Positive electrode active material precursor for lithium secondary battery, positive electrode active material manufactured by using thereof, and lithium secondary battery including the same
10950856 ยท 2021-03-16
Assignee
- IUCF-HYU (INDUSTRY-UNIVERSITY COOPERATION FOUNDATION HANYANG UNIVERSITY) (Seoul, KR)
- ENERCERAMIC INC. (Seoul, KR)
Inventors
- Gang-Jun Park (Seoul, KR)
- Hyung-Joo Noh (Bucheon-si, KR)
- Yang-Kook SUN (Seoul, KR)
- Jang-Wook Park (Bucheon-si, KR)
Cpc classification
H01M4/505
ELECTRICITY
H01M4/131
ELECTRICITY
Y02E60/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M2004/021
ELECTRICITY
H01M4/525
ELECTRICITY
C01G53/50
CHEMISTRY; METALLURGY
H01M10/0525
ELECTRICITY
C01P2002/80
CHEMISTRY; METALLURGY
C01G53/006
CHEMISTRY; METALLURGY
International classification
H01M4/36
ELECTRICITY
H01M4/505
ELECTRICITY
H01M4/131
ELECTRICITY
Abstract
Positive electrode active materials are provided. The positive electrode active materials include a primary particle formed of a plurality of metals including a first metal and a secondary particle formed of at least one of the primary particle. The secondary particle includes a center part, a surface part, a seed region where the primary particle having concentration gradient of the first metal is disposed, and a maintain region where the primary particle having constant concentration of the first metal is disposed, the seed region adjacent to the core part and a maintain region adjacent to the surface part, the length of the seed region in a direction from the center part to the surface part is 1 m.
Claims
1. A positive electrode active material comprising: a plurality of primary particles, each of the plurality of primary particles comprising a plurality of metals; and a secondary particle comprising the plurality of primary particles wherein each of the plurality of primary particles has an a-axis and a c-axis in a crystal structure, wherein in each of the plurality of primary particles, an a-axis directional length is longer than a c-axis directional length, wherein the secondary particle comprises a center part and a surface part surrounding the center part, and wherein the a-axis directional length of the primary particles in the surface part is longer than the a-axis directional length of the primary particles in the center part.
2. The positive electrode active material of claim 1, wherein each of the plurality of primary particles comprises an oxide of at least one of nickel, cobalt, manganese and aluminum and lithium.
3. The positive electrode active material of claim 1, wherein the secondary particle has a concentration gradient of a metal.
4. The positive electrode active material of claim 1, wherein the primary particles are adjoining each other and grow to a fixed route, and a lithium ion is easily inserted to a space formed between the fixed routes.
5. The positive electrode active material of claim 1, wherein the a-axis and the c-axis are defined by a diffraction pattern of a Fourier transform obtained from a TEM image of the plurality of primary particles.
6. A positive electrode active material comprising: a plurality of primary particles, each of the plurality of primary particles comprising a plurality of metals; and a secondary particle comprising the plurality of primary particles, wherein each of the plurality of primary particles has an a-axis and a c-axis in a crystal structure, wherein the a-axis and the c-axis are defined by a diffraction pattern of a Fourier transform obtained from a TEM image of the plurality of primary particles, wherein the secondary particle comprises a center part and a surface part surrounding the center part, and the a-axis of at least a part of the plurality of primary particles extends in a direction toward the surface part.
7. The positive electrode active material of claim 6, wherein each of the plurality of primary particles has a rod shape having a long side and a short side.
8. The positive electrode active material of claim 7, wherein the long side corresponds to the a-axis so that the plurality of primary particles extend from the center part to the surface part.
9. The positive electrode active material of claim 8, wherein each of the plurality of primary particles has a concentration gradient of a metal from a portion adjacent to the center part to a portion adjacent to the surface part.
10. The positive electrode active material of claim 6, wherein an aspect ratio of the primary particles in the center part is smaller than an aspect ratio of the primary particles in the surface part.
11. The positive electrode active material of claim 6, wherein a concentration gradient of a metal is provided inside each of the plurality of primary particles in a longitudinal direction of each of the plurality of primary particles.
12. The positive electrode active material of claim 11, wherein the metal is at least one of nickel, cobalt, manganese, and aluminum, and a concentration gradient of the metal is provided inside the primary particles.
13. A positive electrode active material comprising: an oxide of at least one of nickel, cobalt, manganese and aluminum and lithium; and a secondary particle comprising a plurality of primary particles, wherein each of the plurality of primary particles has an a-axis and a c-axis in a crystal structure, wherein the a-axis and the c-axis are defined by a diffraction pattern of a Fourier transform obtained from a TEM image of the plurality of primary particles, wherein the secondary particle comprises a seed region, an intermediate region, and a maintain region in a direction from a center part to a surface part, wherein a length of the primary particles of the maintain region in the direction from the center part to the surface part is longer than a length of the primary particles of the seed region, and wherein a content of a metal of the maintain region is smaller than a content of a metal of the seed region.
14. The positive electrode active material of claim 13, wherein each of the plurality of primary particles has a hexagonal crystal structure.
15. The positive electrode active material of claim 13, wherein the primary particles in the intermediate region comprise: a concentration gradient part in which a concentration of any one or more of the nickel, the cobalt, the manganese, and the aluminum is changed; and a concentration maintaining part in which a concentration of any one or more of the nickel, the cobalt, the manganese, and the aluminum is constant.
16. The positive electrode active material of claim 13, wherein the secondary particle comprises the center part and the surface part, and a concentration of nickel of the center part is higher than a concentration of nickel of the surface part.
17. The positive electrode active material of claim 13, wherein an average concentration of nickel is about 80 mol % or more.
18. The positive electrode active material of claim 13, wherein a length of the seed region from the center part to the surface part is at least 1 m or more.
