Mat. Res. But1., Vol. 15, p p . 379-385, 1980. P r i n t e d in the USA.

0025-5408/80/030379-07502.00/0 C o p y r i g h t (c) 1980 Pergamon P r e s s Ltd.

PHASE DIAGRAM OF THE LISICON, SOLID ELECTROLYTE SYSTEM,

Li4GeO4-Zn2GeO4

P.G. Bruce and A.R. West

University of Aberdeen, Department of Chemistry,
Meston Walk, Old Aberdeen AB9 2UE, Scotland

(Received J a n u a r y 21, 1980; Communicated b y J. B. Goodenough)

ABSTRACT
The phase diagram of the system Li4GeO,-Zn2Ge04 is f a i r l y similar to
the corresponding silicate system and contains a wide range of solid
solutions that extend to either side of the composition Li2ZnGeO,.
These solid solutions are polymorphic. The high temperature YII
solid solutions have a crystal structure derived from that of
YII Li3P04 and a formula. Li242~Zn1-~(GeO~ : -0.36 < < +0.87.
LISICON. ~ = 0.75. is one member of the YII solid solution series.
The compositional extent of the YII solid solutions is temperature
dependent and eg. the LISICON composition is stable as a single phase
YII structure only ~ 630C. On annealing LISICON and other lithium-
rich. YII solid solutions in the range ~lO0 to 600C. various
reactions occur, including l) precipitation of Li,Ge04. 2) phase
transition(s) to metastable low temperature, y-derivative structure(s)
and 3) atmospheric attack to give Li2Ge03. Li2C03 and other phases.
The low temperature BII. BII ~ solid solutions occur over a much
smaller range of compositions to either side of Li2ZnGeO, and have a
crystal structure derived from that of BII Li3P04. Li4Ge04 forms a
short range of solid solutions.

Introduction
In the search for new Li + ion conducting solid electrolytes, considerable
attention has been focused on lithium-rich oxides such as Li4SiO, (1.2) and
its solid solutions with Li,Ge04 (3.4). Li3P04 (5-7) and Li2SO,. Recently.
a new group of materials typified by Li14Zn(Ge04)4 has been prepared with a
conductivity at 300C higher than that of any other Li + ion conductor (8).
This material has been named LISICON. I t was claimed that Li1,Zn(GeO.), is
one member of a complete range of solid solutions between Li,GeO, and
Li2ZnGeO, but since Li.GeO, and Li2ZnGe04 have different crystal structures.
complete solid solution between them is not possible. The crystal structure
of LISICON has a rigid, three-dimensional framework of composition
[Li1~Zn(GeO,).] 3- with the remaining three Li + ions in i n t e r s t i t i a l sites;
379
380 P.G. BRUCE, et. al. Vol. 15, No. 3

migration of Li + between these sites causes the high Li + conductivity. The

crystal structure of Li3Zno-5Ge04 (or Li12Zn2(Ge04)4) was determined
independently and the s i m i l a r i t y of the structure to that of YII Li3P04 noted,
but with extra i n t e r s t i t i a l lithiums (9). The number of i n t e r s t i t i a l lithiums
was reported to vary with composition over the range Li3.sZno.iGe04 to
Li2.BZn0.7GeO, (9). Recently i t has been found that the LISlCON composition
is metastable at room temperature, although the rate of decomposition, by
precipitation of Li4GeO, , is appreciable only at higher temperatures,
350C ( I 0 ) .
The objective of the present work has been to determine the phase diagram
of the system Li,GeO4-Zn2Ge04. Such information is essential to understanding
the s t a b i l i t y of LISICON and as an aid to studying compositionsthat have
improved conductivity. A correlation between the phase diagram and the
conductivity of the various orthogermanate phases and solid solutions will be
reported subsequently.

E_xperimental
Reagents used were Li2C03, ZnO (both Analar) and Ge02 (electronic grade).
Compositions were mixed into a paste with acetone, dried and f i r e d in gold
f o i l boats, i n i t i a l l y at 600C for a few hours to drive o f f C02 and f i n a l l y
at 800 to 900C for 12 to 24 hrs to complete the reaction. More Zn-rich
compositions were fired in Pt crucibles at I000 to 1200C for 12 - 24 hrs.
Some compositions were prepared d i r e c t l y from the three oxides; for others,
stock quantities of Li4GeO, and Li2ZnGe04 were prepared, mixed in various
ratios and reacted.

