1. Electrochemical systems for energy storage devices A. Lisowska-Oleksiak, A.P. Nowak, M. Wilamowska, K. Szybowska Gdansk University of Technology, Chemical Faculty Narutowicza 11/12, 80-233 Gdańsk International EcoEnergy Clusters Meeting | 12.05.2010 |

2. Energy sources can be divided into three broad categories Chemical (oxidizing some reduced substance) or photophysical energy (absorbing sunlight to generate either heat or electricity) Nuclear reactions (splitting heavy nuclei or by fusing light nuclei) Thermomechanical (wind, water, or geological sources of steam or hot water) International EcoEnergy Clusters Meeting | 12.05.2010 |

3. 1)Generation 2)Transmission 3)Convertion 4) Storage ( mechanical, chemical, and thermal ) 5) Consumption Steps in electric energy consume: International EcoEnergy Clusters Meeting | 12.05.2010 |

4. The storage techniques can be divided into four categories 1) Low-power application in isolated areas, essentially to feed transducers and emergency terminals, 2) Medium-power application in isolated areas (individual electrical systems, town supply), 3) Network connection application with peak leveling, 4) Power-quality control applications. International EcoEnergy Clusters Meeting | 12.05.2010 |

5. Electricity storage systems (for high and medium power application) Pumped hydro storage (PHS) – uses for high power applications with 60-85% of conversion efficiency Pump-storage power station in Żarnowiec International EcoEnergy Clusters Meeting | 12.05.2010 |

6. Compressed air energy storage (CAES) – high power applications, energy density ~ 12 kWh/m 3 with efficiency 70% International EcoEnergy Clusters Meeting | 12.05.2010 | Electricity storage systems (for high and medium power application)

7. Energy storage using flow batteries (FBES) Regenesys Technologies (England) ~ 120MWh with 75% effficiency International EcoEnergy Clusters Meeting | 12.05.2010 | Electricity storage systems (for high and medium power application for peak leveling)

8. Fuel cells – Hydrogen energy storage (FC– HES) Alkaline Fuel Cell (AFC), Polymer Exchange Membrane Fuel Cell (PEMFC), Direct Methanol Fuel Cell (DMFC), Phosphoric Acid Fuel Cell (PAFC), Molten Carbonate Fuel Cell (MCFC), Solid Oxide Fuel Cell (SOFC) Main components: 1) Electrolyzer (to produce hydrogen), 2) Fuel cell (to consume hydrogen), 3) tank (to store hydrogen if needed) FC-HES is a low-efficiency solution: Electrolyzer (70%) The fuel cell (50%) Total efficiency ~ 35% International EcoEnergy Clusters Meeting | 12.05.2010 | Electricity storage systems (for low and medium power application)

9. Chemical storage - transform chemical energy into electrical energy using Faradaic process International EcoEnergy Clusters Meeting | 12.05.2010 | Electricity storage systems (for low and medium power application) Ox + ne - = Red Batteries - Primary (source of the energy) - Secondary (storage and source of the energy)

10. (lead–acid, nickel–cadmium, nickel–metal hydride, nickel–iron, zinc–air, iron–air, sodium–sulphur, lithium–ion, lithium–polymer, etc.) (+) high energy densities up to 200 Wh/kg (lithium) (-) low cycleability (up to 4000 cycles) Batteries International EcoEnergy Clusters Meeting | 12.05.2010 |

11. Electricity storage systems Lithium and Lithium-ion batteries (for 3 C technologies) Item Panasonic (cylindrical) Panasonic (prismatic) Nominal voltage3.6 – 3.7 V Nominal capacity720 – 3100 mAh920 – 1950 mAh Mass18 – 95 g16 – 39 g Item Sony (Li-Ion) Sony (Li-polymer) Nominal voltage2.5 – 4.2 V3.0 – 4.2 V Nominal capacity1600 - 2550 mAh830 – 1050 mAh Mass44 – 90 g14.3 – 22.5 g Item A123Systems (cylindrical) A123Systems (prismatic) Nominal voltage3.3 V Nominal capacity1100 – 2300 mAh20 Ah Mass39 – 70 g- International EcoEnergy Clusters Meeting | 12.05.2010 |

12. Electricity storage systems Lithium and Lithium-ion batteries in the future Nowadays the challenge is to obtain material for high power and high energy application able to be used in electric vehicles http://www.treehugger.com/files/2008/02/lithium-ion_battery_factory.php International EcoEnergy Clusters Meeting | 12.05.2010 |

