Mixed anion materials and compounds for novel proton conducting membranes

Full text

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Mixed anion materials and compounds for novel

proton conducting membranes

Steven A. Poling

Iowa State University

Carly R. Nelson

Iowa State University

Steve W. Martin

Iowa State University

, swmartin@iastate.edu

Follow this and additional works at:

http://lib.dr.iastate.edu/patents

Part of the

Materials Science and Engineering Commons

Recommended Citation

Poling, Steven A.; Nelson, Carly R.; and Martin, Steve W., "Mixed anion materials and compounds for novel proton conducting membranes" (2006).Iowa State University Patents. 252.

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Mixed anion materials and compounds for novel proton conducting

membranes

Abstract

The present invention provides new amorphous or partially crystalline mixed anionchalcogenide compounds

for use in proton exchange membranes which are able to operate over a wide variety of temperature ranges,

including in the intermediate temperature range of about 100 ° C. to 300° C., and new uses for

crystallinemixed anion chalcogenide compounds in such proton exchange membranes. In one embodiment,

the proton conductivity of the compounds is between about 10

−8

S/cm and 10

−1

S/cm within a temperature

range of between about −60 and300° C. and a relative humidity of less than about 12%.

Keywords

Materials Science and Engineering

Disciplines

Materials Science and Engineering

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COMPOUNDS FOR NOVEL PROTON CONDUCTING MEMBRANES

(75) Inventors: Steven Andrew Poling, Moore?eld, WV (US); Carly R. Nelson, Ames, IA

(US); Steve W. Martin, Ames, IA (US)

(73) Assignee: Iowa State University Research

Foundation, Inc., Ames, IA (US)

( * ) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35

U.S.C. 154(b) by 121 days.

(21) App1.No.: 10/848,967

(22) Filed:

May 19, 2004

(51) Int. Cl.

C01B 17/00 (2006.01) C01D 13/00 (2006.01) C01G 17/00 (2006.01)

(52) US. Cl. ... .. 423/592.1; 423/593.1;

423/508; 423/511; 423/512.1; 423/518; 423/618;

423/263

(58) Field of Classi?cation Search ... .. 423/592.1,

423/593.1, 508, 511, 512.1, 518, 618, 263

See application ?le for complete search history.

(56) References Cited U.S. PATENT DOCUMENTS

3,771,073 A 11/1973 Krause et al. 3,962,141 A 6/1976 Inoue et al. 4,199,357 A 4/1980 Yoshida et a1.

4,439,411 A 3/1984 Manganaro et a1. ... .. 423/560

4,454,244 A * 6/1984 Woltermann ... .. 502/208

4,542,108 A 9/1985 Susman et a1. 4,880,761 A 11/1989 Bedard et a1. 5,531,936 A 7/1996 Kanatzidis et a1. 5,618,471 A 4/1997 Kanatzidis et a1. 5,830,427 A 11/1998 Bedard et a1.

7,018,604 B1 3/2006 Poling et a1.

2004/0096720 A1* 5/2004 Poling et al. ... .. 429/33

FOREIGN PATENT DOCUMENTS

WO WO-0045447 8/2000

OTHER PUBLICATIONS

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L124.

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LA-UR-99-3231,(1999),1-36.

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Alberti, G, “Solid state protonic conductors, present main applica

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Colomban, Philippe, “Tabe of Contents”, In.‘ Proton conductors .'

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New York : Cambridge University Press,(1992).

DZimitroWicZ, D J., et al., “AC proton conduction in hydrous oxides”, Materials Research Bulletin, 17(8), (Aug. 1982),971-9. Haile, S M., et al., “Solid acids as fuel cell electrolytes”, Nature,

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dioxide as an electrolyte for fuel cells at intermediate temperature”,

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2002),679-85.

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cations”, Chemistry ofMaterials, 8(3), (Mar. 1996),610-641.

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2001),877-8.

Stelle, B C., et al., “Materials for fuel-cell technologies”, Nature,

414(6861), (Nov. 15, 2001),345-52.

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for application in direct methanol fuel cells”, Proceedings of the

Second International Symposium on Proton Conducting Membrane

Fuel Cells II, (1999),358-64.

Abe, Yoshihiro , et al., “Electrical conduction due to protons and

alkali-metal ions in oxide glasses”, Physical Review B (Condensed

Matter), 48(21), (Dec. 1, 1993),15621-5.

(Continued)

Primary ExamineriStanley S. Silverman

Assistant ExamineriTimothy C. Vanoy

(74) Attorney, Agent, or F

irmiSchWeqman, Lundberg,

Woessner & Kluth P.A.

