CN107204432B - Positive electrode active material, method for producing same, and lithium secondary battery comprising same - Google Patents
Positive electrode active material, method for producing same, and lithium secondary battery comprising same Download PDFInfo
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- CN107204432B CN107204432B CN201610252174.6A CN201610252174A CN107204432B CN 107204432 B CN107204432 B CN 107204432B CN 201610252174 A CN201610252174 A CN 201610252174A CN 107204432 B CN107204432 B CN 107204432B
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
The present invention relates to a positive electrode active material, a method for producing the same, and a lithium secondary battery including the positive electrode active material, wherein the positive electrode active material is characterized in that: comprises a lithium composite metal oxide and zirconia, and has an X-ray diffraction spectrum having a first peak appearing at a diffraction angle 2 theta of 27 to 29 DEG and a second peak appearing at 30.5 to 32.5 deg. In the positive electrode active material of the present invention, the zirconia having a monoclinic structure is present not only on the surface but also inside, and therefore, when the positive electrode active material is applied to a lithium secondary battery, the capacity and the life characteristics of the lithium secondary battery can be improved by securing the mobility and the structural stability of lithium ions.
Description
Technical Field
The present invention relates to a positive electrode active material used in the production of a lithium secondary battery and a method for producing the same.
Background
The battery generates electricity by using a material capable of undergoing an electrochemical reaction in the positive electrode and the negative electrode. A typical example of such a battery is a lithium secondary battery in which electric energy is generated by a change in chemical potential (chemical potential) at the time of lithium ion intercalation/deintercalation in a positive electrode and a negative electrode.
The lithium secondary battery is manufactured by using a material capable of repeating intercalation/deintercalation of lithium ions as active materials of a positive electrode and a negative electrode, respectively, and filling an organic electrolyte or a polymer electrolyte between the positive electrode and the negative electrode.
Conventionally, as a positive electrode active material for a lithium secondary battery, a lithium composite metal oxide in which lithium and a metal (for example, Co, Mn, Ni, Al, etc.) are bonded has been used, but the lithium composite metal oxide has a limitation in improving the life characteristics of the lithium secondary battery due to its structural instability, difficulty in synthesis, and the like.
Therefore, as a method for solving the structural instability of the lithium composite metal oxide, a technique for producing a positive electrode active material by replacing the surface of the lithium composite metal oxide with zirconia has been proposed. That is, in order to compensate for the unstable structure of the lithium composite metal oxide, a positive electrode active material is produced by coating the surface thereof with zirconia (see fig. 7).
However, the positive electrode active material produced by the above-described technique has a limitation in ensuring a lithium ion transport path because zirconia is present only on the surface. Further, since the zirconia used is composed of only a tetragonal and/or cubic structure which is easily transformed, there is a problem that the stability of the lithium secondary battery is lowered due to volume expansion caused by transformation of the zirconia during the use of the lithium secondary battery.
Documents of the prior art
Patent document
Korean laid-open patent publication No. 2003-0034762
Disclosure of Invention
Problems to be solved
In order to solve the above problems, an object of the present invention is to provide a positive electrode active material having a stable structure and capable of ensuring mobility of lithium ions.
Another object of the present invention is to provide a method for producing the positive electrode active material.
Another object of the present invention is to provide a positive electrode produced using the positive electrode active material, and a lithium secondary battery including the positive electrode.
Means for solving the problems
In order to achieve the above object, the present invention provides a positive electrode active material comprising a lithium composite metal oxide and zirconium oxide, wherein the zirconium oxide has an X-ray diffraction spectrum having a first peak appearing at a diffraction angle (2 θ) of 27 to 29 ° and a second peak appearing at a diffraction angle (2 θ) of 30.5 to 32.5 °.
Here, the zirconia is a substance that replaces the inside of the lithium composite metal oxide or coats the lithium composite metal oxide to compensate for corrosion or surface defects (defects) of the positive electrode active material, and therefore may be present inside the lithium composite metal oxide or both inside and on the surface.
In the present invention, the zirconia has a monoclinic crystal structure, and the ratio (X) of the monoclinic structure contained in the zirconia is determined by X-ray diffraction analysism) Satisfies the following mathematical formula 1.
