[

Vol.7 No.2 June 2000 J. CENT. SOUTH UNIV. TECHNOL.

Article ID: 1005-9784(2000)02-0057-04

Synthesis of Lithium-cobalt Oxides by Sol-gel Method

and their Cathodical Discharge Behavior at 500 °C

LI Zhi-you,HUANG Bai-yun,ZHU Yong-li,LIU Zhi-jian,QU Xuan-hui

(State Key Laboratory for Powder Metallurgy, Central South University of Technology, Changsha 410083, China)

Abstract: Three kinds d lithium-cobalt oxides with lithium to cobalt atomic ratios of 0.6, O. 8 and 1.0 respectively were pre-
pared using r,ltrates and citric acid by sol-gel process. During the baking of the dry-gel powder, two exothermic peaks occur, fol-
lowed by the fcmnation of Li20 and Co~04 and then the combination of LiCo~, which is testified by DTA and XltD. The powder
formed from an alkaline sol is finer than that from the acidic one. There are a single phase intercalation of lithium ion and an elee-
troch~aical reduction reaction for higher-valence cobalt ion when simulating the discharging process of Li-B/LiCI-KCl/lithimn-co-
bait oxides at 500 °C, and the voltage and specific capacity are not sensitive to the initial ratios of lithium to cobalt.
Key words: sol-gel; LiGo~; thermal battery; cathode
Docun't~ code: A

Li-alloys/FeS2 (or CoS2) thermal batteries have been
the most widely-used electrochemical system, but their
low discharge voltage (about 2 . 0 V) deteriorates their
specific capacity and specific energy. The potential of Li-
alloys anode such as Li-B alloys[1'21 is almost equal to that
of pure lithium, therefore, developing new kinds of cath-
ode materials with high voltage and low impedance has be-
come an important research subject on thermal battery for
many years.
Transit/on-metal oxides have received a good deal of
attention over the last two decades as cathode materials for
rechargeable lithium-ion batteries, especially for
LiCoO2[3] , LiNiO2[4] and LiMn204 I5~, which have an in-
sertiorgde-insertion potential about 4 . 0 V vs Li/Li*, and
layered structural LiCoO2 has been used practically for its
easy preparation and good reversibility. Completely crys-
talline LiCoO2 is synthesised usually through high-temper-
ature solid-phase reaction of lithic and cobaltic alkalis or
salts that have decomposable anion, and initial lithic re-
actants must be excessive in order to prevent the formation
of Co304 E6.7]. Lithium-deficiency Lil.~ Co02 can be ob-
tained by oxidizing LiCo02 chemically or electrochemi-
callytsJ , but its stability is not good enough so that deoxi-
dation takes place easily above 220 °C and weight-loss oc-
curs at the same time E91. We aim to synthesize such low-
lithium lithium-cobalt oxides by Sol-Gel technique using
nitrates and citric acid, analyze the structure evolution of
the precursor in the course of heat-treating, and investi-
gate their discharge behavior as a cathode material for
thermal cells with a lithium-boron alloy anode.
1 Expenmental
1.1 Preparation and characterization of powders
Samples were prepared with l.iN%,
C o ( N O 3 ) 2 ' 6 H 2 0 , citric acid and ammonia (these chemi-
cals are all chemical-pure reagent grade). After dissolving
nitrates in de-ionized water (the atomic ratios of lithium to
cobalt were 0 . 6 , O. 8 and 1.0, respectively), citric acid
was added to the solution with stirring (the molar ratio of
citric acid to metal ion was 2 : 1 ) , and then ammonia was
added'to control the pH value in the range of 3 - 4 or 8 ~
9. After the solution had been cohobated at 100~ 110 °C
for 6 h, it was dried slowly at 80 °C to obtain aqueous
gel, loose and porous dry gel was obtained by drying the
aqueous gel at 110 % . The powder of dry gel was heated
in air at proper t~rnperature in terms of the TG and DTA
experiment results. Phase determination and morphology
observation for the baked products were carried out with a
mode 314-XRD analyzer (CuKa) and an Amray SEM, re-
spectively.
1.2 Measurements of cathode behavior
The discharging process of Li-B/LiCl-KC1/oxides
pellet cells was simulated at 500 °C and three current
densities, and the curves vs time were monitored by an
x-y function recorder. The Li-B alloy anode with 67 % Li
(mass fraction, the same below) was a two-phases mixed
material with LiTB6 and pure Li ( prepared in our

item: The DoctoralF~tmdati~d the Educati~ Ministryof China(No.96053311)

