... 3 1.4 The Problem of Load Leveling ...................................... 3 1.5 Methods That Can Be Used to Reduce the Magnitude of the Variations in Energy Demand ................................. 5 1.6 Short-Term Transients ................................................ 7 1.7 Portable Applications That Require Energy Storage ................ 7 1.7.1 Storage Methods for Use with Portable Electronic Devices ............................................. 8 1.7.2 Energy Use and Storage in Vehicles . ......................... 8 1.8 Hydrogen Propulsion of Vehicles .................................... 9 1.9 Temperature Regulation in Buildings ............................... 10 1.10 Improved Lighting Technologies ................................... 10 1.11 The Structure of This Book ......................................... 11 References . . ............................................................... 12 2 General Concepts ........................................................ 13 2.1 Introduction .......................................................... 13 2.2 The Mechanical Equivalent of Heat ................................ 13 2.3 The First Law of Thermodynamics – Conservation of Energy ..... 14 2.4 Enthalpy ............................................................. 14 2.5 Entropy .............................................................. 15 2.5.1 Thermal Entropy ............................................. 15 2.5.2 Configurational Entropy ...................................... 16 2.6 The Energy Available to Do Work ................................. 16 2.7 The Temperature Dependence of G, H and S ....................... 17 2.8 Irreversible and Reversible Storage Modes . ........................ 17 2.9 The Carnot Limitation ............................................... 18 2.10 Energy Quality ...................................................... 18 References . . ............................................................... 19 3 Thermal Energy Storage ................................................ 21 3.1 Introduction ........................................................... 21 3.2 Sensible Heat ......................................................... 22 3.3 Latent Heat ............................................................ 23 3.3.1 Inorganic Phase Change Materials ............................ 24 3.3.2 Organic Phase Change Materials .............................. 26 3.4 Quasi-Latent Heat .................................................... 27 3.5 Heat Pumps ........................................................... 27 References . . ............................................................... 27 4 Reversible Chemical Reactions ......................................... 29 4.1 Introduction ........................................................... 29 4.2 Types of Non-congruent Chemical Reactions ........................ 29 4.2.1 Insertion Reactions ............................................ 30 4.2.2 Formation Reactions ........................................... 31 4.2.3 Decomposition Reactions ...................................... 32 4.2.4 Displacement Reactions ....................................... 32 4.3 Phase Diagrams ....................................................... 33 4.3.1 The Gibbs Phase Rule ......................................... 33 4.3.2 Binary Phase Diagrams ........................................ 34 4.3.3 The Lever Rule ................................................ 36 4.3.4 Three-Phase Reactions in Binary Systems .................... 37 4.3.5 Examples of Materials Systems with Peritectic Reactions .... 39 4.3.6 Binary Systems That Contain Eutectic Reactions ............. 39 4.4 Thermal Effects Related to Liquid and Solid Reactions ............. 42 4.5 Thermal Effects Related to Reversible Gas Phase Reactions ........ 45 References . . ............................................................... 48 5 Energy Storage in Organic Fuels ....................................... 49 5.1 Introduction ........................................................... 49 5.2 Storage of Energy in Living Biomass ................................ 49 5.3 Storage via Animals .................................................. 51 5.4 Hard Biomass ......................................................... 52 5.5 Synthetic Liquid Fuels ................................................ 52 5.6 Gaseous Fuels Stored as Liquids ..................................... 52 5.7 The Energy Content of Various Materials Used as Fuels ............ 53 References . . ............................................................... 54 6 Mechanical Energy Storage ............................................. 55 6.1 Introduction ........................................................... 55 6.2 Potential Energy Storage ............................................. 55 6.3 Energy Storage in Pressurized Gas ................................... 57 6.4 Potential Energy Storage Using Gravity ............................. 