Precursor For Preparing Lithium Composite Transition Metal Oxide Method For Preparing Same And Lithium Composite Transition Metal Oxide Using Same
Abstract:
The present invention relates to a precursor for preparing lithium composite transition metal oxide a method for preparing the same and lithium composite transition metal oxide using the same and more specifically to a precursor for preparing lithium composite transition metal oxide wherein the precursor has a composition represented by chemical formula 1 and is prepared while a basic material is added to an aqueous transition metal solution mixed with a transition metal containing salt to a method for preparing the same and to lithium composite transition metal oxide using the same. MnM(OH)A (1) wherein in the chemical formula M is at least one selected from the group consisting of Ni Ti Co Al Cu Fe Mg B Cr Zr Zn and transition metals of period 2 in the Periodic Table of the Elements; A is at least one selected from the group consisting of PO BO CO F and NO anions; 0.5=a=1.0; 0=b=0.5; a+b=1; 0
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Notices, Deadlines & Correspondence
Research Park LG Chem Ltd.
188 Munji ro
Yuseong gu
Daejeon 305 380
2. SHIN Sun Sik
Research Park LG Chem Ltd.
188 Munji ro
Yuseong gu
Daejeon 305 380
3. PARK Byung Chun
Research Park LG Chem Ltd.
188 Munji ro
Yuseong gu
Daejeon 305 380
4. JEON Hye Lim
Research Park LG Chem Ltd.
188 Munji ro
Yuseong gu
Daejeon 305 380
5. LEE Bo Ram
Research Park LG Chem Ltd.
188 Munji ro
Yuseong gu
Daejeon 305 380
Specification
The present invention relates to a precursor for preparation of a lithium
composite transition metal oxide, a method for preparing the same and a lithium
composite transition metal oxide obtained fi·om the same. More patticularly, the present
10 invention relates to a transition metal precursor which has a specific composition and is
prepared in an aqueous transition metal solution, mixed with a transition metalcontaining
salt, including an alkaline material, a method for preparing the same and a
lithium composite transition metal oxide obtained fi·om the same.
15
[BACKGROUND ART]
As mobile device technology continues to develop and demand therefor
continues to increase, demand for secondary batteries as energy sources is rapidly
increasing. Among these secondary batteries, much research has focused on lithium
-1-
secondary batteries having high energy density and discharge voltage. Such batteries are
commercially available and widely used.
Generally, as cathode active materials for lithium secondary batteries, lithiumcontaining
cobalt oxides such as LiCo02 are mainly used. In addition thereto, use of
5 lithium-containing manganese oxides such as LiMn02 having a layered crystal
structure, LiMn204 having a spinel crystal structure, and the like and lithium-containing
nickel oxides such as LiNi02 is also under consideration.
Among cathode active materials, LiCo02 is widely used due to excellent
overall physical properties such as excellent cycle properties, and the like. However,
10 LiCo02 is low in safety and expensive due to resource limitations of cobalt as a raw
15
material. Lithium nickel based oxides such as LiNi02 are cheaper than LiCo02 and
exhibit high discharge capacity when charged to a voltage of 4.25 V. However, the
lithium nickel based oxides have problems such as high production costs, swelling due
to gas generation in batteries, low chemical stability, high pH and the like.
In addition, lithium manganese oxides, such as LiMn02, LiMn204, and the like,
are advantageous in that they contain Mn, which is an abundant and environmentally
friendly raw material, and thus are drawing much attention as a cathode active material
that can replace LiCo02. In particular, among the lithium manganese oxides, LiMn20 4
has advantages such as a relatively cheap price, high output and the like. On the other
-2-
hand, LiMn204 has lower energy density, when compared with LiCo02 and three
component-based active materials.
To overcome these drawbacks, a variety of materials have been developed.
Especially, layered structure transition metal oxides such as LiNil/3Mnl/3Col/302,
S LiNio.sMno.3Coo.202 and the like including two or more materials of Ni, Mn and Co
have been highlighted.
However, these materials do not satisfY requirements of medium and large
batteries such as those used in electric vehicles, systems for storing power and the like.
