CATHODE ACTIVE MATERIAL FOR LITHIUM SECONDARY BATTERY, PRODUCTION METHOD THEREFOR, AND LITHIUM SECONDARY BATTERY COMPRISING SAME

Abstract

It is related to a positive active material for lithium secondary battery, a manufacturing method thereof, and a lithium secondary battery containing the same, provides that a positive active material for lithium secondary battery, wherein, it is a layered lithium metal compound comprises nickel, cobalt, and manganese, and aluminum, zirconium, and boron are doped.

Claims

1. A positive active material for lithium secondary battery, wherein, it is a layered lithium metal compound comprises nickel, cobalt, and manganese, and aluminum, zirconium, and boron are doped.

2. The positive active material of claim 1, wherein: the lithium metal compound is represented by Chemical Formula 1 below:
Li.sub.aNi.sub.xCo.sub.yMn.sub.z(M).sub.1−(x+y+z)O.sub.b  [Chemical Formula 1] in the Chemical Formula 1, it is 0.8≤a≤1.3, 1.8≤b≤2.2, 0.8≤x≤0.92, 0<y≤0.15, 0<z≤0.1, and 0<x+y+z<1; and the doping element M comprises Al, Zr, and B.

3. The positive active material of claim 2, wherein: the positive active material comprises a core portion and a shell portion of the core portion surface, the core portion and the shell portion is made of a composition containing Ni, Co, Mn, and M elements in the Chemical Formula 1.

4. The positive active material of claim 1, wherein: the core portion is 70 to 80% for 100% of the entire positive active material diameter.

5. The positive active material of claim 3, wherein: the content of nickel in the core is higher than that of nickel in the shell.

6. The positive active material of claim 5, wherein: a distribution of nickel in the core is uniform.

7. The positive active material of claim 6, wherein: a distribution of nickel content in the shell has a concentration gradient that decreases as it approaches the active material surface.

8. The positive active material of claim 2, wherein: with respect to 1 mole of the entire metal containing Ni, Co, Mn, and M, a doping ratio of Al among the doping elements M is 0.0002 to 0.01 mole.

9. The positive active material of claim 2, wherein: with respect to 1 mole of the entire metal containing Ni, Co, Mn, and M, a doping ratio of Zr among the doping elements M is 0.0015 to 0.005 mol.

10. The positive active material of claim 2, wherein: with respect to 1 mole of the entire metal containing Ni, Co, Mn, and M, a doping ratio of B among the doping elements M is 0.001 to 0.01 mol.

11. The positive active material of claim 1, wherein: the positive active material has a crystal size (Crystalline size) of 90 nm or more.

12. The positive active material of claim 1, wherein: the positive active material has an I003/I104 value of 1.2 or higher.

13. The positive active material of claim 1, wherein: a R factor of the positive active material is 0.52 or less.

14. The positive active material of claim 1, wherein: the positive active material, further comprises a coating layer positioned on the surface of the shell portion.

15. The positive active material of claim 14, wherein: the coating layer comprises boron, boron oxide, lithium boron oxide or combination thereof.

16. The positive active material of claim 1, wherein: the positive active material is a bimodal mixed with large particle and small particle.

17. The positive active material of claim 16, wherein: a D50 of the large particle is 13 to 17 μm.

18. The positive active material of claim 16, wherein: A D50 of the small particle is 4 to 7 μm.

19. A method of manufacturing a positive active material for lithium secondary battery, comprising: preparing precursor particles comprising nickel, cobalt, and manganese; obtaining lithium metal oxide by mixing and sintering the precursor particles, lithium raw material, and doping raw material; forming a coating layer by mixing and heating a coating raw material on the lithium metal oxide; wherein, the doped raw material comprises Al raw material, Zr raw material, and B raw material.

20. The method of claim 19, wherein: in the step of obtaining lithium metal oxide by mixing and sintering the precursor particles, lithium raw material, and doping raw material; a sintering condition is continues to primary and secondary temperatures while inflowing oxygen, and the primary temperature is 450 to 550° C., and the secondary temperature is 700 to 750° C.

21. (canceled)

Description

BRIEF DESCRIPTION OF DRAWINGS

[0085] FIG. 1 is a FIB cross-section SEM image measurement result of a cathode material prepared according to an exemplary embodiment.

[0086] FIG. 2 is a positive electrode material mapping result prepared according to an exemplary embodiment.

