Abstract:
The present invention provides a cathode having a complex between the surface of a cathode active material and an aliphatic nitrile compound, as Well as an electrochemical device comprising the cathode. Also, the comprising : (1) a cathode having a complex between the surface of cathode active material and an aliphatic nitrile compound ; (2) an anode having a passivation layer formed by a compound selected from the group consisting of vinylene carbonate, its derivative and an ether compound ; and (3) an electrolyte solution containing a lithium salt and a solvent.
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Notices, Deadlines & Correspondence
LG TWIN TOWER 20, YODIO-DONG, YOUNGDUNGPO-GU, SEOUL 150-721
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 a cathode
(positive electrode) having complex (an interfacial
reaction) between the surface of a cathode active
material and an aliphatic nitrile compound, as well as
an electrochemical device comprising the cathode.
Background Art
Recently, as electronic devices become
increasingly wireless and portable, a non-aqueous
electrolyte battery with high capacity and high energy
density is practically used as a power source for
driving these electronic devices. However, this non-
aqueous electrolyte secondary battery has a problem in
that its capacity is reduced with the progression of
charge/discharge cycles for the following various
reasons, and particularly when it. is exposed to a high-
temperature environment, its capacity will be more
remarkably reduced:
(1) A transition metal contained in a composite
oxide constituting a cathode is dissolved in a non-
aqueous electrolyte and deposited on an anode, resulting
in the structural breakdown of the composite oxide in
the cathode or an increase in interfacial resistance;
(2) The dissolved cathode transition metal
continues to grow, thus causing micro-short circuits
between the cathode and the anode;
(3) The cathode transition metal deposited on the
anode acts as a catalyst promoting the decomposition of
the non-aqueous electrolyte, thus causing gas generation
within the battery;
(4) The SEI layer of the anode becomes thicker
with the progression of charge/discharge cycles and
prevents the migration of Li+; and
(5) The expansion and contraction of the anode
active material causes slow breakdown of the SEI layer.
Generally, the non-aqueous electrolyte secondary
battery has a problem in that the electrode performance
and efficiency are remarkably reduced, particularly at
high temperature, for the following reasons: (1) the
electrode resistance is increased due to a reaction
between a cathode active material such as a lithium-
containing metal oxide capable of absorbing and
releasing lithium and/or lithium ions, and an
electrolyte solution containing a carbonate solvent and
a lithium salt; and (2) a solid electrolyte interface
(SEI) layer formed on the surface of an anode active
material capable of absorbing and releasing lithium
and/or lithium ions is slowly broken at high temperature
due to continuous charge/discharge cycles, while a poor
SEI layer is produced from the carbonate solvent so as
to accelerate irreversible reactions, including Li
corrosion.
Meanwhile, in the non-aqueous electrolyte
secondary battery, the cause of a problem in the battery
safety upon overcharge is as follows: A cathode active
material such as a lithium-containing metal oxide
capable of absorbing and releasing lithium and/or
lithium ions is changed into a thermally unstable
material by lithium release upon overcharge. When the
battery temperature reaches the critical temperature,
the structural breakdown of the cathode active material
which has been unstable occurs to release oxygen. The
released oxygen and an electrolyte solvent, etc., cause
an exothermic chain reaction, resulting in thermal
runaway.
Generally, factors which can influence the safety
of the battery upon overcharge may include: (1)
exothermic heat caused by the oxidation of the
electrolyte solution, and (2) exothermic heat caused by
the structural breakdown of the cathode.
These exothermic heats occurring alone or in
combination during the progression of overcharge result
in an increase in the temperature within the battery,
which leads to the fire or explosion of the battery,
thus causing a problem in the battery safety upon
overcharge.
Meanwhile, the fire and explosion phenomena of a
lithium secondary battery, which are caused by thermal
runaway, occur in the following cases: [1) local short
circuits occur by external physical impacts (e.g., high
temperature exposure, by heating) in a state where the
lithium secondary battery has been charged or
overcharged; (2) the battery is exploded due to
exothermic heat caused by a reaction between a flammable
electrolyte solution and a cathode active material at
high temperature; and (3) the combustion of the
electrolyte solution is accelerated by oxygen generated
from the electrodes (particularly, cathode).