13. Electricity storage systems Lithium-ion batteries (materials) Specific capacity [mAh/g] Potential [V] cathode LiCoO 2 1553.5 – 4.3 LiMn 2 O 4 1403.7 – 4.3 Li(Co,Ni) y Mn 2- y O 4 1604.5 – 5.0 LiMnPO 4 1503.6 – 4.4 LiFePO 4 1703.0 – 3.3 LiNi x Co y Al z O 2 1803.6 – 4.2 anode graphite3500.1 – 0.22 hard carbons > 3500.6 lithium38000 Li 4 Ti 5 O 12 1551.5 Li 4.4 Si42000.3 LiSiCN5500.1 – 0.4 International EcoEnergy Clusters Meeting | 12.05.2010 |

14. Electricity storage systems Chemical storage (Photovoltaic cells) - transform solar energy into electrical energy Problem: To store excess of the energy in one device!!! International EcoEnergy Clusters Meeting | 12.05.2010 |

15. Electricity storage systems Bifunctional TiO 2 for energy storage Materials: WO 3, MoO 3, phosphotungstic acid (PWA), Mechanism of energy storage of TiO 2 /WO 3 composite system International EcoEnergy Clusters Meeting | 12.05.2010 |

16. Schematic Diagram of the Photoelectrolysis Cell for Hydrogen Generation International EcoEnergy Clusters Meeting | 12.05.2010 |

17. ‘I believe that water will one day be used as a fuel because the hydrogen and oxygen which constitute it, used separately or together, will furnish an inexhaustible source of heat and light. I therefore believe that, when coal deposits are oxidised, we will heat ourselves by means of water. Water is the coal of the future’ ‘L’Ile Mysterieuse’, Jules Verne 1875, International EcoEnergy Clusters Meeting | 12.05.2010 |

18. VisUV  E Vis =1.15 V  E UV =0.15 V  E UV-Vis =1.30 V Mehcf TiO 2 Current collector hv Combine photoanode system International EcoEnergy Clusters Meeting | 12.05.2010 |

19. electrochemical double layer capacitors (EDLC) pseudo–capacitors Electrochemical capacitors – store energy in the form of an electric field Electricity storage systems Electrochemical capacitors International EcoEnergy Clusters Meeting | 12.05.2010 |

20. electrochemical double layer capacitors (EDLC) - store energy using ion adsorption (no faradaic (redox) reaction) - high specific surface area (SSA) electrodes (carbon) 100 – 120 F/g (nonaqueous electrolyte) 150 – 300 F/g (aqueous electrolyte) International EcoEnergy Clusters Meeting | 12.05.2010 |

21. pseudo–capacitors (store energy using fast surface redox reactions ) - redox reaction occurs at the surface of the active material (metal oxides (RuO 2, Fe 3 O 4, MnO 2 ), conducting polymers (polyaniline, polypyrrole, polythiophene etc.) Metal oxides: Capacity 1300 F/g (RuO 2 ) Nominal voltage 1.2 V Conducting polymers: Capacity 30 – 40 mAh/g Nominal voltage 1.0 V Materials International EcoEnergy Clusters Meeting | 12.05.2010 |

22. Electrochemical capacitorBattery Charge time 70% charged in secondshours Discharge timeshortlong Charge/discharge cycles10000-1000000500-1000 Pollutantsnonemetals International EcoEnergy Clusters Meeting | 12.05.2010 |

23. BatterySupercapacitor International EcoEnergy Clusters Meeting | 12.05.2010 |

24. pseudo–capacitors (hybrid systems consisted of organic and inorganic conducting materials, e.g. poly(3,4-ethylenedioxythiophene) modified with transition metal hexacyanoferrate* Electricity storage systems * M. Wilamowska, A. Lisowska-Oleksiak, J. Power Sources, 194 (2009) 112-117 ** Snook et al. Electrochem Commun., 9 (2007) 83-88 * ~ 90 F/cm 3 Micro-nanoporous pEDOT** 100 F/cm 3 International EcoEnergy Clusters Meeting | 12.05.2010 |

25. http://www.citytransport.info/Electbus.htm Supercapacitors – alternative way for public transport Prototype Shanghai super-capacitor electric bus at a recharging station Costs ~ 8000 € (after 12 years one may save 160 000 €) Speed (max) 45 km/h Capacity 6 Wh/kg Distance (max) 5-9 km Charging time 5-10 min International EcoEnergy Clusters Meeting | 12.05.2010 |

26. Supercapacitors for wind power station International EcoEnergy Clusters Meeting | 12.05.2010 |

27. Supercapacitors for solar power station ProductionApplication Supercapacitors International EcoEnergy Clusters Meeting | 12.05.2010 |

28. Summary 1 hour3.6 s 41 days Supercapacitors Batteries Flow batteries Pumped hydro storage Compresed air energy storage International EcoEnergy Clusters Meeting | 12.05.2010 |

30. Our laboratory members Prof. A. Lisowska-Oleksiak and the team International EcoEnergy Clusters Meeting | 12.05.2010 |