Novel materials for future energy Evgeny Antipov Department of Chemistry, Moscow State University Black Sea Horizon International Workshop “Applied research in chemistry: Smart materials for a smart future” Sofia, Bulgaria 31 March 2016

Top 10 threats to the Sustainability of the Human Civilization 10. Paris Hilton on the road (summer 2007) 9. Over/under population- low risk now, most model predict sustainable population 8. Global warming/Climate change- low risk now, uncertainty high. time scale for irreversible damage is long 7. Ozone layer depletion- under control after banning freones 6. Alien invasion- risk uncertain -students’ idea 5. Religion and Politics- global terrorism and local wars-not reversing progress -just slowing down 4. Pandemic diseases- been confined in the past (AIDS, Ebola, Bird Flu, Flu 1918) 3. Collision with an asteroid- risk low?-moderate uncertainty in risk and timeline, potentially preventable. 2. Nuclear Holocaust- comprehensive nuclear weapons ban 1. End of fossil fuels- solution??? Energy Consumption: 1998: World total: 12.8 TW ( 1 TW= 1012 W) 2050: World total: 30 TW 30% from oil, 80% from all fossil fuels Currently, only a small fraction comes from renewable resources With the current known oil reserves and the current rate of oil consumption there will be no oil left on this planet by 2100 (peak of oil production in )

World Energy Demand Energy consumption predicted to increase 56% from Require TW to support >10 billion by 2050

IPCC, Climate Change 2007: Synthesis Report Global Greenhouse Gas Emissions By Consumption By Source Emissions predicted to rise considerably

Alternative Energy Versus Conventional Energy Closed Loop, Carbon Neutral Versus Open Loop, Carbon Emission

Electrochemical Energy Technologies Chemical energy directly into electrical energy – clean energy technologies Fuel cells, batteries, supercapacitors (electrochemical) Heat Electrolyte AnodeCathode e-e- 2e - Air 1 /2O2 H + conductor H2O 2e - + H2 2H + H2O H2 e-e- Load Electrolyte e-e- e-e- CathodeAnode Li + Charge Discharge o o Electrode Electrolyte Fuel CellBatterySupercapacitor Conversion Device Portable, transportation, & stationary Storage Device Portable & transportation Storage Device Portable & transportation

Energy storage systems Consumer electronics Stationary energy storage HEV, EV Increase of Energy and Power up to 250 Wh/kg

Perspectives for Li-ion batteries Share (’19) CAGR (’09-’19) Robot 17.6%52.4% Storage 18.5%18.2% EV 40.5%79.8% IT 23.3%9.1% Yunil HWANG, A. D. Little Korea, Korea, “Nano-enhanced Market Perspectives in Solar & Li-ion Battery”OECD workshop on "Nanotechnology for sustainable energy options", 2010

Nissan leaf Total weight 1500 kg Batteries weight 300 kg Stored Energy 24 kWh Power 120 h.p. Distance 70 – 220 (150) km Maximum speed 150 km/h Cathode material – LiMn 2 O 4 (E g = 80 Wh/kg) La Jamais Contente electric motors with 50 kW in total 200 individual Pb-PbO 2 cells Total mass 1450 kg Battery mass > 700 kg Max. speed 106 km/h Development of Electric Vehicles

Daily Mail, Safety problem

Key Role of Electrode Materials J.Goodenough & Y.Kim, Chem.Mat. 22 (2010) 587 (Oxidation and reduction of electrolyte outside the window) LiFeBO3 Electrolyte window H 2 O – 1.23 V, Li-electrolyte – up to 4 V To increase specific energy to higher cathode potential and capacity To increase power to higher Li-ion diffusion rate How to reach this value?

Impact of crystallography Design of new structures: -crystal chemistry concepts -data mining -ab initio structure predictions Design of new structures: -crystal chemistry concepts -data mining -ab initio structure predictions Crystallographic aspects of electrochemical reactions: -in situ and ex situ X-ray and neutron diffraction studies -spectroscopic methods (EXAFS, XPS, XANES etc) -microstructure evolution Crystallographic aspects of electrochemical reactions: -in situ and ex situ X-ray and neutron diffraction studies -spectroscopic methods (EXAFS, XPS, XANES etc) -microstructure evolution Electrochemical processes on atomic scale: -ex situ electron diffraction (PED) studies, atomic resolution TEM imaging and spectroscopy -in situ TEM Electrochemical processes on atomic scale: -ex situ electron diffraction (PED) studies, atomic resolution TEM imaging and spectroscopy -in situ TEM J. Hadermann et al., Chem. Mat. 23 (2011) 3540 I.A. Bobrikov et al., J. Power Soc (2014) 356

AVPO 4 F (A = Li, K) – a novel cathode material for high-power rechargeable batteries Fedotov S.S. et al, Chem. Mater. 28 (2016) High operating voltage (> 4 V) High specific capacity(up to ~300 mAh/g) due to multi-electron redox transitions High discharge rate (up to 40С) retaining more than 75% from initial capacity Volume variation on cycling less than 2% !

Possible topics for cooperation New materials for energy applications: batteries fuel cells superconductors photovoltaic water splitting thermoelectrics etc.