Brief Description Of The Accompanying Drawings(s)
FIG. 1 shows X-Ray Photoelectron Spectroscopy data
showing a reaction between the cathode surface and
succinonitrile (SN), which is an aliphatic nitrile
compound, as an electrolyte additive.
FIG. 2 is a schematic diagram of a complex
structure formed by binding the cyano group of the
aliphatic nitrile compound to the cobalt of the cathode.
FIG. 3 shows differential capacity-voltage(dQ/dV)
plots obtained to examine irreversibility and reactivity
with the anode according to the presence or absence of a
VC additive in an initial charge process.
FIG. 4 graphically shows the results of
differential scanning calorimetry (DSC) analysis
conducted to examine the thermal safeties of a battery
containing aliphatic dinitrile (Example) and a battery
containing no aliphatic dinitrile (Comparative Example).
FIG. 5 graphically shows the comparison of 45 °C
cycles between a battery comprising an electrolyte
solution containing carbonate solvent and 1M LiPF6 salt,
and a battery Comprising an electrolyte solution;
containing succinonitrile (SN) in addition to carbonate
solvent and 1M LiPF6 salt.
FIG. 6 graphically shows the comparison of 45 °C
cycles between a battery passivated with both VC and SN
and a battery passivated with only VC without SN.
FIG. 7 graphically shows the comparison of 45 °C
cycles between a battery containing sebaconitrile, which
is an aliphatic nitrile compound, as an electrolyte
additive (Example 4) and a battery containing SN as an
electrolyte additive.
FIG. 8 graphically shows the comparison of 45 °C
cycles between a battery containing dicyanopentane,
which is an aliphatic nitrile compound, as an
electrolyte additive (Example 5) and a battery
containing SN as an electrolyte additive.
FIG. 9 graphically shows the comparison of 45 °C
cycles between a battery containing dicyanohexane, which
is an aliphatic nitrile compound, as an electrolyte
additive (Example 6) and a battery containing SN as an
electrolyte additive.
FIG. 10 graphically shows the 45 °C cycle of a
battery containing cyclohexylbenzene (CHB) and biphenyl
as additive of passivating the cathode upon overcharge,
together with SN (Example 6).
FIG. 11 graphically shows the results of EIS for a
battery of Comparative Example 2 conducted in a charged
state after storing the battery in a discharged state at
60 °C for each of 1 day, 2 day and 3 day.
FIG. 12 graphically shows the results of EIS for a
battery of Example 1 conducted in a charged state after
storing the battery in a discharged state at 60 °C for
each of 1 day, 2 day and 3 day.
FIG. 13 graphically shows the results of hot box
test for a battery of Comparative Example 2 conducted in
a fully charged state after storing the battery in a
discharged state at 60 °C for 3 days.
FIG. 14 graphically shows the results of hot box
test for a battery of Example 1 conducted in a fully
charged state after storing the battery in a discharged
state at 60 °C for 3 days.
FIG. 15 graphically shows the results of hot box
test at 160 °C for a battery of Example 1 or 8.
FIG. 16 graphically shows the results of hot box
test at 160 °C for a battery of Example 2 or 9.
FIG. 17 graphically shows the results of hot box
test at 160 °C for a battery of Comparative Example 1.
FIG. 18 graphically shows the results of
overcharge test at 20V and 1C for batteries fabricated
in Examples 8 and 9.
FIG. 19 graphically shows the results of
overcharge test at 6V and 1A for batteries fabricated in
Comparative Examples 2 and 3.
Disclosure of the Invention
The present inventors have found that, when a
protection layer is formed on a cathode by coraplexation
between the surface of a cathode active material and an
aliphatic nitrile compound, such as succinonitrile, the
safety of a battery upon overcharge and/or physical
impact (e.g., high temperature exposure by heating) from
the outside of the battery can be improved. The present
invention is based on this finding.