[ mathematical formula 1]
Xm＝1-Xt
In the above-mentioned mathematical formula 1,
Xtthe ratio of the tetragonal structure and the cubic structure contained in the zirconia,
Xtin the range of 0. ltoreq. Xt≤0.5。
Further, the present invention provides a method for producing a positive electrode active material, including: a) a step of mixing a lithium compound, a metal hydroxide precursor, and zirconia containing a monoclinic structure to produce a mixture; b) a step of producing a powder by firing the mixture for 1 time and then pulverizing the fired mixture; and c) firing the powder for 2 times.
The present invention also provides a positive electrode produced using the positive electrode active material, and a lithium secondary battery including the positive electrode.
Effects of the invention
In the positive electrode active material of the present invention, the zirconia having a monoclinic structure is present not only on the surface but also inside, and therefore, when the positive electrode active material is applied to a lithium secondary battery, the capacity and the life characteristics of the lithium secondary battery can be improved by securing the mobility and the structural stability of lithium ions.
Drawings
Fig. 1 is a sectional view showing a positive electrode active material according to an example of the present invention.
FIG. 2 is a graph showing the results of Experimental example 1 of the present invention.
Fig. 3 and 4 are graphs showing the results of experimental example 2 of the present invention.
Fig. 5 and 6 are graphs showing the results of experimental example 3 of the present invention.
Fig. 7 is a cross-sectional view showing a conventional positive electrode active material.
Description of the symbols
10: lithium composite metal oxide
20: zirconium oxide
Detailed Description
The present invention will be described below.
1. Positive electrode active material
Unlike a conventional positive electrode active material having a structure in which zirconia is coated on the surface of a lithium composite metal oxide, the positive electrode active material of the present invention has a structure in which zirconia is present inside or both inside and on the surface of the positive electrode active material, and this will be specifically described with reference to fig. 1, the contents of which are as follows.
The positive electrode active material of the present invention contains a lithium composite metal oxide 10. The lithium composite metal oxide 10 is not particularly limited, and may be 1 or more selected from the group consisting of lithium-cobalt oxides, lithium-manganese oxides, lithium-nickel-cobalt oxides, lithium-nickel-manganese oxides, lithium-nickel-cobalt-aluminum oxides, lithium-manganese-cobalt oxides, and lithium-nickel-manganese-cobalt oxides.
The positive electrode active material of the present invention contains zirconia 20.
The above-mentioned zirconia 20 exists inside or inside and on the surface of the lithium composite metal oxide, and contains a monoclinic phase structure. Preferably, the structure may be one in which the above-mentioned zirconia 20 is substituted inside the crystal structure of the lithium composite metal oxide, or may be one in which the zirconia 20 is uniformly distributed both inside and on the surface of the lithium composite metal oxide.
Here, in the case where the inside of the lithium composite metal oxide is substituted with the zirconia 20, the lithium composite metal oxide and the zirconia may be mixed with each other or exist in the form of a solid solution thereof (solid solution).
Further, the zirconia 20 contains a monoclinic structure, and thus structural stability of the positive electrode active material can be ensured. That is, although zirconia has been conventionally used as a coating agent for a positive electrode active material, zirconia conventionally used is limited in terms of securing structural stability of a positive electrode active material because it is composed of only a tetragonal phase (tetragonal phase) structure and/or a cubic phase (cubic phase) structure, which are easily transformed. Specifically, when the phase transition occurs in the zirconia composed only of the tetragonal crystal structure and/or the cubic crystal structure, the volume expansion causes cracks in the positive electrode active material, thereby deteriorating the life and stability of the lithium secondary battery.
In contrast, the zirconia 20 of the present invention includes a monoclinic structure in which a phase transition does not easily occur, and thus the structural stability of the positive electrode active material can be improved. Further, the zirconia 20 including a monoclinic structure has higher kinetic energy than zirconia having only a tetragonal (tetragonal phase) structure and/or a cubic (cubic phase) structure, and therefore, when a positive electrode active material is produced using the zirconia 20, mixing with a raw material substance is easily achieved, and thus, a positive electrode active material in which the zirconia 20 is distributed (substituted) on the surface or even inside can be provided.
