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High-temperature superconductivity
in the Li--Ti--O ternary system
HARI PRAKASH

Materials Research Bulletin

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 Mat. Res. Bull. Vol. 8, pp. 777-784, 1973. Pergamon Press, Inc. Printed
in the United States.

H I G H TEMPERATURESUPERCONDUCTIVITY IN THE
Li-Ti-O TERNARY SYSTEM

D. C. Johnston*
Institute for Pure and Applied Physical Sciences
University of California, San Diego, La Jolla, California 92037

H. Prakash**
Department of Chemistry
University of California, San Diego, La Jolla, California 92037

W. H. Zachariasen
Physics Department
University of Chicago, Chicago, lllinois 60637

and

R. Viswanathan ~
Department of Applied Physics and Information Science
University of California, San Diego, La Jolla, California 92037

(Received M a y 7, 1973; C o m m u n i c a t e d by B. T. Matthias)

ABSTRACT
The first high temperature superconducting oxide compound is
reported. The compound is Lil+xTi2_xO 4 and has o the face-
centered cubic spinel structure, with a o ~ 8.40A. The transi-
tion temperatures of this compound range from ~ 7°K to 13.7°K.

Introduction

Recently, two ternary sulphide systems have been reported to have

rather high superconducting transition temperatures (Tc). LixTil.iS 2
(0.i < x ! 0.3) was reported to become superconducting over the temperature

Supported by the Air Force Office of Scientific Research, Air Force Systems
Command, USAF, under AFOSR contract #AFOSR/F-44620-72-C-0017.
Supported by the Office of Naval Research under contract NR 053-529.
±Supported by the U.S. Atomic Energy Commission under contract AEC-
AT- (04-3)-34.
777
??8 THE Li-Ti-O TERNARY SYSTEM Vol. 8, No. 7

range from 10-15°K(1), and MO6_xAxS 6 (A = Cu, Ag, Pb, Sn, Zn, Mg, Cd) in
the temperature range 2.5 - 13°K(2). In our study of these and similar
systems, we have found superconductivity to occur in the Li-Ti-O ternary
system with T c values ranging from 1.5°K to 13.7°K. We report here our
preliminary measurements in this system.

Experimental Details

We have synthesized superconducting Li-Ti-O samples with a variety

of methods and starting materials. Our first samples were made by arc-
melting Li2C03, Ti02, and Ti metal together. Arc melting tends to produce
multiphase samples, and was initially a valuable technique for defining
the various ranges of T in the Li-Ti-0 system. Samples were also produced
c
by sintering mixtures of Li2Ti205 (K & K Laboratories) and Ti203 (Alfa
Inorganics) at 800-1480°C under a helium or argon atmosphere. The reduction
of pre-reacted mixtures of Li2CO3-TiO 2 with hydrogen was also used to synthesize
some of the samples.

Transition temperatures were determined with an ac resistance method

(20 Hz) using a four-probe technique, with standard ac inductance bridge
techniques (20 Hz), and with ac heat capacity measurements (3). The accuracy
of the temperature measurements was 0.1°K for the resistivity and inductance
measurements, and 0.01°K for the heat capacity measurements.

X-ray data were obtained on a G.E. XRD-6 diffractometer with CuK~

radiation and a crystal monochromator to eliminate the CuKB line. X-ray
examination of most samples was carried out in air. However, a few samples
were crushed and ground (230dmesh) under an argon atmosphere, and transferred
(also under argon) into a vacuum x-ray dewar with beryllium windows for the
x-ray beam. The x-ray diffraction patterns thus obtained did not differ
significantly from the patterns obtained when the samples were powdered and
x-rayed in air. Exposure of samples to air for a few hours or storage under
argon for long periods of time (~ i month) had no effect on their super-
conducting properties.

Results

We have found that the spinel structure (4) occurs in the Li-Ti-O system
with a homogeneity range from Lil.33Til.6704 (a° = 8.36A) (5) to approximately
Li0.sTi2.204 (a° ~ 8.40A). There also appears to be a small homogeneity
range for the metal-oxygen ratio. The lithium and/or oxygen rich compositions
have a white to light-blue color, and do not become superconducting down to
Vol. 8, No. 7 THE Li-Ti-O TERNARY SYSTEM 779

1.5°K, the low-temperature limit of our cryostat. However, as the Ti/Li

and/or Ti/O ratio is increased towards the ideal spinel composition LiTi204,
the samples become dark blue to blue-black in color, and become superconducting
in the temperature range ~ 7 ° to 13.7°K. In many of our multi-phase samples,
we see superconducting transitions at 1.5°K to 6.5°K, sometimes in addition
to the higher spinel Tc, but we have not yet isolated this phase.