Accordingly, study into Mn-enriched (l-x)LiMOrxLhM03 based materials
10 stable under high voltage is being conducted. However, the Mn-emiched (l-x)LiM02-
xLhM03 based materials include a large amount of Mn and thereby are easily oxidized
15
by dissolved oxygen inside an aqueous transition metal solution during synthesis of a
transition metal precursor through a co-precipitation method, and, accordingly,
synthesis is not easy.
To compensate for this problem, methods such as surface treatment, formation
of a core-shell structure and substitution with hetero elements and the like have been
tried. However, the methods also are not suitable for easy synthesis. In addition, there
are still problems such as additional costs during processes, deterioration of precursor
tap density and the like.
-3-
As described above, a precursor for preparation of a lithium composite
transition metal oxide having satisfactory performance and a lithium composite
transition metal oxide obtained from the same has yet to be developed.
[DISCLOSURE]
5 [TECHNICAL PROBLEM]
The present invention aims to address the aforementioned problems of the
related art and to achieve teclmical goals that have long been sought.
As a result of a variety of extensive and intensive studies and experiments, the
inventors of the present invention developed a transition metal precursor having a
10 specific composition resulting in improvements in crystallizability, spheroidization
degree of a pulvemlent body and tap density, and confirmed that, when a lithium
composite transition metal oxide prepared using the transition metal precursor was used
as a cathode active material, an electrode preparation process is easy and
electrochemical characteristics of a secondary batte1y based on the lithium composite
15 transition metal oxide are improved, thus completing the present invention.
[TECHNICAL SOLUTION]
In accordance with one aspect of the present invention, provided is a transition
metal precursor, having a composition represented by Formula I below, prepared in an
-4-
aqueous transition metal solution mixed with a transition metal-containing salt and
including an alkaline material:
wherein M is at least one selected form the group consisting of Ni, Ti, Co, AI,
5 Cu, Fe, Mg, B, Cr, Zr, Zn and Period 0 transition metals;
A is at least one selected form the group consisting of anions of P04, B03,
0.5:SU:Sl.O; 0:Sb:S0.5; a+ b =I; O
After filling a 4 L wet reactor tank with 3 L of distilled water, nitrogen gas was
continuously added to the tank at a rate of 2 Llmin to remove dissolved oxygen. Here,
the temperature of distilled water in the tank was maintained ·at SOD using a temperature
-20-
maintenance device. In addition, the distilled water in the tank was stirred at 1000 to
1500 rpm using an impeller connected to a motor installed outside the tank.
Manganese sulfate, nickel sulfate, and cobalt sulfate were mixed in a molar
ratio of 0.50: 0.45: 0.05 to prepare a 1.5 M aqueous transition metal solution.
5 Subsequently, to substitute anion sites, 0.5 mol% of phosphate and 4.0 mol% of sucrose
which provide P04 anions were mixed therewith. Separately, a 3 M aqueous sodium
hydroxide solution was prepared. The aqueous transition metal solution was
continuously pumped into the wet reactor tank, using a metering pump, at a rate of 0.18
L!lu·. The aqueous sodium hydroxide solution was pumped in a rate-variable manner by
10 a control unit for adjusting a pH of the distilled water in the tank such that the distilled
water in the wet reactor tank was maintained at a pH of 11.5. In this regard, a 14%
ammonia solution as an additive was continuously co-pumped to the reactor at a rate of
0.04 L!lu·.
Flow rates of the aqueous transition metal solution, the aqueous sodium
15 hydroxide solution and the aqueous all11l1onia solution were adjusted such that an
average residence time of the solutions in the wet reactor tank was approximately 6
hours. After the reaction in the tank reached a steady state, a certain duration of time
was given to synthesize a composite transition metal precursor with a higher density.
-21-
After reaching the steady state, the manganese-nickel composite transition
metal precursor, which was prepared by 20-hour continuous reaction of transition metal
ions of the aqueous transition metal solution, hydroxide ions of the sodium hydroxide
and anm10nia ions of the ammonia solution, was continuously obtained through an
5 overflow pipe installed on the top side of the tank.
