The 21st Century Frontier

과학기술부 21세기 프론티어연구개발사업 21st Century Frontier R&D Program

APPLICATIONAPPLICATION OFOF NANOTECHNOGYNANOTECHNOGY ONON HYDROGENHYDROGEN PRODUCTIONPRODUCTION ANDAND STORAGESTORAGE ININ KOREAKOREA

April 26~27, 2007

Jong Won Kim Director Hydrogen Energy R&D Center http://www.h2.re.kr

4th US-Korea NanoForum, Honolulu, USA, April 26-27, 2007 1 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 1 The 21st Century Frontier

Outline

I. Hydrogen Economy- Vision II. Technical barrier III. Current R&D activities related to nanotechnology IV. Conclusions

4th US-Korea NanoForum, Honolulu, USA, April 26-27, 2007 2 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 2 The 21st Century Frontier

1. Hydrogen economy-vision Hydrogen Economy Nuclear Hydrogen storage/transportation/distribution Ship

Water Electrolysis Wind Infrastructure Bus

Solar Photochemical/ Vehicle Thermochemical/ Biological H2 Production

Biomass Distributed Power Residential Mobile Submarine

3 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 3 The 21st Century Frontier

2. Technical barriers Production/ Amounts Utilization Utilization *Oil refinery (desulfurising, reforming) ~ 1% TPES *Chem.Ind.: Ammonia, fertilizer, methanol (Total Primary *Metal Industry *Food( Fat, oil) *welding *Electronics Energy supply) *cryogenic *Electric generator-cooling

Raw materials User ~95% fossil fuel (NG etc) About 50million tons ~ 45% petroleum ~40% Chem. Ind. ~ 5% electrolysis ~15% others <35% sales >65% self-consumption DomesticDomestic 0.970.97 millionmillion tonton TradeTrade 4848 thousandthousand ton*ton*

* Source: Bongjin Kim et al: “The status of domestic hydrogen production, consumption and distribution”, Trans. Of the Korea Hydrogen and New Energy Society, 16(4)391-399(2005) 4 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 4 The 21st Century Frontier

3-1 current R&D activities Summary of Hydrogen & Fuel Cell R&D program

Table 1. Hydrogen & Fuel Cell R&D program in Korea

Program Sponsor Period

21st Frontier Program (Hydrogen Energy R&D Center) MOST 2003-2013 (www.h2.re.kr) National RD&D Organization for hydrogen and fuel cell MOCIE 2003- (www.h2fc.or.kr) Nuclear Hydrogen Development and Demonstration MOST 2004-2021 Project (NHDD) (www.hydrogen.re.kr) Korea IGCC RDD&D Organization (www.igcc.or.kr) MOCIE 2006-2014

MOCIE: Ministry of Commerce, Industry and Energy MOST : Ministry of Science and Technology

5 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 5 The 21st Century Frontier

3-1 current R&D activities HERC (Hydrogen Energy R&D Center)

Role - Developing the National Hydrogen Energy R&D Program * 21st Century Frontier Program R&D Period 01 Oct. 2003 ~ 31 March 2013 (109.5 years for 3 phases) R&D Fund Total 90 million US dollars (Government : 80 million dollars, Industry : 10 million dollars) Sponsoring Ministry Ministry of Science & Technology, Republic of Korea

Source: www.h2.re.kr 6 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 6 The 21st Century Frontier

3-1 current R&D activities National RD&D Organization for Hydrogen and Fuel cell

Exclusive Ministry of Commerce, International Evaluation Industry and Energy Collaboration Committee (New & Renewable Energy Center) (IEA, IPHE)

Steering National RD&D Organization Committee for Hydrogen and Fuel Cell

Subcommittee

Industrial/ Monitoring Hydrogen Commercial/ Transportation Portable (Validation Infra Residential Fuel Cell Fuel Cell Demonstration) Fuel Cell

„ Established in 2003 to expedite the commercialization of hydrogen and fuel cell technology. „ Propose the vision for hydrogen economy in Korea. „ Develop a national plan, road maps and action plans to create a new industry. „ Coordinate and manage RD&D programs supported by government. 7 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 7 The 21st Century Frontier

3-1 current R&D activities Nuclear Hydrogen Development and Demonstration Project

