June 19-22, 2005, Lucca, ITALY IPHE - Hydrogen Storage ...Advanced Hydrogen Storage Functions of Destabilized and Mixed Complex Hydrides June 19-22, 2005, Lucca, ITALY IPHE - Hydrogen

Shin-ichi ORIMO, Yuko NAKAMORI

Institute for Materials Research (IMR)Tohoku University

Advanced Hydrogen Storage Functions of

Destabilized and MixedComplex Hydrides

June 19-22, 2005, Lucca, ITALYIPHE - Hydrogen Storage Technology Conference

hydrogen.imr.tohokuProgram No. H-14Program No. H-14

www.hydrogen.imr.tohoku.ac.jp

Research project

“Development for Safe Utilizationand Infrastructure of Hydrogen”

S. Towata www.tytlabs.co.jp

collaborated with

supported by

focused on

www.nedo.go.jp/index.html

communicated withE. Akiba, AIST-TsukubaH. Fujii, Hiroshima Univ.C.M. Jensen, Univ. HawaiiT. Kiyobayashi, AIST-KansaiD.K. Ross, Univ. SalfordG. Sandrock, Sunatech.S. Suda, Kogakuin/MERITH.T. Takeshita, Kansai Univ.J.C.F. Wang, K.J. Gross, SNLR. Zidan, SRNLA. Züttel, Univ. Fribourg

1. Destabilization of LiBH4 and LiNH22. Combination of amide and hydride3. Prevention of NH3-contamination4. Provision of new reaction pathway

Trinary collaboration

First-Principles Calculationand Simulation

In-situ Characterization

Theory MaterialSynthesis

Analysis

K. Miwa, N. Ohba Y. Nakamori, M. Aoki

SR and Neutron Diffractions

T. Noritake, G. Kitahara, A. Ninomiya, K. Ohyama

Ultrasoft-pseudopotential

based onDFT (GGA)

Solid-gas reaction, MillingEvaporation

Metallurgical material synthesis

hydrogen booster(without electricity)

reaction cell

purified-Ar glove box

reserver

boosterH2

0-15 MPa 0-90 MPa

200MPa ～pu

rific

atio

n

H2

0-15 MPa 0-90 MPa

200MPa ～pu

rific

atio

n

vac.~ 90 MPa

samples

-

H2

0-15 MPa 0-90 MPa

200MPa ～pu

rific

atio

n

H2

0-15 MPa 0-90 MPa

200MPa ～

vac.~ 90 MPavac.~ 90 MPa

samples

試料容器

加熱部~100 mm

250 30

20

386

ネジ

75

~100

5~10

昇圧装置(~90 MPa)

圧力計減圧弁(~1 MPa)

M5ネジ

冷却水

冷却水

38

ハーウッド1/8インチネジ

スペ－サ

スペ－サ

試料容器

加熱部~100 mm

250 30

20

386

386

ネジネジ

75

~100

5~10



M5ネジ

冷却水

冷却水

38


スペ－サ

スペ－サスペ－サ

TMP

purif

icat

ion

2) evaporation

3) milling

1) reactive synthesis (or sintering)

hydrogen booster(without electricity)

reaction cell

purified-Ar glove box

reserver

boosterH2

0-15 MPa 0-90 MPa

200MPa ～pu

rific

atio

n

H2

0-15 MPa 0-90 MPa

200MPa ～pu

rific

atio

n


samples

-

H2

0-15 MPa 0-90 MPa

200MPa ～pu

rific

atio

n

H2

0-15 MPa 0-90 MPa

200MPa ～


samples

試料容器

加熱部~100 mm

250 30

20

386

ネジ

75

~100

5~10



M5ネジ

冷却水

冷却水

38


スペ－サ

スペ－サ

試料容器

加熱部~100 mm

250 30

20

386

386

ネジネジ

75

~100

5~10



M5ネジ

冷却水

冷却水

38


スペ－サ

スペ－サスペ－サ

TMP

purif

icat

ion

2) evaporation

3) milling

1) reactive synthesis (or sintering)