In the X-ray diffraction spectrum (XRD) of the zirconia 20 according to the present invention, 2 specific peaks appeared, which showed to contain a monoclinic (monoclinic phase) crystal structure.
More specifically, in the X-ray diffraction spectrum (XRD) of the zirconium oxide of the present invention, there are simultaneously a first peak appearing at a diffraction angle (2. theta.) of 27 to 29 DEG and a second peak appearing at 30.5 to 32.5 deg. In contrast, in the X-ray diffraction spectrum (XRD) of zirconia having a tetragonal structure and a cubic structure, there is one peak at a diffraction angle (2 θ) of 29 to 31 ° (see fig. 2 below).
The ratio (X) of the monoclinic structure contained in the zirconia 20m) Without particular limitation, it is preferable to satisfy the following equation 1 in consideration of structural stability of the cathode active material and characteristics of the lithium secondary battery. That is, when the zirconia 20 of the present invention is subjected to X-ray Diffraction (XRD) analysis, the ratio (X) of the monoclinic structure contained in the zirconia 20m) Satisfies the following mathematical formula 1.
[ mathematical formula 1]
Xm＝1-Xt
In the above-mentioned mathematical formula 1,
Xtis the ratio of the tetragonal structure to the cubic structure contained in zirconia when the zirconia is subjected to X-ray diffraction analysis,
Xtin the range of 0. ltoreq. Xt≤0.5。
At this time, XtValue passing through It(101)/(Im(-111)+It(101)+Im(111) Obtained by the following formula (iv).
In the above formula, It(101) Is the intensity of XRD peak (ZrO) indicating tetragonal structure and cubic structure contained in zirconia2@2θ＝29～31°)，Im(-111) and Im(111) Is the intensity of XRD peak (ZrO) showing monoclinic structure contained in zirconia2@2θ＝27～29°,ZrO2@2θ＝30.5～32.5°)。
In the above mathematical formula 1, when X istA value of 0 means that the zirconia 20 of the present invention is composed of only a monoclinic structure, and when X istA value of 0.5 means that the monoclinic structure is 50% of a non-monoclinic structure (e.g., tetragonal structure, cubic structure, etc.) is 50%. That is, in the zirconia 20 of the present invention, it is preferable that 50 to 100% of the monoclinic structure is present based on 100% of the crystal grains.
In the present invention, the content of the zirconia 20 may be appropriately included in consideration of the capacity and life characteristics of the battery, and may be, for example, in the range of 0.001 mol% to 0.1 mol%.
On the other hand, the zirconia 20 of the present invention is preferably combined with the stabilizer (a). This is because, when the zirconia 20 is bonded to the stabilizer (a), the phase transition rate of the zirconia 20 can be further reduced. Specifically, the zirconia 20 to which the stabilizer (a) is bonded is preferably represented by the following chemical formula 1.
[ chemical formula 1]
ZrO2·A
In the chemical formula 1 described above,
a is selected from CaO, MgO, CeO2And Y2O3Group (d) of (a).
The content ratio of the stabilizer (a) is not particularly limited, and is preferably 0.01 to 0.1 mol% based on 100 mol% of the entire of the zirconia 20 and the stabilizer (a). This is because, in the case where the stabilizer (a) is less than 0.01 mol%, phase transition to tetragonal system and cubic system may occur during firing, and in the case where it exceeds 0.1 mol%, diffusion and substitution of the zirconia 20 may be reduced.
2. Method for producing positive electrode active material
The present invention provides the above-described method for producing a positive electrode active material. Unlike the conventional method of producing a positive electrode active material by mixing zirconia after 1 firing, the method of producing a positive electrode active material according to the present invention is specifically described below by mixing zirconia before 1 firing.
a) Mixture manufacture
First, a lithium compound, a metal hydroxide precursor, and zirconia containing a monoclinic structure are mixed to produce a mixture. The method for producing the above mixture is not particularly limited as long as it is a method known in the art.