[0087] FIG. 3 is a SEM photograph showing the zone 1 in FIG. 1., and point of EDS measurement position.

[0088] FIG. 4 is a SEM image showing the zone 2 in FIG. 1, and point of EDS measurement position.

[0089] FIG. 5 is the particle strength measurement before and after boron doping.

[0090] FIG. 6 is an XRD measurement result before and after boron doping.

[0091] FIG. 7 is the result of the initial charge and discharge analysis before and after boron doping.

[0092] FIG. 8 is a result of analyzing the discharge capacity of each C-rate before and after boron doping.

[0093] FIG. 9 is a high temperature DCIR increase rate (45° C., SOC 100%) analysis result before and after boron doping.

[0094] FIG. 10 is a schematic diagram of a lithium secondary battery according to an embodiment of the present invention.

DESCRIPTION

[0095] Hereinafter, various embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention belongs can easily practice. The present invention can be implemented in many different forms and is not limited to the implementations described herein.

[0096] In order to clearly describe the present invention, parts not related to the description are omitted, and the same reference numerals are assigned to the same or similar constituent elements throughout the specification.

[0097] In addition, since the size and thickness of each component shown in the drawing are arbitrarily shown for convenience of explanation, the present invention is not necessarily limited to what is shown. In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. And in the drawing, for convenience of explanation, the thickness of some layers and regions is exaggerated.

[0098] In addition, It will be understood that when an element such as a layer, film, region, or substrate is referred to as being “on” another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present. Also, being “above” or “top” of a reference part is to position above or below the reference part, and does not necessarily mean to be “above” or “top” toward the opposite direction of gravity. .

[0099] In addition, In addition, unless explicitly described to the contrary, the word “comprise”, and variations such as “comprises” or “comprising”, will be understood to imply the inclusion of stated elements but not the exclusion of any other elements.

Exemplary Embodiment 1

[0100] Preparation of Ni 88 Mol % Precursor

[0101] Prior to the preparation of the positive active material, the precursor having the composition (Ni.sub.0.88CO.sub.0.095Mn.sub.0.025, OH).sub.2 was prepared by a general co-precipitation method.

[0102] The raw material supply solution was designed with (Ni.sub.0.98CO.sub.0.01Mn.sub.0.01, OH).sub.2 as the core portion composition and (Ni.sub.0.64Co.sub.0.23Mn.sub.0.13, OH).sub.2 as the shell portion composition. The core portion kept the Ni concentration constant to form a core-shell gradient (CSG). In order to change the Ni concentration in the shell portion, Feeding tank 1 with high Ni concentration and Feeding tank 2 with low Ni concentration were arranged in series.

[0103] During the preparation of the precursor, the core portion was maintained for more than 10 hours of co-precipitation to increase the constant concentration of Ni, and to make the slope of the shell gradient region where the concentration of Ni changes steep. The thus prepared (Ni.sub.0.88CO.sub.0.095Mn.sub.0.025, OH).sub.2 large particle precursor was grown to have an average particle size diameter of 14.8 μm. At this time, the diameter of the core portion was 11.1 μm, and the core portion diameter was maintained at 75% of the entire precursor diameter. The small particle precursor was also prepared in the same manner as described above. The precursor composition was also the same, and the average particle size diameter D50 was 5-6 μm. Based on the average particle size, the core part diameter was maintained at about 75% of the total diameter to make it 3.8-4.5 μm.

[0104] The precursor solution was commonly prepared by dissolving NiSO.sub.4.6H.sub.2O, CoSO.sub.4.7H.sub.2O, MnSO.sub.4.H.sub.2O in DI water. NH.sub.4(OH) was added as a co-precipitation chelating agent, and NaOH was used to adjust the pH.

[0105] N.sub.2 was purged to prevent oxidation of Ni during co-precipitation, and the reactor temperature was maintained at 50° C. The prepared precursor was filtered, washed with DI water, and dried in an oven at 100° C. for 24 h.

[0106] Zr, Al, and B Co-Doping CSG Ni 88% Positive Active Material Manufacturing

[0107] A large-diameter and small-diameter precursor having a core-shell gradient (Ni.sub.0.88CO.sub.0.095Mn.sub.0.025, OH).sub.2 composition, and LiOH.H.sub.2O (Samjeon Chemical, battery grade) were mixed in a 1:1.05 molar ratio.