58 6.5 Hydroelectric Power .................................................. 60 6.6 Pumped-Hydro Storage ............................................... 61 6.7 Use of the Kinetic Energy in Moving Water . ........................ 62 6.8 Kinetic Energy in Mechanical Systems .............................. 62 6.8.1 Linear Kinetic Energy ......................................... 63 6.8.2 Rotational Kinetic Energy ..................................... 64 6.9 Internal Structural Energy Storage ................................... 67 References . . ............................................................... 68 7 Electromagnetic Energy Storage ....................................... 69 7.1 Introduction ........................................................... 69 7.2 Energy Storage in Capacitors ......................................... 70 7.2.1 Energy in a Parallel Plate Capacitor . . . ........................ 70 7.3 Electrochemical Charge Storage Mechanisms ....................... 71 7.3.1 Electrostatic Energy Storage in the Electrical Double-Layer in the Vicinity of an Electrolyte/Electrode Interface ........................................................ 72 7.3.2 Underpotential Faradaic Two-Dimensional Adsorption on the Surface of a Solid Electrode . . . ........................ 73 7.3.3 Faradaic Deposition That Results in the Three-Dimensional Absorption of the Electroactive Species into the Bulk Solid Electrode Material by an Insertion Reaction .................. 73 7.3.4 Faradaically – Driven Reconstitution Reactions .............. 76 7.4 Comparative Magnitudes of Energy Storage . ........................ 77 7.5 Importance of the Quality of the Stored Energy ..................... 78 7.6 Transient Behavior of a Capacitor .................................... 79 7.7 Modeling Transient Behavior of Electrochemical Systems Containing Capacitive Components Using LaPlace Transforms ............................................................ 81 7.7.1 Introduction .................................................... 81 7.7.2 Use of LaPlace Transform Techniques ........................ 82 7.7.3 Simple Examples .............................................. 83 7.8 Energy Storage in Magnetic Systems ................................ 84 7.8.1 Energy in a Material in a Magnetic Field ..................... 85 7.8.2 Energy Storage in Superconducting Magnetic Systems ...... 89 7.8.3 Superconductive Materials .................................... 90 References . . ............................................................... 92 8 Hydrogen Storage ........................................................ 95 8.1 Introduction ........................................................... 95 8.2 The Production of Hydrogen ......................................... 96 8.2.1 The Steam Reforming Process ................................ 96 8.2.2 The Reaction of Steam with Carbon . . ........................ 98 8.2.3 Electrolytic Production of Hydrogen . . ....................... 100 8.2.4 Thermal Decomposition of Water to Produce Hydrogen .... 102 8.2.5 Chemical Extraction of Hydrogen from Water .............. 103 8.2.6 Additional Approaches ....................................... 107 8.3 Governmental Promotion of the Use of Hydrogen ................. 107 8.4 Current On-Board Hydrogen Storage Alternatives ................. 109 8.4.1 Storage of Gaseous Hydrogen in High Pressure Tanks ...... 110 8.4.2 Storage of Liquid Hydrogen in Insulated Tanks ............. 110 8.4.3 Storage of Hydrogen as Protons in Solids; Metal Hydrides ...................................................... 110 8.5 Other Approaches to Hydrogen Storage ............................ 111 8.5.1 Hydrogen from the Decomposition of Materials Containing Hydride Anions .................................. 112 8.5.2 Ammonia and Related Materials as Hydrogen Storage Media ................................................ 113 8.5.3 Storage of Hydrogen in Reversible Organic Liquids ........ 114 8.6 The Question of Safety ............................................. 116 References . . .............................................................. 117 9 Introduction to Electrochemical Energy Storage .................... 119 9.1 Introduction ......................................................... 119 9.2 Simple Chemical and Electrochemical Reactions .................. 120 9.3 Major Types of Reaction Mechanisms in Electrochemical Cells . . 124 9.3.1 Formation Reactions .......................................... 125 9.3.2 Displacement Reactions ...................................... 127 9.3.3 Insertion Reactions ........................................... 127 9.4 Important Practical Parameters ..................................... 128 9.4.1 The Operating Voltage and the Concept of Energy Quality ........................................................ 130 9.4.2 The Charge Capacity ......................................... 132 9.4.3 The Maximum Theoretical Specific Energy ................. 