19. A lithium secondary battery comprising: a positive electrode comprising the positive electrode active material of claim 1; a negative electrode spaced apart from the positive electrode; and an electrolyte between the positive electrode and the negative electrode.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The above and other objects and features of the present invention will become apparent from the following description of the invention taken in conjunction with the following accompanying drawings, which respectively show:
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DETAILED DESCRIPTION OF THE EMBODIMENTS
(28) The inventive concepts will now be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the inventive concepts are shown. The advantages and features of the inventive concepts and methods of achieving them will be apparent from the following exemplary embodiments that will be described in more detail with reference to the accompanying drawings. It should be noted, however, that the inventive concepts are not limited to the following exemplary embodiments, and may be implemented in various forms. Accordingly, the exemplary embodiments are provided only to disclose the inventive concepts and let those skilled in the art know the category of the inventive concepts. In the drawings, embodiments of the inventive concepts are not limited to the specific examples provided herein and are exaggerated for clarity.
(29) The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. As used herein, the singular terms a, an and the are intended to include the plural forms as well, unless the context clearly indicates otherwise. As used herein, the term and/or includes any and all combinations of one or more of the associated listed items. It will be understood that when an element is referred to as being connected or coupled to another element, it may be directly connected or coupled to the other element or intervening elements may be present.
(30) Similarly, it will be understood that when an element such as a layer, region or substrate is referred to as being on another element, it can be directly on the other element or intervening elements may be present. In contrast, the term directly means that there are no intervening elements. It will be further understood that the terms comprises, comprising,, includes and/or including, when used herein, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
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(32) As shown in
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(34) In one embodiment of the present invention as shown in
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(36) In one embodiment of the present invention, the primary particle of the first interior is characterized that the a-axis direction length to c-axis direction length ratio of the primary particle of the first interior may be 0.5 to 2.0, and the a-axis direction length to c-axis direction length ratio of the primary particle of the second interior may be 2 to 30.
(37) Namely, the positive electrode active material for a lithium secondary battery 100 according to one embodiment of the present invention is characterized that primary particles of relatively circular type having width and length of 0.8 to 1.2 are formed in the interior, and primary particles having increased aspect ratio as going to the surface are agglutinated. In the present invention, the a-axis direction length to c-axis direction length ratio is highly increased in the second interior, compared with the first interior.
(38) In one embodiment of the present invention, it is characterized that the a-axis direction length of the primary particle is in the range of 0.01 to 0.95 of the secondary particle radius. In the present invention, the primary particles are adjoined each other and grow to a fixed route, but in the range thereof, it is preferred that the a-axis direction length of the primary particle is in the range of 0.01 to 0.95 of the secondary particle radius.
(39) In one embodiment of the present invention, it is characterized that the first interior of the secondary particle of the positive electrode active material for a lithium secondary battery is expressed by an empirical formula of Li[Ni.sub.1(a+b+c)CO.sub.aMn.sub.bM.sub.c]O.sub.2 (1.01.2, 0.00a0.40, 0.00b0.35, 0.00c0.05, 0.05a+b+c0.5), and the secondary interior of the secondary particle of the positive electrode active material for a lithium secondary battery is expressed by an empirical formula of Li.sub.[Ni.sub.1(x+y+z)Co.sub.xMn.sub.yM.sub.z]O.sub.2 (1.01.2, 0.07x0.3, 0.2y0.5, 0.00z0.1, 0.3x+y+z0.7), wherein M is at least one selected from the group consisting elements Al, Mg, Fe, Cr, V, Ti, Mo, Sc, Ce and La. Namely, in one embodiment of the present invention, the positive electrode active material for a lithium secondary battery is characterized by high Ni content in the first interior, and low Ni content and high Mn content in the second interior.
(40) In the positive electrode active material according to the present invention, the secondary particle of the positive electrode active material for a lithium secondary battery is characterized that oxidation numbers, +2 and +3, of Ni are mixed from the particle surface to the part having radius 0.1 to 0.7 time of the particle radius, i.e., at the part where the active material particles are directly contacted to an electrolyte solution. In accordance with mixing the oxidation numbers of Ni, higher oxidation number than the average oxidation number of Ni used in the existing positive electrode active material is maintained, and electric charge also becomes higher as the oxidation number of Ni becomes higher, thereby Coulomb force between the transition metal atom and oxygen is also increased. Accordingly, a stable binding structure and higher binding force between the transition metal atom and oxygen can be obtained.
(41) In one embodiment of the present invention, it is characterized that at least one metal making up the primary particle of the positive electrode active material for a lithium secondary battery shows continuous concentration gradient in the primary particle, and particularly, at least one metal making up the primary particle existing in the second interior of the secondary particle shows continuous concentration gradient in the primary particle itself.
(42) In the present invention, the positive electrode active material for a lithium secondary battery grows while also showing continuous concentration gradient inside of the primary particle. Further, the a-axis orientation of the primary particle is headed to the center part of the positive electrode active material as a secondary particle, and the particles are adjoining each other and grow to a fixed route.
EXAMPLE
(43) Hereinafter, Examples and Comparative Example will be described. The Examples are presented for illustrative purposes only, and do not limit the present invention.
<Example 1> Manufacture of Precursor and Active Material Having Constant Mn Concentration in Entire Particle and Showing Concentration Gradients of Ni and Co in Entire Particle
(44) Distilled water 4 liter was poured into a coprecipitation reactor (Volume: 4 L, Power of a rotary motor: 80 W or more), and then nitrogen gas was supplied into the reactor at the rate of 0.5 liter/min to remove dissolved oxygen followed by stirring at 1000 rpm while keeping the reactor temperature at 50 C.
(45) In order to make the Mn concentration in the entire particle constant as 0.25 and concentration gradients of Co and Ni transition metal ions, first of all, 2.4 M metal aqueous solution, wherein nickel sulfate, cobalt sulfate and manganese sulfate are mixed at the molar ratio of 75:0:25 was continuously put into the reactor at the rate of 0.3 liter/hour, and 4.8 mol ammonia solution was continuously put into the reactor at the rate of 0.03 liter/hour. Further, for adjusting pH, 4.8 mol sodium hydroxide solution was supplied thereto to keep pH at 11. Impeller speed was controlled to 1000 rpm. Average retention time of the resulting solution in the reactor became about 6 hours by controlling flow rate. After fixing the volume of the metal aqueous solution of nickel sulfate, cobalt sulfate and manganese sulfate, which was supplied, to 4 L at the time when the particle size of the composite metal hydroxide became 2-5 m, concentration was changed until the molar ratio of nickel sulfate, cobalt sulfate and manganese sulfate of the metal aqueous solution became from 75:0:25 to 55:20:25, and the reaction was continued with the changing metal aqueous solution. The metal composite hydroxide was filtered and washed with water followed by drying in a 110 C. hot air dryer for 15 hours, thereby a metal composite hydroxide as a positive electrode active material precursor was manufactured.