Furthermore, the present inventors have found
that, when a passivation layer is formed on an anode by
vinylene carbonate (VC), its derivative or an ether
compound, and at the same time, a protection layer is
formed on a cathode by complexation between the surface
of a cathode active material and an aliphatic nitrile
compound, the cycle life characteristics of a battery at
high temperature can be improved without deterioration
in the battery performance due to a synergistic effect
resulted from the stable protection layers on both the
electrodes {anode/cathode) during charge/discharge
cycles, and also found that these protection layers
prevent the structural breakdown of both the electrodes
and control increases in side reaction and resistance
caused by reaction with an electrolyte solution, thus
r
improving various safety problems (e.g., explosion,
bursting, etc.) occurring upon the exposure of the
battery to high temperature. The present invention is
based on these findings.
In one aspect, the present invention provides a
cathode having a complex between the surface of a
cathode active material and an aliphatic nitrile
compound, as well as an electrochemical device
comprising the cathode.
In another aspect, the present invention provides
an electrochemical device comprising: (1) a cathode
having a complex between the surface of a cathode active
material and an aliphatic nitrile compound; (2) an anode
having a passivation layer formed by a compound selected
from the group consisting of vinylene carbonate, its
derivative and an ether compound; and (3) an electrolyte
solution containing a lithium salt and a solvent.
Hereinafter, the present invention will be
described in detail.
In the present invention, a compound for forming a
complex on the cathode surface is an aliphatic nitile
compound. Examples of the aliphatic nitrile compound
include compounds represented by the following formula
1:
wherein R represents an alkane group having 1-15 carbon
atoms.
A polar cyano group with high dipole moment in the
aliphatic nitrile compound forms . a bond with a
transition metal, such as cobalt, in the cathode,
particularly at high temperature, the cyano group
strongly binds to the cathode surface so as to form a
complex structure (or ligand) (see FIGS. 1, 2 and 12).
X-ray photoelectron spectroscopy data in FIG. 1
show that a complex is formed by a bond between a cobalt
metal oxide and the cyano group of the dinitrile
compound.
The formation of the protection layer on the
cathode surface by the complex can not only prevent some
of transition metal ions from being dissolved during the
progression of charge/discharge cycles so as to be
deposited on the anode, but also inhibit the side
reaction and gas generation caused by a reaction between
the electrolyte solution and the cathode so as to allows
lithium ions to be smoothly absorbed and released even
at high temperature, thus preventing a reduction in the
cycle life characteristics of the battery. Particularly,
the aliphatic nitrile compound has an advantage in that
it can provide a thermally stable electrode since it
more strongly protects the electrode surface at a higher
temperature than ambient temperature.
Moreover, the complex formed on the cathode surface
by the aliphatic nitrile compound can control exothermic
heat caused by a reaction between the electrolyte
solution and the cathode and exothermic heat caused by
the structural breakdown of the cathode, and reduce
exothermic heat generation. This can prevent the fire or
explosion of the battery from occurring due to the
acceleration of combustion and the generation of thermal
runaway, which are caused by oxygen generated by the
structural breakdown of the cathode upon overcharge, the
excessive heat generated by internal short circuits, or
'high temperature exposure.
Furthermore, electrolyte additives, such as
cyclohexyl benzene (CHB) , biphenyl (BP) and anisole,
which are used as overcharge inhibitors for lithium
secondary batteries which are generally used at 3V-4.2V,
form a passivation layer on the cathode surface upon
overcharge. Even when these additives are used in
combination with the aliphatic nitrile compound, they
independently act in the formation of the passivation
layer without competitively reacting with the nitrile
compound, such that the performance of the lithium
secondary batteries which are generally used at 3V-4.2V
can be maintained (see FIG. 10).
Meanwhile, since the alkane group of the compound
represented by formula 1 has no reactivity, a
possibility for an irreversible reaction in the use of
the compound of formula 1 to occur is low, resulting in
a reduction in the possibility of the battery
performance deterioration caused by the use of the
compound of formula 1. Particularly, succinonitrile is
preferred among the compounds of formula 1.