Preparations were made in general purpose muffle furnaces with temperat-

ures accurate to 25C. For the phase diagram determination, samples wrapped
in Pt or Au f o i l were suspended in the hot zone of a vertical tube quench
furnace and the samples quenched by dropping into Hg at the end of the runs;
temperatures were accurate to 3C. Samples were heated in a i r . Loss of
l i t h i a did not occur below IO00C for times of 12 to 24 hrs; samples could
be heated for shorter times (eg. 1/2 hr) to ~.'1250 C without appreciable
l i t h i a loss.

Samples were analysed by X-ray powder d i f f r ~ t i o n with a Philips H~gg

Guinier camera, monochromatic CuKa~ radiation. For accurate d-spacing
measurements, KC~ (a = 6.2931 A) was added as an internal standard. The films
were analysed by microdensitometry using equipment designed and b u i l t by
Brian Cooksley in Aberdeen. Differential thermal analysis was carried out on
a Du Pont 900 instrument using 850~and 1200C cells and on a 990 model using
the 1600C c e l l .

Results
The Phase Diagram
The experimentally determined phase diagram of the system Li4GeO,-Zn2Ge04
is shown in Fig. I . I t is f a i r l y similar to the system Li4SiO4-Zn2SiO, (14,
15). The system is binary since a l l the phases that occur can be represented
as mixtures of positive quantities of the two end members. The system contains
a congruently melting phase, Li2ZnGe04, melting at 1498C. Crystalline
Li2ZnGe04 exists in three polymorphic modifications with transition
temperatures:

SII. -~592c~ SII

. . . . .
1291C~
---------- ~II ~1498C
_---- ~ melt
Vol. 15, No. 3 LISICON 381

14001-
I liquid

t
.----" ~

~" ....-.-" I
~ ~ " ~ "'"

"h
-~

"'~J"
I I -

L /
r'~' ~ / ;r E + Zn2GeO4
1200F/ "rr / / ' ~

o1Fl / /,,,/
C..^// /_ I - [ 811" * Zn2GeO4

600 ,^ ,
4 8 " +~ 8 B + Zn GeO

Li4GeO410 20 30 Li2ZnGeO 4 70 80 90Zn2GeO 4

mole % Zn2GeO4

FIG. 1
Phase diagram for the system Li4GeO,-Zn2Ge04.
A DTA trace of ~TT'Li2ZnGe04 gave three peaks on the heating cycle, at 592C,
1204C and 1291C~ The 592C peak has been observed previously and assigned
to the B I I ' ~ BII transition ( l l ) . The 1291C peak is assigned to the
formation of YII since this temperature matches with the extrapolated
behaviour of solid solutions to either side of the Li2ZnGeO, composition, as
determined by quenching and X-ray experiments. The cause of the peak at
1204C is not known; i t may represent the formation of a transitional phase
between ~II and YII, such as has been observed in eg. Li3VO, ( l l ) , or
could be oue to partial melting associated with the presence of a small amount
of impurity. Neither YII nor BII polymorphs could be preserved to room
temperature at the stoichiometric composition, even by rapid quenching.

YII Li2ZnGeO, forms a wide range of solid solutions at high temperatures

to either side of the Li2ZnGe04 composition, the lithium-rich solid solutions
being the more extensive. The zinc-rich solid solutions have formula
Li2.-2~Zn1.~GeO, and pc extends to a maximum value of ~X].36 at 1400C. With
increasing Zncontent, the YII solid solutions are staMlised to lower
temperatures and a eutectoid at I080C and z ~ 0.26 represents their lower
l i m i t of s t a b i l i t y . Below I080C, the equilibrium phases are a mixture of
Zn2GeO~ and ~II or BII" Li2ZnGe04 solid solution. Although the YII
structure cannot be quenched to room temperature at the stoichiometric
composition, this is possible for the more zinc-rich solid solutions with
x ~ 0.25 to 0.36.
382 P.G. BRUCE, et al. Vol. 15, No. 3