1. Destabilization of LiBH4 and LiNH2

2. Combination of amide and hydride

3. Prevention of NH3-contamination

4. Provision of new reaction pathway

cation with larger electronegativity

lower Td / faster reaction with “NH3”

“tunable” composition / starting material

intermediate phase formed by dehydriding

4 GuidelinesTheory MaterialSynthesis

Analysis

Dehydriding reaction

dehydriding temp. > 473-550 KIEA target temp. < 353 K

~ 10 mass% H2

LiNH2 + 2 LiH ⇔ Li2NH + LiH + H2 ⇔ Li3N + 2 H2P. Chen Z. Xiong, J. Luo, J. Lin, K.L. Tan, Nature 420 (2002) 302

45~60 (78*)kJ/molH2

116 (124*)kJ/molH2

LiBH4 ⇔ LiH + B + 3/2 H2

A. Züttel, S. Rentsch, P. Fischer, P. Wenger, P. Sudan, Ph. Mauron and Ch. Emmenegger,J. Alloys Compd. 356-357 (2003) 515

69 (74 *)kJ/molH2

*obtained fromcalculation

SR-XRD & MEM(Spring-8, JAPAN)

0.0 0.75 1.5 e/Å3

1Å

N

N N

Li

LiLi

H H

Li Li

N

HH

[110]-

0.0 0.75 1.5 e/Å30.0 0.75 1.5 e/Å3

1Å1Å

N

N N

Li

LiLi

H H

Li Li

N

HH

[110]-

[110]-

T. Noritake, H. Nozaki, M. Aoki, S. Towata,G. Kitahara, Y. Nakamori, S. Orimo,J. Alloys Compd. 393 (2005) 264.

K. Miwa, N. Ohba, S. Towata,Y. Nakamori, S. Orimo, Phys. Rev. B 71 (2005) 195109

First-Principles Calculation

LiNH2a = 0.5037 nmc = 1.0278 nm

Tetra., I4 (No. 82)

LiN

H

LiN

H

Atomic and electronic structures

V.H. Jacobs, R. Juza,Z. Anorg. Allg. Chem.391 (1972) 271

(110)

0.01 e/Å3

~1.0 e/Å3

a

c

a

Charge transfer

Li+cation

[NH2]-（covalent）

complexanion

S. Orimo, Y. Nakamori, G. Kitahara, K. Miwa, N. Ohba,T. Noritake, S. Towata, Appl. Phys. A (Rapid Commun.)79 (2004) 1765

ionic radius

electro-negativityvalence

1+ 0.068 nm 1.0Li

Mcation

Mg 2+ 0.066 nm 1.2

cation substitution…

by the other element withlarger

electronegativitiyProposed in E-MRS 2003, Strasbourg, June 10-13, 2003

Y. Nakamori, S. Orimo,Mater. Eng. Sci. B 108 (2004) 51

Y. Nakamori, S. Orimo,J. Alloys Comp. 370 (2004) 271

K. Miwa, N. Ohba, S. Towata, Y. Nakamori, S. Orimo, Phys. Rev. B 71 (2005) 195109

Li

N

H

Total

Li

N

H

Total

LiNH2

Li

N

Mg

× ××

(1) (2)(4)(3)

(5)× L

MgN

6

Mg

3 N2 (M

g)×

(Li)

Li 3N

(Li)

L

~923K

453K

1088

K

933K

453K

861K

(Mg)

Li

N

Mg

× ××

(1) (2)(4)(3)

(5)× L

MgN

6

Mg

3 N2 (M

g)×

(Li)

Li 3N

(Li)

L

~923K

453K

1088

K

933K

453K

861K

(Mg)

Dehydriding temperatures

targets of

NEDO program

600

550

500

450

400

350

300

Des

orp .

Tem

p. (K

)

1.00.80.60.40.20.0Mg Concentration, x

Sta

rting

of H

ydro

gen

600

IEA program

Initi

al D

ehyd

ridin

g Te

mp.

(K)

Deh

ydrid

ing

Rea

ctio

n (a

.u.)

