Recent Advances in Lithium-Ion and Lithium-Polymer Batteries

H. V. Venkatasetty and Y. U. Jeonga7b

a H.V.Setty Enterprises Inc., 12110 Red Oak Court So, Burnsville, Minnesota 55337
b
Corrosion Research Center, Department of Chemical Engineering and Materials Science,
The University of Minnesota at Twin Cities, Minneapolis,MN 55455

ABSTRACT
In recent years, there have been increasing efforts to develop new and novel electrolytes
and electrode materials to improve the capacity, energy density, cycle life, and the
performance of lithium batteries with enhanced safety. These batteries have the potential
to meet the needs of several new medical device applications as well as the growing needs
of portable electronic devices. Improved cathode materials are being developed and
composite anodes are being prepared and evaluated with some success. On the electrolyte
side, investigations are being carried out in developing new materials with high
conductivity and electrochemical stability to reduce the size and weight of the batteries.
This paper will describe our recent work on the synthesis of new and novel lithium salts
and copolymers and the properties of solid polymer electrolyte films (SPE). The
performance characteristics of prototype cells with SPE films as well as solutions of super
acid-based lithium salts are presented and their results are discussed in terms of their
structure and properties.

INTRODUCTION with lithium metal anode and have

Lithium rechargeable batteries
are very attractive power sources for
portable electronic devices and several
new and emerging medical devices.
Lithium batteries have high energy and
power density and good cycle life
compared to those of nickel metal
hydride and nickel cadmium batteries (1-
3).
One of the challenging areas is to
develop highly conducting and stable
electrolytes for flexible lightweight and
high energy and power density batteries
with improved safety. Both polymer
-gel electrolytes and solid polymer
electrolytes are promising materials.
Although Lithium-ion gel electrolyte
batteries have the capability for reduced
cell thickness and weight and are being
considered for use in portable electronic
devices, they are not highly compatible
problems with leak proof packaging and
safety. Lithium-solid polymer battery
provides an entirely new battery
structure without the conventional metal-
case assembly. Lithium-polymer battery
uses solid polymer electrolyte unlike the
commercial lithium battery which uses
liquid electrolyte and/or lithium-ion gel
electrolyte. The solid electrolyte film
can be physically sandwiched between
electrodes, the anode and the cathode
formed out of thin sheets and then the
cell is contained in laminated foil and
sealed at the edges to form an entire
battery. The resulting cell is extremely
thin and flexible, spill proof, more
resilient under pressure, and capable of
being engineered into any shape.
Therefore, Lithium-polymer batteries are
lighter, flexible and leak resistant.
Lithium-polymer battery with high