(46) The metal composite hydroxide manufactured as described above and lithium hydroxide (LiOH) were mixed at the molar ratio of 1:1.07, heated at the rate of 2 C./min, and then kept at 500 C. for 10 hours for conducting pre-calcination. Then, the resulting material was calcined at 780 C. for 20 hours to obtain positive electrode active material powder of Example 1-1, wherein the first interior was constant as Li[Ni.sub.0.75Mn.sub.0.25]O.sub.2, and in the second interior, the Mn concentration was maintained as 0.25 from Li[Ni.sub.0.75Mn.sub.0.25]O.sub.2 to Li[Ni.sub.0.55Co.sub.0.20Mn.sub.0.25]O.sub.2, and Ni and Co have continuous constant concentration gradient in the entire particle, and average concentration in the particle was expressed by Li(Ni.sub.0.60Co.sub.0.15Mn.sub.0.25)O.sub.2.
(47) The procedure of Example 1-1 was repeated except for continuing the reaction as maintaining the said molar ratio when the molar ratio of the metal aqueous solution reached 55:20:25 during the particle forming process for further comprising a surface maintain regions having thickness of 0.2 m, 0.5 m and 1.0 m, respectively, so as to obtain spherical nickel-manganese-cobalt composite hydroxides of Examples 1-2 to 1-4 containing the second interior having concentration gradient and a surface maintain region.
Comparative Example 1
(48) Particles having constant metal ion concentration expressed by Li(Ni.sub.0.60Co.sub.0.15Mn0.sub..25)O.sub.2 in the entire particle were manufactured.
<Test Example> TEM Imaging
(49) Approximate center parts of the precursors and the active material particles manufactured in Example 1-1, Example 1-3 and Example 1-4, and the powder manufactured in Comparative Example 1 were cut with a hydrogen ion beam, and samples for measurement were prepared. Then, TEM images of each sample were taken, and the results were shown in
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<Test Example> Measuring Battery Characteristic
(54) Batteries were manufactured by using the active material particle powders manufactured in Examples 1-1 to 1-4, and then capacity, life time characteristic and DSC characteristic were measured. The results were shown in the following Table 1.
(55) As shown in the following Table 1, it was confirmed that the batteries using Examples 1-1 to 1-4 having concentration gradient showed improved capacity, life time characteristic and DSC characteristic, compared with the battery using Comparative Example not showing concentration gradient, and in particular, the life time characteristic and the DSC characteristic were improved as the thickness of the surface maintain region was increased.
(56) TABLE-US-00001 TABLE 1 Life Time Capacity Characteristic DSC (mAhg.sup.1) (%, 100.sup.th) ( C.) Example 1-1 193.0 94.5 277.3 Example 1-2 191.1 95.2 280.1 Example 1-3 188.2 96.1 287.2 Example 1-4 184.8 97.3 294.7 Comparative 181.3 93.9 266.3 Example 1
<Example 2> Manufacture of Precursor and Active Material Having Constant Mn Concentration in Entire Particle and Showing Concentration Gradients of Ni and Co in Entire Particle
(57) In order to make the Mn concentration in the entire particle constant as 0.3 and concentration gradients of Co and Ni, first of all, 2.4 M metal aqueous solution, wherein nickel sulfate, cobalt sulfate and manganese sulfate are mixed at the molar ratio of 70:0:30, was used, and then the procedure of Example 1 was repeated except for continuing the reaction by using the metal aqueous solution whose concentration was changing until the concentration became 50:20:30 to obtain a precursor and an active material of Example 2-1.
(58) The procedure of Example 2-1 was repeated except for continuing the reaction as maintaining the said molar ratio when the molar ratio of the metal aqueous solution reached 50:20:30 during the composite particle forming process for further comprising a surface maintain regions having thickness of 0.5 m, so as to obtain a precursor and an active material of Example 2-2.
<Test Example> TEM Imaging
(59) Approximate center part of the active material particle powder manufactured in Example 2-2 was cut with a hydrogen ion beam, and a sample for measurement was prepared. Then, TEM images were taken.
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<Test Example> Measuring Battery Characteristic
(61) Batteries were manufactured by using the active material particle powders manufactured in Examples 2-1 to 2-2, and then capacity, life time characteristic and DSC characteristic were measured. The results were shown in the following Table 2.
(62) As shown in the following Table 2, it was confirmed that the batteries using Examples 2-1 to 2-2 showed improved capacity, life time characteristic and DSC characteristic, and in particular, the life time characteristic and the DSC characteristic were improved as the thickness of the surface maintain region was increased.
(63) TABLE-US-00002 TABLE 2 Life Time Capacity Characteristic DSC (mAhg.sup.1) (%, 100.sup.th) ( C.) Example 2-1 183.9 96.2 291.8 Example 2-2 182.3 97.0 295.3
<Example 3> Manufacture of Precursor and Active Material Having Constant Co Concentration in Entire Particle and Showing Concentration Gradients of Ni and Mn in Entire Particle
(64) In order to make the Co concentration in the entire particle constant as 0.1 and concentration gradients of Ni and Mn, first of all, 2.4 M metal aqueous solution, wherein nickel sulfate, cobalt sulfate and manganese sulfate are mixed at the molar ratio of 85:10:05, was used, and then the procedure of Example 1 was repeated except for continuing the reaction by using the metal aqueous solution whose concentration was changing until the concentration became 60:10:30 to obtain a positive electrode active material precursor and a positive electrode active material, thereby obtaining a positive electrode active material powder of Example 3-1.
