Phase Diagram Evaluations:

S e c t i o n II

The Ge-Li (Germanium-Lithium) S y s t e m

J. S a n g s t e r * a n d A.D. P e l t o n Ecole Polytechnique de Montreal

Equilibrium Diagram
The assessed phase diagram is shown in Fig. 1. Due to the speculative nature of much of the diagram, no table of special points is given. Liquidus points were measured by thermal analysis under argon [66Fed] in the range 0 to 58 at.% Li in graphitized corundum crucibles and in the range 95.5 to 100 at.% Li in Fe crucibles. No suitable container material was found for intermediate compositions. Ge of 99.99% purity was used. The purity of the Li was not given. However, its melting point was 186 ~ which is not in good agreement with the presently accepted value of 180.6 ~ Samples were apparently analyzed after the experiments in order to determine the compositions. These authors report observing the two compounds GesLi22 and GeLi 3 microscopically. The limiting liquidus slope in Fig. 1 at 0 at.% Li was calculated thermodynamically from the enthalpy of fusion of Ge under the assumption of negligible solubility of Li in solid Ge. Agreement with the results of [66Fed] is reasonable. Liquidus composition above 91 at.% Li was determined by resistivity measurements on samples prepared from 99.999% Ge and 99.98% Li that were further purified [81Dad]. These authors also used thermal analysis to measure the eutectic temperature as well as the "melting point of GesLi22," which they reported as 661 ~ Thermal analysis was used [57Pel] to obtain liquidus points at 66.7, 75, and 80 at.% Li as shown on Fig. 1. As well, a thermal arrest was observed at 525 ~ at 66.7 at.% Li. The composition at 80 at.% Li was also studied by [65Joh] by thermal analysis on samples prepared from 99.9% Li and spectroscopically

pure Ge. Cooling was started at 946 ~ The first thermal effect was noticed at 690 ~ Subsequent thermal arrests were observed at 667,655, and 567 ~ Data for the solubility of Ge in liquid Li (that is, for the liquidus at high Li concentrations) have been reviewed [75Ada, 82Hub]. The results of [66Fed] and [81Dad] shown in Fig. I and also plotted in Fig. 2, diverge greatly. A second thermal arrest in the range 90 to 100 at.% Li was observed by [66Fed] as shown in Fig. 1. These authors interpreted this as evidence of a phase transformation. These thermal arrests fall very close to the liquidus of [81Dad] who failed to detect any evidence of such a transformation. It may be that the "phase transformation" of [66Fed] was actually the liquidus and that their points at higher temperatures were caused by impurities. (As discussed above, their Li seems to have been of low purity.) The solubility curve of [81 Dad] in Fig. 2 may be represented by the following equation [81 Dad, 82Hub] for the interval 250 to 450 ~ 2879 logl0(at.% Li) = 4.3708 - - T (K) (Eq 1)

Extrapolation ofEq 1 to the melting point of Li gives a eutectic liquid composition of 99.989 at. % Li. Under the assumption of negligible solid solubility of Ge in Li, the eutectic temperature can then be calculated thermodynamically, from the enthalpy of fusion of Li, to lie 0.06 ~ below the melting point of pure *Permanent address: Sangster Research Laboratories, Suite 402, 3475 rue de la Montagne, Montrral, Qu6bec, Canada, H3G 2A4.

Table 1 Phase

Ge-Li Crystal Structure Data Homogeneityrange, at. % Li

0

Pearson symbol
cF8

Space group
Fd3m Pmn21 141/a(a) 14j/amd(b) Cmcm Cmcrn Cmmm

Strukturbericht designation

Prototype

Reference

(Ge)............................. Gel2Li7....................... GeLi............................ Ge6LilffC)................... Ge4Li9......................... Ge2Li7......................... Ge4Li15....................... GesLi22....................... (~Li)............................ (ff.Li)(d).......................

A4
. ... . ... ... ... . . . . . . . .

C (diamond)
.