Although the present invention exemplifies the
compounds of formula 1 as the aliphatic nitrile
compounds, compounds having a nitrile group only at one
side in the aliphatic nitrile compounds of formula 1 are
also within the scope of the present invention since
they have a high possibility to show the equivalent
safety and/or improvement in the cycle life
characteristics of the battery to the compounds of
formula 1.
It is preferred for the simplification of a battery
fabrication process that a complex between the surface
of the cathode active material and the aliphatic nitrile
compound is formed after the aliphatic nitrile compound
is introduced into an electrolyte solution. However, it
is also possible that a cathode having the complex
formed on the surface thereof is prepared separately and
used in the assembling of a battery.
Preferably, the complex between the surface of the
cathode active material and the aliphatic nitrile
compound is formed by immersing a cathode having a
cathode active material applied on a collector in an
electrolyte solution containing the aliphatic nitrile
compound and then treating the immersed cathode at high
temperature. In this case, the high temperature
treatment may be generally carried out either at a
temperature of less than 180 °C by which the electrode
active materials and binders are not influenced, or a
temperature of less than 120 °C at which the aliphatic
nitrile compounds are not evaporated. Preferably, the
high temperature treatment is conducted at a temperature
of 60-90 °C, in which case it is conduct for at least 12
hours at 60 oC, and for at least 12 hours at more than 80
°C. The reason why the high temperature treatment is
conducted is that the cyano group of the aliphatic
nitrile compound forms a strong complex structure with
cobalt metal or metal oxide as demonstrated in FIGS. 11
and 13.
The upper limit of use amount of the aliphatic
nitrile compound is determined depending on its
solubility in a solvent used in a non-aqueous
electrolyte solution, but the use of an excessively
large amount of the aliphatic nitrile compound can cause
an excessive increase in the viscosity of the
electrolyte solution and a reduction in the ion
conductivity of the electrolyte solution. Thus, the
aliphatic nitrile compound is preferably used at an
amount of less than 20% by weight, and preferably less
than 5% by weight, based on the weight of the
electrolyte solution taken as 100% by weight. The lower
limit of use amount of the aliphatic nitrile compound
varies depending on the purpose for improving the
battery safety according to the present invention and is
preferably more than 1% by weight.
In the present invention, the compound for forming
the passivation layer on the anode is selected from the
group consisting of vinyl carbonate (VC) represented by
the following formula 2, it derivative, and an ether
compound:
Derivative of the compound (VC) of formula 2
include derivatives where a non-polar side chain, such
as an alkyl group having 1-5 carbon atoms, is bonded to
the ring of formula 2.
Examples of. the ether compound include benzyl
methyl ether represented by the following formula 3,
tetraethylene glycol dimethyl ether represented by the
following formula 4, and the like:
The ether compound forms the passivation layer on
the anode like VC so as to show the equivalent effect to
VC. Thus, the ether compound shows a synergistic effect
with the aliphatic nitrile compound (see Table 1).
Table 1 below shows the performance of the ether
additive among additives of passivating the anode, in
the battery.
A passivation layer formed on the anode surface by
a carbonate solvent is porous and non-dense, so that it
increases irreversible reactions during charge/discharge
cycles so as to cause the loss of Li and the production
of dendrite, resulting in a significant reduction in the
battery performance.
The compound of passivating the anode, such as
vinylene carbonate (VC), its derivative or an ether
compound, plays an important role to improve the cycle
life characteristics of the battery not only by forming
a compact and dense protective layer upon initial charge
(generally called "formation") so as to prevent the co-
intercalation of the carbonate solvent into the active
material with a layered structure and the decomposition
reaction of the electrolyte solution, resulting in a
reduction in irreversible reactions in the battery, but
also by allowing only Li+ to be absorbed and released
through the formed protective layer (see FIG. 3).
