25/09/2013

Solid electrolytes (fast ion conductors)

Why are fast ion conductors important:

Electrochemical ener y stora e and con!ersion

"o electronic conduction throu h the solid electrolyte #: anode o$idation % # #n& & ne' (: cathode reduction % ) & ne' )n'

G 0 = nFE 0
*n/(u cell: *n &(u2& *n2& & 2e' (u2& & 2e' *n (u *n2& & (u

(E0 % '0+,- .) (E0 % 0+3/ .)

. % E( 0 E# % 0+3/ 0 ('0+,-) % 1+1 .

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1uel (ell 2echnolo y

Solid 3$ide 1uel (ell #: 42 & 32' 423 & 2e' (: 532 & 2e' 32' ): *r1'$6$32'$/2 7olymer (4&) electrolyte #: 42 24& & 2e' (: 24& & 2e' & 532 ): "#183"

423

9i'ion )atteries
#node: 9i$(- (s) $9i& & -( (s) & $e' 9i$(o32 (s) (athode: $9i& & (o32 (s) & $e' (the electrolyte is a polymer el)

#node and cathode are intercalation compounds 0 insert/e$tract ions

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3$y en Sensors ((oncentration (ell)

A C (athode: 32 & /e' 232' #node: 232' 32 & /e' 32 32

E = E0

2.303RT P pQ q log x y nF X Y

"ernst E:uation ($;&y6 p7 & :<)

E = E0

(pO2 )A 2.303RT log nF (pO2 )C

E=

(pO2 )C 2.303RT log nF (pO2 )A

8onic conducti!ity
8n order for si nificant ionic conduction to occur in crystals certain conditions must =e satisfied:

1+ # lar e num=er of ions of one species should =e mo=ile 2+ 2here should =e a lar e num=er of empty sites for the ions to mo!e into 3+ 2he empty and occupied sites should ha!e a similar potential ener y> ?ith a lo? potential ener y path?ay for mo!ement =et?een the t?o+ /+ 2he structure should ha!e a frame?or@ (prefera=ly 3'dimensional) permeated =y open channels throu h ?hich the mo=ile ions can mi rate 5+ 2he (cation/anion) frame?or@ should =e hi hly polarisa=le -+ 1or hi h mo=ility one needs lo? char es on the mo=ile species

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6ttria Sta=ilised *irconia 0 3$ide 8on (onductor

(reate o$y en !acancies throu h chemical dopin : 1'$*r32 & $631+5 *r1'$6$32'0+5$

9ar er siAe 63& sta=ilises cu=ic polymorph

Sil!er 8on (onduction ' # 8

B -AgI 1+ Sta=le =elo? 1/- C( 2+ WurtAite Structure (tetrahedral coordination) 3+ % 10'/ ' 10'3 S/cm B -AgI 1+ Sta=le a=o!e 1/- C( 2+ )(( #rran ement of 8' ions> molten/disordered # & 3+ 1S/cm> Ea % 0+05 e. RbAg4I5 1+ 4i hest @no?n conducti!ity at room temperature 2+ )(( arran ement of 8'> molten/disordered # 3+ 0+25 S/cm at D2> Ea % 0+0,e.

&

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7olymorphs of # 8

4e$a onal> WurtAite (7-3/mc) # 0 tetrahedral coordination 8odine 0 #)#) (hcp) stac@in

(u=ic (8m'3m) # 0 disordered o!er three lattice sites 8 0 =ody centred cu=ic (=cc> not close pac@ed) .ery hi h conducti!ity

'#lumina: "a& ion conductor

1ormula: E23 n;233> ?ith n % 5'11 E %"a&> # &>+++ ; % #l3&> Fa3&> 1e3& (lose pac@ed o$y en layers> ?ith G of 32' missin in e!ery 5th layer+ / o$y en layer thic@ spinel =loc@s+ Eo=ile "a& in o$y en deficient planes+ "on'stoichiometry: ("a23)1&$;233

(onducti!ities are similar to those of li:uid electrolytes

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(omposition> synthesis and characterisation of *eolites

Structures =uilt from corner lin@in tetrahedra

Si32: Deplace a fraction of silicon in Si32 =y aluminium

*eolites JSi1'$#l$32K$'

*eolites (- different structures) H 100 different Structures ?ith tunnels I ca!ities Eolecular Sie!es (atalysts

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*eolites
# class of naturally'occurrin crystalline aluminosilicates ?hich ha!e a frame?or@ consistin of JSi3/K/' and J#l3/K5' tetrahedra lin@ed =y all of their corners

Synthetic #nalo ues

8sostructural ?ith those in nature E+ + *eolite 6 (1auLasite)

"e? structure types e+ + *SE'5

Feneral Structural 1eatures

(orner lin@ed Si3/ tetrahedra

"eutral frame?or@

Si32
Deplace Si ?ith #l

"e ati!ely char ed frame?or@

JSi1'$#l$32K$'
(ations: En&

E$/nJSi1'$#l$32KMS
"on'frame?or@ cations 1rame?or@ Sor=ed phase

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2he #luminosilicate 1rame?or@

#l'Si'3 frame?or@ has a 3'O net?or@ of 2unnels I (a!ities Si:#l ratio is al?ays 1+0 (9o?ensteins Dule) # particular frame?or@ may =e sta=le o!er a ran e of composition

E+ + "a12#l12Si123/NM2,423 and "a9#l9Si153/NM2,423 =oth ha!e the same (*eolite #) frame?or@ (hemical characteristics are determined =y the frame?or@ composition fe?er cations increased sta=ility to acids sorption properties chan e

e+ + 4i her Si:#l ratio PP PP

"on'1rame?or@ (ations
2he num=er is determined =y num=er of #l3/ units and hence =y the Si:#l ratio (ations reside ?ithin the tunnels or ca!ities of the frame?or@+ E$amples: al@ali metal ions al@aline earth metal ions lanthanide ions transition metal ions or anic cations 7rotons (ations are loosely =ound and hence mo=ile

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2he Sor=ed 7hase

B Small molecules may =e a=sor=ed into the pores of the Aeolite E$amples: 423 "43 (32

B 2he sor=ed phase is easily remo!ed =y heatin + 3ri in of the name Aeolite: Zein + Lithos (Greek) = Boiling Stones