(65) The procedure of Example 3-1 was repeated except for continuing the reaction as maintaining the said molar ratio when the molar ratio of the metal aqueous solution reached 60:10:30 during the composite particle forming process for further comprising a surface maintain regions having thickness of 0.2 m and 0.5 m, respectively, so as to obtain spherical nickel-manganese-cobalt composite hydroxide precursors of Examples 3-2 and 3-3 containing the second interior having concentration gradient and a surface maintain region.
<Test Example> TEM Imaging
(66) TEM images of the cross-sections of the nickel-manganese-cobalt composite hydroxide precursors and the positive electrode active material of Examples 3-2 to 3-3 were taken, and the results were shown in
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Comparative Example 2
(68) Particles having constant metal ion concentration expressed by Li(Ni.sub.0.65Co.sub.0.10Mn.sub.0.25)O.sub.2 in the entire particle were manufactured, and the cross-sectional TEM image thereof was shown in
<Test Example> Measuring Battery Characteristic
(69) Batteries were manufactured by using the active material particle powders manufactured in Examples 3-1 to 3-3, and then capacity, life time characteristic and DSC characteristic were measured. The results were shown in the following Table 3.
(70) As shown in the following Table 3, it was confirmed that the batteries using Examples 3-1 to 3-3 having concentration gradient showed improved capacity, life time characteristic and DSC characteristic, compared with the battery using Comparative Example 2 not showing concentration gradient, and in particular, the life time characteristic and the DSC characteristic were improved as the thickness of the surface maintain region was increased.
(71) TABLE-US-00003 TABLE 3 Life Time Capacity Characteristic DSC (mAhg.sup.1) (%, 100.sup.th) ( C.) Example 3-1 197.1 94.5 270.3 Example 3-2 196.0 95.2 273.5 Example 3-3 194.8 96.1 278.1 Comparative 185.8 91.8 261.2 Example 2
<Example 4> Manufacture of Precursor and Active Material Having Constant Ni Concentration in Entire Particle and Showing Concentration Gradients of Co and Mn in Entire Particle
(72) In order to make the Ni concentration in the entire particle constant as 0.8 and concentration gradients of Co and Mn, first of all, nickel sulfate, cobalt sulfate and manganese sulfate were mixed at the molar ratio of 80:20:00, and then the procedure of Example 1 was repeated except for continuing the reaction by using the metal aqueous solution whose concentration was changing until the concentration became 80:01:19 to obtain a positive electrode active material powder of Example 4-1, wherein the first interior had concentration of Li[Ni.sub.0.80Co.sub.0.20]O.sub.2 and the second interior had constant continuous concentration gradient from Li[Ni.sub.0.80Co.sub.0.20]O.sub.2 to Li[Ni.sub.0.80Co.sub.0.01Mn.sub.0.19]O.sub.2.
(73) The procedure of Example 4 was repeated except for continuing the reaction as maintaining the said molar ratio when the molar ratio of the metal aqueous solution reached 80:01:19 during the composite particle forming process for further comprising a surface maintain regions having thickness of 0.2 m and 0.5 m, respectively, so as to obtain spherical nickel-manganese-cobalt composite hydroxides of Examples 4-2 and 4-3 containing the second interior having concentration gradient and a surface maintain region.
<Test Example> TEM Imaging
(74) TEM images of the cross-sections of the nickel-manganese-cobalt composite hydroxide precursor and the positive electrode active material of Example 4-3 were taken, and the results were shown in
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Comparative Example 3
(76) Particles having constant metal ion concentration expressed by Li(Ni.sub.0.65Co.sub.0.10Mn.sub.0.25)O.sub.2 in the entire particle were manufactured.
<Example 5> Manufacture of Precursor and Active Material Having Constant Ni Concentration in Entire Particle and Showing Concentration Gradients of Co and Mn in Entire Particle
(77) In order to make the Ni concentration in the entire particle constant as 0.75 and concentration gradients of Co and Mn as Example 5-1, first of all, nickel sulfate, cobalt sulfate and manganese sulfate were mixed at the molar ratio of 75:25:00, and then the procedure of Example 1 was repeated except for continuing the reaction by using the metal aqueous solution whose concentration was changing until the concentration became 75:02:23 to obtain a positive electrode active material powder, wherein the first interior had concentration of Li[Ni.sub.0.75Co.sub.0.25]O.sub.2 and the second interior had constant continuous concentration gradient from Li[Ni.sub.0.75Co.sub.0.25]O.sub.2 to Li[Ni.sub.0.75Co.sub.0.02Mn.sub.0.23]O.sub.2.
(78) The procedure of Example 4 was repeated except for continuing the reaction as maintaining the said molar ratio when the molar ratio of the metal aqueous solution reached 75:02:23 during the composite particle forming process for further comprising a surface maintain regions having thickness of 0.2 m and 0.5 m, respectively, so as to obtain spherical nickel-manganese-cobalt composite hydroxides of Examples 5-2 and 5-3 containing the second interior having concentration gradient and a surface maintain region.
<Example 6> Manufacture of Precursor and Active Material Having Constant Ni Concentration in Entire Particle and Showing Concentration Gradients of Co and Mn in Entire Particle
(79) In order to make the Ni concentration in the entire particle constant as 0.70 and concentration gradients of Co and Mn as Example 6, first of all, nickel sulfate, cobalt sulfate and manganese sulfate were mixed at the molar ratio of 70:30:00, and then the procedure of Example 1 was repeated except for continuing the reaction by using the metal aqueous solution whose concentration was changing until the concentration became 70:02:28 to obtain a positive electrode active material powder, wherein the first interior had concentration of Li[Ni.sub.0.70Co.sub.0.30]O.sub.2 and the second interior had constant continuous concentration gradient up to Li[Ni.sub.0.70Co.sub.0.02Mn.sub.0.28]O.sub.2.
(80) The procedure of Example 4 was repeated except for continuing the reaction as maintaining the said molar ratio when the molar ratio of the metal aqueous solution reached 70:02:28 during the composite particle forming process for further comprising a surface maintain regions having thickness of 0.2 m and 0.5 m, respectively, so as to obtain spherical nickel-manganese-cobalt composite hydroxides of Examples 6-2 and 6-3 containing the second interior having concentration gradient and a surface maintain region.