600500400300Temperature (K)

x = 0.3

(Li1-xMgx)(NH2)y

0.1 MPa argon, 10 K・min.-1

x = 0.1

x = 0

Deh

ydrid

ing

Rea

ctio

n (a

.u.)


x = 0.3

(Li1-xMgx)(NH2)y

0.1 MPa argon, 10 K・min.-1

x = 0.1

x = 0

Li1-xMgx833 K, 2 h, 0.3 MPa N2

↓

LiMgN +Li(Mg)3N + Mg3(Li)2

623 K, 2 h, 35 MPa H2

↓

Li(Mg)NH2 +Li(Mg)H + Mg3(Li)2

S. Orimo, Y. Nakamori, G. Kitahara, K. Miwa, N. Ohba,T. Noritake, S. Towata, Appl. Phys. A (Rapid Commun.)79 (2004) 1765-1767

Ar 0.1 MPa10 K/min

S. Orimo, Y. Nakamori, G. Kitahara,K. Miwa, N. Ohba, S. Towata, A. Züttel,J. Alloys Compd., in press

M = Li-10at%Mg

Hyd

roge

n D

esor

ptio

n (a

.u.)

800700600500 Temperature (K)

M = Li

Ar 0.1 MPa10 K/min

M = Li-10at%MgM = Li-10at%Mg

Hyd

roge

n D

esor

ptio

n (a

.u.)

800700600500 Temperature (K)

M = Li

Ar 0.1 MPa10 K/min

Deh

ydrid

ing

Rea

ctio

n(a

.u.)

Li

BH

Li

BH

Li

HB

B

H

Total

LiBH4

Li

Mg substitution in LiBH4

K. Miwa, N. Ohba, S. Towata,Y. Nakamori, S. Orimo, Phys. Rev. B 69 (2004) 245120

A. Züttel et al.,J. Alloys Compd.(to be submitted)

LiBD4

a = 0.718 nmb = 0.444 nmc = 0.680 nm, at 408 K

Ortho., Pnma (No. 62)

J-Ph. Soulié et al.,J. Alloys Compd.346 (2002) 200

A. Züttel et al.,J. Alloys Compd. 356 (2003) 515

a

bc

a

bc







Analysis

Amide and hydride

Hydriding Partial Dehyd. Dehyd.

IdealHydrogen (mass%)

LiNH2 + 2LiH Li3N + 2H2Ca2NH + CaH2 CaNH + 2H2 2.1

Mg3N2 + 4Li3N + 12H2

10.4

4.2

5.6

9.1

7.0

5.6

LiNH2 + NaH

2LiNH2 + MgH2

3Mg(NH2)2 + 12LiH

3Mg(NH2)2 + 8LiH

3Mg(NH2)2 + 6LiH

Ref.

Li2NH + LiH + H2Dafert et al.,Monatsh. Chem.(1910) , Chen et al., Nature (2002)

LiNaNH + H2Ichikawa et al.,JPChem B (2004)

Li2Mg(NH)2 + 2H2Luo, JALCOM (2004)Wang, DOE Report(2004)

Mg3N2 + 4Li2NH + 8H2

Leng et al.,JPChem B (2004)

Mg3N2 + 4Li2NH + 4LiH + 8H2

Nakamori et al.,Appl. Phys. A,J. Power Sources(2004)

3Li2Mg(NH)2 + 6H2

Luo et al., MH2004, Xiong et al.,Adv. Mater. (2004)

dehydriding processdehydriding process

and so on…

Dehydriding process

P. Chen, Z. Xiong, J. Luo, J. Lin, K.L. Tan, J. Phys. Chem. B 107 (2003) 10967

“redox process”

Y.H. Hu, E. Ruckenstein, J. Phys. Chem. A 107 (2003) 9737T. Ichikawa, N. Hanada, S. Isobe, H. Leng, H. Fujii, J. Phys. Chem. B 108 (2004) 7887

“NH3 mediating process”