36.8 50.0 64.7 69.2 77.8 78.9 81.5

100 1O0

0*76
t132 oC68 oC52 oC36

GaMg
.

Ge6Lill Na9Sn4 Ge2Li7

Cu 15S i4

c/76 cF432
c12 hP2

/43d F23
Im'3m

D86

... A2
A3

P63/ntmc

Li22Pb5 W Mg

[Kingl] [81Gru, 82Gru] [69Men] [87Eve] [75Fra] [70Hop] [72Hop] [61Gla,65Job] [6401e, 64Gla] [Kingl] [Massalski2]

(a) Spacegroupof GeLiis 14lind accordingto [6401e]. (b) High-pressureform.(c) The existenceof this compoundhas beenquestioned[86Nes]. (d) <-201 ~

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S e c t i o n II: P h a s e D i a g r a m E v a l u a t i o n s

Li. This is in very good agreement with an unpublished cryoscopic study [81Hub], quoted by [81Dad], in which a eutectic at 99.988 at.% Li at 0.06 ~ below the melting point of Li was observed. The eutectic temperature measured by [81 Dad] was the same as the melting point of pure Li within _+0.1 ~ These results thus support the assumption that terminal solid solubility of Ge in Li is very small.

Several compounds have been reported in this system, but their temperatures of fusion and transformation are, for the most part, unknown. The assessed diagram drawn in Fig. 1 is highly speculative, and is one possible interpretation of the available data. Coulometric titration between a Li-Ge electrode and a Li-A1 electrode with a molten salt electrolyte was carried out between 360 and 440 ~ [82Stj]. Five plateaus

Weight %Lithium
0
1000 i i i i i i J i 10 20 30 I i ~ h ~ J L tIII,~.,.HI.....h,. 4 0 50

70 100

93~.3 '~: x L

900-

800-

700-

5"

600-

500-

[-..

400-

300180.6 ~

2~o-

~a

ioo-~
0

~:g,

.-2
li,,,,, i.n,,,,,,,,l .

-i ~llLIIHIIIIIIIIIIlltlllllllllHlill~llllHIIILFI
Io Ge 20 3o

.........

i,,,.,,,

.......
100

40 50 60 Atomic %Lithium Atomic %Lithium

70

80

90

Li

0 20 40 50 60

70

80

90

100

tc~4
,-----" 938.3 '~C 900800. 700J~"T-'''~'. L

200
aT~

0-

10

20

30

40

50

60

70

80

90

100

Ge Fig. 1 Assessed Ge-Li phase diagram.

Weight %Lithium

Li

290

Journal of Phase Equilibria Vol. 18 No. 3 1997

Phase Diagram Evaluations: Section H

were observed. These were identified [82Stj] with the following five compounds: GeLi, GeaLi9, GesLil6, Ge4Lils, and GesLi22.

5~ 10 9-8-7-6-5~ 4~
X

4~

3~

3~

250

2~

Ge12Li7
Ge12Li7 was reportedly prepared by cooling from the melt, and its crystal structure was determined in single-crystal x-ray studies [81Gru, 82Gru]. The melting point was reported as 290 K [81Gru], but this is probably a misprint. This compound was not observed in the coulometric titration study [82Stj]. Hence, it may decompose below 360 ~ It seems unlikely that the compound would form at such low temperatures without extensive annealing. The two articles [81Gru, 82Gru] are extremely brief summaries. The existence and characterization of this compound require verification.
GeLi

X X X

~m

t-0.9-0.8-0.7-0.6-0.5~ 0.4-0.3-0.2--

GeLi was prepared by fusion at 750 ~ [69Men] or 650 ~ [87Eve], followed by slow cooling, and its crystal structure was determined in single-crystal x-ray studies [69Men]. Its presence at 400 ~ was observed by coulometric titration [82Stj], and its existence at 500 ~ was confirmed by [87Eve], who converted it to a high-pressure form at this temperature. If the liquidus and eutectic data of [66Fed] are correct, GeLi must decompose in a peritectoid reaction between 500 and 525 ~ or it must melt, either congruently or incongruently, at a temperature close to 525 ~ In Fig. 1, peritectic melting at 528 ~ is shown, but only as a possibility.