<Example 7> Manufacture of Precursor and Active Material Having Constant Ni Concentration in Entire Particle and Showing Concentration Gradients of Co and Mn in Entire Particle
(81) In order to make the Ni concentration in the entire particle constant as 0.65 and concentration gradients of Co and Mn as Example 7, first of all, nickel sulfate, cobalt sulfate and manganese sulfate were mixed at the molar ratio of 65:35:00, and then the procedure of Example 1 was repeated except for continuing the reaction by using the metal aqueous solution whose concentration was changing until the concentration became 65:02:33 to obtain a positive electrode active material powder, wherein the first interior had concentration of Li[Ni.sub.0.65Co.sub.0.35]O.sub.2 and the second interior had constant continuous concentration gradient up to Li[Ni.sub.0.65Co.sub.0.02Mn.sub.0.33]O.sub.2.
(82) The procedure of Example 4 was repeated except for continuing the reaction as maintaining the said molar ratio when the molar ratio of the metal aqueous solution reached 65:02:33 during the composite particle forming process for further comprising a surface maintain regions having thickness of 0.2 m and 0.5 m, respectively, so as to obtain spherical nickel-manganese-cobalt composite hydroxides of Examples 7-2 and 7-3 containing the second interior having concentration gradient and a surface maintain region.
Comparative Example 4
(83) Particles having constant metal ion concentration expressed by Li(Ni.sub.0.62Co.sub.0.15Mn.sub.0.23)O.sub.2 in the entire particle were manufactured.
<Test Example> Measuring Battery Characteristic
(84) Batteries were manufactured by using the active material particle powders, which were manufactured in Examples 4 to 7 and had constant Ni concentration and concentration gradients of Co and Mn in the entire particle, and then capacity, life time characteristic and DSC characteristic were measured. The results were shown in the following Table 4.
(85) As shown in the following Table 4, it was confirmed that the batteries using Examples 4 to 7 having concentration gradient showed improved capacity, life time characteristic and DSC characteristic, compared with the battery using Comparative Example 4 not showing concentration gradient, and in particular, the life time characteristic and the DSC characteristic were improved as the thickness of the surface maintain region was increased.
(86) TABLE-US-00004 TABLE 4 Life Time Capacity Characteristic DSC (mAhg.sup.1) (%, 100.sup.th) ( C.) Example 4 211.3 86.1 244.7 Example 4-2 210.8 86.8 245.5 Example 4-3 209.7 87.2 247.1 Example 5 205.6 91.0 256.5 Example 5-2 204.7 91.7 258.8 Example 5-3 203.9 92.5 260.1 Example 6 200.8 92.9 266.9 Example 6-2 199.8 93.5 268.2 Example 6-3 198.5 94.2 270.0 Example 7 195.7 94.3 275.1 Example 7-2 195.2 94.9 275.9 Example 7-3 194.5 95.7 277.2 Comparative 200.9 53.2 229.9 Example 4
<Example 8> Manufacture of Precursor and Active Material Having Constant Ni Concentration in Entire Particle and Showing Concentration Gradients of Co and Mn in Entire Particle
(87) In order to make the Ni concentration in the entire particle constant as 0.9 and concentration gradients of Co and Mn as Example 8, first of all, nickel sulfate, cobalt sulfate and manganese sulfate were mixed at the molar ratio of 90:10:00, and then the procedure of Example 1 was repeated except for continuing the reaction by using the metal aqueous solution whose concentration was changing until the concentration became 90:01:09 to obtain a positive electrode active material powder, wherein the first interior had concentration of Li[Ni.sub.0.90Co.sub.0.10]O.sub.2 and the second interior had constant continuous concentration gradient up to Li[Ni.sub.0.90Co.sub.0.01Mn.sub.0.09]O.sub.2.
<Example 9> Manufacture of Precursor and Active Material Having Constant Ni Concentration in Entire Particle and Showing Concentration Gradients of Co and Mn in Entire Particle
(88) In order to make the Ni concentration in the entire particle constant as 0.6 and concentration gradients of Co and Mn as Example 9, first of all, nickel sulfate, cobalt sulfate and manganese sulfate were mixed at the molar ratio of 60:40:00, and then the procedure of Example 1 was repeated except for continuing the reaction by using the metal aqueous solution whose concentration was changing until the concentration became 60:02:38 to obtain a positive electrode active material powder of Example 9-1, wherein the first interior had concentration of Li[Ni.sub.0.60Co.sub.0.40]O.sub.2 and the second interior had constant continuous concentration gradient up to Li[Ni.sub.0.60Co.sub.0.02Mn.sub.0.38]O.sub.2.
(89) Further, first of all, nickel sulfate, cobalt sulfate and manganese sulfate were mixed at the molar ratio of 60:20:20, and then the procedure of Example 1 was repeated except for continuing the reaction by using the metal aqueous solution whose concentration was changing until the concentration became 60:02:38 to obtain a positive electrode active material powder of Example 9-2, wherein the first interior had concentration of Li[Ni.sub.0.60Co.sub.0.20Mn.sub.0.20]O.sub.2 and the second interior had constant continuous concentration gradient up to Li[Ni.sub.0.60Co.sub.0.02Mn.sub.0.38]O.sub.2.
<Example 10> Manufacture of Precursor and Active Material Having Constant Ni Concentration in Entire Particle and Showing Concentration Gradients of Co and Mn in Entire Particle
(90) In order to make the Ni concentration in the entire particle constant as 0.5 and concentration gradients of Co and Mn as Example 10, first of all, nickel sulfate, cobalt sulfate and manganese sulfate were mixed at the molar ratio of 50:50:00, and then the procedure of Example 1 was repeated except for continuing the reaction by using the metal aqueous solution whose concentration was changing until the concentration became 50:20:30 to obtain a positive electrode active material powder of Example 10-1, wherein the first interior had concentration of Li[Ni.sub.0.50Co.sub.0.50]O.sub.2 and the second interior had constant continuous concentration gradient up to Li[Ni.sub.0.50Co.sub.0.2Mn.sub.0.3]O.sub.2.