132 9.4.4 Variation of the Voltage as Batteries are Discharged and Recharged ................................................ 133 9.4.5 Cycling Behavior ............................................. 133 9.4.6 Self-Discharge ................................................ 135 9.5 General Equivalent Circuit of an Electrochemical Cell ............ 136 9.5.1 Influence of Impedances to the Transport of Ionic and Atomic Species Within the Cell . . ....................... 137 9.5.2 Influence of Electronic Leakage Within the Electrolyte ..... 138 9.5.3 Transference Numbers of Individual Species in an Electrochemical Cell ................................... 139 9.5.4 Relation Between the Output Voltage and the Values of the Ionic and Electronic Transference Numbers .......... 140 9.5.5 Joule Heating Due to Self-Discharge in Electrochemical Cells ...................................... 141 9.5.6 What if Current is Drawn from the Cell? .................... 141 References . . .............................................................. 143 10 Principles Determining the Voltages and Capacities of Electrochemical Cells ................................................ 145 10.1 Introduction ........................................................ 145 10.2 Thermodynamic Properties of Individual Species ................ 145 10.3 A Simple Example: The Lithium/Iodine Cell ..................... 147 10.3.1 Calculation of the Maximum Theoretical Specific Energy ............................................ 149 10.3.2 The Temperature Dependence of the Cell Voltage ....... 150 10.4 The Shape of Discharge Curves and the Gibbs Phase Rule ...... 151 10.5 The Coulometric Titration Technique ............................ 157 References . . .............................................................. 160 11 Binary Electrodes Under Equilibrium or Near-Equilibrium Conditions ............................................................... 161 11.1 Introduction ...................................................... 161 11.2 Relationship Between Phase Diagrams and Electrical Potentials in Binary Systems ..................................... 161 11.3 A Real Example, The Lithium: Antimony System Again ....... 164 11.4 Stability Ranges of Phases ....................................... 168 11.5 Another Example, The Lithium: Bismuth System .............. 168 11.6 Coulometric Titration Measurements on other Binary Systems . . . 169 11.7 Temperature Dependence of the Potential . ...................... 170 11.8 Application to Oxides and Similar Materials .................... 172 11.9 Ellingham Diagrams and Difference Diagrams ................. 174 11.10 Liquid Binary Electrodes ........................................ 175 11.11 Comments on Mechanisms and Terminology ................... 176 11.12 Summary ......................................................... 178 References . . .............................................................. 179 12 Ternary Electrodes Under Equilibrium or Near-Equilibrium Conditions ............................................................... 181 12.1 Introduction ........................................................ 181 12.2 Ternary Phase Diagrams and Phase Stability Diagrams .......... 181 12.3 Comments on the Influence of Sub-triangle Configurations in Ternary Systems ............................................... 183 12.4 An Example: The Sodium/Nickel Chloride “Zebra” System . . . 186 12.5 A Second Example: The Lithium–Copper–Chlorine Ternary System .................................................. 189 12.5.1 Calculation of the Voltages in This System ............. 190 12.5.2 Experimental Arrangement for/Copper Chloride Cells ............................................ 192 12.6 Calculation of the Maximum Theoretical Specific Energies of Li/CuCl and Li/CuCl2 Cells .................................. 193 12.7 Specific Capacity and Capacity Density in Ternary Systems ........................................................... 194 12.8 Another Group of Examples: Metal Hydride Systems Containing Magnesium .......................................... 194 12.9 Further Ternary Examples: Lithium-Transition Metal Oxides . . . 200 12.10 Ternary Systems Composed of Two Binary Metal Alloys ..................................................... 204 12.10.1 An Example, The Li–Cd–Sn System at Ambient Temperature ............................................. 205 12.11 What About the Presence of Additional Components? ......... 205 12.12 Summary ......................................................... 206 References . . .............................................................. 206 13 Insertion Reaction Electrodes .......................................... 207 13.1 Introduction ...................................................... 207 13.2 Examples of the Insertion of Guest Species into Layer Structures ............................................. 209 13.3 Floating and Pillared Layer Structures .......................... 