[0108] ZrO.sub.2 (Aldrich, 4N) was mixed in the mixture so that Zr 3,400 ppm compared to positive active material weight. Al was mixed with Al(OH).sub.3 (Aldrich, 4N) to be 140 ppm. H.sub.3BO.sub.3 (Aldrich, 4N) was uniformly mixed so that B was 540 ppm. Subsequently, it was charged in a tube furnace (interior diameter 50 mm, length 1,000 mm) and sintered while inflowing oxygen at 200 mL/min.

[0109] The sintering condition was maintained at 480° C. for 5 h, and then at 700-750° C. for 16 h, and the heating rate was 5° C./min.

[0110] The calcined large-diameter and small-diameter positive active materials were uniformly mixed in a weight ratio of 80:20 (large-diameter: small-diameter) to prepare a bi-modal form. The bimodal positive active material was washed with water to remove residual lithium. After H.sub.3BO.sub.3 was dry mixed and heat treated at a temperature of 200° C. or higher, B was uniformly coated on the surface.

Comparative Example

[0111] Zr, and Al Co-Doping CSG Ni 88% Positive Active Material Manufacturing

[0112] For comparison, a Ni88 positive active material was prepared in which only Zr and Al were co-doped without doping B. The manufacturing method is the same as the exemplary embodiment, where both large and small diameters were applied.

Experimental Example

[0113] Electrochemical Characteristic Evaluation Method

[0114] Electrochemical evaluation was performed using a CR2032 coin cell. The slurry for electrode plate production was positive electrode:conductive material (denka black):binder (PVDF, KF1100)=92.5: 3.5: 4 wt %, and NMP (N-Methyl-2-pyrrolidone) was added so that the solid content was about 30% for adjusting the viscosity.

[0115] The prepared slurry was coated on a 15 μm-thick Al foil using a Doctor blade, and then dried and rolled. The electrode loading amount was 14.6 mg/cm.sup.2, and the rolling density was 3.1 g/cm.sup.3.

[0116] As the electrolyte solution, 1.5M VC was added to 1M LiPF.sub.6 in EC:DMC:EMC=3:4:3 (vol %). Coin cell was manufactured using PP separator and lithium negative electrode (200 μm, Honzo metal). Thereafter, aging was performed at room temperature for 10 hours, and a charge and discharge test was performed.

[0117] For capacity evaluation, 215 mAh/g was used as the reference capacity, and CC/CV 2.5-4.25V, 1/20C cut-off was applied for charging and discharge conditions.

[0118] The initial capacity was 0.1C charging/0.1Cdischarge followed by 0.2C charging/0.2Cdischarge.

[0119] The output characteristic was 0.1C/0.2C/0.5C/1C/1.3C/1.5C/2C, and the discharge capacity was measured while increasing the C-rate. The high temperature cycle characteristic was measured 30 times at 0.3C charge/0.3C discharge condition at high temperature of 45° C.

[0120] The high temperature DC-iR was calculated by measuring the voltage after 60 seconds after applying discharge current at 100% charging of 4.25V as the charging and discharging cycle proceeds at 45° C.

[0121] FIG. 1 is a SEM image result of measuring a cross-section after FIB (Focused Ion Beam) milling of the central portion of the positive active material spherical particles prepared in exemplary embodiment 2. It can be seen that approximately 75% of the core portion of the average particle diameter of 14.8 μm represents bulk-type primary particles, and approximately 25% of the shell portion has rod-shaped primary particles having a large aspect ratio. It can be confirmed that the positive active material is synthesized close to the precursor design value in the exemplary embodiment.

[0122] The FIB cross-section SEM image of FIG. 1 can map elements by each added material in positive active materials and the result of this is shown in FIG. 2.

[0123] As in the element mapping of FIG. 2, it can be seen that the main elements Ni, Co, and Mn are uniformly distributed inside the positive active material. In addition, it can be seen that the Zr, Al, and B added during the sintering the positive active material are uniformly distributed inside as well as the main element.

[0124] It is observed that the H.sub.3BO.sub.3 raw material added during doping melts in the temperature rising region and uniformly diffuses into the positive active material.

[0125] To find out what concentration of the six elements in the positive active material primary particle, EDS analysis was performed. The primary part of the rod in the shell gradient zone is designated as zone 1, and the primary part of the bulk type in the core section is designated as zone 2. At this time, the beam size was 2-3 nm, and the acceleration voltage was 200 kV.