(91) Further, first of all, nickel sulfate, cobalt sulfate and manganese sulfate were mixed at the molar ratio of 50:30:20, and then the procedure of Example 1 was repeated except for continuing the reaction by using the metal aqueous solution whose concentration was changing until the concentration became 50:20:30 to obtain a positive electrode active material powder of Example 10-2, wherein the first interior had concentration of Li[Ni.sub.0.50Co.sub.0.30Mn.sub.0.20]O.sub.2 and the second interior had constant continuous concentration gradient up to Li[Ni.sub.0.50Co.sub.0.20Mn.sub.0.30]O.sub.2.
(92) Further, first of all, nickel sulfate, cobalt sulfate and manganese sulfate were mixed at the molar ratio of 50:20:30, and then the procedure of Example 1 was repeated except for continuing the reaction by using the metal aqueous solution whose concentration was changing until the concentration became 50:05:45 to obtain a positive electrode active material powder of Example 10-3, wherein the first interior had concentration of Li[Ni.sub.0.50Co.sub.0.20Mn.sub.0.30]O.sub.2 and the second interior had constant continuous concentration gradient up to Li[Ni.sub.0.50Co.sub.0.05Mn.sub.0.45]O.sub.2.
<Test Example> Measuring Battery Characteristic
(93) Batteries were manufactured by using the active material particle powders, which were manufactured in Examples 8 to 10 and had constant Ni concentration and concentration gradients of Co and Mn in the entire particle, and then capacity, life time characteristic and DSC characteristic were measured. The results were shown in the following Table 5.
(94) As shown in the following Table 5, it was confirmed that the batteries using the active material particle powders manufactured in Examples 8 to 10 having concentration gradient showed improved life time characteristic and DSC characteristic.
(95) TABLE-US-00005 TABLE 5 Life Time Capacity Characteristic DSC Tap (mAhg.sup.1) (%, 100.sup.th) ( C.) density Example 8 215.4 87.6 241.2 2.39 Example 9 189.8 93.6 279.2 2.48 Example 9-2 188.2 94.8 282.2 2.53 Example 10 184.2 95.1 291.2 2.49 Example 10-2 182.7 95.9 295.1 2.51 Example 10-3 178.5 93.2 302.5 2.58
<Example 11> Case of Showing Concentration Gradients of Co, Ni and Mn in Entire Particle
(96) In order to make the concentration gradients of Co, Ni and Mn, first of all, nickel sulfate, cobalt sulfate and manganese sulfate were mixed at the molar ratio of 80:05:15, and then the procedure of Example 1 was repeated except for using the metal aqueous solution whose concentration was changing until the molar ratio became as shown in the following Table to obtain positive electrode active material powders having constant continuous concentration gradients of Co, Ni and Mn.
(97) TABLE-US-00006 TABLE 6 Ni:Co:Mn Example 11-1 55:15:30 Example 11-2 55:20:25 Example 11-3 60:15:25 Example 11-4 60:10:30
(98) Samples of the nickel-manganese-cobalt composite hydroxide and the positive electrode active material manufactured in Example 11-4 were manufactured, and then TEM images were taken. The result was shown in
Comparative Example 5
(99) Particles having constant metal ion concentration expressed by Li(Ni.sub.0.62Co.sub.0.13Mn.sub.0.25)O.sub.2 in the entire particle were manufactured.
<Test Example> Measuring Battery Characteristic
(100) Batteries were manufactured by using the active material particle powders manufactured in Examples 11 to 11-4, and then capacity, life time characteristic and DSC characteristic were measured. The results were shown in the following Table 7.
(101) As shown in the following Table 7, it was confirmed that the batteries using Examples 11 to 11-4 having concentration gradient showed improved capacity, life time characteristic and DSC characteristic, compared with the battery using Comparative Example 5 not showing concentration gradient, and in particular, the life time characteristic and the DSC characteristic were improved as the thickness of the surface maintain region was increased.
(102) TABLE-US-00007 TABLE 7 Life Time Capacity Characteristic DSC (mAhg.sup.1) (%, 100.sup.th) ( C.) Example 11 191.2 94.7 275.9 Example 11-2 192.8 94.2 270.7 Example 11-3 195.8 93.3 269.9 Example 11-4 196.2 94.4 272.5 Comparative 183.6 92.8 264.1 Example 5
<Example 12> Case of Showing Concentration Gradients of Co, Ni and Mn in Entire Particle
(103) In order to make the concentration gradients of Co, Ni and Mn, first of all, nickel sulfate, cobalt sulfate and manganese sulfate were mixed as shown in the following Table 8, and then the procedure of Example 1 was repeated except for using the metal aqueous solution whose concentration was changing until the concentration became 55:15:30 to obtain nickel-manganese-cobalt composite hydroxides and positive electrode active material particles having constant continuous concentration gradients of Co, Ni and Mn.
(104) TABLE-US-00008 TABLE 8 Ni:Co:Mn Example 12-1 80:00:20 Example 12-2 80:10:10 Example 12-3 80:15:05 Example 12-4 80:20:00
(105) Samples of the nickel-manganese-cobalt composite hydroxide and the positive electrode active material manufactured in Example 12-1 were manufactured, and then TEM images were taken. The result was shown in
Comparative Example 6
(106) Particles having constant metal ion concentration expressed by Li(Ni.sub.0.62Co.sub.0.15Mn.sub.0.23)O.sub.2 in the entire particle were manufactured.
<Test Example> Measuring Battery Characteristic
(107) Batteries were manufactured by using the active material particle powders manufactured in Examples 12 to 12-4, and then capacity, life time characteristic and DSC characteristic were measured. The results were shown in the following Table 9.
(108) As shown in the following Table 9, it was confirmed that the batteries using Examples 12-1 to 12-4 having concentration gradient showed improved capacity, life time characteristic and DSC characteristic, compared with the battery using Comparative Example 6 not showing concentration gradient, and in particular, the life time characteristic and the DSC characteristic were improved as the thickness of the surface maintain region was increased.