(57)

ABSTRACT

The present invention provides neW amorphous or partially crystalline mixed anion chalcogenide compounds for use in

proton exchange membranes Which are able to operate over a Wide variety of temperature ranges, including in the

intermediate temperature range of about 100 ° C. to 3000 C.,

and neW uses for crystalline mixed anion chalcogenide

compounds in such proton exchange membranes. In one

embodiment, the proton conductivity of the compounds is

between about 10'8 S/cm and 10'1 S/cm Within a tempera

ture range of betWeen about —60 and 3000 C. and a relative

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US 7,101,527 B1

Page 2 OTHER PUBLICATIONS

Abe, Yoshihiro , et al., “Protonic conduction in alkaline earth

metaphosphate glasses containing Water”, Journal of Non-Crystal line Solids, 51(3), (Nov. 1982),357-65.

Angell, C A., “Mobile Ions in Amorphous Solids”, Annual Review

ofPhysical Chemistry, 43, (Oct. 1992),693-717.

Blomen, L. et al., EDS. , “Fuel Cell Systems”, Copyright 1993, Plenum Press, New York, ISBN 0-306-44158-6,(1993),Xi-XiX,

37-69.

Boolchand, P , et al., “Structure of GeS/ sub 2/ glass: spectroscopic evidence for broken chemical order”, Physical Review B (Con densed Matter), 33(8), (Apr. 15, 1986),5421-34.

Cho, J , et al., “Infrared spectroscopy study of XRb2S+(1-X)B2S3

glasses and polycrystals in the range 0§X§075”, Physics and

Chemistry of Glasses, 36(6), (Dec. 1995),239-43.

Julien, C. , et al., “Solid State Batteries: Materials Design and

Optimization”, Copyright 1994, Kluwer Academic Publishers,

ISBN 0-7923-9460-7,(1994),v-viii, 97-175, 183-277.

Kaesaer, J A., “Hydrosul?des of Group I and Group II Metals”,

Inorganic Chemistry 12, (1973),3019-3020.

Kamitsos, E I., et al., “Structure and optical conductivity of silver thiogermanate glasses”, Journal of Solid State Chemistry, 112(2),

(Oct. 1994),255-61.

Karthikeyan, A , et al., “New Method to prepare polycrystalline

meta-thioboric acid, (HBS2)3”, Inorganic Chemistry 41,

(2001),622-624.

Kawamoto, Yoji , et al., “Infrared and Raman spectroscopic studies

on short-range structure of vitreous GeSZ”, Materials Research

Bulletin, 17(12), (Dec. 1982),1511-16.

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500

1000 1500 2000 2500 3000 3500 4000

(6)

U.S. Patent

Sep. 5, 2006

Sheet 2 0f 17

US 7,101,527 B1

FIG. 2

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(10)

U.S. Patent

Sep. 5, 2006

Sheet 6 0f 17

US 7,101,527 B1

Raman

xMSH+GeO2+yH2O

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(11)

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(12)

U.S. Patent

Sep. 5, 2006

Sheet 8 0f 17

US 7,101,527 B1

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(14)

U.S. Patent

Sep. 5, 2006

Sheet 10 0f 17

US 7,101,527 B1

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(16)

U.S. Patent

Sep. 5, 2006

Sheet 12 0f 17

US 7,101,527 B1

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(18)

U.S. Patent

Sep. 5, 2006

Sheet 14 0f 17

US 7,101,527 B1

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(21)

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(22)

US 7,101,527 B1

1

MIXED ANION MATERIALS AND COMPOUNDS FOR NOVEL PROTON

CONDUCTING MEMBRANES STATEMENT OF GOVERNMENT RIGHTS

This invention Was made With support of the United

States Government under Department of Energy’s Hydro gen Program under Cooperative Agreement No. DE-FC36

00GO10-531. The Government has certain rights in this invention.

RELATED APPLICATION

This application is related to US. patent application Ser. No. 10/627,584 entitled, “Compounds for Novel Proton Conducting Membranes and Methods of Making Same,” ?led on Jul. 25, 2003, noW issued as US. Pat. No. 7,018,604 and entitled “Compounds for Novel Proton Conducting

Membranes,” Which is hereby incorporated by reference in

its entirety.

FIELD

The present invention relates to materials and compounds

useful for membranes, and, in particular to materials and compounds for novel proton conducting membranes and

methods of making same.

BACKGROUND

Hydrogen-based fuel cells are becoming increasingly popular as an alternative to crude oil-based internal com bustion engines. Speci?cally, hydrogen can be converted to

electricity through the use of a hydrogen-oxygen fuel cell. The by-product of this type of a fuel cell is Water, making this a “green” or environmentally-friendly technology. At the heart of the fuel cell is the proton exchange membrane

(PEM), Which transports protons from the anode to the

cathode While providing electronic insulation betWeen them. There are many types of electrolyte materials, each With

speci?c limitations. Generally, such materials either have

too loW a proton mobility or don’t operate in the interme diate temperature range (100 to 300° C.) to be useful for

intermediate-temperature fuel cells.