[0126] FIG. 3 is an image showing only the zone 1 of FIG. 1, and the result of measuring the point EDS in the lengthwise/horizontal rod length direction is shown in Table 1.

TABLE-US-00001 TABLE 1 at % 1 2 3 4 5 B 33.03 6 4.53 — 6.27 Al 0.03 0.46 0.12 0.32 — Mn 1.21 5.76 4.03 2.3 2.85 Co 2.52 15.08 15.74 13.48 9.64 Ni 54 72.48 75.3 83.89 81.24 Zr 9.21 0.22 0.28 0.01 — at % 6 7 8 9 10 B 3.32 5.42 13.28 3.56 4.56 Al 0.43 0.09 0.3 0.38 0.29 Mn 2.6 1.99 2.88 4.17 4.09 Co 11.44 11.76 7.71 9.79 11.25 Ni 82.04 80.58 75.78 82.1 78.87 Zr 0.17 0.16 0.05 — 0.94

[0127] Table 1 is a point EDS measurement result (zone 1) for each element of positive active material shell gradient in which B is co-doping.

[0128] As shown in Table 1, when B is co-doped with Zr and Al, it can be seen that boron is uniformly present inside the primary particle of the rod of the shell gradient. It was confirmed that an amount of less than 3.56 at % and more than 10 at % was detected. However, the detection of a large amount of B on the surface part is due to the coating of Boron on the surface and is independent of doping.

[0129] EDS analysis was performed to confirm that the boron is uniformly doped even for the bulk primary particles (zone 2) that do not have a concentration gradient in the core portion of the positive active material. Specifically, Points EDS analysis was performed for each position as shown in FIG. 4, and the results are shown in Table 2.

TABLE-US-00002 TABLE 2 at % 1 2 3 4 5 6 7 B 1.25 3.21 2.52 1.71 2.5 — 3.26 Al 0.21 0.22 0.53 0.34 0.32 0.33 0.47 Mn 2.1 1.12 2.02 1.92 1.83 2 1.94 Co 9.02 8.11 7.5 7.93 7.32 7.58 6.91 Ni 87.06 87.02 87.43 87.95 87.72 90.09 87.35 Zr 0.36 0.32 — 0.15 0.31 — 0.07 at % 8 9 10 11 12 13 14 B 2.15 0.28 1.57 5.17 1.87 4.95 2.45 Al 0.26 0.23 0.19 — 0.58 0.29 0.34 Mn 2.12 1.63 3.13 2.01 1.91 2.47 1.76 Co 7.84 8.79 9.43 9.51 8.26 7.53 7.89 Ni 87.1 88.79 85.31 82.58 87.13 84.5 87.56 Zr 0.53 0.28 0.37 0.73 0.25 0.26 — at % 15 16 17 18 19 20 B 6.63 6.47 3.1 5.07 2.21 5.61 Al 0.29 0.44 0.25 0.21 0.12 0.38 Mn 1.83 1.66 1.82 1.8 1.35 2.55 Co 6.79 7.28 8 7.7 8.72 9.1 Ni 84.26 84.03 86.59 85.13 87.23 81.66 Zr 0.2 0.12 0.24 0.09 0.37 0.7

[0130] Table 2 is a point EDS measurement result (zone 2) for each element of the positive active material core bulk portion in which B is co-doping.

[0131] As shown in Table 2, when B is doped in zone 2 during sintering, it can be seen that B is measured from as little as 0.28 at % to as much as 6.63 at %. It can be seen that B is uniformly present in the primary particle of the core bulk part.

[0132] In this case, it can be seen that the distribution of B is slightly different compared to Zone 1. This phenomenon is a relative value for each element and is independent of the difference in the doping amount of the core portion and the shell portion.

[0133] FIG. 5 is a result of measuring particle strength before doping B and after doping 0.005 mol. Specifically, 20 large particles corresponding to 13.5 μm-13.9 μm size were selected, and measurement results for 15 particles with maximum and minimum values and noise removed using Shimadzu MCT-W500 Micro particle compression test sequence.

[0134] The particle strength is calculated by dividing the force applied to the particle by the cross-section of the positive active material particle, and is calculated by the following equation, and has the unit of MPa.

St=2.8P/πd.sup.2

[0135] At this time, St is the particle strength (tensile strength, MPa), P is the applied pressure (test force, N) and d is the particle diameter (mm).