210 13.4 More on Terminology Related to the Insertion of Species into Solids ........................................................ 210 13.5 Types of Inserted Guest Species Configurations ................ 211 13.6 Sequential Insertion Reactions ................................... 211 13.7 Co-insertion of Solvent Species ................................. 215 13.8 Insertion into Materials with Parallel Linear Tunnels ........... 216 13.9 Changes in the Host Structure Induced by Guest Insertion or Extraction ..................................................... 216 13.9.1 Conversion of the Host Structure from Crystalline to Amorphous ............................................ 217 13.9.2 Dependence of the Product upon the Potential .......... 219 13.9.3 Changes upon the Initial Extraction of the Mobile Species ........................................... 219 13.10 The Variation of the Potential with Composition in Insertion Reaction Electrodes .............................................. 220 13.10.1 Introduction ............................................. 220 13.10.2 The Variation of the Electrical Potential with Composition in Simple Metallic Solid Solutions ....... 221 13.10.3 Configurational Entropy of the Guest Ions ............. 222 13.10.4 The Concentration Dependence of the Chemical Potential of the Electrons in a Metallic Solid Solution . . . 223 13.10.5 Sum of the Effect of These Two Components upon the Electrical Potential of a Metallic Solid Solution .................................................. 223 13.10.6 The Composition-Dependence of the Potential in the Case of Insertion Reactions That Involve a Two-Phase Reconstitution Reaction ................................. 225 13.11 Final Comments .................................................. 227 References . . .............................................................. 227 14 Electrode Reactions that Deviate from Complete Equilibrium ..... 229 14.1 Introduction ........................................................ 229 14.2 Stable and Metastable Equilibrium ............................... 229 14.3 Selective Equilibrium ............................................. 231 14.4 Formation of Amorphous Vs. Crystalline Structures ............. 232 14.5 Deviations from Equilibrium for Kinetic Reasons ................ 234 15 Lead-Acid Batteries ..................................................... 237 15.1 Introduction ...................................................... 237 15.2 Basic Chemistry of the Pb-Acid System . . . ...................... 238 15.2.1 Calculation of the MTSE ................................ 239 15.2.2 Variation of the Cell Voltage with the State ofCharge ................................................. 239 15.3 Potentials of the Individual Electrodes .......................... 240 15.4 Relation to the Mechanism of the Electrochemical 15.4 Relation to the Mechanism of the Electrochemical Reactions in the Electrodes ...................................... 242 15.5 Construction of the Electrodes ................................... 242 15.5.1 Volume Changes and Shedding .......................... 243 15.6 Alloys Used in Electrode Grids .................................. 244 15.7 Alternative Grid Materials and Designs . . . ...................... 246 15.8 Development of Sealed Pb-Acid Batteries ...................... 246 15.9 Additional Design Variations .................................... 247 15.9.1 Other Improvements ..................................... 249 15.10 Rapid Diffusion of Hydrogen in PbO2 ........................... 250 References . . .............................................................. 250 16 Negative Electrodes in Other Rechargeable Aqueous Systems ..... 251 16.1 Introduction ........................................................ 251 16.2 The Zinc Electrode in Aqueous Systems . . . ...................... 251 16.2.1 Introduction .............................................. 251 16.2.2 Thermodynamic Relationships in the H–Zn–O System . 252 16.2.3 Problems with the Zinc Electrode . ...................... 253 16.3 The “Cadmium” Electrode ........................................ 253 16.3.1 Introduction .............................................. 253 16.3.2 Thermodynamic Relationships in the H–Cd–O System .................................................... 254 16.3.3 Comments on the Mechanism of Operation of the Cadmium Electrode ............................... 255 16.4 Metal Hydride Electrodes ......................................... 256 16.4.1 Introduction .............................................. 256 16.4.2 Comments on the Development of Commercial Metal Hydride Electrode Batteries . ...................... 257 16.4.3 Hydride Materials Currently Being Used ................ 257 16.4.4 Disproportionation and Activation . ...................... 258 16.4.5 Pressure–Composition Relation .......................... 259 16.4.6 The Influence of Temperature ........................... 260 16.4.7 AB2 Alloys ............................................... 