10
15
The resulting composite transition metal precursor was washed several times
with distilled water and dried in a 120 oc constant-temperature drying oven for 24 hours
to obtain a manganese-nickel composite transition metal precursor.
A transition metal precursor was prepared in the same manner as in Example 1,
except that sucrose was not mixed with the aqueous transition metal solution.
A transition metal precursor was prepared in the same manner as in Example 1,
except that phosphate was not mixed with the aqueous transition metal solution.
A transition metal precursor was prepared in the same manner as in Example 1,
except that sucrose and phosphate were not mixed with the aqueous transition metal
solution.
-22-
5
SEM images of the transition metal precursors prepared according to Examples
1 and 2, and Comparative Examples 1 and 2, respectively, captured using FE-SEM
(model S-4800 available from Hitachi), are illustrated in FIGS. 1 to 4.
Referring to FIGS. 1 to 4, it can be confirmed that the transition metal
precursor of Example 1 using 2mol% of sucrose exhibited stronger cohesive strength of
primary patiicles than that of the precursor of Comparative Example 1 and thus pmiicles
of the precursor of Example I had a more spherical shape
Referring to FIG. I to FIG. 4, it was confirmed that the precursor prepared
10 according to Example I, which uses sucrose and anion sites of which were substituted
with P04, has many pores, a wide specific surface area and a uniform diameter, when
compared with the precursors prepared according to Comparative Examples I and 2. In
addition, it was confirmed that, in the precursor prepared according to Example 1,
pnmary pmiicles exhibited improved cohesive force and thereby particle
15 crystallizability and pmiicle spheroidization degree were improved. Furthermore, it was
confirmed that, although sucrose was not used, the precursor prepared according to
Example 2, anion sites of which were substituted with P04, exhibited improved particle
crystallizability and pmiicle spheroidization degree, when compared with the precursors
prepared according to Comparative Examples 1 and 2.
-23-
The tap densities of the precursors prepared according to Examples I and 2,
and Comparative Examples I and 2, respectively, were measured and summarized in
Table 1 below.
5 [Table 1]
Tap density (glee)
Example 1 1.54
Example2 0.95
Comparative 0.55
Example 1
Comparative 0.80
Example2
As shown in Table 1, it can be confirmed that the precursors prepared
according to Examples 1 and 2, anion sites of which were substituted, exhibit improved
tap densities, when compared with the precursorsprepared according to Comparative
Examples 1 and 2, anion sites of which were not substituted. Such a result is caused by
10 easy precipitation of the transition metal hydroxide due to anion sites substituted with
P04 and thereby improved crystallizability and cohesive force of the primary particles.
Manufacture of coin cell
-24-
Each of the manganese-nickel-cobalt composite transition metal precursors
prepared according to Examples I and 2, and Comparative Examples I and 2 was mixed
with LhC03 in accordance with the molar ratio of each composition and then sintered at
900 to 950 oc for 5 to I 0 hours by heating at a heating rate of 3 to 5 °C/min to prepare a
5 cathode active material powder.
The prepared cathode active material powder, Denka as a conductive material,
and KF! I 00 as a binder were mixed in a weight ratio of 95:2.5:2.5 to prepare a slurry.
The slurry was uniformly coated on AI foil having a thickness of20 f.!m. The coated AI
foil was dried at 130 °C, thereby completing fabrication of a cathode for a lithium
10 secondary battery.
The fabricated cathode for a lithium secondary battery, lithium metal foil as a
counter electrode (i.e., an anode), a polyethylene membrane as a separator (Celgard,
thickness: 20 f.!m), and a liquid electrolyte containing I M LiPF6 dissolved in a mixed
solvent of ethylene carbonate, dimethylene carbonate, and diethyl carbonate in a volume
15 ratio of I :2:1 were used to manufacture a 2016 coin cell.