[0136] As shown in FIG. 5, the particles without B doping have an averaged a particle strength of 157.8 MPa, whereas the doping of B with 0.005 mol have a 182.8 MPa, resulted in an increase in particle strength of about 16%.

[0137] FIG. 6 is the result of measuring XRD before and after doping Boron. XRD was measured using PANalytical's X′pert3 powder (model name), and the scan rate was 0.328°/s.

[0138] As shown in FIG. 6, both before and after doping the boron, it can be seen that both samples were well developed 003 layer as the main peak at around 18.7°. It can be seen that splitting of 006/102 peak between 37.5° and 38.5° and 108/110 peak between 63.5° and 65.5° appears. This means that it has good crystalline ordering in the hexagonal layer. Therefore, it can be seen that it represents a typical hexagonal α-NaFeO.sup.2 (space group R-3m) structure.

[0139] For crystallographic considerations by doping, Rietveld analysis was performed using high score plus Rietveld software, and the results are shown in Table 3. For Rietveld analysis, the XRD measurement range was fitted using a result measured at 10°-130°, and as the GOF (Goodness of Fit) value is calculated within 1.7, this simulation result can be said to be a reliable value.

TABLE-US-00003 TABLE 3 a(Å) c(Å) c/a Crystalline size (nm) I 003/I 104 R_factor GOF Zr + Al doped 2.871 14.192 4.943 87.5 1.10 0.543 1.701 Zr + Al + B doped 2.873 14.193 4.940 98.0 1.22 0.514 1.063

[0140] As shown in Table 3, there was little change in a-axis and c-axis before and after B doping. On the other hand, it can be seen that Boron is effective in increasing the crystal size, because the crystalline size increases about 10 nm, (98.0 nm) when B is doped.

[0141] The cation mixing degree of Li.sup.+ and Ni.sup.2+ was measured through the peak area ratio I003/I104 of I003 and I104. In addition, the R factor value to determine the hexagonal ordering degree was obtained through the peak area ratio of I006+I102/I101.

[0142] The sample before B doping showed I003/I104=1.10, while the B additional doped sample was found to slightly increase to I003/I104=1.22. It can be seen that the R factor value decreases from 0.543 before doping to 0.514 after doping.

[0143] Resultantly after the doped B, cation mixing was reduced, and the hexagonal structure was well grown.

[0144] The charge and discharge a curved line before and after doping B is shown in FIG. 7. Before doping B, the charging capacity was 236.3 mAh/g, the discharge capacity was 211.7 mAh/g, and the efficiency was 89.6%. On the other hand, after doping B, the charging capacity was 235.4 mAh/g, the discharge capacity was 213.5 mAh/g, and the efficiency was 90.7%. It can be seen that it is slightly advantageous in terms of the initial discharge capacity when doping B, but there is no significant difference in the charge and discharge profile.

[0145] FIG. 8 is a graph showing the output characteristics of each C-rate before and after B doping. It showed 86.7% in 2C before B doping, and 86.9% in 2C after B doping. It can be seen that there is no significant difference in the output characteristic from B doping.

[0146] However, the effect of B doping is clearly seen in the high temperature DCIR measurement result, which measures the voltage after 60 seconds when discharge current is applied after full charging 4.25 V at 45° C. high temperature.

[0147] FIG. 9 is a high temperature DCIR increase rate (45° C., SOC 100%) analysis result before and after boron doping.

[0148] As can be seen in FIG. 9, the B-doped sample showed a resistance increase rate of 84.6% compared to the initial value after 30 cycles. In the case of doping B, it showed a resistance increase rate of 66.7% so that it can be seen that the effect of improving the resistance increase rate of about 21%.

[0149] This is a very huge effect in actual rechargeable battery design and manufacturing. The high DCIR increasing rate according to the charge/discharge cycle reduces the design margin of the battery, but brings about a very good increase rate of resistance when doping B. This has the effect of enabling a variety of designs of medium and large rechargeable batteries.

TABLE-US-00004 TABLE 4 High Temp. Initial DCIR discharge retention Increasing Particle capacity (%) rate (%) Amount of B Strength (mAh/g (30 cycle (30 cycle (based on B) (MPa) @0.2 C) @45° C.) @45° C.) 0.001 mol 164.5 211.9 94.5 80.2 0.003 mol 173.7 213.3 95.3 70.3 0.005 mol 182.8 213.5 95.5 66.7  0.01 mol 185.5 208.7 94.2 90.2 0.015 mol 185.2 202.3 92.5 130.3 *Comparison of particle strength and coin cell performance as the amount of boron doping increases (Zr and Al are the same)

[0150] Table 4 shows the results of increasing particle strength and initial discharge capacity, high temperature charging and discharge cycle-life and DCIR increase rate while increasing the amount of boron doping in Zr Al doping. As B reaches 0.005 mol, it can be seen that the particle strength, initial capacity, charge and discharge capacity retention rate, and high temperature DCIR value are the most optimal.