0.1-0.09-0.08 - 0.07-0.06 m 0.05 0.04-0.03 - -

GeeLix x
Ge6Lill was prepared by direct reaction of the elements and characterized by its XRD pattern [75Fra]. A later investigation [86Nes] failed to find this compound, and the authors suggested that what the earlier workers had thought was Ge6Lill was actually LisMgSi 6. This statement was based on similarities in crystal structure but, if true, leaves unanswered the question of the origin of the Mg and Si in the earlier study [75Fra]. The coulometric titration curves at 400 ~ [82Stj] exhibited a small deflection which, the authors say, could be interpreted to correspond to the formation of Ge6Lil v

0.02

I 1.4

I 1.6

I 1.8

I 2.0

1.0

1.2

I O00/T (K)

Fig. 2 Solubility of Ge in liquid Li.

Ge4Li 9
Ge4Li9 was prepared by fusion at 1000 ~ followed by slow cooling, and its crystal structure was determined in singlecrystal studies [70Hop]. From the meager liquidus data, it is tentatively postulated in Fig. 1 that this compound melts congruently.

1. An alternative hypothesis is that both GesLil6 and Ge2Li7 exist, but GezLi7 decomposes below 360 ~ However, it seems unlikely that Ge2Li7 could have been formed in sufficient quantities for single-crystal x-ray studies (see below) at such low temperatures without extensive annealing.

Ge2Li7
Ge2Li7 was prepared by fusion at 1000 ~ followed by slow cooling, and its crystal structure was determined in singlecrystal studies [72Hop].

GesLile
The alloy of composition "GeLi3" was reported [57Pel] to have a "well-defined" melting point of 800 ~ Unindexed powder patterns were obtained by [57Pel] and [66Fed], although the d-spacings obtained by the two authors are different. The coulometric titration measurements [82Stj] were interpreted as indicating a compound of stoichiometry GesLil6. This was the only compound observed in the coulometric titration between Ge4Li9 and Ge4Li15. That is, Ge2Li7 was not reported. Possibly the plateau really was caused by Ge2Li7. This is the interpretation presented tentatively in Fig.

Ge4Li15
Ge4Li~5 was prepared from the elements and its crystal structure was determined in single-crystal x-ray studies [61Gla, 65Joh]. The alloy of composition "GeLi4" was earlier thought to be a stoichiometric compound with a "welldefined" melting point of 750 ~ [57Pel]. However, [65Joh] showed that the alloy at this composition consists of the two phases Ge4Lil5 and GesLi22 and has a liquidus temperature

Journal of Phase Equilibria Vol. 18 No. 3 1997

291

Section

H: P h a s e

Diagram

Evaluations

-1X 9 56Rei,58Rei X 5"/Pel O 7lKeg

-2

00:0
.3 ~

o
-4' O -5

-6=

-7

0.5

1.0

1.5

2.0

2.5

3.0

3.5

1000/T (K)
Fig. 3 Solid solubility of Li in Ge.

Table 2 Phase
Ge

G e - L i Lattice P a r a m e t e r Data at 25 ~ Composition, at. % Li

0

a
0.56574 1.1541 0.438 0.975 0.40529(b) 0.438 0.449 0.924 1.072 1.0783 1.887 1.886 0.35093 0.3111

Lattice parameters, nm b
. . 0.8073 ... ... ... 2.455 0.787 1.321 . . . . . . . . . . ... . . . .

c
1.5359 0.580 0.578 2.3282(b) 1.064 2.444 0.463

Reference
[Kingl] [82Gru](a) [6401e] [69Men] [87Eve] [75Fra] [70Hop] [72Hop] [65Joh] [61Gla] [640!e, 65Joh] [64Gla] [Kingl] [Massalski2]

.....................................

Gel2Li7 ............................. GeLi ..................................