Of ~ first aulhot: LI 2~xi-you,born in 1968, majoringin mat~als for theama]battery.
Reos~d date: Nov. 15, 1999
 58 doumal ~
laboratory, thickness 0.4 ram) El°l , the electrolyte separa-
tor ( thickness 0 . 8 ram) was a powder-pressed pellet of
LiC1-KCI eutectic salt (with 45% LiC1, melting point 352
% ) including 45 % porous powdered MgO binder. In or-
der to improve the conductivity of the cathode, 40% pow-
dered LiC1-KC1 and 10% graphite were added, and this
mixture was exposed to air at 400 °C for 1 h to make
LiC1-KC1 adsorbed homogeneously. After being cooled
down and crushed, the mixture was pressed out as the
cathode pellet, whose weight was 0.4 g. The diameter of
electrode was 17.5 ram, a piece of pure nickel (thickness
1.0 ram) was used as the collector. Preparalion of elec-
trodes was performed in a glove-bag box (relative humidi-
ty lower than 3 % ) in order to prevent the electrodes from
being wetted or oxidized. Before discharging, the cells
were kept between two isothermal metallic tablets for 1
min to be heated to the experimental temperature (500
°C).
2 Results and Discussion
2.1 Procedureof phase evolution
Thermal analysis (TG and DTA) thermogram for the
dry-gel powder of Lio.sCoO2 is shown in Fig. 1. An endo-
thermie peak appears at 130 °C with the beginning of
weight-loss, which indicates that the volatilization of water
and the decomposition of solvent begin. Beginning at
295 °C, two linked exothennic peaks at 329.3 °C and
386.5 °C exist, and the sample weight loses quickly (up
to 80.4% ). The dry-gel powder was baked respectively
at 250, 350,400 and 480 °C for6 h in air, phase com-
position of the baked products was determined by XtLD
(shown in Fig. 2). It can be seen from Fig. 2 that after
being heated at 250 °C, the product is corc~sed of
Co304, LiOH and LiOH" H20, where LiOH and
LiOH'H20 may be the reaction product of Li20 with
moisttrre while the specimens are cooled. There is not
distinct difference between the product heated at 350 °C
1.0 85.0
5
-3.2 56.0
-7.4 27.0
-11.6 -2.0
- 15.8 -31.0
-20.0 t
0 100 7oo-6°'°
tl%
Fig. 1 TG and DTA thermogram for dry-gel Li0.sCoO~
powder in N2(acidic solution)
Vol.7
and that at 250 °C. After being heated at 400 °C or
480 %, the distinguishable spectra for LiCOO2 appear,
whose intensity increases with 'increasing temperature.
The valence of cobalt in Co(N03)2 "6H20, a mate-
rial chosen for this experiment, is + 2, but the average
valence in C%04 and LiCoO2 appearing after heat treat-
ment is + 2.7 and + 3, respectively. So Co2÷ has un-
dergone two oxidization reactions (exothermic reaction) in
the course of heating, that is, CoO through Co304 to
LiCoO2 (combining with Li20). These two exothennic
peaks shown in the DTA thermograph may result from the
heat of the oxidi~ation of Co2+ during the decoml~ition of
citric acid and nitrates. Because the thermal analysis is
peffomaed in N2, the oxygen for the oxidization of Co2+ is
obtained only from NOr and the decomposing products of
citric acid. But in the course of baking, it can come also
from air directly, so the oxidization of Co2+ goes on more
easily than that in N2 atomsphere, and the formation of
Co304 can be carried out at 250 °C under the latter condi-
tion.
It's clear from the above discussion that LiCOO2 is
the product of the reaction of C0304 and Li2O, so C0304
phase will exist unavoidably ff the mole ratio of lithium to
cobalt is loss than one, and even when the ratio equals
one, pure LiCoOz powder has not been obtained (shown
in Fig. 3) due to the influences of heating condition and
other intrinsic factors.
o ~ LIOH,LiOH.H20 ]
~ ~c~o~
~ D
~ D ~l X
10 20 30 40 50 60 70
2o/(o)
(a) 25O~ ; (b) 35O°C; (~) 40O~C; (d) 48O~C
R 0. 2 XRD spectra for the baked products (all from
acidic solution) at different temperatures
 No.2 LI 2lai-yonet al: Sythesisof Li-Co Oxidesby Sol-geland their DischargeBehavior 59