(109) TABLE-US-00009 TABLE 9 Life Time Capacity Characteristic DSC (mAhg.sup.1) (%, 100.sup.th) ( C.) Example 12-1 190.8 95.1 277.9 Example 12-2 191.4 95.0 274.7 Example 12-3 191.5 94.7 272.9 Example 12-4 191.9 94.5 271.8 Comparative 184.1 92.0 260.8 Example 6
<Example 12> Case of Showing Concentration Gradients of Co, Ni and Mn in Entire Particle
(110) In order to make the outside composition constant as 63:12:25 but concentration gradients of Co, Ni and Mn in the entire particle, first of all, nickel sulfate, cobalt sulfate and manganese sulfate were mixed at the molar ratio shown in the following Table 10, and then the procedure of Example 1 was repeated except for using the metal aqueous solution whose concentration was changing until the concentration became 63:12:25 to obtain positive electrode active material particles, so as to obtain positive electrode active material powder, wherein the concentrations of Co, Ni and Mn showed gradient in the entire particle.
(111) TABLE-US-00010 TABLE 10 Ni:CO:Mn Example 13-1 75:00:25 Example 13-2 80:00:20 Example 13-3 85:00:15 Example 13-4 75:10:15 Example 13-5 80:10:10 Example 13-6 85:10:05
(112) A sample of the nickel-manganese-cobalt composite hydroxide manufactured in Example 13-6 was manufactured, and then a TEM image was taken. The result was shown in
Comparative Example 7
(113) Particles having constant metal ion concentration expressed by Li(Ni.sub.0.68Co.sub.0.12Mn.sub.0.20)O.sub.2 in the entire particle were manufactured.
<Test Example> Measuring Battery Characteristic
(114) Batteries were manufactured by using the active material particle powders manufactured in Examples 13-1 to 13-6, and then capacity, life time characteristic and DSC characteristic were measured. The results were shown in the following Table 11.
(115) As shown in the following Table 11, it was confirmed that the batteries using Examples 13-1 to 13-6 having concentration gradient showed improved capacity, life time characteristic and DSC characteristic, compared with the battery using Comparative Example 7 not showing concentration gradient, and in particular, the life time characteristic and the DSC characteristic were improved as the thickness of the surface maintain region was increased.
(116) TABLE-US-00011 TABLE 11 Life Time Capacity Characteristic DSC (mAhg.sup.1) (%, 100.sup.th) ( C.) Example 13-1 196.9 94.6 271.2 Example 13-2 197.5 94.0 269.9 Example 13-3 198.2 93.2 267.4 Example 13-4 197.1 94.2 270.0 Example 13-5 198.1 93.7 268.9 Example 13-6 198.9 92.8 266.9 Comparative 188.3 90.2 257.5 Example 7
Example 14
(117) In order to manufacture a positive electrode active material precursor and a positive electrode active material continuously comprising the first interior, wherein the Co composition was constant, and the Ni and Mn compositions showed concentration gradient, and the second interior, wherein the Mn composition was constant, and the Co and Ni compositions showed concentration gradient, the procedure of Example 1 was repeated except for using a metal aqueous solution whose concentration was changing until the concentration became 55:20:25 while mixing a mixture of nickel sulfate, cobalt sulfate and manganese sulfate at the composition of 65:10:25 to a mixture of nickel sulfate, cobalt sulfate and manganese sulfate at the composition of 75:10:15 to manufacture a positive electrode active material particle, so as to obtain a positive electrode active material precursor positive electrode active material of Example 14-1, wherein in the first interior, the Co composition was constant, and the Ni and Mn compositions showed concentration gradient, and in the second interior, wherein the Mn composition was constant, and the Co and Ni compositions showed concentration gradient.
(118) The procedure of Example 4 was repeated except for continuing the reaction as maintaining the said molar ratio when the molar ratio of the metal aqueous solution reached 55:20:25 during the particle forming process for further comprising surface maintain regions having thickness of 0.2 m and 0.5 m, respectively, so as to obtain spherical nickel-manganese-cobalt composite hydroxides of Examples 14-2 and 14-3 containing the second interior having concentration gradient and a surface maintain region.
<Test Example> Measuring Battery Characteristic
(119) Batteries were manufactured by using the active material particle powders manufactured in Examples 14-1 to 14-3, and then capacity, life time characteristic and DSC characteristic were measured. The results were shown in the following Table 12.
(120) As shown in the following Table 12, it was confirmed that the batteries using Examples 14-1 to 14-3 having concentration gradient showed improved capacity, life time characteristic and DSC characteristic, compared with the battery using Comparative Example 7 not showing concentration gradient, and in particular, the life time characteristic and the DSC characteristic were improved as the thickness of the surface maintain region was increased.
(121) TABLE-US-00012 TABLE 12 Life Time Capacity Characteristic DSC (mAhg.sup.1) (%, 100.sup.th) ( C.) Example 14-1 193.1 94.2 275.7 Example 14-2 191.0 95.0 278.8 Example 14-3 189.5 95.9 285.9 Comparative 181.3 93.9 266.3 Example 7
<Example 15> Manufacturing Core-Gradient Shell Precursor and Active Material
(122) A positive electrode active material precursor and a positive electrode active material of Example 15-1, wherein the nickel:manganese:cobalt composition was constant as 90:05:05 in the first interior, and the composition of Co, Ni and Mn showed concentration gradient from 90:05:05 to 0.33:0.33:0.33 in the second interior, were manufactured.
(123) A positive electrode active material precursor and a positive electrode active material of Example 15-2, wherein the composition was constant as 90:05:05 in the first interior, and the composition of Co, Ni and Mn showed concentration gradient from 70:10:20 to 60:10:30 in the second interior, were manufactured.
<Test Example> TEM Imaging
(124) TEM images of the cross-sections of the nickel-manganese-cobalt composite hydroxide precursors and the positive electrode active material of Examples 15-1 and 15-2 were taken, and the results were shown in
(125)
<Example 16> Manufacturing Core-Shell Precursor and Active Material
(126) Positive electrode active material precursors and positive electrode active materials having a core-shell structure, wherein the composition of nickel:manganese:cobalt at the center part and the surface part were as shown in the following Table 13, were manufactured.