261 16.4.8 General Comparison of These Two Structural Types . . . 262 16.4.9 Other Alloys That Have Not Been Used in Commercial Batteries ................................. 264 16.4.10 Microencapsulation of Hydride Particles ................ 264 16.4.11 Other Binders ............................................ 264 16.4.12 Inclusion of a Solid Electrolyte in the Negative Electrode of Hydride Cells ............................... 265 16.4.13 Maximum Theoretical Capacities of Various Metal Hydrides .................................................. 265 References . . .............................................................. 266 17 Positive Electrodes in Other Aqueous Systems ....................... 267 17.1 Introduction ........................................................ 267 17.1 Introduction ........................................................ 267 17.2 Manganese Dioxide Electrodes in Aqueous Systems ............. 268 17.2.1 Introduction ................................................ 268 17.2.2 The Open Circuit Potential ................................ 269 17.2.3 Variation of the Potential During Discharge .............. 270 17.3 The “Nickel” Electrode ........................................... 270 17.3.1 Introduction ................................................ 270 17.3.2 Structural Aspects of the Ni(OH)2 and NiOOH Phases ........................................ 271 17.3.3 Mechanism of Operation .................................. 272 17.3.4 Relations Between Electrochemical and Structural Features .................................................... 274 17.3.5 Self-Discharge ............................................. 276 17.3.6 Overcharge ................................................ 278 17.3.7 Relation to Thermodynamic Information ................. 278 17.4 Cause of the Memory Effect in “Nickel” Electrodes ............. 281 17.4.1 Introduction ................................................ 281 17.4.2 Mechanistic Features of the Operation of the “Nickel” Electrode ................................................... 282 17.4.3 Overcharging Phenomena ................................. 285 17.4.4 Conclusions ................................................ 287 References . . .............................................................. 288 18 Negative Electrodes in Lithium Systems .............................. 291 18.1 Introduction ........................................................ 291 18.2 Elemental Lithium Electrodes ..................................... 292 18.2.1 Deposition at Unwanted Locations . ...................... 292 18.2.2 Shape Change ............................................. 292 18.2.3 Dendrites ................................................... 293 18.2.4 Filamentary Growth ....................................... 293 18.2.5 Thermal Runaway ......................................... 294 18.3 Alternatives to the Use of Elemental Lithium .................... 295 18.4 Lithium–Carbon Alloys ........................................... 295 18.4.1 Introduction ................................................ 295 18.4.2 Ideal Structure of Graphite Saturated With Lithium ...... 297 18.4.3 Variations in the Structure of Graphite ................... 298 18.4.4 Structural Aspects of Lithium Insertion into Graphitic Carbons .................................................... 299 18.4.5 Electrochemical Behavior of Lithium in Graphite ........ 300 18.4.6 Electrochemical Behavior of Lithium in Amorphous Carbons .................................................... 302 18.4.7 Lithium in Hydrogen-Containing Carbons ................ 303 18.5 Metallic Lithium Alloys ........................................... 304 18.5.1 Introduction ................................................ 304 18.5.2 Equilibrium Thermodynamic Properties of Binary Lithium Alloys ............................................ 305 18.5.3 Experiments at Ambient Temperature .................... 305 18.5.3 Experiments at Ambient Temperature .................... 305 18.5.4 Liquid Binary Alloys ...................................... 306 18.5.5 Mixed-Conductor Matrix Electrodes ...................... 306 18.5.6 Decrepitation .............................................. 309 18.5.7 Modification of the Micro- and Nanostructure of the Electrode ............................................ 313 18.5.8 Formation of Amorphous Products at Ambient Temperatures .............................................. 315 References . . .............................................................. 316 19 Positive Electrodes in Lithium Systems ............................... 319 19.1 Introduction ........................................................ 319 19.2 Insertion Reaction, Instead of Reconstitution Reaction, Electrodes .......................................................... 320 19.2.1 More Than One Type of Interstitial Site or More Than One Type of Redox Species . . ...................... 321 19.3 Cells Assembled in the Discharged State . . . ...................... 