0-7803-7132-1/02/$10.00 02002 IEEE. 173

conductivity electrolyte film (SPE) has
the potential to deliver the best power
available for rechargeable batteries.
However, the state-of-the-art
solid polymer electrolytes based on
polyethylene oxide (PEO) have poor
conductivity at room temperature (-loa
to 10-7S/cm)due to the crystallinity of
PEO. There are several approaches to
achieving high conductivity solid
polymer electrolyte materials. One such
approach is to synthesize novel l i h u m
imide salts, some with two or more
lithium ions per molecule and a large
anion. These imide salts with
delocalized charge density can facilitate
high degree of dissociation into lithum
ions with amorphous phase in the
polymer matrix of solid polymer
electrolytes. The imide salts and
particularly the salts containing two or
more lithium ions, on dissociation, can
promote multiple lithium ions resulting
in high conductivity. There is a
phenomenogical relation between ionic
conductivity and the segmental motion
of the PEO chains, and therefore, our
research efforts are directed toward
synthesizing amorphous and low glass
transition temperature polymers (4). Our
approach is to modify the molecular
architectures and compositions of
polymers to suppress crystallization (4).
This paper describes research
and development efforts devoted to
synthesize new and novel lithium imide
salts with large anions. figh molecular
weight co-polymers and /or in
combination with a small amount of
polyethylene oxide have the potential to
provide high conductivity when
complexed with lithium salts. Therefore,
a number of co-polymers have been
synthesized to minimize andor eliminate
the crystallinity problem associated with
polyethylene oxide polymer commonly
174
used for lithium-polymer batteries. We
have successfully synthesized fifteen
new imide salts of lithium and
characterized them for conductivity and
electrochemical stability in nonaqueous
solvent mixtures. While all these salts
are electrochemically stable from 0 to
4.5 V vs. LdLii, the conductivity values
of many salts are quite low for practical
lithium battery applications. Our efforts
are directed toward salts with high
conductivity. These salts and their
solutions have been investigated for use
in both lithium-polymer batteries and
lithium-ion batteries.
EXPERIMENTAL PROCEDURES
Synthesis of new salts: CF$302NLiSO&F$
was synthesized by reaction of
perfluorobutylsulfonyl fluoride with
ammonia and n-butyl lithium followed
by treating with suitable perfluoroalkyl-
sulfonyl fluoride. Similar methods were
used used for all other lithium salts (3-
5). Lithium salts were dissolved in a
solvent mixture of EC:DMC:DEC
(34:33:33 vol%)
Synthesis of copolymer: Starting materia
-1s of 5.54g of MeO-PEG-MA (M.W. of
llOOg, Aldrich) was dissolved in 26 ml
of aqueous medium, then this solution
was degassed with N2 gas for 10
minutes. In this solution 25mg of 2,2’-
Dipyridyl (bpy) as a chelating agent,
llmg of Cu~Br2~4.9mg of Cu, and 15pl
of Ethyl 2-bromoisobutyrate (EBB)
were added and left for reaction for 1-2
days. The polymerized product was
transferred to 200 ml of Tetrahydrofuran
(THF) and 40g of MgS04 was added to
remove water contents in polymer. The
sample was washed with THF, then THF
was removed by evaporation through
vacuum. This sample was passed
through A1203 column for purification.
This sticky product was vigorously
stirred and washed several times with
warm petroleum ether and dried under
vacuum. Several copolymers with
varying molecular weight were
synthesized and purified by liquid
phase chromatography.
Preparation of Composite Polymer
Films: Composite polymer thin film
were prepared in the dry room with
copolymer, polyethylene oxide (M.W. of
600,000 or 5,00O,OOOg), lithium salts
such as C F $ ~ O ~ N L ~ S O ~ (Cl-C2),
C~FS
CF$O2NLiSO2C& (Cl-C4), or
LiN(S02C2F& (C2-C2) were dissolved
in acetonitrile at - 7OoC, and small
amount of Ti02 (particle size of 0.2pm),
polyvinylidene fluoride (PVDF), carbon
were dispersed homogeneously in the
solutions. The excess solvent was
evaporated with stirring at - 7OoC to
make viscous solutions. The viscous
solution was cast into films on Teflon
substrate. These films were dried in
vacuum oven at -70°C for 12 to 24
hours to remove any solvent completely
in the films.
Electrochemical Characterizations: The
conductivities of the liquid electrolytes
with new lithium salts were measured at
room temperature using calibrated cells
with platinum electrodes at 10 KHz
using a Hewlett Packard Impedance
Analyzer 4277A. In the case of solid
polymer electrolytes, dried films were
cut into a circle (diameter lcm) and
pressed between two stainless steel
electrodes and loaded in special cell for
impedance measurement. AC impedance
measurements were carried out as a
function of frequency from 1 Hz to 10
MHz using a Solatron 1260 Impedance
Analyzer with 1268 Electrochemical
Interface to evaluate the conductivity of
the polymer films at room temperature.
Potentiostat (EG & G Model
175
173) with Model 175 programmer were
used to measure the electrochemical
stabilities from 0 to 4.5 V versus Li
reference for both liquid electrolytes and
solid polymer electrolyte films.
Platinum foil was used for working
electrode and Li foils were used as both
the reference and counter electrodes.
Arbin battery tester was used for
charge/discharge characteristics of the
test cells. For Li-ion battery, cathode
prepared by mixing LiMn204 with
conducting carbon, MCMB anode and
liquid electrolyte were assembled in a
pouch type cell. In the case of Li-
polymer battery, cathode was prepared
by mixing LiMn204, conducting carbon,
and composite polymer. Test cell was
assembled by pressing solid polymer
films, Li metal anode, and cathode
between two glass plates.
RESULTS A N D DISCUSSIONS
Fifteen new salts with
heterocyclic ring or linear imide types
were characterized. The solubilities of
lithium salts were depended on the
structure and molecular weight. While
the majority of heterocyclic ring type
salts were not very soluble, linear type
salts could be easily dissolved in mixed
solvent systems. As shown in Figure 1,
most of conductivities at room
temperature vary from 10” to lo4 S/cm.
# 14 (C1 - C2) and ## 15 (C1 - C4 - C1)
exhibit higher conductivities even at low
concentration. The low conductivities of
lithium salts with six member rings can
be attributed to poor dissociation of Li’
ions due to the stabilization of the
structure from resonance effect. These
enhanced transport properties are
attributed to easier dissociation of Li’
ions from large anions. These salts were
found to be electrochemically stable
from 0 to 4.5 V versus Li reference.
 O L I O
#1 II II 0.1348 M
#I1 C2&0-P-NNS-CF3
I II u = 3.36'1H Wcm
m2H5 0
0.1353 M
#2 u = 8.235*10-5 Wcm O L I O
kJ II II 0.1134 M
#I2