[0151] In the case of particularly particle strength, the slope increased linearly with increasing B doping amount. At 0.01 mol, it was found that 0.005 mol was the maximum in terms of particle strength, as there was little increase in particle strength even when the concentration increased. In addition, in the case of 0.01 mol, the particle strength increased slightly, but the initial capacity, cycle capacity retention rate and the high temperature DCIR increase rate were rather worse. The optimal doping value of B can be confirmed to be 0.003 mol-0.005 mol.

TABLE-US-00005 TABLE 5 Initial High Temp. discharge Retention DCIR Particle Capacity (%) increasing Amount strength (mAh/g (30 cycle rate (%) of Al (MPa) @0.2 C) @45° C.) (30 cycle @45° C.) 0.0001 mol 178.8 214.1 92.1 92.3 0.0002 mol 180.3 214.0 94.5 71.5 0.0005 mol 182.8 213.5 95.5 66.7  0.001 mol 181.7 213.2 95.4 67.2  0.005 mol 180.2 212.2 95.3 70.2  0.01 mol 180.1 211.0 94.7 73.2  0.015 mol 181.3 207.3 94.5 82.3

[0152] The Table 5 is a comparison result of coin cell performance according to the amount of Al doping. (Zr 0.036 mol, B 0.005 mol is the same)

[0153] When Al was doped 0.0001 mol compared to the positive active material standard, the particle strength was 178.8 MPa due to the effect that B contained 0.005 mol. The initial discharge capacity is also 214.1 mAh/g, which is a high value. However, the 30 cycle retention and high temperature DCIR increase rate were 92.1% and 92.3%, respectively, indicating poor results.

[0154] Simultaneously, if the amount of Al doping is greatly increased, the particle strength does not change significantly due to the B effect. The retention rate and the high temperature DCIR increase rate by Al doping effect also show good results. However, it can be seen that the initial discharge capacity is greatly reduced due to the Al effect of not participating in capacity expression.

[0155] From the result, it can be seen that the doping range in which the Al effect can be seen is 0.0002 mol to 0.01 mol.

TABLE-US-00006 TABLE 6 Initial High Temp. discharge Retention DCIR increasing Amount Particle capacity (%) rate (%) of strength (mAh/g (30 cycle (30 cycle Zr (MPa) @0.2 C) @45° C.) @45° C.)  0.001 mol 180.3 215.2 92.3 98.2 0.0015 mol 181.2 214.4 95.3 81.2 0.0036 mol 182.8 213.5 95.5 66.7  0.005 mol 179.2 212.1 95.0 73.2  0.007 mol 175.2 205.5 94.3 80.3

[0156] The Table 6 is a comparison result of coin cell performance according to the amount of Zr doping. (Al 0.0005 mol, B 0.005 mol same)

[0157] When Zr is doped by 0.001 mol compared to the positive active material standard, the particle strength is 180.3 MPa by the effect of containing 0.005 mol of B. The initial discharge capacity is also 215.2 mAh/g, which is a high value. However, the 30 cycle retention rate and the high temperature DCIR increase rate were 92.3% and 98.2%, respectively, indicating poor results.

[0158] Simultaneously, when the Zr doping amount is increased to 0.007 mol, the capacity retention rate and the high temperature DCIR increase rate show relatively good results. However, it can be seen that the particle strength decreases to 175.2 MPa, and the initial capacity is particularly reduced to 205.5 mAh/g.

[0159] From the result, it can be seen that the doping range in which the Zr effect can be seen is 0.0015 mol to 0.005 mol.

[0160] The present invention is not limited to the embodiments and/or exemplary embodiments, but may be manufactured in various different forms, and those having ordinary knowledge in the technical field to which the present invention belongs may have technical ideas or essential features of the present invention. It will be understood that it may be implemented in other specific forms without changing the. Therefore, the embodiments and/or exemplary embodiments described above are illustrative in all aspects and should be understood as non-limiting.