However, it can be seen that the passivation layer (SEI
layer) formed by this compound is also broken slowly by
the expansion and contraction of the active material
during charge/discharge cycles at high temperature while
a poor SEI layer is formed in the broken area by the
carbonate solvent so as to accelerate irreversible
reactions, including Li corrosion, such that the cycle
life characteristics of the battery are significantly
deteriorated with the passage of time (see FIG. 6) . As a
result, it can be found that the cycle life
characteristics of the battery cannot be improved only
by the passivation of only the anode.
Meanwhile, when only the cathode is protected with
the aliphatic nitrile compound, the cathode surface will
be stabilized by the interaction between the nitrile
compound and the cathode. In this case, however, there
is a problem in that a poor SEI layer formed by the
carbonate solvent prevents smooth migration of Li+ ions,
so that the balance within the battery is broken down
while lithium metal is deposited on the anode surface,
resulting in a remarkable reduction in the cycle life
characteristics of the battery at ambient temperature
and high temperature.
Accordingly, it can be seen that the high-
temperature cycle life characteristic (performance and
efficiency) of the battery cannot be maintained by the
protection of only one of the cathode and the anode.
Thus, the present invention provides a secondary battery
where both the cathode and the anode are protected by
passivation in order to improve the high-temperature
cycle life characteristics of the battery.
Although it is preferred for the simplification of
a battery fabrication process that additives allowing
the passivation of each of both the electrodes are
introduced into the electrolyte solution, passivated
cathode and anode may also be prepared separately for
use in assembling a battery.
In order to be able to cause a synergistic effect
between the protective layers, the protective layer on
the anode should be formed by a compound capable of
forming a compact and strong SEI layer, and the cathode
should be protected with the aliphatic nitrile compound
capable of preventing the dissolution of transition
metal and forming a strong complex with transition metal
or metal oxide
Meanwhile, an aromatic dinitrile compound is
decomposed by reduction faster than vinylene carbonate
(VC) so as to form a poor SEI layer, thus interfering
with the formation of a compact and dense protection
layer by VC. However, the aliphatic nitrile compound
does not cause this problem.
When the compound of passivating the anode, such as
vinylene carbonate (VC), its derivative or an ether
compound, is used as an electrolyte additive, the upper
limit of use amount of this compound will be determined
regardless of the kind of a solvent used in the non-
aqueous electrolyte. However, the use of an excessive
amount of this compound results in the generation of gas
at high temperature, thus causing the problem of battery
swelling. Accordingly, this compound is preferably used
at an amount of less than 5% by weight based on 100% by
weight of the electrolyte solution. The lower limit of
use amount of this compound varies depending on the
purpose for improving high-temperature cycle life
characteristics of the battery according to the present
invention and is preferably more than 1% by weight.
The non-aqueous electrolyte solution generally
contains a flammable, non-aqueous organic solvent, such
as cyclic carbonate, linear carbonate or a combination
thereof. Examples of the cyclic carbonate include
ethylene carbonate (EC), propylene carbonate (PC),
gamma-butyrolactone (GBL), and the like, and examples of
the linear carbonate include diethyl carbonate (DEC),
dimethyl carbonate (DMC), ethylmethyl carbonate (EMC),
and the like.
The non-aqueous electrolyte solution contains a
lithium salt. Examples of the lithium salt include, but
are not limited to,, LiClO4, LiCF3SO3, LiPF6, LiBF,, LiAsF6,
and LiN(CF3SO2)2.
A typical example of an electrochemical device
which can be fabricated according to the present
invention is a lithium secondary battery. The lithium
secondary battery may comprise:
(1) a cathode capable of absorbing and releasing
lithium ions;
(2) an anode capable of absorbing and releasing
lithium ions;
(3) a porous separator; and
(4) an electrolyte solution containing an lithium
salt and an electrolyte solvent.
Generally, the lithium secondary battery contains a
lithium-containing transition metal oxide as a cathode
active material, and examples of the lithium-containing
transition metal oxide are at least one selected from
the group consisting of LiCoO2, LiNiO2, LiMn2O4, LiMnO2
and LiNi1-xCoxO2 where 0