H in LiNH2 : Hδ+in LiH : Hδ−

→ redox pair Hδ− + Hδ+ → H2Nδ− + Liδ+ → Li3N

H in LiNH2 : Hδ+in LiH : Hδ−

→ redox pair Hδ− + Hδ+ → H2Nδ− + Liδ+ → Li3N

M(NH2)2 → “NH3” + MNH→ “NH3” + M3N2

MH + “NH3” → MNH2 + H2

1st step

2nd step

M(NH2)2 → “NH3” + MNH→ “NH3” + M3N2

MH + “NH3” → MNH2 + H2

1st step

2nd step

Point : MNH2 with lower decomp. temp. TdM(NH2)y → y/2 M2/yNH + y/2 NH3

Td : Mg(NH2)2 < LiNH2 < NaNH2

→ Mg for M

1st step (formation of “NH3”)

-30

-20

-10

0W

eigh

t Los

s (%

)

800700600500400300Temperature (K)

Mg(NH2)2

LiNH2

NaNH2

-30

-20

-10

0W

eigh

t Los

s (%

)

800700600500400300Temperature (K)

Mg(NH2)2

LiNH2

NaNH2

Y. Nakamori et al.,Mater. Trans., in press

He 0.1 MPa5 K/min

→ Li for M

Point : MH with faster reaction with “NH3”MHy + y NH3 → M(NH2)y + y H2

×

×

××

×× ×

○

○○

○○

○○

○ ○

○

○

MgH2

Mg(NH2)2

Inte

nsity

(a.u

.)

60504030202θ (degree)

NaH

NaNH2

××

×

×

×

×

○○○

○○ ○

○○○

○○

○

Inte

nsity

(a.u

.)

60504030202θ (degree)

Inte

nsity

(a.u

.)

60504030202θ (degree)

LiH

LiNH2

×

×

×

○

○○○ ○

×

×

××

×× ×

○

○○

○○

○○

○ ○

○

○

MgH2

Mg(NH2)2

Inte

nsity

(a.u

.)

60504030202θ (degree)

×

×

××

×× ×

○

○○

○○

○○

○ ○

○

○

MgH2

Mg(NH2)2

Inte

nsity

(a.u

.)

60504030202θ (degree)

Inte

nsity

(a.u

.)

60504030202θ (degree)

NaH

NaNH2

××

×

×

×

×

○○○

○○ ○

○○○

○○

○

Inte

nsity

(a.u

.)

60504030202θ (degree)

NaH

NaNH2

××

×

×

×

×

○○○

○○ ○

○○○

○○

○

Inte

nsity

(a.u

.)

60504030202θ (degree)

Inte

nsity

(a.u

.)

60504030202θ (degree)

Inte

nsity

(a.u

.)

60504030202θ (degree)

LiH

LiNH2

×

×

×

○

○○○ ○

Inte

nsity

(a.u

.)

60504030202θ (degree)

LiH

LiNH2

×

×

×

○

○○○ ○

2nd step (H2 emission)

Y. Nakamori et al.,Mater. Trans., in press

time (hour)temp. (K)

12493LiH

16861348573NaH12493LiH

168613MgH2MgH2

573

MH

Optimized combination

Mg(NH2)2 → “NH3” + MgNH→ “NH3” + Mg3N2

LiH + “NH3” → LiNH2 + H2

Mg

NH2

Y. Nakamori, G. Kitahara, S. Orimo, J. Power Sources 137 (2004) 309

fasterreaction

with “NH3”

Lowerdecomposition

temp.

Li HMg(NH2)2 + x LiH

?composition ratio







Analysis

yes

noyes

yes

no

noyes

nono

heating belowLi2NH phase

adding catalyst

heating slowly

x < 4

homogeneous dispersion

x = 4

yeskeeping from air

NH3H2

at any temp.

NH3highly toxic for FC reaction

Y. Nakamori, S. Orimo, submitted

H2 / NH3 from Mg(NH2)2 + x LiH

Affected by composition and …

-16

-12

-8

-4

0

Wei

ght L

oss

(mas

s%)


x = 4 (max. 9.1 mass%)

x = 2 (max. 5.6 mass%)x = 8/3 (max. 6.9 mass%)

TGHe 0.1 MPa5 K/min

In

tens

ity (a

.u.)