• To build 200MWth class VHTR and to produce 20 thousand tons of hydrogen . ¾ Period : 2004 – 2021 (18years) ¾ Budget : ~ US$ 1.0 Billion (under discussion) PCU

Compre-

Cooler ssor

H H2 2

Recup- TBN erator I-S Process HTES

AC/DC Converter O2

H2SO4 Decomposition H SO 1000oC 970oC 2 4 Electrolyser

SO2+H2O + ½O2

H 2 H2+ H2O+ H2SO4 Evaporator O2 HI Decomposition O HX O2 VHTR IHX 2HI

H2 + I2 + Condenser

H2+ 2HI H2SO4 H2O+ O2 H2+ Separator H2O I2 + SO2+H2O + H2O

Bunsen Reaction

H2O H O H2O Source: www.hydrogen.re.kr 8 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 8 The 21st Century Frontier III. -3 IGCC Project

3-1 current R&D activities □ Korea IGCC RDD&D organization

MOCIE (New and Renewable nd Energy Center) - Launched on 22 December, 2006 - In the year 2014, 300MW IGCC plant will be constructed and operated Korea IGCC RDD&D - 599.2 billion won (Government 165.2) . Organization

*MOCIE; Ministry of Commerce, Industry and Energy

1st subdivision 2nd subdivision 3rd subdivision 4th subdivision (Heavy industry, (Power company, (Power company, (Research Institute Research Institute) construction Research Institute) and University) Design of company) Operation of Localization of unit Gasification plant and Design, manufacture demonstration plant process process and construction of demonstration plant 9 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 9 The 21st Century Frontier

3-1 current R&D activities

R&D Activities in the Phase II (HERC)(2006-2009)

Hydrogen Production Action type NG steam reforming for hydrogen station (AR/DE) (Mid) Biological hydrogen production (BR/AR/DE) (Long) Thermo-chemical hydrogen production (BR/AR/DE) (Long) Photocatalytic and photochemical hydrogen production (BR/AR/DE) (Long) Water electrolysis using PEM and THE (BR/AR/DE) (Long)

Hydrogen Storage Hydrogen storage using metal hydrides (BR/AR/DE) (Long) Hydrogen storage using nano-structured materials (BR/AR/DE) (Long) Hydrogen storage using chemical hydrides (BR/AR/DE) (Long)

Hydrogen Utilization Linear power/generation system of hydrogen combustion (AR/DE) (Long) Hydrogen sensor (AR/DE) (Long)

Supporting Project Measurement techniques for hydrogen storage materials Policy and technology assessment

BR: basic research, AR: applied research, DE: demonstration 10 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 10 The 21st Century Frontier II. Current R&D Activities 3-2. current R&D activities related to nanotechnology Biological Hydrogen Production

™ R & D Objectives

-Scale-up and optimization of fermentative H2 production process and development of bio-mimetic

H2 production system ▶ Fermentative bioreactor scale : > 500 L 3 3 ▶ Fermentative H2 productivity : 15 Nm H2/day/m ▶ H productivity by bio-mimetic system : 40 L H /kg 2 2 ™ Recent publications: protein/hr Int.J.Hydrogen Energy,31(2006)812-816 Int.J.Hydrogen Energy,31(2006)121-127 Korea Patent 2005-0032480

Project Manager: Dr. Kim, Mi-Sun, Bioreactors for photosynthetic and fermentative H2 production [email protected] 11 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 11 The 21st Century Frontier

3-2. current R&D activities related to nanotechnology Nanotechnology and Biological hydrogen production Flow direction • Introducing nano-size membrane to bioreactor for enhancing hydrogen production • Adjusting the pore size(40,100nm) for long term operation

L

G B MembraneMembrane F H bioreactorbioreactor (working(working K F M vol.vol. 2.42.4 L)L) usingusing J E PVDFPVDF hollow-fiberhollow-fiber B I B B

N

C A 12 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu, USA, April 26-27, 2007 Hydrogen Energy R&D Center 12 , 2004.7.9D The 21st Century Frontier

3-2. current R&D activities related to nanotechnology HydrogenHydrogen productionproduction usingusing membranemembrane bioreactorbioreactor atat 6060ooCC