36.8 50.0

Ge6Li11(c)......................... Ge4Li9............................... Ge2Li7............................... Ge4Li15 ............................. Ge5Li22 .............................

64.7 69.2 77.8 78.9 81.5 100 100

....................................

. . . . .

. . . . .

. . . . .

. . . . . 0.5093

ctLi(d) ...............................

(a) The same authors in an earlier pubfication [81Gru] quote different parameter values (see text). The existence of this compound requires verification. (b) Parameters of the metastable high-pressure phase, quenched from 4 GPa and 500 ~ (e) The existence of this compound has been questioned [86Nes]. (d) <-201 ~ o f 690 ~ Ge4Li15 was o b s e r v e d in the c o u l o m e t r i c titration study [82Stj] at 4 0 0 ~ c o n f i r m i n g that GesLi22 has the highest Li content o f all c o m p o u n d s in this system. GesLi22 was also identified as the precipitated phase f r o m a supersaturated solid solution of Li in G e [84Kot].

GesLi22
GesLi22 was p r e p a r e d by reaction o f the e l e m e n t s and characterized by single-crystal x-ray studies. Its e x i s t e n c e at 400 ~ was c o n f i r m e d by c o u l o m e t r i c titration [82Stj]. T h e c o m p o u n d was identified by X R D in equilibrium with Li in samples c o n t a i n i n g o n l y a f e w percent G e [81Dad], thereby

Other Compounds
T h e existence o f Ge6Lil4 and GeTLil2 has been c l a i m e d [81 Gru], but without any supporting e v i d e n c e .

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P h a s e Diagram Evaluations: S e c t i o n II Terminal Solid S o l u b i l i t y in (Ge)

Much attention has been devoted to the solubility of Li in solid Ge in connection with the preparation and properties of doped Ge semiconductors. The data have been reviewed and discussed [57Hal, 57Mor, 58Rei, 60Tru]. In the studies by [56Rei] and [71Keg], Li was permitted to diffuse into Gadoped Ge either from a bath of pure Li [56Rei, 58Rei] or from a Li-Pb alloy [71Keg]. Li is an electron donor in Ge, and Ga is an electron acceptor. The concentration of free electrons and holes is thus a known function of the Li content. From conductivity measurements on quenched samples at room temperature, and from the known mobilities of electrons and holes in Ge, the Li contents of the samples could be measured. A small correction for the presence of ion-pairs was discussed by [58Rei]. Errors could be caused by precipitation inside the samples. The results of these two studies are in good agreement as can be seen in Fig. 3. The two highest temperature points of [56Rei] and [58Rei] are presumably compositions on the solidus because these were taken at temperatures above 525 ~ Solidus measurements were also performed by [57Pel] who equilibrated solid Ge with the melt, quenched the samples, and analyzed the solid for Li by flame photometry. Results shown in Fig. 3 are in reasonable agreement with those of [56Rei]. Below the eutectic temperature, the solubilities are represented by: 2610
- T(K)

Ge6Lill is orthorhombic and contains isolated planar fivemember Ge rings in addition to isolated atoms [75Fra]. Subsequent to this work, it was claimed [86Nes] that Ge6Li n (as reported by [75Fra]) is really the ternary compound LisMgSi6, based on the "striking similarity" of structure of the two substances. For reasons cited in the previous section, this claim is not deemed to be decisive, but the existence of Ge6Litl requires verification. Ge4Li9 is orthorhombic and is characterized by the presence of Ge 2 dumbbells [70Hop] in layers. The Li atoms are distributed both within and between the Ge layers. Ge2Li7 is not isostructural with Si2Li 7, but there are many structural similarities [72Hop]. Ge4Li15 is bcc and isostructural with CulsSi 4 and NalsPb 4. This type of structure represents the closest possible packing of atoms of unequal size [61Gla]. GesLi22 is fcc and isostructural with Li22Sn5, Li22Si5, and Li22Pb 5.