/, I~OII,I~OH.H~O The complexation action of citric acid and the characteris-

~PJC~2
tics of the complex compound are influenced by the pH
X
value of the solution. In the alkaline solution, citric acid
not only complexes Co2÷ and Li ÷ , but also combines with
(d) many NI-I4÷ . Some NI-I4+ can de-combine and escape from
X X the gel in the form of NH3 if the gel is dehydrated. This
de-combination reaction acts as a foamer and wakes the
dry-gel much more loose, which has been verified by the
experiment. After removing NO3- and citric acid, finer
particles of C0304 and Li20 can be obtained, which will
X make subsequent Li2C002 particles fmer too.
2.3 Cathodicaldischarge behavior
× × The typical voltage vs specific capacity curves
(shown in Fig. 5) for mixed oxides discharging at the
same current densities at 500 °C are not sensitive to the
initial ratio of lithium to cobalt, with the same open cir-
10 20 30 40 50 60 70 cuit voltage about 2.45 V. Under load, the voltage re-
2e/( °) duces steeply to 1.5 V, corresponding to a close specific
(a) 0.6; (b) 0.8 (from acidic solution); capacity about 200 A" s" g- 1(oxides), and then a voltage
(c) 0.8 (from alkalinesolution); (d) 1.0 plateau appears, which terminates almost at a total speci-
~.a XRD spectra for the baked productsafter being baked at fic capacity of 950 A" s" g-~. There is no remarkable dif-
480 °C far 6 h with differentinitial ratios of Li to Co
ference in voltage for the finer powder obtained from the
2.2 Morphology of powders alkaline solution and the coarser from the acidic solution.
The diameter of particles, obtained by heating the
dry-gel of Lio.sCo(~ at 480 °C for 6 h, varies in the range 2.5i
of several micrometers, and those from an alkaline solu-
tion are fmer than from acidic solution, ~ indicated in 2.0
Fig.4. 1 2 3

1.0

0.5
0 ldoo ,25o
Spectiilc capacity/(A" s'g -1 )

at 500 ¢C with Li0.sCo~ cathode,

Li-B alloymode, LiC1-KC1electrolyte
1---50 mA'cm-2; 2--100 mA'cm'-2; 3--200 mA'cm -2
Fig. 5 Typical discharge curves

In the beginning of discharging, the voltage reduces

linearly with the increase of capacity, and this is just the
characteristics of the intercalation of lithium in a single
phase region. So it can be concluded that 1 mole LiCoO2
can intercalate more than 0.2 mole Li ÷ without structural
transformation which occurs only after discharging further,
which can be calculated by the following formula:
200 A ' s ' g -1 x98 g/(9.648 x 104)A's'mo1-1 ~-0.2 tool
pH: (a) 3~4; (b) 8~9
Assume that Co304 intercalates less or the same amount of
~.4 SEM photographs of products heated at 480 "(2 for 6 h
with lithium to cobalt ratio O. 8 lithium. For the voltage plateau, the theoretical specific
capacity, corresponding to Co3÷ in LiCoO2 being reduced
 60 JOUfl~l[ C~U'["
to Co2+ , is 985 A ' s ' g - ~ , which is reflected in Fig. 5 at
the terminal of the plateau. The initial ratio of lithium to
cobalt has small influence on the capacity, possibly be-
cause C0304 can also discharge in the ph~eau region. In
addition, the experimental observation that LiCoO2 can
exist stably after intercalating a small amount of lithium
shows in another aspect that surplus lithium nitrate must
be added to make Cos 04 react completely to form LiCo02
because some lithium has been immobilized by HCoO2 in
this process. The above results also agree with the report
that lithiashould be excessive in order to eliminate Co3 04
if LiCoOz is synthesized by solid-phase reaction of carbo-
nates a t h i g h - t e m p e r a t u r e [61 .
3 Conclusions
I) Co~04, Li20 and the subsequent LiCoOz were
obtained by heating the dry-gel prepared with lithium ni-
trate, cobalt nitrates and citricacid;
2) Baked products are free powders in the range of
several micrometers, while those obtained from an alka-
line solution are much freer than that from the acidic solu-
tion;
3) When mixed oxides of LiCo02 and Co~04 cathodi-
cally discharge at 500 °C, there are a single-phase inter-
calation where voltage r~iuces with the increase of dis-
Vol.7
charge capacity and a electrochemically reduction where
the plateau voltage is about 1.5 V.
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