CSTR MBR 16 2.5 3.0 (A) Production (A) 100 nm pore-size 2.0 2.5 12 Yield 40 nm pore-size 2.0 1.5

/L/day) 8 1.5 2 1.0

Cell (g/L) Cell 1.0

(L H (L 4 production rate 2 0.5 0.5 H yield (mol/mol glucose) 0 0.0 2 0.0 H 100 3 0.5 (B) 100 nm pore-size 80 Glucose 0.4 40 nm pore-size

2 )

Biomass 2 60 0.3 (B) 40 1 0.2 (kgf/cm 20 (g/L) Biomass 0.1 Glucose removal (%) 0 0 0.0

10.3 6.7 Pressure across membrane 4.0 4.0 0 5 10 15 20 25 30 HRT (h) Time (day)

13 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 13 The 21st Century Frontier

3-2. current R&D activities related to nanotechnology SchematicSchematic diagramdiagram ofof bio-mimeticbio-mimetic HH22 productionproduction systemsystem e- R&D Contents:

ElectronElectron donor/carrierdonor/carrier (photosystem,(photosystem, microorganism)microorganism) H2O sun e- e- Biopolymer immobilization 2 H+ O2 System integration

organics hydrogenase e- H2 o separation/purification

CO2 o microorganism modification Genome sequencing photo-sensitizer (chlorophyil) Proteomes microorganism hydrogenase 14 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 14 The 21st Century Frontier

3-2. current R&D activities related to nanotechnology Photocatalytic and Photoelectrochemical Hydrogen Production Technology

™ R&D Objectives - Highly active water splitting photocatalysts- material - Development of the system for 3% solar light conversion design efficiency (@AM 1.5) utilizing solar light-sensitizing - Tandem-type photoelectrochemical cell modules photocatalyst - System establishment for PEC cell of 7% efficiency - PEC cell of 7% efficiency - Photo/Biocatalyst ™ Content of R&D Activities ™ - Q-sized photocatalysts and mesoporous media - Layered Perovskite and Composite Photocatalysts Solar light Designed & controlled photocatalyst KRICT, KIER, KIST, POSTECH, Nanopac

+ e- h

+ H2O or H

Enzyme Mechanism

Sensitizer System Waste design resources PEC Reactor related design If any question, contact: Dr. Moon,Sang-Jin [email protected] H2 + (1/2 O2 or Red) 15 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 15 The 21st Century Frontier

3-2. current R&D activities Nanotechnology and sensorrelated to nanotechnology z Enhancement of gas sensitivity using ceramic nano particles with high surface area • Semiconductor type hydrogen sensor

- measure the change of resistance of semiconducting material (such as SnO2, In2O3, TiO2 etc) according to the adsorption of hydrogen gas. Nano sized semi-conducting material could enhance the sensitivity. • Catalytic combustion type sensor - nano sized supporting material could enhance the sensitivity of sensor

Chi-Hwan Han et. al, "Micro-bead of nano-crystalline F-doped SnO2 as a sensitive hydrogen gas sensor", Sensors & Actuators B, 2005, 109, 264-269.

Chi-Hwan Han et. al, "Enhancement of H2-sensing Properties of F-doped SnO2 Sensor by Surface Modification with SiO2", Sensors, 2006, 6, 492-502. 16 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 16 The 21st Century Frontier

3-2. current R&D activities related to nanotechnology Enhancement of sensitivity using nano materials

• Enhancement of sensitivity of catalytic combustion type • Linearity of sensitivity of ceramic hydrogen sensor using nano hydrogen sensor using nano particle particle or nano rod of Pd/TiO2, Pt/TiO2 17 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 17 The 21st Century Frontier Pressurized hydrogen storage vessel 3-2. current R&D activities related to nanotechnology

TYPE 3

Process design and analysis Filament winding and Proto type vessel solidification

TYPE 4

liner Analysis using finite element method Storage vessel after coating process

Tucsan using a high pressure vessel 18 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 18 The 21st Century Frontier

3-2. current R&D activities related to nanotechnology

PE-Clay nano composite liner : gas interrupting characteristic -> increased to 30% than its predecessors liner thickness -> could be reduced.