Thermodynamics
From the emfof the concentration cells used in the coulometric titration studies, [82Stj] deduced the Gibbs energies of formation of several compounds in the range 360 to 440 ~ From the temperature dependence of the emf measurements, the entropies of formation were calculated. These, however, are probably very imprecise due to the small temperature range studied. The following results were obtained: Ge(S) + Li(L) = GeLi AGO=-61.9 + 0.096TkJ/mol (Eq 3) 4Ge(S) + 9Li(L) = Ge4Li9 AGo = -515 + 0.132T kJ/mol 5Ge(S) + 16Li(L) = GesLi16 AGo = -797 + 0.236TkJ/mol 4Ge(S) + 15Li(L) = Ge4Lil5 AGo = -688 + 0.219T kJ/mol (Eq 6) (Eq 5) (Eq 4)

lOgl0(at.% Li) = 0.625

(Eq 2)

Crystal S t r u c t u r e s and Lattice Parameters

Crystal structure and lattice parameter data are summarized in Tables 1 and 2, respectively. Get2Li7 is orthorhombic and contains the two-dimensional infinite polyanion (Ge7~); one Li atom lies within the Ge cage, and the other six are intercalated between the Ge layers [81Gru, 82Gru]. The lattice parameters for Ge12Li7 in Table 2 are those of the later report [82Gru]. In the same authors' earlier report [81Gru], different values are quoted: a = 1.5418 nm, b = 1.1583 nm, c = 0.8055 nm. Gel2Li 7 is a Zintl phase [81Gru]. As discussed above, the existence of this phase requires verification. GeLi is tetragonal and has a three-dimensional Ge network characterized by puckered eight-member rings; the Li atoms lie, as distorted Li 4 tetrahedra, in the cavities of the eightmembered rings [87Eve]. This phase, stable at atmospheric pressure, is a Zintl phase of 16 formula units per unit cell. The high-pressure modification of this phase contains the same puckered eight-member Ge rings, but the Li atoms lie both within the Ge rings and also alternately above and below the two-coordinate Ge bridging atoms [87Eve]. The high-pressure modification has 12 GeLi units per unit cell and has been described as a "near-Zintl" type phase [90She]. In an earlier study [64Ole], the space group was given as

Note that Eq 5 is given for the compound GesLi 16according to the authors' interpretation. However, as discussed above, this compound may actually be Ge2Li7, in which case AGOof formation of Ge2Li7 is 7/'16 of the value in Eq 5. Measurements of the Knight shift K and of dKIdT for liquid alloys were made in the vicinity of 800 ~ by [84Alb]. Peaks were observed near compositions corresponding to the compositions GeLi 4 and Ge3Li4 (the latter is not far from GeLi). This is evidence that the liquid alloys exhibit local ordering (clustering) with maximum ordering occurring near these compositions.

141md.