-
CF3-C-N-S-CF3
II
#3 x
AhmF,
0.0961 M

a=l.O75*10~~cm
0
0 = 2.9wlc-4 Sm

0.0986 M

#4 a I1.9699'10-4 Wcm

0.0648 M

9 = 1.18'10-4 Wcm
#5 Flcccu,

#I5 0 u 0 o u o
II
CF3-S-N-S
II-C4Fg- 11S-N-S-CF3 11 0.0206M

#6 II II 0 11 11
0 u = 1.045'10-3 Wcm
0 0

Figure 1. Structures and conductivities of

#7 r
V
O.O-M
a = 2.31'104 Wcm
#8
#!3
#10
Figure 2 shows the first cycle of
charge and discharge voltage vs.
capacity plot for Li-ion cell with
LiMn204 cathode, MCMB anode, and
liquid electrolyte (0.0206 M of Cl-C2).
Surface area of electrode was 5cm2 and
0.1mNcm2 of current density was
applied.
Synthesized copolymers were of
molecular weight in the range of
-214,OOOg and completely amorphous at
room temperature. In order to improve
the mechanical strength of SPE films,
PEO were added, as PEO is compatible
Li-salts
with this copolymer. The results of
several composite films are shown in
Table 2. Small amounts of nanoscale
particles (Ti02) and PVDF were added
to the composite to get better mechanical
property.
In the case of sample #6 in Table
2, X-ray diffraction data show that the
mixture of PEO and copolymer shows
PEO crystalline peaks. Adding of
lithium salts reduces crystallinity, and
adding Ti02 further reduces the
crystallinity of SPE films. As shown in
Table 2, a variety of blending conditions
for SPE films were canied out. The
conductivities of SPE films vary from 1
to 3 x 10-~ S/cm.
Conductivities and mechanical
properties of SPE films depend on each
preparation conditions. Higher PEO
content samples have better mechanical
properties but lose their ionic mobility
with time due to the crystallization of the
samples. Addition of carbon with small
amount (< 2 wt%) in SPE films were

176
 First Cycle of
LiMn,O,/Celgard 2300/MCMB 2528
(a) Fifth Cycle of LiMn20dSPE#9/Li
with C1-C2SuperAcid (Dried)
4.5 t I
A 2 8 I
4.0
3 3.5
5 3.0
U

