Abstract:
Disclosed is an electrode comprising an aliphatic nitrile compound, wherein the aliphatic nitrile compound is coated on a surface of the electrode or is incorporated into the electrode active materials. A lithium secondary battery having the electrode is also disclosed. The lithium secondary battery has excellent safety so as to prevent ignition and explosion generated when the internal temperature of the battery is increased due to the heat emission caused by the reaction of an electrolyte with a cathode and the structural collapse of a cathode occurring upon overcharge. Additionally, it is also possible to prevent ignition and explosion when the battery is exposed to high temperature due to an increase in temperature resulting from heating or local short circuit caused by physical impacts. Further, it is possible to solve the problems of an increase in viscosity and degradation in battery performance at a low temperature occurring when an aliphatic nitrile compound is used as an additive for electrolyte.
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Notices, Deadlines & Correspondence
LG TWIN TOWER 20, YOIDO-DONG, YOUNGDUNGPO-GU, SEOUL 150-271
Inventors
1. KIM, YOUNG-SOO
202, 122-17, SHINSUNG-DONG, YUSEONG-GU, DAEJEON 305-345
2. AHN, SOON-HO
109-1004, SAMSUNG HANWOOL APARTMENT, SHINSUNG-DONG, YUSEONG-GU, DAEJEON 305-707
Specification
Technical.Field
The present invention relates to an electrode
including an aliphatic nitrile compound. More
particularly, the present invention relates to an
electrode whose surface is coated with an aliphatic
nitrile compound or which comprises an electrode active
material comprising an aliphatic nitrile compound, as
well as to a lithium secondary battery having the same
electrode.
Background Art
In general, a non-aqueous electrolyte comprising a
lithium salt such as LiPFs and a carbonate solvent reacts
continuously with the surface of a cathode active
material (particularly, LiCoO2) . during repeated
charge/discharge cycles, resulting in the continuous
formation of a resistance layer that causes an increase
in resistance and interrupts conduction: of. Li+ ions Such
resistance layer causes the active material particles to
be isolated among themselves or from a current collector'
(Al foil), thereby detracting from battery performance
and life characteristics. Further, such problems
increasingly and predominantly . occur at a high
temperature to accelerate side reactions between an
electrolyte and the surface of a cathode when a battery
is stored at a high temperature (45°C or 60oC) for a long
time, resulting in a significant decrease in the
lifetime of a battery.
Meanwhile, non-aqueous electrolyte-based secondary
batteries have problems related with safety upon
overcharge for the following reasons. Cathode active
materials such as lithium and/or lithium ion-containing
metal oxides capable of lithium' ion intercalation/
deintercalation are converted into thermally unstable
substances due to the release of lithium during
overcharge. When the temperature of a battery reaches
the critical temperature, oxygen is liberated from such
unstable substances and the free oxygen may react with
the solvent of an electrolyte, etc., through a highly
exothermic reaction mechanism. Therefore, such a series
of exothermal reactions by heating results in thermal
runaway.
Generally, factors affecting the safety of a
battery include: (1) heat emission due to oxidation of
electrolytes; and (2) heat emission resulting from the
structural collapse of a cathode due to overcharge. When
overcharge proceeds, heat emission occurring from the
above factors independently or simultaneously causes an
increase in the internal temperature of a battery,
followed by ignition or explosion of the battery. Thus,
batteries show a safety problem upon overcharge.
Meanwhile, when external physical impacts (for
example, exposure to high temperature such as a
temperature of 150°C or higher by heating) are applied to
a battery while the battery is charged or overcharged,
the battery is overheated due to the heat emission
caused by the reaction of an inflammable electrolyte
with a cathode active material, and the structure of an
electrode (particularly, a cathode) is collapsed to
generate oxygen, which accelerates the combustion of the
electrolyte. Therefore, a separator disposed between a
cathode and an anode is melted and the electrical energy
induces thermal runaway, resulting in ignition and
explosion of the battery.
Disclosure of the Invention
The present inventors have found that an aliphatic
nitrile compound that forms a strong bond with a
transition metal or transition metal oxide in an
electrode active material can improve the safety of a
battery, when the battery is overcharged and/or
subjected to physical impacts applied from the exterior
of the battery (for example, exposure to high
temperature by heating) . Meanwhile, we have also
recognized a problem in that when an aliphatic dinitrile
compound is used as an additive for electrolyte, there
is an increase in viscosity of the electrolyte so that
diffusion of Li ions cannot be made smoothly under
extreme conditions (a low temperature of between -20oC
and -10°C), resulting in degradation of battery
performance, at a low temperature.
Therefore, the present invention has been made in
view of the above-mentioned problems. It is an object of
the present invention to improve the safety of a battery
with no degradation of battery performance by
incorporating an aliphatic dinitrile compound uniformly
into an electrode so that the aliphatic nitrile compound
can contribute only to the formation of a complex with
an electrode active material.