Journal of Phase Equilibria Vol. 18 No. 3 1997

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Section

II: P h a s e D i a g r a m E v a l u a t i o n s
72Hop: V. Hopf, W. Miiller, and H. Sch~ifer,"The Structure of LiTGe2," Z. Naturforsch. B, 27B(10), 1157-1160(1972) in German. (Equi Diagram, Crys Structure; Experimental) 75Ada: P.F. Adams, P. Hubberstey, and R.J. Pulham, "Review of the Solubility of Non-Metals in Liquid Li," J. Less-Common Met., 42(I), 1-11 (1975). (EquiDiagram; Review) 75Fra: U. Frank and W. MUller, "Li 11Ge6,A Phase with Isolated Planar Five-Membered Ge-Rings," Z. Naturforsch. B, 30B(5-6), 313-315 (1975) in German. (Equi Diagram, Crys Structure; Experimental) 77Mor: J.A. Morrison and R.J. Lagow, "Chemislry of Polylithiated Species: Reactions of Polylithiated Silanes and Germanes," Inorganic Chem., 16(11), 2972-2974 (1977). (Experimental) 81Dad: A.D. Dadd and P. Hubberstey,"Solubilities of Si and Ge in Liquid Li," J. Chem. Soc. Faraday Trans. I, 77(8), 1865-1870 (1981). (Equi Diagram; Experimental; #) 81Itub: P. Hubberstey, R.J. Pulham, and A.E. Thunder, Unpublished Data Quoted by [81Dad] ( 1981). (Equi Diagram; Experimental) 81Gru: A. Grtittner, R. Nesper, and H.G. von Schnering, "New Phases in the Li-Ge System: Li7Ge12, Li12Ge7, and Li14Ge6,'' Acta Crystallogr. A, 37 (SuppL), C-161 (1981). (Equi Diagram, Crys Structure; Experimental) 82Gru: A. Griittner, R. Nesper, and H.G. von Schnering, "Novel Metastable Ge Modifications: Allo-Ge and 4H-Ge from Li7Gel2," Angew. Chem., 94(12), 933 (1982) in German; TR:Angew. Chem. Int. Ed. EngL, 21(12), 912-913 (1982). (Equi Diagram, Crys Structure; Experimental) 82Hub: P. Hubberstey, A.T. Dadd, and P.G. Roberts, "Solubilities of Non-Metals in Liquid Li--A Review," in Material Behavior and Physical Chemistry in Liquid Metal Systems, H.U. Borgsledt, Ed., Plenum Press, New York, 445 -453 (1982). (Equi Diagram; Review) 82Stj: M.R. St. John, A.J. Furgala, and A.F. Sammells, '~I~ermodynamic Studies of Li-Ge Alloys: Application to Negative Electrodes for Molten Salt Batteries," J. Electrochem. Soc., 129(2), 246-250 (1982). (Equi Diagram, Crys Structure; Thermo; Experimental) 84Alb: B.P. Alblas, C. van der Marel, W. Geertsma, J.A. Meijer, A.B. van Oosten, J. Dijkstra, P.C. Stein, and W. van der Lugt,"Experimental Results for Liquid Alkali--Group IV Alloys," J. Non-Cryst. Solids, 61-62, 201-206 (1984). (Thermo; Experimental) 84Kot: I.M. Kotina, V.V. Kuryatkov, G.N. Mosina, S.R. Novikov, and L.M. Sorokin, "Formation of a New Phase During Precipitation of a Supersaturated Solid Solution of Li in Ge," Fiz. Tverd. Tela (Leningrad), 26(2), 436-440 (1984) in Russian; TR: Soviet. Phys.~Solid State, 26(2), 259-261 (I 984). (Equi Diagram; Experimental) 86Nes: R. Nesper, L Curda, and H.G. von Schnering, "Li8MgSi6, A Novel Zintl Compound Containing Quasi-Aromatic Si5 Rings," J. Solid State Chem., 62(2), 199-206 0986). (Equi Diagram, Crys Structure; Experimental) 87Eve: J. Evers, G. Oehlinger, G. Sextl, and H.-O. Becker, "HighPressure LiGe with Layers Containing Two- and Four-Coordinate Ge Atoms," Angew. Chem., 99(1), 69-71 (1987) in German; TR: Angew. Chem. Int. Ed. Engl., 26(1), 76-78 (1987). (Equi Diagram, Crys Structare, Pressure; Experimental) 90She: P. Sherwood and R. Hoffmann, "Ge-Ge Bonding in the HighPressure Modification of LiGe: A Near-Zintl Phase," Z Am. Chem. Soc., 112(8), 2881-2886 (1990). (Crys Structure, Pressure; Theory) #Indicates presence of a phase diagram.

Pressure
GeLi was transformed to a high-pressure modification by subjecting it to 4 GPa pressure at 500 ~ for 10 min in BN or Fe crucibles [87Eve]. Samples were quenched to ambient temperature and pressure for analysis. The metastable phase reverts to the normal low-pressure phase upon heating to about 200 ~ at atmospheric pressure [87Eve]. The structure of highpressure GeLi was elucidated by calculations using the extended Hiackel method in the tight-binding model [90She].