Superconductivity data for a sample (#570) of nominal composition

Li0.8Ti2.204 are shown in Fig. i. The resistivity transition temperature for

F
#570
]
Lio,8Ti22 04 ~! I
0 , 4

~ 03
0.0~- Tc MEASUREMENT "
l

• MAGNETIC SUSCEPTIBILITY(X) o

' • RESISTIVITY
02 ~
I ° F--
Q_

__j
4
01

: ~-_ £.$.$i T S L "

L
00
0 5 I0 15 20
T(°K)
FIG. 1

Low-temperature magnetic susceptibility and resistivity data

plotted vs. temperature for a sample prepared by sintering
Li2Ti205 and Ti203 at 800°C for one day.

this sample (Tonset = 12.2°K) lies slightly above the magnetic susceptibility
c
transition temperature, probably due to filamentary superconductivity in the
o
sample. X-ray analysis of this sample yielded a lattice parameter ao= 8.403A
for the superconducting spinel phase, and showed ~ 1% of unreacted starting
materials. The x-ray data for the spinel phase are shown in Table i.
The systematic extinction of 00& lines (~ # 4 n) and hk0 lines
h+k
Todd) in the fcc pattern of Table i is characteristic of the space
group Fd 3m (6) of which the spinel structure (4) is a member. We point
780 THE Li-Ti-O TERNARY SYSTEM Vol. 8, No. 7

TABLE I

X-ray data for sample #570 Li 0 8Ti2 20 L (nominal composition) with spinel
structure. The observed and calculated d spacings are indicated in the two
left-hand columns. The calculated d spacings are based on a cubic unit cell
with lattice constant a ° = 8.403A. The observed intensities (lobs) are peak
heights of the diffraction lines on a diffractometer tracing. The calculated
intensities (Icalc) are for an ideal spinel of composition LiTi204.

hkl dob s (~) dcalc (A) lob s Icalc

111 4.850 4.851 i00 82

220 2.971 0 0.5
311 2.534 2.534 58 59
222 2.425 2.426 6 5
400 2.100 2.101 73 73
331 1.927 1.928 8 18
422 1.715 0 0.2
511,333 1.617 1.617 18 17
440 1.486 1.485 29 45
531 1.420 1.420 i0 12
620 1.329 0 0.i
533 1.282 1.281 3 5
622 1.267 1.267 3 3
444 1.213 1.213 6 ii
711,551 1.177 1.177 5
731,553 1.094 1.094 4
800 1.051 1.050 3
751,555 0.971 0.970 3
840 0.940 0.939 7
911,753 0.923 0.922 3
931 0.88 0.88 i
844 0.858 0.858 5

out that these extinctions and the observed intensity data are inconsistent
with the NaCI structure (space group Fm 3m). We have calculated the diffracted
intensities for an ideal spinel of composition LiTi204, assuming that only
Li occupies the tetrahedral sites and only Ti occupies the octahedral sites
("normal spinel" configuration). The calculated intensities were scaled such
that lob s = Icalc for the 400 line. The results for the fourteen lowest angle
lines are shown in Table i. The following formula was used in the calculations:
Vol. 8, No. 7 THE Li-Ti-O TERNARY SYSTEM 781

I (hk~) I F(hk~)l 2 1 + cos 2 2e P(hk~)

sin28 cos 6

where

F(hk~) ~ spinel structure factor for the hk~ reflection

P(hk~) ~ multiplicity of the hk~ reflection.

The general agreement between observed and calculated intensities is quite

good. The intensities of the 220, 422, and 620 lines depend only on the form
factors of the atoms occupying the tetrahedral sites, and increase rapidly
with occupation by Ti atoms. The measured intensities for these lines (~ 0)
therefore indicate that very few Ti atoms occupy tetrahedral positions in the
spinel lattice of sample #570.
In Fig. 2 are shown the low temperature magnetic susceptibility and
heat capacity data for sample #449B Li-Ti-0 prepared by arc-melting Li2C03,
Ti02, and Ti metal together. The nominal composition for this sample was
Li2Til.503, but there was a 14% weight loss during arc-melting over that
expected for the loss of CO 2 so the final composition is not known precisely.
The two measurements agree closely in the superconducting onset temperature
of the upper transition (i1.3 - II.4°K), and the heat capacity data indicate

06 I I T r
0 F ......

/
X //
0.4 D/

o
E ./

E
Os"
,-- 0.2 l

I
m~lr"