According to an. aspect of the present invention,
there is provided an electrode comprising an aliphatic
nitrile compound, preferably a compound represented by
the following formula 1, whose surface is coated with
the aliphatic nitrile compound or which comprises an
electrode active material comprising the aliphatic
nitrile compound. According to another aspect of the
present invention, there is provided a lithium secondary
battery having the above-described electrode.
wherein R is a C2-C15 alkane.
Preferably, the aliphatic nitrile compound,
preferably the compound represented by formula 1 is
coated uniformly on the surface of an electrode active
material in an electrode.
Additionally, it is preferable that the electrode
according to the present invention includes a complex
formed between the surface of the electrode active
material and the aliphatic nitrile compound.
Hereinafter, the present invention will be
explained in more detail.
According to the present invention, the electrode
for a lithium secondary battery is characterized by
comprising an aliphatic nitrile compound, preferably the
compound represented by the above formula 1.
Aliphatic nitrile compounds can form a strong bond
with a transition metal or transition metal oxide such
as cobalt exposed to the surface of an electrode active
material through their cyano functional groups having
high dipole moment. Particularly, the cyano functional
groups can form a stronger complex on the surface of an
electrode active material at a temperature of 45°C or
higher (see, FIG. 1).
An electrode coated with an aliphatic nitrile
compound has a -strong protection surface that protects
the surface of electrode from side reactions with an
electrolyte. Therefore, it is possible to accomplish
efficient lithium ion intercalation/deintercalation
without varying viscosity of the electrolyte and ion
conductivity, and to prevent the formation of a
resistance layer capable of detracting from battery
performance by the reaction of the electrolyte with
electrode during repeated charge/discharge cycles, on
the surface of electrode. As a result, it is possible to
maintain battery performance. Further, according to the
present invention, a lithium secondary battery having an
electrode uniformly coated with an aliphatic nitrile
compound on the surface of an electrode active material,
and preferably comprising an aliphatic nitrile compound
forming a strong complex with a transition metal and/or
transition metal oxide present on the surface of
electrode active material, can stabilize the transition
metal and transition metal oxide to prevent a partial
release of the transition metal from the electrode
active material during repeated charge/discharge cycles.
In addition, when external physical impacts are applied
to a battery (particularly, when a battery is exposed to
high temperature such as a temperature of 150°C or
higher), it is possible to efficiently inhibit an
exothermic reaction caused by the reaction of an
electrolyte directly with the electrode surface and to
retard the structural collapse of the electrode active
material, thereby preventing ignition and explosion
resulting from an increase in temperature inside of the
battery. More particularly, because aliphatic nitrile
compounds can protect the electrode surface more
strongly at a high temperature of 45°C or higher than
room temperature, it is possible to provide thermally
stable electrodes.
Although the compound represented by the above
formula 1 is exemplified as an aliphatic nitrile
compound that can be incorporated into an electrode
according to the. present invention, another aliphatic
nitrile compound having a nitrile group only at one
side, compared to the compound represented by formula 1,
has a great possibility for providing safety and/or
battery performance in such a degree as to be equivalent
to the compound represented by formula 1, and thus it is
also included in the scope of the present invention.
Meanwhile, alkanes present in the compound
represented by formula 1 have no reactivity. Therefore,
when the compound represented by formula 1 is
incorporated into an electrode, a possibility for an
irreversible reaction is low. As a result, addition of
the compound represented by formula 1 does not cause
degradation in battery performance.
Because an aromatic nitrile compound decomposes at
an anode during the initial charge cycle (during
formation) to increase irreversible capacity and to
degrade battery performance significantly, it is not
preferable to incorporate an aromatic nitrile compound
into an electrode and to coat an electrode with an
aromatic nitrile compound.
Particular examples of the compound represented by
formula 1 include succinonitrile (R=C2H4) , glutaronitrile
(R=C3H6) , adiponitrile (R=C4H8) , pimelonitrile (R=C5H10),
octanedinitrile (R=C6H12), azelonitrile (R=C7H14),
sebaconitrile (R=CbH16), 1, 9-dicyanononane (R=C9H18) ,
dodecanedinitrile (R=C10H20), etc., but are not limited
thereto.
Particularly,. succinonitrile forms the strongest
protection layer among the compounds represented by
formula 1. The longer the allcane is, the weaker the
protection layer to be formed becomes. Therefore, it is
most preferable to use succinonitrile as a coating
material among the above compounds.
The aliphatic nitrile compound is present in an
electrode preferably in an amount of 0.1-20 wt% based on
the weight of electrolyte or 1-10 wt% based on the
weight of active material, more preferably in an amount
of 10 wt% or less based on the weight of electrolyte or
5 wt% or less based on the weight of active material,
and most preferably in an amount of 5 wt% or less based
on the weight of electrolyte or 2.5 wt% or less based.on
the weight of active material.