Some of the most popular electrolyte materials are poly

mer exchange membranes, phosphoric acid membranes, and solid oxide membranes. Polymer exchange membranes, or

more speci?cally solid organic polymer poly-per?uorosul

fonic acids such as Na?on®, require hydration to maintain

high proton conductivity. HoWever, this limits their opera

tion to temperatures below 1000 C., thus requiring the use of

expensive noble metal catalysts such as platinum. These

electrolytes also suffer from fuel cross-over due to their porous hydrated nature. Phosphoric acid membranes are typically operated from 1500 C. to 200° C. Since these membranes are liquid electrolytes, they suffer from mem

brane leakage and fuel cross-over problems. They also require the use of expensive platinum catalysts. Solid oxide

membranes are typically operated betWeen 700° C. to 1000°

C., a temperature range in Which the use of platinum as an

electrode material can be reduced. Additionally, this tem perature range is used to achieve the desired oxide anion conductivity. Since, these membranes are solid in nature, they do not suffer from fuel cross-over problems. HoWever, there remains a temperature region betWeen about 100° C.

20 25 30 35 40 45 50 55 60 65

2

and 300° C. for Which no one membrane currently available

can provide optimum performance.

Thus, What is needed are materials and compounds for use in proton exchange membranes Which are able to operate in a Wide variety of temperature ranges, including in the intermediate temperature range of betWeen about 100° C. to

300° C.

SUMMARY

An inorganic material or compound comprising AVMWD,C

(EH)y'(ZH2O), Wherein A is one or more modifying cations;

M is a metal, metalloid, transition metal or rare earth

element; D and E are different Group VIB elements selected

from the group consisting of O, S, Se, and Te; v, W, x, and y are positive integer numbers; and Z20 is provided. (As used herein, the term “rare eart ” is intended to include all

of the lanthanide elements). In one embodiment, the material

or compound has a mixed complex anion MWDxEy_(x+y). In one embodiment, the material or compound has a mixed

complex cation MWDxEy” Where u is an integer. In one embodiment, M is a transition metal. In a speci?c embodi ment, the transition metal is yterrium, titanium or Zirconium.

In one embodiment, M is Ge. In one embodiment, the rare

earth is a lanthanide. In a particular embodiment, the lan

thanide is lanthanum. In one embodiment, the one or more

modifying cations (A) are selected from the group consisting of an alkali metal cation, alkaline earth cation, yterrium

cation, rare earth cation and combinations thereof.

The proton conducting materials and compounds of the present invention are amorphous, crystalline or mixed phase,

i.e., partially crystalline. The proton conductivity for the

materials and compounds of interest ranges from about 10'8

S/cm and 10'1 S/cm Within a temperature range of betWeen about —60 and 300° C. at a relative humidity ranging from 0 to 100%. In one embodiment, the proton conductivity ranges from about 10-3 to 10-2 S/cm for temperatures betWeen about 100 and 275° C. under loW relative humidi ties of less than about 12%.

In one embodiment, protonated compounds are obtained

from an aqueous mixture of starting materials. In some embodiments the aqueous solution is heated. In one embodi ment, crystalline proton conducting compounds are pro

duced at room temperature by adding excessive amounts of

acetone to the solution. In one embodiment, X-ray amor

phous proton conducting materials are produced by sloW

heating (25° C.<T<100° C.) of the solution over a period of several days, Which alloWs suf?cient evaporation to occur to

produce a recoverable ?lm of proton conducting material. The resulting products are amorphous, crystalline or mixed phase structures With structural incorporated protons

(protonated). Some of these protonated materials and com

pounds, such as hydrated alkali thio-hydroxogermanates,

have been found to be relatively stable in air and Water, Which is a requirement for hydrogen-oxygen fuel cell use.

(Structural characterization of the obtained protonated mate

rials and compounds Was carried out using IR and Raman

spectroscopies, DSC, TGA, and X-ray diffraction).

The present invention further provides a method compris

ing utiliZing crystalline sodium thio-hydroxogermanate

compounds in a proton conducting membrane. In one

embodiment, the sodium thio-hydroxogermanate compound

is Na3GeS3(OH)~8H2O. In one embodiment, the sodium

thio-hydroxogermanate compound is Na2GeS2(OH)2~5H2O.

The protonated compounds or membrane materials

described herein can easily be converted to membranes to

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Figure

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