The lithium compound used in the production of the above mixture is not particularly limited, and is preferably selected from the group consisting of Li2CO3、LiNO3LiOH and LiOH H2O. Further, the metal hydroxide precursor is not particularly limited, but is preferably Ni1-x-yCoxMy(OH)2The precursor (0.02. ltoreq. x.ltoreq.0.4, 0. ltoreq. y.ltoreq.0.25, M is 1 or more selected from the group consisting of Al, Mn, Mg, Ti, Zr, Fe, V, W, Si and Sn). Further, the zirconia is preferably represented by the above chemical formula 1.
In this case, the amount of zirconia used is not particularly limited, and for example, 0.001 mol% to 0.1 mol% can be used.
On the other hand, when the structural stability of the positive electrode active material and the physical properties of the lithium secondary battery are taken into consideration, the ratio (X) of the monoclinic structure contained in the zirconiam) It preferably satisfies the above mathematical formula 1.
b) 1-time firing and powder production
The mixture was fired 1 time and then pulverized to produce a powder. The conditions for 1-time firing of the mixture are not particularly limited, but the firing temperature is preferably 550 to 950 ℃, and the firing time is preferably 10 to 20 hours. The size of the obtained powder is also not particularly limited, but is preferably 5 to 20 μm.
c) Cleaning of
The powder is washed to remove residual lithium as necessary. In this case, the cleaning method is not particularly limited as long as it is a method known in the art.
d)2 times of firing
The powder was fired 2 times. The conditions for firing the powder 2 times are not particularly limited, but the firing temperature is preferably 550 to 950 ℃, and the firing time is preferably 5 to 10 hours.
As described above, in the present invention, since the positive electrode active material is produced by mixing with the raw material materials (lithium compound and metal hydroxide precursor) before the zirconia is fired 1 time, the positive electrode active material in which the zirconia is present inside and/or on the surface can be produced. That is, since zirconia has been conventionally used as a coating agent, zirconia is mixed not before 1 firing but after 1 firing to produce a positive electrode active material. Therefore, the conventional positive electrode active material has a structure in which zirconia is present only on the surface, and thus has a limitation in securing mobility of lithium ions.
However, in the present invention, since the positive electrode active material is produced by mixing the raw material before the zirconia is fired 1 time, the positive electrode active material in which the zirconia is contained or present in both the inside and the surface can be produced, and thus the mobility of lithium ions can be ensured.
On the other hand, in the present invention, a form in which monoclinic zirconia is mainly substituted in the lithium composite metal oxide or present in the inside and the surface of the above-described oxide has been described, but in addition to this, a form in which monoclinic zirconia is present on the surface of the lithium composite metal oxide also belongs to the scope of the present invention.
3. Positive electrode and lithium secondary battery
The present invention provides a positive electrode manufactured using the positive electrode active material described above, and a lithium secondary battery including the same, which will be described in detail below.
The positive electrode of the present invention is produced using the above-described positive electrode active material, and other materials and methods known in the art.
The lithium secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte. The lithium secondary battery of the present invention is manufactured by a material and a method known in the art, in addition to the positive electrode described above.
Since the lithium secondary battery of the present invention includes the positive electrode manufactured using the positive electrode active material described above, the positive electrode active material has minimal cracking during continuous use of the lithium secondary battery, has increased acid resistance to hydrofluoric acid, and has excellent capacity and life characteristics.
The present invention will be described in detail below with reference to examples, which are as follows. However, the following examples are only for illustrating the present invention, and the present invention is not limited to the following examples.
[ example 1]
Mixing Ni0.80Co0.15Al0.05(OH)2A metal hydroxide precursor represented by the formula, a lithium compound represented by LiOH, and ZrO2·Y2O3(Y2O3The content ratio of (A): 0.02 mol%) was charged into a dry powder mixer and uniformly mixed to prepare a mixture. In this case, the mixing ratio of the metal hydroxide precursor and the lithium compound was set to 1:1.01 molar ratio, and the ratio of the monoclinic structure (X) was usedm) Zirconia of 1.