In order to incorporate an aliphatic nitrile
compound into an electrode, a coating solution
containing an aliphatic nitrile compound may be applied
on an electrode. Otherwise, an aliphatic nitrile
compound may be added to slurry for electrode active
material to form an electrode.
For the purpose that the nitrile compound
participates only in complex formation with a transition
metal oxide of an electrode active material, a coating
solution containing an aliphatic nitrile compound is
applied to an electrode or an aliphatic nitrile compound
is added to electrode active material-containing slurry
in an adequate amount. Preferably, the electrode or
slurry comprising the nitrile compound is treated at a
high temperature. Then, the surface of electrode, namely
the surface of electrode active material can be
protected uniformly with the aliphatic nitrile compound.
In addition to the above-mentioned high-temperature
treatment applied to an electrode or slurry, a battery
may be preferably treated at a high temperature after
the assemblage thereof.
The aliphatic nitrile compound is dispersed or
dissolved into a solvent to provide a solution, the
solution is coated on the surface of an electrode and
then the solvent is dried in order to coat the electrode
surface, preferably the surface of electrode active
material with the aliphatic nitrile compound. The
coating method may include dip coating, spray coating,
or the like. -
There is no particular limitation in selection of
the solvent for use in the coating solution containing
an aliphatic nitrile compound, as long as the solvent
has good compatibility. It is preferable to use, as a
solvent for coating solution, non-polar solvents such as
THF (tetrahydrofuran) and polar solvents such as NMP (N-
methyl-2-pyrollidone) and carbonate solvents used as a
solvent for electrolyte. Although the amount of
aliphatic nitrile compound varies with the amount to be
coated on an electrode, the aliphatic nitrile compound
may be used in the range of between 1:9 and 9:1,
expressed in the weight ratio to the solvent.
The method for forming an electrode by adding an
aliphatic nitrile compound to slurry for electrode
active material includes the steps of: mixing an
aliphatic nitrile compound with an electrode active
material and other additives such as a binder and
conductive agent, as necessary, to form slurry for
electrode active material; applying the slurry for
electrode active material on a collector; and removing
the solvent used in the slurry by drying, etc.
In order to apply the slurry for electrode active
material, die coating, roll coating, comma coating and
combinations thereof may be used.
Meanwhile, because the compound represented by
formula 1 starts to be slightly volatilized at a high
temperature of 100°C or higher and then be substantially
evaporated without leaving residues at a temperature of
about 150°C, it is necessary to maintain an adequate
drying temperature, drying rate and vent flow for the
purpose of coating an electrode smoothly with the
compound represented by formula 1 from slurry containing
NMP as a solvent.
To prevent the compound represented by formula 1
from being volatilized and to remove residual NMP, the
drying temperature preferably ranges from 90oC to 110°C.
The drying rate is preferably 3 m/min or less, more
preferably 2 m/min or less, but may be varied with the
length of a drying furnace and the drying temperature of
slurry. The vent flow is preferably 2000-3000 rpm.
More particularly, when the electrode comprising
the compound represented by formula 1 is dried at an
excessively low temperature in order to retain the
compound in the electrode, NMP content and water content
in the electrode increase, thereby causing a problem in
that battery performance is degraded. On the other hand,
when the electrode is dried at an excessively high
temperature, NMP content in the electrode decreases but
the compound represented by formula 1 is substantially
volatilized, and thus it is not possible to obtain a
uniformly coated electrode. Therefore, it is important
that the drying temperature, drying rate and vent flow
are maintained within the above ranges.
Meanwhile, it is preferable that aliphatic nitrile
compounds form a complex with the surface of an
electrode active material. Preferably, for the purpose '
of forming a complex, an electrode comprising an
electrode active material whose surface is coated with
an aliphatic nitrile compound is further treated at a
high temperature. Particularly, the high-temperature
treatment may be performed at such a temperature range
as not to affect the electrode active material and
binder, generally at a temperature of 180°C or lower.
Otherwise, although the high-temperature treatment
varies with the kind of the aliphatic nitrile compound,
it may be performed at such a temperature range as to
prevent evaporation of the aliphatic nitrile compound,
generally at a temperature of 120°C or lower. In general,
the high-temperature treatment is suitably performed at
a temperature of between 60°C and 90oC. Long-time storage
at a temperature of between 30°C and 40°C may result in
the same effect.
As a cathode active material for use in
electrodes, lithium-containing transition metal oxides
may be used. The cathode active material can be at least
one selected from the group consisting of LiCo02, LiNiO2,
LiMn2O4, LiMn02 and LiNi1-xCox02 (wherein 0