Initial charge and discharge characteristics
Electrical characteristics of the cathode active material of each of coin cells
manufactured according to Examples 3 and 4, and Comparative Examples 3 and 4 were
-25-
evaluated at 3.0 to 4.4 V using an electrochemical analyzer (Toscat 3100U available
from Toyo Systems).
To evaluate performance of each coin cell, charge and discharge capacity of
each coin cell was measured at a current of 1 C and at a voltage range of 3.0 to 4.4 V.
5 Results of discharge capacities and charge and discharge efficiencies of the coin cells
are summarized in Table 2 below.
[Table 2]
Initial discharge Initial charge and
Initial charge Samples capacity discharge efficiency
capacity (mAh/g) (%)
(mAhlg)
Example 3 185 172 93
Example4 183 169 92
Comparative
Example3
169
153 90
Comparative 162 90
180
Example4
As shown in Table 2, it can be confirmed that the precursors prepared
according to Examples 1 and 2, anion sites of which were substituted, have superior
10 initial charge and discharge capacity and efficiency, when compared with the precursors
prepared according to Comparative Examples 1 and 2, anion sites of which were not
substituted.
-26-
Lifespan characteristics
Each of com cells manufactured according to Examples 3 and 4, and
Comparative Examples 3 and 4 was charged and discharged thirty times at a current of
5 0.5 C to evaluate lifespan characteristics. Results are summarized in Table 3 below.
[Table 3]
Lifespan characteristics
301hll st discharge capacity (%)
Example} 97.0
Example4 92.0
Comparative 92.2
Example 3
Comparative 96.0
Example4
As shown in Table 3, it can be confirmed that the precursor prepared according
to Example 1, which uses sucrose and anion sites of which were substituted with P04,
exhibits lifespan characteristics of 97%, which is the highest value.
10
Output characteristics
-27-
To evaluate output characteristics, each of coin cells manufactured according
to Examples 3 and 4, and Comparative Examples 3 and 4 was charged and discharged at
a current of 0.5 C and then discharged at a current of 1.0 C and 2.0 C. Results are
summarized in Table4 below.
5 [Table 4]
0.1 c discharge 2 c discharge Output characteristics
capacity capacity
0.1 C/2.0 C (%)
(mAhlg) (mAh/g)
Example 3 172 146 85
Example4 172 136 79
Comparative 155 121 78
Example}
Comparative 166 112 67
Example4
As shown in Table 4, it can be confirmed that the precursors prepared
according to Examples 1 and 2, anion sites of which were substituted, exhibit improved
output characteristics when compared with the precursors prepared according to
Comparative Examples 1 and 2, anion sites of which were not substituted.
10 Those skilled in the mt will appreciate that various modifications, additions and
substitutions are possible, wit)10ut departing from the scope and spirit of the invention
as disclosed in the accompanying claims.
-28-
[INDUSTRIAL APPLICABILITY]
As described above, a transition metal precursor for preparing a lithium
composite transition metal oxide according to the present invention is prepared in a state
including a reducing agent to prevent oxidation of Mn and, as such, a precursor having a
5 larger specific surface area and a uniform diameter may be synthesized. At the same
time, by substituting anion sites, precipitation suppression due to addition of a reducing
agent may be solved and, as such, the crystallizability, spheroidization degree and tap
density of the precursor may be improved.
In addition, when a lithium composite transition metal oxide prepared using the
1 0 precursor is used as a cathode active material, an electrode process becomes easy and a
secondary battery based on the lithium composite transition metal oxide may exhibit
15
excellent initial discharge capacity and efficiency, and improved output characteristics
and lifespan characteristics.
[CLAIMS]
[Claim 1] A transition metal precursor having a composition represented by
Formula I below and parepared in an aqueous transition metal solution, mixed with a
transition metal-containing salt, comprising an alkaline material:
(I)
wherein M is at least one selected form the group consisting of Ni, Ti, Co, AI,
Cu, Fe, Mg, B, Cr, Zr, Zn and Period II transition metals;
A is at least one selected form the group consisting of anions of P04, B03,
O.S:sa:Sl.O;
O:Sb:SO.S;
a+b=I;
O