Then, the mixture was fired at 750 ℃ for 1 time for 15 hours in an oxygen atmosphere to obtain a solid material. Thereafter, the obtained solid matter was pulverized and classified to produce LiNi substituted with zirconia0.80Co0.15Al0.05O2The powder is formed.
Next, the produced powder was washed with water at room temperature for 30 minutes to remove residual lithium. In this case, the powder/water ratio was 1:1.5 by weight. Thereafter, the filtrate was removed through a filtration step, and the powder was dried at 120 ℃ for 12 hours.
Then, the powder was fired at 720 ℃ for 2 times of 8 hours to produce a particulate positive electrode active material.
[ example 2]
Ratio (X) using monoclinic structurem) A positive electrode active material was produced in the same manner as in example 1, except that the amount of zirconia was 0.75.
Comparative example 1
A positive electrode active material was produced in the same manner as in example 1, except that zirconia containing no monoclinic structure was used.
Comparative example 2
A positive electrode active material was produced in the same manner as in example 1, except that zirconia was not mixed before 1 firing, but mixed before 2 firings.
Production examples 1 and 2
The cathode active materials manufactured in examples 1 and 2 were mixed with PVDF (polyvinylidene fluoride) as a binder and acetylene black as a conductive material at a weight ratio of 96:2:2, respectively, and NMP (N-Methyl pyrrolidone) as a solvent was added to produce cathode slurry. The produced positive electrode slurry was coated on an aluminum foil, rolled, and dried in a vacuum dryer at 130 ℃.
The positive electrode, the negative electrode of Li metal, the polypropylene separator, and the additive 1M LiPF were used6The electrolyte solutions mixed in a weight ratio of 5:2:3 were used to manufacture lithium secondary batteries in the form of button cells.
Comparative production examples 1 and 2
A lithium secondary battery was manufactured by the same method as in the above manufacturing example 1, except that the positive electrode active materials manufactured in comparative examples 1 and 2 were applied.
[ Experimental example 1] XRD analysis
XRD (X-ray Diffraction) of the zirconia used in examples 1 and 2 and comparative example 1 was analyzed by a method known in the art, and the results are shown in fig. 2.
Referring to fig. 2, it was confirmed that the zirconia used in examples 1 and 2 exhibited M (-111) and M (111) peaks due to the inclusion of a monoclinic structure. On the other hand, it was confirmed that the zirconium oxide used in comparative example 1 did not have a monoclinic structure, and thus did not have M (-111) and M (111) peaks.
[ Experimental example 2] EPMA analysis
The positive electrode active materials produced in example 1 and comparative example 1 were analyzed by EPMA (Electron Probe Micro-Analysis), and the results are shown in fig. 3 and 4, respectively.
Referring to fig. 3, it was confirmed that when the positive electrode active material (example 1) was produced using zirconia having a monoclinic structure, a positive electrode active material having zirconia at a high content from the center to the surface of the positive electrode active material was produced.
On the other hand, referring to fig. 4, it was confirmed that when a positive electrode active material was produced using zirconia not containing a monoclinic structure, the positive electrode active material containing a very low amount of zirconia was produced because the zirconia was not substituted up to the inside of the positive electrode active material (comparative example 1).
Experimental example 3 evaluation of lithium Secondary Battery Performance
The capacity and life characteristics of the lithium secondary batteries manufactured in each of manufacturing examples 1 and 2 and comparative manufacturing examples 1 and 2 were evaluated in the range of 4.3V to 3.0V, and the results thereof are shown in fig. 5 and 6. At this time, the charge and discharge and 1C/1C lifetime were evaluated at a rate (rate) under the charge and discharge conditions of 0.1C/0.1C/0.2C/0.5C/1.0C/2.0C/3.0C/5.0C.
Referring to fig. 5 and 6, it can be confirmed that the lithium secondary battery of the present invention is excellent in performance.