Cited References 56Rei: H. Reiss, C.S. Fuller, and F.J. Morin, "Chemical Interactions Among Defects in Germanium and Silicon," BelISyst. Tech. J., 35(3), 535 (1956). (Equi Diagram; Experimental) 57Hah R.N. Hall, "Variation of the Distribution Coefficient and Solid Solubility with Temperature," J. Phys. Chem, Solids, 3(1-2), 63-73 (1957). (Equi Diagram; Review) 57Mor: F.J. Morin and H. Reiss, "Precipitation of Li in Ge," J. Phys. Chem. Solids, 3(3-4), 196-209 (1957). (Equi Diagram; Review) 57Pel: E.M. Pell, "Solubility of Li in Ge," J. Phys. Chem. Solids, 3(1-2), 74-76 (1957). (Equi Diagram; Experimental) 58Rei: H. Reiss and C.S. Fuller, 'qaae Effect of Ion Pair and Ion Triplet Formation on the Solubility of Li in Ge. Effect of Ga and Zn," J. Phys. Chem. Solids, 4(1-2), 58-67 (1958). (Equi Diagram, Review) 60Tru: F.A. Trumbore, "Solid Solubilities of Impurity Elements in Ge and Si," Bell Syst. Tech. J., 39(1), 205-233 (1960). (Equi Diagram; Review) 61Gla: E.I. Giadyshevskii and P.I. Kripyakevich, "Crystal Structure of LilsGe4," Kristallographiya, 5(4), 574-576 (1960) in Russian; TR: Sov. Phys.-Cryst., 5(4), 549-551 (1961). (Equi Diagram, Crys Structure; Experimental) 64Gla: E.I. Gladyshevskii, G.I. Oleksiv, and P.I. Kripyakevich, "New Examples of the Structural Type Li22Pbs," Kristallografiya, 9(3), 338-341 (1964) in Russian; TR: Soy. Phys.-Cryst., 9(3), 269-271 (1964). (Crys Structure; Experimental) 6401e: G.I. Oleksiv, "Crystal Structures of Binary Compounds of Li with Sr, Ba, AI,T1, Si, andGe," Probl. Rozvitku Prirodn. Tochn. Nauk, Sb., 76-77 (1964) in Russian. (Crys Structure; Experimental) 6Kloh: Q. Johnson, G.S. Smith, and D. Wood, "The Crystal Structure of LilsGe4," Acta Crystallogr., 18, 131-132 (1965). (Equi Diagram, Crys Structure; Experimental) 66Fed: P.I. Fedorov and V.A. Molochko, "The Li-Ge System," Izv. Akad. Nauk SSSR, Neorg. Mater., 2(10), 1870-1871 (1966) in Russian; TR: lnorg. Mater., 2(I0), 1614-1616 (1966). (Equi Diagram; Experimental) 69Men: E. Menges, V. Hopf, H. Sch~fer, and A. Weiss, 'q'he Crystal Structure of LiGe--A New Three-Dimensional Unit of Group IV Elements,"Z. Naturforsch. B, 24B(10), 1351-1352 (1969) in German. (Equi Diagram, Crys Structure; Experimental) 70Hop: V. Hopf, H. Sch~ifer, and A. Weiss, 'The Crystal Structure of Li9Ge4,"Z. Naturforsch. B, 25B(6), 653 (I 970) in German. (Equi Diagram, Crys Structure; Experimental) 71Keg: G.H.R. Kegel, R.J. Laramee, and B.D. Bhardwaj,"TheFreeEnergy of Mixing in the Li-Ge Binary System," J. Electrochem. Soc., 118(10), 1662- 1665 (1971). (Equi Diagram, Experimental)

Ge-Li evaluationcontributedby J. Sangster and A.D. Peiton, Centre de Rechercheen Calcul Thermochimique,Ecole Polytechnique,P.O. Box 6079, Station A, Montrral, Qurbec, Canada, H3C 3A7. This work was supported by ASM International. Literature searched through 1992. Dr. Pelton is the Alloy Phase Diagram Program Category Co-Editor for Binary Alkali Systems.

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