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H 2 STOR-18. Progress of Hydrogen Storage and Container Materials. YiYi LI* YuTuo ZHANG. February 26, 2008 Cocoa Beach, Florida. Institute of Metal Research, Chinese Academy of Sciences. Heilongjiang. Jilin. Inner Mongolia. IMR. Xinjiang. Beijing. Liaoning. Gansu. Tianjin. Hebei.

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slide1

H2 STOR-18

Progress of Hydrogen Storage and Container Materials

YiYi LI* YuTuo ZHANG

February 26, 2008 Cocoa Beach, Florida

Institute of Metal Research, Chinese Academy of Sciences

slide2

Heilongjiang

Jilin

Inner Mongolia

IMR

Xinjiang

Beijing

Liaoning

Gansu

Tianjin

Hebei

Ningxia

Qinghai

Shanxi

Sandong

Jiangsu

Henan

Anhui

Shanghai

Tibet

Sichuan

Hubei

Zhejiang

Chongqing

jiangxi

Hunan

Fujian

Yunnan

Guangdong

Taiwai

Guangxi

Hongkong

Macau

Hainan

Location of IMR

Shenyang

slide3

Thanks for my colleagues

Dr.Huiming CHENG

Dr.Ping WANG

Dr.Dong CHEN

Dr.Lijian RONG

Dr.Xiuyan LI

Prof. Lian CHEN

Prof.Luming MA

Prof.Cungan FAN

slide4

Outline

  • Introduction
  • Hydrogen Storage Materials
  • Hydrogen Container Materials
  • Conclusions
slide5

1. Introduction

  • Premier Wen Jiabao tasked that up to 2020 China’s energy consumption per unit GDP decreases of 20%.
  • Premier Wen also urged that those consuming more energy and releasing more pollutants have to in a bid.

From: http://www.efchina.org/FHome.do a speech addressed to the national working teleconference on energy saving and pollutants reduction on April 27, 2007.

slide6

The Development Policy for China Automobile

  • Up to the end of 2007, there are 160 million automobiles in China.
  • In order to decrease emission of automobiles, Chinese government supports R&D of clean fuel such as ethanol, NG to hybrid, electric vehicles.
  • Pushing and encouraging EV development.
  • Developing new TiAl valves for cars.
slide7

Alternative Fuel Vehicles

  • There are 215,000 gas-powered vehicles which are operating with 712 gas-refilling stations.
  • The number of natural gas-powered vehicles has been ranked the seventh and liquefied petroleum gas vehicles on the 11th in the world.
fuel cell vehicle development in china
Fuel Cell Vehicle Development in China
  • Hydrogen fuel cell vehicles start development in 1990s.
  • There are 30kW car and 60kW bus as well as 100kW FC bus.
  • 2008: during the Olympic Games it has demonstration buses with hydrogen fuel cells in Beijing.

60 kW

100 kW

2 hydrogen storage materials
2. Hydrogen Storage Materials
  • AB5 Alloy
  • AB2 Nanocrystalline Alloy
  • Ti-NaAlH4 Complex Hydride
  • Mg/MWNTs Composite
slide10

The AB5 Hydrogen Storage Alloy

  • The AB5 hydrogen storage alloy for the production of NiMH batteries has been industrialized in China or international market.
  • In 2005, global sales volume of the alloy was around 20,000 tons, 60% of which was mainly consumed by small NiMH batteries and with proportion of 40% for dynamic batteries.
  • Production scale of the alloy reached 12,000 tons in China in 2005. It is estimated that global demand for hydrogen storage alloy will exceed 40,000 tons in 2010.

*

slide11

AB2 Nanocrystalline Alloys

  • Zr-based AB2 Laves phase alloys consist of cast polycrystalline and nanocrystalline structure. Nanocrystalline microstructure could be obtained from quenching of melt-spun alloys after annealing.

Composition

AB2-1 alloy Zr[(Ni V Mn Co)1-ySny]2+(y=0,0.025,0.05)

AB2-4 alloy(Zr1-xTix)(Ni V Mn Co) 2+(0.05<X<0.15,0<<0.3)

slide12

SEM Micrographs of the Cast Polycrystalline AB2 Alloys

(a) AB2-1 alloy (b) AB2-4 alloy

  • Microstructures of AB2-1 alloys consist of cubic C15 Laves phase, hexagonal C14 Laves phase and of AB2-4 is C15
  • The white one of non Laves phase in AB2-1 and AB2-4 is Zr9Ni11 and Zr7Ni10, respectively.
slide13

100nm

TEM Micro-analysis QAB2-4 Alloy

The transmission electron microscopy (TEM) and correlated electron diffraction patterns of quenched QAB2-4 alloy.