Claims (7)
1. A positive electrode active material comprising a lithium composite metal oxide and zirconium oxide,
and the X-ray diffraction spectrum of the zirconia has a first peak appearing at a diffraction angle 2 theta of 27-29 DEG and a second peak appearing at 30.5-32.5 DEG,
wherein the zirconia is combined with a stabilizing agent,
the stabilizer-bound zirconia is represented by the following chemical formula 1,
[ chemical formula 1]
ZrO2·A
In the chemical formula 1 described above,
a is selected from CaO, MgO, CeO2And Y2O3Group of and
the content ratio of the stabilizer is 0.01 to 0.1mo 1% based on 100 mol% of the entire stabilizer-bonded zirconia,
wherein the zirconia is present in the inside or both the inside and the surface of the lithium composite metal oxide.
2. The positive electrode active material according to claim 1, wherein the zirconia is monoclinicA crystal structure, a ratio X of a monoclinic structure contained in zirconia in X-ray diffraction analysismSatisfies the following mathematical formula 1,
[ mathematical formula 1]
Xm＝1-Xt
In the above-mentioned mathematical formula 1,
Xtis the ratio of the tetragonal structure and the cubic structure contained in the zirconia,
Xtin the range of 0. ltoreq. Xt≤0.5。
3. A positive electrode produced using the positive electrode active material according to any one of claims 1 to 2.
4. A lithium secondary battery comprising the positive electrode according to claim 3.
5. A method for producing the positive electrode active material according to claim 1, comprising:
a) a step of mixing a lithium compound, a metal hydroxide precursor, and zirconia containing a monoclinic structure to produce a mixture;
b) a step of producing a powder by pulverizing the mixture after firing the mixture 1 time; and
c) and (3) sintering the powder for 2 times.
6. The method for producing a positive electrode active material according to claim 5, wherein the amount of zirconia used is 0.001 mol% to 0.1 mol%.
7. The method for producing a positive electrode active material according to claim 5, wherein a ratio X of a monoclinic structure contained in the zirconia when the zirconia is subjected to X-ray diffraction analysismSatisfies the following mathematical formula 1,
[ mathematical formula 1]
Xm＝1-Xt
In the above-mentioned mathematical formula 1,
Xtis the ratio of the tetragonal structure and the cubic structure contained in the zirconia,
Xtin the range of 0. ltoreq. Xt≤0.5。
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| EP4181235A1 (en) * | 2012-10-02 | 2023-05-17 | Massachusetts Institute Of Technology | High-capacity positive electrode active material |
| CN103078109A (en) * | 2013-01-16 | 2013-05-01 | 中南大学 | Gradient coated LiNiO2 material and preparation method |
| EP3062373B1 (en) * | 2013-10-31 | 2019-05-22 | LG Chem, Ltd. | Cathode active material, method for preparing same, and lithium secondary battery comprising same |
| KR101592752B1 (en) * | 2014-08-18 | 2016-02-12 | 현대자동차주식회사 | Garnet powder, manufacturing method thereof, solid electrolyte sheet using hot-press and manufacturing method thereof |
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2016
- 2016-03-17 KR KR1020160032002A patent/KR20170108310A/en not_active Application Discontinuation
- 2016-04-21 CN CN201610252174.6A patent/CN107204432B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102203988A (en) * | 2009-04-03 | 2011-09-28 | 松下电器产业株式会社 | Positive electrode active material for lithium ion secondary battery, method for producing same, and lithium ion secondary battery |
| CN102484244A (en) * | 2010-06-30 | 2012-05-30 | 松下电器产业株式会社 | Negative electrode for nonaqueous electrolyte secondary battery, method for producing same, and nonaqueous electrolyte secondary battery |
| CN103765637A (en) * | 2012-03-23 | 2014-04-30 | 株式会社东芝 | Negative electrode active material for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, battery pack, and process for producing negative electrode active material for nonaqueous electrolyte secondary battery |
| CN104659343A (en) * | 2013-11-19 | 2015-05-27 | 三星Sdi株式会社 | Negative active material and negative electrode and lithium battery containing the material, and method of manufacturing the same |
| CN104681818A (en) * | 2013-11-27 | 2015-06-03 | 三星Sdi株式会社 | Positive active material, method of preparing same, and rechargeable lithium battery including the same |
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| KR20170108310A (en) | 2017-09-27 |
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