The lithium-rich Yll solid solutions, of formula Li2.2~Zn1. Ge04, are

remarkable for two reasons. First, at high temperatures they extend to
x ~ 0.86, which is almost to the Li,GeO, composition. Second, they are
stabilised to much lower temperatures with increasing x; for x ~ 0.45 to
0.55 ( i . e . 27.5;~to 22.5% Zn2Ge04) they appear to be stable down to below
300C. For small values of x (~0.45) partial or complete transformation
to the BII and BII" structures occurs during cooling, although this
transformation is kinetically slow for x i~ 0.15. For larger values of
x (3 0.55), precipitation of Li,Ge04 occurs on cooling the TII solid
solutions but again, this takes place slowly and the YII structure can be
quenched to room temperature. Thus, for compositions in the range O.l < x <
0.86, i t is possible to quench YII without transformation to 811 or
exsolution of Li,Ge04 occurring, provided sufficiently fast cooling rates are
used. For compositions O.l < x < 0.2, orthorhombic YII cannot be obtained
at room temperature but instead converts to monoclinic To (similar to the
behaviour in the system Li4SiO4-Zn2Si04 (14,15)

BII and BII" solid solutions e x i s t over a r e l a t i v e l y narrow ranqe of

compositions to e i t h e r side of Li2ZnGeO,, with Xmax ~ 0 . I . The ~ I I s t r u c t -
ure could not be quenched to room temperature f o r any composition.

Li4Ge04 e x h i b i t s a r e v e r s i b l e DTA heat e f f e c t at 755 3C which has been

a t t r i b u t e d to the t r a n s i t i o n from the orthorhombic low form to the monoclinic
high form (3). Li4Ge04 forms a short range of s o l i d solutions of formula
Li4.z~Zn~Ge04, with x max ~ 0.I at 1250C. The temperature of the high-
low t r a n s i t i o n f a l l s to a minimum value of 725C at x = 0 . I . Pure high
Li4GeO, cannot be quenched to room temperature but with rapid quenching of
small samples, the z i n c - r i c h s o l i d solutions may sometimes be preserved to
room temperature. A two phase region separates the f i e l d s of YII and
Li4GeO, s o l i d solutions at a l l temperatures. This region is narrow, ~3%
wide, at high temperatures but opens out below ~700C.

Melting temperatures have been determined only approximately by observing

the physical appearance of samples that had been quenched from different
temperatures. This enabled solidus temperatures to be estimated f a i r l y well.
The melting points of Li4GeO~ and Zn2Ge04 are 1300C (12) and 1490C (13)
respectively.

The l a t t i c e parameters of the orthorhombic ~II solid solutions as a

function of composition are given in Fig. 2. On the lithium-rich side of
Li2ZnGe04, the parameters are essentially constant but, on the zinc-rich side,
a large change in a occurs. The change in slope (of a) that appears to occur
at the Li2ZnGe04 composition is consistent with a change-over in solid
solution mechanism ( i . e . from avacancymechanism on the zinc-rich side to an
i n t e r s t i t i a l mechanism on the lithium-rich side). Similar effects were
observed in the system Li4SiO,-Zn2Si04.

Applications to Solid EleFt[olytes

The diagram given in Fig. l is an equilibrium phase diagram. On heating
samples above ~ 600C, equilibrium is usually attained f a i r l y quickly, and
for heating times of l to 2 days, equilibrium may be attained down to ~400C.
Departures from equilibrium may occur i f temperatures are changed rapidly and
in particular, high temperature phases or solid solutions may become frozen-
in on quenching to room temperature. The LISICON composition reported by
Hong is an example of a quenched, high temperature solid solution. According
to Fig. l, under equilibrium conditions, precipitation of Li4Ge04 from the
LISICON composition should occur below ~630C and the amount of Li4Ge04
Vol. 15, No. 3 I,IS1CON 383

LI.GeO4 lo 20 30 40 50 mole% Zn2GeO4 9 0 Zn2GeO4

/
/
/
/
/
11 20

/
i1 lO !
/
!
/
11 oo /
A
lO 90
FIG. 2

V a r i a t i o n of l a t t i c e parameters
10 8o
with composition f o r the Li:~ZnGe04
6 4o
solid solutions with the YII
structure.
6 3o