×50

300 400 500 600 700 800Temperature (K)

mass spectroscopyHe 0.1 MPa, 5 K/min

H2

NH３

starting fromhydrides

x = 4

x = 2x = 8/3

x = 4

starting fromnitrides

Y. Nakamori, G. Kitahara, A, Ninomiya, K. Aoki, T. Noritake, S. Towata, S. Orimo, Mater. Trans., in press

MASSHe 0.1 MPa5 K/min

Mg(NH2)2 + x LiH

Inte

nsity

(a.u

.)

60504030202θ /degree

x = 2

x = 8/3

x = 4

2θ (degree)

Inte

nsity

(a.u

.)

60504030202θ /degree

x = 2

x = 8/3

x = 4

2θ (degree)2θ (degree)

XRD(aft. 513 K)

Mg(NH2)2 + 4 LiH

amide + hydride

3Mg(NH2)2 + 12LiH Mg3N2 + 4Li2NH + 4LiH + 8H2 Mg3N2 + 4Li3N + 12H2hydriding nitrides

starting materials

Y.H. Hu, E. Ruckenstein, J. Phys. Chem. A 107 (2003) 9737T. Ichikawa, N. Hanada, S. Isobe, H. Leng, H. Fujii, J. Phys. Chem. B 108 (2004) 7887S. Hino, T. Ichikawa, N. Ogita, M. Udagawa, H. Fujii, Chem. Commun., in pressY. Nakamori, G. Kitahara, A, Ninomiya, K. Aoki, T. Noritake, S. Towata, S. Orimo, Mater. Trans., in press

affected by… composition,starting material (= elemental dispersion),atmosphere,heating rate,open/close system, …

“NH3 mediating process”

dehydriding

(1/3･Mg3N2 + 4/3･Li2NH + 4/3･LiH + 8/3･H2)

1/3･Mg3N2 + 4/3･Li3N + 4･H2

(Li2Mg(NH)2 +2･LiH + 2･H2)

Mg(NH2)2 + 4･LiH

(1/3･Mg3N2 + 4/3･Li2NH + 4/3･LiH + 8/3･H2)

1/3･Mg3N2 + 4/3･Li3N + 4･H2

(Li2Mg(NH)2 +2･LiH + 2･H2)

Mg(NH2)2 + 4･LiH

DehydridingPartial DehydridingHydriding DehydridingPartial DehydridingHydriding

1/3･Mg3N2 + 4/3･Li2NH + 8/3･H2

Mg(NH2)2 + 8/3･LiH

1/3･Mg3N2 + 4/3･Li2NH + 8/3･H2

Mg(NH2)2 + 8/3･LiH

Li2Mg(NH)2 +2･H2

Mg(NH2)2 + 2･LiH

Li2Mg(NH)2 +2･H2

Mg(NH2)2 + 2･LiH

6.1 mass%6.1 mass%

4.6 mass%4.6 mass%

9.1 mass%9.1 mass%

6.9 mass%6.9 mass%

5.6 mass%5.6 mass%

**

x, depending on applications

x = 4

x = 8/3

x = 2

possibility of NH

3 emission

H2 concentration

～ 500 K 500 ～ 700 K 700~ Kdehydriding temperatures

Nakamori et al.

Leng et al.

Luo et al.Chen et al.

Nakamori, S. Orimo,submitted.

(Intermediate phase)




4. Provision of new reaction pathwayIntermediate phase formed by dehydriding


Analysis

LiH⇔ Li + 1/2 H2

LiNH2 → 1/2 Li2NH + 1/2 NH3 → 1/3 Li3N + 2/3 NH3

13.8 mass%H2, 953 K

NH3 emission, 600 K

LiNH2 + 2 LiH ⇔ Li2NH + LiH + H2 ⇔ Li3N + 2 H2 5.5 mass%H2, 473 K 5.2 mass%H2, 700 K

Mixing effect

LiBH4 + LiNH2 : “Li-B-N(-H)” existsLiBH4 + LiAlH4 : “Li-B-Al(-H)” may not exist×

Any intermediate phase after/during dehydriding?