~..~Jj-.- e.1 • It 40"K

#449B Li-Ti-O
6,56°K

O' 1 I
0 ,.50 I00 150 200 25O
Tz in °K z
FIG. 2

Low-temperature magnetic suscept~2bility (×) and ac heat capacity

data plotted vs. (temperature) showing the superconducting
transitions for a sample prepared by arc-melting techniques.
78Z THE Li-Ti-O TERNARY SYSTEM Vol. 8, No. 7

that the superconductivity is a bulk effect. G.E. 7031 varnish was used
to attach thermocouple leads to the sample for the ac heat capacity
measurement, and the heat capacity data include its contribution. A lower
transition temperature at ~ 6.5°K is also apparent.in the heat capacity data.
The x-ray data for this sample (#449B) indicate the presence of three
phases: i) ~ 50% spinel (a° = 8.39A). 2) ~30% of an fcc structure (a° = 8.30~),
and 3) ~ 20% of a phase of undetermined structure denoted "PHASE I". These
three phases also occurred in many other samples near a composition typical
for a spinel structure. X-ray data on the latter phase (Phase I) are shown
in Table 2 . Samples have been prepared for which the x-rays contain only
the lines shown in Table 2 and were not found superconducting above 1.5°K.
A few of our multi-phase samples had transition temperatures somewhat
higher than those indicated in Figures 1 or 2. The highest T c occurred for
sample #533C LiTi204 which was prepared by sintering Ti203 and Li2Ti205 (i:i
ratio) at 800°C for one day. It had an inductive T C of 9.5 - 12.4°K (10%-
90% of the transition), and a superconducting onset temperature of 13.7°K.
o
X-ray examination showed that the sample was predominantly spinel (a° = 8.404A),
with about 20% of unreacted Li2Ti205 (spinel, a ° = 8.30A).

TABLE 2

X-ray d-spacings and intensity data for a phase (denoted "PHASE I")
found in many samples with compositions near that of the spinel
• " The intensity data (I) indicate the peak height of
Lll+~T12-xO4"the lines on a diffractometer tracing.

d (A) I d (~) I

4.45 58 1.64 6
2.71 25 1.53 i0
2 51 19 1.47 4
2 46 12 1.44 i0
2 25 i0 1.41 2
2 17 4 1.40 3
2 O0 13 1.35 3
1 98 3 1.33 4
1 86 i0 1.29 Ii
1 78 31
Vol. 8, No. 7 THE Li-Ti-O TERNARY SYSTEM 783

Discussion

The spinel L11+xTl2_xO 4 is an example of a ternary high Tc superconductor°

Neither the structure nor a similar high T occur in any of the basis binary
c
systems Li-O, Ti-O, or Li-Ti. In these binary systems, the only known super-
conductor is TiO which has the NaCI structure with a maximum T of 2.3°K (7).
' C

The reason for the high transition temperatures for the Lil+xTi2_xO 4 spinel
is not clear. The spinel structure itself does not seem to be conducive to
superconductivity. Of the ~ 200 known spinel compounds, only three have been
found to be superconducting: CuRh2S4, CuV2S 4 and CuRh2Se4, with Tc values of
4.8°K, 4.5°K, and 3.5°K, respectively (8). Many of the other spinel compounds
are semiconducting and/or magnetic (5,9,10).

An interesting feature of the spinel phase in the Li-Ti-O system is that

its homogeneity range contains both insulating compositions (Li 1.3Tiji.704)
and metallic, superconducting compositions (Li 1.0Ti 2.004). Li 1.0Tir~2.004
is metallic in the sense that its electrical resistivity vs. temperature shQws
Sp(T)/DT > 0 for T < T < 300°K and a resistivity ratio p(300°K)/p(15°K) ~ 2.5(11);
C
however, it has a large room-temperature resistivity of ~ 4 x 104~S-cm(ll).

That the superconducting spinel composition is in the vicinity of a composition-

induced metal-insulator (semiconductor) transition could be associated with
its high T . Experiments are currently underway to study the composition
C
dependence of T and p(T).
C

In conclusion, Lil+xTi 2 x04 is the first high T superconductor to contain

-- C

oxygen as a primary constituent. Previously, the highest T reported for an

C
oxidic compound was 6-7°K, which was for Rb o.2W03(12).

Acknowledgements

We would like to thank Professors B. T. Matthias and G. N. Schrauzer

for their interest in this work. We are also grateful to A. C. Lawson and
R. Fitzgerald for help received in metallographic preparation and electron
microprobe analysis of some of our samples. Helpful discussions with Z. Fisk,
M. B. Maple, D. Wohlleben, and A. C. Lawson are gratefully acknowledged.

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Science 175, 1465 (1972).
784 THE Li-Ti-O TERNARY SYSTEM Vol. 8, No. 7

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