6 2o

61q
5 20) ~
- y
Y
5 10

500l J
08 014 ' 0 ' -0!4 ' 018 1
X : Li2+2xZnl.~GeO 4

should increase with decreasing temperature. At the same time, the 711
composition becomes increasingly richer in zinc. Since precipitation of
poorly conducting Li4Ge04 leads to a reduction in overall conductivity (lO),
i t is necessary to keep the temperature of quenched LISICON to b e l o w ~ 200C
in order that its rate of decomposition is slow. Alternatively, i t may be
better to modify the composition of LISICON so that the ~ I I structure is
stable to lower temperatures (e.g. to increase its zinc content to 25%
Zn2Ge04.

Although not e x p l i c i t l y recognised as such by Hong, LISICON is a solid

solution based on high temperature, ~ I I Li2ZnGe04 which is isostructural
with YII Li3P04. The l a t t e r has a ~ tetrahedral structure and is one
member of a family of tetrahedral oxide phases (16) that includes:
- A2BX04: A = Li, Na; B = Be, Mg, Zn, Fe, Mn, Cd; X = Si, Ge.
- AYO~ : A = Li, Na; Y = A~, Ga, Fe
- A3Z04 : A = Li, Na; Z = P, As, V

The occurrence of high Li ion conductivity in LISICON indicates that

other y tetrahedral oxides, or their solid solutions, may be good solid
electrolytes.

On annealing lithium-rich I I solid solutions, e.g. LISICON, in the range

50~to 150C for a few hours a minor phase transformation occurs. This is
characterised by the doubling of certain lines in the X-ray powder pattern,
Fig. 3. The transition is reversible and at e.g. 200C, the line splitting
384 P.G. BRUCE, et al. Vol. 15, No. 3

moo
I
60 A. Low Y

?0
I()0

: I llI,]
60 C, Low Y

>"
I-- ~o
'I iL
z
60

20 t Y,,

i I IN,,
+o E.Pm

'
I
2O

iO01
so F, H Li4GeO4

20

i
I
I I h,
ef2o I . L- Li4C:~O4

L. ,
70 6'0 5:0 J I, Ji,I 2:o
J' 40 3.0
d -spacing
FIG. 3
Powder d i f f r a c t i o n patterns of some Li, Zn Orthogermanate phases.
Compositions in mole % Zn2Ge04 : A. lowY, 30; B. Iow~,
12.5; C. low i , 7.5; D. Y I I , 12.5; E. BII" 50;
F. High Li4GeO~, ~ 4 ; G. low Li4Ge04, O. Doublet
formation in the low y phases (A to C), indicated by brackets.

disappears and the orthorhombic YII structure is regained. Different Yll

compositions give rise to s l i g h t l y d i f f e r e n t X-ray patterns, Fig. 3 and i t is
possible that a family of s t r u c t u r a l l y related phases may e x i s t . Further
attempts to characterise them have not been made; they have all been included
under the t i t l e "low y phase". The effect of the t r a n s i t i o n from YII to
low y on the conductivity of Li + ions has yet to be determined.

Lithium-rich YII solid solutions, including LISICON, are sensitive to

atmospheric attack, especially in the range ~I00 to 500C. The main products
are Li2C03 and Li2Ge03 but otheG unidentified phases form in smaller amounts.
The reactions that occur may be understood by considering the effect of C02
on Li4GeO,, which behaves in a s i m i l a r way to the l i t h i u m - r i c h YII solid
solutions. The following equilibrium exists :
Vol. 15, No. 3 LISICON 385

Li4Ge04 + C02 " Li2Ge03 + Li2C03

In a i r at high temperatures, ~ 600C, equilibrium is displaced to the l e f t .
Hence Li4Ge04 can be synthesised >600C and is stable. At lower temperatures,
500C equilibrium is displaced to the r i g h t and the reaction takes place
within a few hours at ~300~to500C. A detailed study of this reaction has
not been made but these observations are s u f f i c i e n t to account for the
s e n s i t i v i t y of Li4GeO, and LISICON to atmospheric attack.

Acknowledgements

We thank the S.R.C. for financial support and Tioxide International for
supporting a CASE studentship.

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133, 260 (1971).
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