Combination of LiBH4 + LiNH2 T

herm

al D

esor

p. (a

.u.)


2LiNH2 + LiBH4 LiBH4

Inte

nsity

(a.u

.)

6040202θ (degree)

Li3BN2

The

rmal

Des

orp.

(a.u

.)


The

rmal

Des

orp.

(a.u

.)


2LiNH2 + LiBH4 LiBH4

Inte

nsity

(a.u

.)

6040202θ (degree)

Li3BN2

Inte

nsity

(a.u

.)

6040202θ (degree)

Li3BN2

Y. Nakamori, A. Ninomiya, G. Kitahara, K. Aoki, T. Noritake, K. Miwa Y. Kojima,S. Orimo, J. Power Sources in press

LiBH4 + 2LiNH2 → Li3BN2H8 →

→ Li3BN2Hx (x~0) → α-Li3BN2

milling 650 K

800 K

M. Aoki, K. Miwa, T. Noritake, G. Kitahara,Y. Nakamori, S. Orimo, S. Towata,Appl. Phys.A 80 (2005) 1409

0-2-4-6-8-10-12Hydrogen desorption (ｗｔ%)

Hyd

roge

n pr

essu

re (M

Pa)

LiBH4 (430℃)

LiBH4 + 2LiNH2(250℃)

10-1

10-2

10-3

101

100

~8 (11.9*) mass%H2(23*) kJ/molH2

LiBH4+2LiNH2 (523 K)

LiBH4(703 K)

10.6 (13.8*) mass%H269 (74*) kJ/molH2





cation with larger electronegativity



intermediate phase formed by dehydriding


Analysis

Theory Material Synthesis

Analysis

Recent publications

K. Miwa et al., “First principles study onlithium borohydride LiBH4”,Phys. Rev. B 69 (2004) 245120

K. Miwa et al., “First-principles study onlithium amide for hydrogen storage”, Phys. Rev. B 71 (2005) 195109

T. Noritake et al., “Crystal structure and chargedensity analysis of Li2NH by synchrotron X-raydiffraction”, J. Alloys Compd. 393 (2005) 264

Y. Nakamori, S. Orimo, “Destabilization of Li-based complex hydrides”, J. Alloys Compd. 370 (2004) 271

S. Orimo et al., “Material properties ofMBH4 (M = Li, Na, and K)”,Mater. Sci. Eng. B 108 (2004) 51

K. Ohoyama et al., “Revised crystal structuremodel of Li2NH by neutron powder diffraction”,J. Phys. Soc. Jan. 74 (2005) 483

S. Orimo et al., “Destabilization and enhanced dehydriding reaction of LiNH2 – an electronic structure viewpoint”,Appl. Phys. A (Rapid Commun.) 79 (2004) 1765

S. Orimo et al., “Dehydriding and rehydriding reactions of LiBH4”, J. Alloys Compd. in press

Y. Nakamori, et al., “Guidelines for developing amide based hydrogen storage materials”, Mater. Trans., in press

Y. Nakamori, et al., “Synthesis and dehydriding studies of Mg-N-H systems”, J. Power Sources 138 (2004) 309

Y. Nakamori et al., “Reversible hydrogen storage functions for the mixtures of Li3N and Mg3N2”, Appl. Phys. A 80 (2005) 1

M. Aoki et al., “Destabilization of LiBH4 by mixing with LiNH2”,Appl. Phys. A 80 (2005) 1409.

Y. Nakamori et al., “Dehydriding reaction of mixed complex hydrides”, J. Power Sources, in press

Theory MaterialSynthesis

Analysis

June 19-22, 2005, Lucca, ITALY IPHE - Hydrogen Storage ...Advanced Hydrogen Storage Functions of Destabilized and Mixed Complex Hydrides June 19-22, 2005, Lucca, ITALY IPHE - Hydrogen

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