> 2.5
v
Q 2.0
CD -Charge
-
0 1.5
c 0 1.5

’
0 1.0
0.5
0.0
> 1.0 *Discharge

0 10 20 30 40 50 SO 70 SO 90 100 110
0 1 0 2 0 3 0 4 0 5 0 6 0
Capacity (mAh/g)
Capacity (mAhlg)
Figure 2. Charge-discharge plot for Li-ion
battery
(b) LiM%O@PE#sRi
70 I

--c Discharge Capacity

E
.-
m
-
L

0 1 2 3 4 5 6 7 6

Cycle Mmber

Figure 4. Charge-dischargeplot for Li-

10 15 20 25 30 35 40 45 50 polymer battery
Degree (CuK a)
In an attempt to achieve better
Figure 3. X ray diffraction data for
mechanical property as well as higher
Samde #6 in Table 2
conductivities, our strategy is to use
previously reported that shown improved lower molecular weight PEO and add the
conductivity (6). However, SPE films microporous PVDF along with Ti02 in
were sticky and had poor mechanical the samples. Too high a content of
properties. PVDF or Ti02 reduces conductivity.
Table 2. Conductivity data for each fabrication conditions

177
However, this could be avoided by
varying Li/O ratio and combination of
lithium salts with polymers. This SPE
films are electrochemically stable from 0
to 4.5 V versus Li reference.
Figure 4 (a) shows the fifth cycle -
E
$ 2.5
of charge and discharge voltage vs.
capacity plot for Li-polymer battery.
Cathode was LiMn204 (82% LiMn204,
8% super P carbon, and 10% composite
e
.-
.-
9
2

U
polymer). Li metal anode and SPE film 0
1.5

(sample #9 in Table 2) was used. Surface -

0
C
area of electrode was 2.1cm2 and current - 1
rates of C/25 for charge and C/50 for
discharge were applied at 37OC with the 0 5 10 15
operating voltage range from 4.15 to3.0 wt% PVDF
V (Figure 4a). The charge/discharge
capacities range from 55 to 57 mAh/g. Figure 5. Comparison of conductivity
The cyclability data was shown in Figure for several SPE films
4 (b). The delivered charge/discharge Heart Lung and Blood Institute is
capacities as a function of cycle are gratefully acknowledged. Authors thank
about 55 to 57 mAh/g (Figure 4b). Professor Thomas R. Hoye of The
Conductivity values of composite SPE University of Minnesota for his help in
films as a function of composition are the preparation of lithium imide salts and
shown in Figure 5. copolymers.
CONCLUSIONS REFERENCES
Various new lithium imide salts 1. M.Armand, Solid State Ionics 69,
and copolymers have been synthesized 309( 1994)
and characterized. Systematic 2. H.V.Venkatasetty, in:
investigations for various preparation Proceedings of the 16&Annual
conditions for solid polymer electrolyte Battery Conference on
are reported. These lithium salts and Applications and Advances,
solid polymer electrolyte films exhibit California State University, Long
good electrochemical stabilities and Beach, California, 09-12 January
-
conductivities up to 3x10-’ S/cm along 2001 pp277
with dimensional stabilities at room 3. H.V.Venkatasetty, J. of Power
temperature. Higher conductivity Sources, 97-98,671 (2001)
lithium salts (Cl-C2 and Cl-C4-C1) and 4. M.Armand, European patent 89-
optimized blending conditions for solid 402744,891004; Chem. Abstr.
polymer electrolytes show the promising 113 (15) 131568r. (1981).
properties for lithium rechargeable 5. W.Qui, D.J.Burton, J.Fluorine
batteries. Chem. 60,90 (1993).
6. G.B.Appetecchi and S.Passerini,
ACKNOWLEGEMENTS
Electrochim.Acta, 45,2139
Financial support from NIH, the (2000).

178