321 19.4 Solid Positive Electrodes in Lithium Systems .................... 323 19.4.1 Introduction ................................................ 323 19.4.2 Influence of the Crystallographic Environment on the Potential ............................................ 326 19.4.3 Oxides with Structures in Which the Oxygen Anions Are in a Face-Centered Cubic Array ...................... 327 19.4.4 Materials in Which the Oxide Ions Are in a Close-Packed Hexagonal Array ................. 335 19.4.5 Materials Containing Fluoride Ions . ...................... 339 19.4.6 Hybrid Ion Cells ........................................... 340 19.4.7 Amorphization ............................................. 340 19.4.8 The Oxygen Evolution Problem .......................... 340 19.4.9 Final Comments on This Topic ........................... 346 19.5 Hydrogen and Water in Positive Electrode Materials ............ 346 19.5.1 Introduction ................................................ 346 19.5.2 Ion Exchange .............................................. 347 19.5.3 Simple Addition Methods ................................. 347 19.5.4 Thermodynamics of the Lithium–Hydrogen–Oxygen System ..................................................... 348 19.5.5 Examples of Phases Containing Lithium That Are Stable in Water .................................. 349 19.5.6 Materials That Have Potentials Above the Stability Window of Water ......................................... 350 19.5.7 Absorption of Protons from Water Vapor in the Atmosphere ......................................... 350 19.5.8 Extraction of Lithium from Aqueous Solutions .......... 351 References . . .............................................................. 351 20 Primary, Nonrechargeable Batteries .................................. 355 20.1 Introduction ........................................................ 355 20.1 Introduction ........................................................ 355 20.2 The Common Zn/MnO2 “Alkaline” Cell . . . ...................... 355 20.3 Ambient Temperature Li/FeS2 Cells .............................. 356 20.4 Li/I2 Batteries for Heart Pacemakers .............................. 357 20.5 Lithium/Silver Vanadium Oxide Defibrillator Batteries .......... 357 20.6 Zn/Air Cells ....................................................... 359 20.7 Li/CFx Cells ....................................................... 362 20.8 Reserve Batteries .................................................. 363 20.8.1 Introduction ................................................ 363 20.8.2 The Li/SO2 System ........................................ 364 20.8.3 The Li/SOCl2 System ..................................... 365 20.8.4 Li/FeS2 Elevated Temperature Batteries .................. 365 References . . .............................................................. 366 21 Energy Storage for Medium-to-Large Scale Applications ........... 367 21.1 Introduction ........................................................ 367 21.2 Utility Load Leveling, Peak Shaving, Transients ................. 367 21.3 Storage of Solar- and Wind-Generated Energy ................... 368 21.4 Storage Technologies that are Especially Suited to these Applications .............................................. 368 21.4.1 Lead-Acid Batteries for Large Scale Storage ............. 368 21.4.2 Sodium/Sulfur Batteries ................................... 369 21.4.3 Flow Batteries ............................................. 370 21.4.4 All-Liquid Batteries ....................................... 374 21.5 Storage of Energy for Vehicle Propulsion . . ...................... 376 21.5.1 Introduction ................................................ 376 21.5.2 ZEBRA Batteries .......................................... 379 21.5.3 General Comments on Hybrid System Strategies ........ 380 References . . .............................................................. 381 22 A Look to the Future ................................................... 383 22.1 Introduction ........................................................ 383 22.2 Recently Discovered Large Natural Gas Source .................. 384 22.3 Emerging Technological Directions .............................. 385 22.4 Examples of Interesting New Research Directions ............... 387 22.4.1 Organic “Plastic Crystal” Materials ...................... 387 22.4.2 Organic Electrode Materials for Lithium Batteries ................................................... 387 22.4.3 New Materials Preparation and Cell Fabrication Methods .................................................... 388 22.4.4 Alternate Electrolytes ..................................... 389 22.5 Final Comments ................................................... 389 References . . .............................................................. 389 Index .......................................................................... 391 1.jpg |
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