(a) bright field (b) SAED pattern of the white area

It was clearly observed that white area has turned into amorphous phase, indicating bright continuous ring.

slide14

TEM Micrographs and SAED Patterns of QHAB2-4

(a) bright field (b) dark field (c) SAED patterns

  • The electron diffraction pattern is discontinuous rings consisting of scattered dots at annealing temperature of 1173K, the alloy has turned into nanocrystalline completely and the grain size is about 80nm.
slide15

380

360

340

320

300

Discharge Capacity(mAh/g)

280

AB2 -1, as-cast

260

QHAB2-1-heat-treated at 1173K

AB2- 4, as-cast

240

QHAB2-4-heat-treated at 1173K

220

0

50

100

150

200

250

300

Charge-discharge Cycle (n)

The Charge-discharge Cycle-life for QHAB2-1 and QHAB2-4

The discharge capacity of nanocrystalline electrodes can be increased to 370mAh/g and cycle life decreased only 3% after 300 cycles.

*

slide16

Ti-NaAlH4 Complex Hydride

Target:

LiBH4

Al(BH4)3

Medium & long-term

NaBH4

LiAlH4

MgH2

Near-term

NaAlH4

CNT

kgH2/m3

  • We are interested in the sodium aluminum hydride system.
slide17

5

+KH+Ti

5

4.7%

4

+LiH+Ti

After KH addition

4

3

H-amount desorbed, wt.%

+Ti

2

3

H-capacity, wt.%

1

DH at 150oC

2

High and stable!

0

1

0 2 4 6 8 10

Time, h

1 2 3 4 5 6 7 8 9 10

Cycle Number

High Capacity of KH+Ti co-doped NaAlH4

From P.Wang H.M.Cheng

Potassium hydride and Titanium

  • After adding of potassium hydride and Titanium to NaAlH4, the hydrogen capacity is high and stable.
slide18

Ti with TiH2 doped to NaAlH4

Kinetic performance

Cycling performance

Direct utilization of metallic Ti as dopant to prepare Ti-doped NaAlH4 offers the same performance as TIH2.

slide19

cycled

As-milled

Ti in situ formed TiH2

In situ formed Ti hydride keeps its phase stability in ab/desorption cycles

slide20

(b)

(a)

(a)

(b)

Morphological Observation

DH performance

Back Scattering Electron images

EDS analyses

(a)

(b)

Milling time for 1 h, the sample is metallic Ti. While in the 10 h, particles consist of nanocrystalline TiH2.

*

slide21

Composite of Mg/MWNTs

Mg- 5 wt.% MWNTs were developed by a catalytic reaction of ball-milling with different materials such as matrix Mg magnesium, multi-walled carbon nanotubes (MWNTs).

slide22

XRD Patterns of Hydrogen Storage Composite Mg/MWNTs

From: Chen Dong et al

(a) Without ball milling; (b) Ball milling for 0.5h; (c) Ball milling for 3 h;

(d) After hydriding and dehydriding cycles.

XRD peak of Mg disappeared and hydride MgH2 appeared after hydriding and dehydriding cycles.

slide23

1: 298 K, 2: 373 K, 3: 473 K, 4: 553 K

Absorption & Desorption Kinetics for Mg- 5 wt.% MWNTs

  • At each temperature, 80 % of maximum hydrogen storage capacity can be obtained in 20, 15, 2 and 1 min, respectively.
  • The largest hydrogen absorption rate exhibited at 553K
  • The hydrogen desorption rates were as the same.
slide24

at 2.0 MPa hydrogen pressure

PCT Curves for Composite Mg/MWNT-H2 System

The maximum amount of hydrogen storage capacity of Mg-5 wt.% MWNTs is 0.4wt.%,3.4wt.%, 5.7wt.%, 6.2wt.% respectively.

*

slide25

3. Hydrogen Container Materials

  • FeNiCr stainless steel and FeNiCr stainless steels strengthened with N and Mn.
  • Nanosize -precipitates strengthened superalloys.

Two kinds of alloys can be applied to hydrogen resistant container:

slide27

Effect of thermal H2 charging on mechanical properties

Thermal H2-charged: 300 oC, 10days, 10MPa, H2

saturated

  • 20# FeNiCr stainless steel
  • 40# & 50# FeNiCr stainless steels strengthened with N and Mn
slide28

The Stability of Austenite Alloy Used for H Storage Container

Metastable austenite transformed -  or  --after cooling or deformation, then the hydrogen brittleness or degradationcan occur.

From:http://www.outokumpu.com/

- Austenite

 -Martensite

*

nano strengthened fe based alloys
Nano-  Strengthened Fe-based Alloys

Excellent combination of

  • Hydrogen resistance
  • High strength at room temp.
  • High temperature strength
  • Fe-based alloys better than Ni-based alloys

Hydrogen resistance of nano-  strengthened Fe-based alloys is better than other precipitates strengthened alloys.

tensile properties of the alloys
Tensile Properties of the Alloys

Thermal H2-charged: 300 oC, 10days, 10MPa, H2

typical microstructure
Typical Microstructure



size should be controlled within 10 nm, then the H2 could not be settled in the interface between -. Then, the degradation of the alloy become small.

slide33

4. Conclusions

  • AB2 nano-crystalline alloy, Ti-NaAlH4 complex hydride and Mg/MWNTs composite are promising hydrogen storage materials.
  • It is important to use the stable austenite alloys for hydrogen container materials.
slide34

Bei

Jing

Huan

Ying

Nin

One world One dream

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