7% clay-> the tensile modulus increased about 49% the tensile strength increased about 15% as compared with pure Fig. Gas Permeability of the nanocomposites for polyethylene. various clay contents

Source: Joong-Hee Lee et al, “Properties of polyethylene-layered silicate nanocomposites prepared by melt intercalation with a PP-g-MA compatibilizer”, Composite Science and Technology (2005)) 19 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 19 The 21st Century Frontier

3-2. current R&D activities related to nanotechnology

Effective hydrogen storage capacity < Target

20 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 20 The 21st Century Frontier

3-2. current R&D activities related to nanotechnology Nanotechnology and Alanate

• Alanate- complex metal hydride with more than 5 wt% effective hydrogen storage capacity • decomposition temperature of alanate • Introducing nano sized particles – generating nanocrystallites through ball-milling – introducing the titanium nanoparticle as a catalyst

Ball-milling LiAlH4 and Li3AlH6 causes "the formation of a fine grain size below 20 nm (Chen et al.,2001)

21 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 21 The 21st Century Frontier

3-2. current R&D activities related to nanotechnology Lithium alanate system

DSC and TG curves of Li3AlH6 with and without catalysts

•Li3AlH6 -> 3 LiH + Al +3/2 H2

Amount of hydrogen released from Li3AlH6 during thermal decomposition at 150oC as a function of time

• Y.W.Cho et al, Thermal decomposition of Li3AlH6 with TiAl3 catalyst, catalysis today (Feb.2007) 22 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 22 The 21st Century Frontier Carbon base nanomaterials 3-2. current R&D activities related to nanotechnology

Raw Graphitized

(a) (b)

Ball milled Acid treat ed

(c) (d) PVdF based Carbon Nanofiber Surface Modified ACFs Ni doped ACF15 Ni doped ACF15 Ni doped ACF15 Fluorinated ACF15 Fluorinated Fluorinated ACF15 Fluorinated Fluorinated ACF15 Fluorinated Hydrogen storage site of carbon nanotube fullerene

23 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 23 The 21st Century Frontier

3-2. current R&D activities related to nanotechnology Nanotechnology and carbon base materials - High surface materials with nano pore for high hydrogen storage capacity - Nanopore exposition- surface oxidation at high temperature.

2400 2011 m2/g /g) 2 1800

1200

600 314 m2/g Specific surface area (m

0 VGNFs Porous GNFs Carbon nanofiber with surface area about 300 m2/g could be changed to multipore nanofiber with high surface area ( >2000 m2/g ) through a series of oxidation processes

24 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 24 The 21st Century Frontier

3-2. current R&D activities related to nanotechnology Metal nanoparticle loading

- introduction of metal nano particles in order to control hydrogen adsorption sites - introducing metal particles with controlled size- current density and time using electrolysis and non-electrolysis

Carbon fiber

Metal nano particle Introduction of Ni nanoparticle to the nanofiber surface using electrolysis and non-electrolysis

• Y.S,Lee et al, “The adsorption properties of surface modified activated carbon fibers for hydrogen storages”, catalysis today (Feb.,2007) 25 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 25 The 21st Century Frontier

4. conclusions

• We have investigated various materials including MOF, organo- porous nanomaterial, inorganic materials based on molecular modeling and we attempted to MOF-5 : Zn O(BDC) improve surface functionality of 4 3 (a) (b) those materials. FeBTBC: Fe4O2(BTB)8/3 • But the hydrogen storage capacity is still low at moderate condition.

• We will investigate the mechanism Contour Maps for the adsorption of hydrogen on Zn(dhBDC): Zn2O2(BDC) nanoporous material. of electrostatic potentials ; (a) IRMOF-1, (b) IRMOF-3 • we will setup the virtual screening protocol for the nanoporous materials.

26 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 26 The 21st Century Frontier

4. conclusions Think Together!

• There are lots of hurdles to hydrogen production and storage • Nanotechnology will help to overcome those barriers.

™ There is nothing either good or bad. But thinking make it so. ™ Value is always every where!

27 th 4수소에너지사업단US-Korea NanoForum, 업무보고 Honolulu,, 2004.7.9 USA, April 26-27, 2007 Hydrogen Energy R&D Center 27