(127) TABLE-US-00013 TABLE 13 Core Shell Shell Composition Composition Thickness Example 16-1 90:05:05 50:20:30 0.2 m Example 16-2 80:10:10 50:20:30 0.2 m Example 16-3 70:10:20 50:20:30 0.2 m Example 16-4 70:10:20 40:20:40 0.2 m Example 16-5 60:20:20 50:20:30 0.2 m Example 16-6 70:10:20 50:20:30 0.5 m Example 16-7 70:10:20 50:20:30 1.0 m Example 16-8 70:10:20 50:20:30 1.5 m Example 16-9 70:10:20 50:20:30 2.0 m Example 16-10 70:10:20 50:20:30 2.5 m
(128) Batteries were manufactured by using the manufactured active material particle powders, and then capacity, life time characteristic and DSC characteristic were measured. The results were shown in the following Table 14.
(129) TABLE-US-00014 TABLE 14 Life Time Capacity Characteristic DSC Tap (mAhg.sup.1) (%, 100.sup.th) ( C.) Density Example 16-1 191.4 92.7 269.7 2.45 Example 16-2 186.7 94.1 273.2 2.44 Example 16-3 181.9 95.5 275.5 2.44 Example 16-4 182.8 94.9 272.5 2.46 Example 16-5 177.9 96.5 279.8 2.45 Example 16-6 185.7 93.9 271.8 2.43 Example 16-7 181.9 95.5 275.2 2.44 Example 16-8 179.4 96.0 279.8 2.44 Example 16-9 176.2 97.1 284.6 2.46 Example 16-10 172.1 97.5 288.4 2.45
<Test Example> Measuring X-Ray Photoelectron Spectroscopy
(130) In order to measure oxidation number of the active material particle manufactured in Example 1-1 to the direction of the particle radius, X-ray photoelectron spectroscopy was measured. The result was shown in
(131) As shown in
(132) In the positive electrode active material precursor for a lithium secondary battery of the present invention and a positive electrode active material manufactured by using thereof, the a-axis direction length to c-axis direction length ratio is changed primary particle from the center part to the surface part in the interior of the secondary particle, and the a-axis orientation of the primary particle is headed to the center part of the positive electrode active material as a secondary particle, and the particles are adjoining each other and grow to a fixed route. Accordingly, it has effects that insertion and secession of a lithium ion may become easier, and high capacity can be obtained by reduced electric resistance between particles.
(133)
(134) The negative electrode 120 may include a negative electrode active material. For example, the negative electrode active material may include at least one of a carbon such as graphite or hard carbon, a metal such as Li, Na, Mg, Al, Si, In, Ti, Pb, Ga, Ge, Sn, Bi, Sb or an alloy thereof, silicon, silicon oxide, and Ti based oxide such as Li4Ti5O12.
(135) The membrane 140 may include at least one microporous film of polyolefin based resin, fluorine based resin, polyester based resin, polyacrylonitrile resin or cellulose material, and the microporous film coated by inorganic material such as ceramic. For example, the polyolefin based resin may include polyethylene, polypropylene or etc., the fluorine based resin may include polyvinylidenefluoride, polytetrafluoroethylene or etc., the polyester based resin may include polyethylene terephthalate, polybutylene terephthalate or etc.
(136) The electrolyte 130 may be impregnated in the membrane 140, the positive electrode 110 and/or the negative electrode 120. The electrolyte 130 may be gel polymer type electrolyte or liquid electrolyte. For example, the electrolyte 130 may be formed of adding a co-solvent including at least one of dimethyl carbonate (DC), ethyl methyl carbonate (EMC) and etc. into a principle solvent including at least one of ethylene carbonate (EC) and propylene carbonate (PC), and dissolving a lithium salt therein. For example, the lithium salt may be at least one selected from lithium hexafluorophosphate (LiPF.sub.6), lithium perchlorate (LiClO.sub.4), lithium tetrafluoroborate (LiBF.sub.4), lithium hexafluoroacetate (LiAsF.sub.6), lithium bis-oxalatoborate (LiBOB), lithium trifluoromethanesulfonate (LiCF.sub.3SO.sub.3) and lithium tri(fluoromethanesulfonyl)imide (LiCF.sub.3SO.sub.3)
(137) The positive electrode 110 may include a positive electrode active material. The positive electrode active material may include a primary particle and a secondary particle wherein the primary particle includes a primary particle of the seed region, a primary particle of the intermediate region and a primary particle of the maintain region, and the secondary particle is formed by gathering at least one of the primary particle. The positive electrode active material will be described below with reference to exemplary embodiments
(138)
(139) The secondary particle E2 may include a center part 210 and a surface part 220. The center part 210 may include a core region of the secondary particle E2 and/or a portion of the secondary particle interior. The surface part 220 may be an exterior surface of the secondary particle E2.
(140) Although sphere shaped secondary particle E2 was illustrated in
(141) The secondary particle E2 may have a seed region 310, an intermediate region 320 and a maintain region 330 from the center part 210 toward the surface part 220. The seed region 310, the intermediate region 320 and the maintain region 330 are arranged in direction 320 of the surface part 220 from the center part 210. According to an embodiment, the seed region 310 may have length of at least 1 m in the direction 230 of the surface part 220 from the center part 310.
(142) At least one of the primary particles E1 may compose the secondary particle E2. According to an embodiment, the primary particle E1 may be rod shape extending toward the surface part 220 from the center part 210. That is to say, the primary particles E1 may be rod shape radiating in every direction from the center part 210.
(143) A flow channel for metal ions (for example, lithium ions) and electrolyte (the electrolyte described with reference to
(144) As shown in
(145) If the a-axis direction of the primary particle E1 may radiate from the center part 210 such that the primary particle has rod shape, the flow channel of the metal ion and the electrolyte may be provided on the surface of the primary particle in parallel with the a-axis. In other words, the flow channel may be provided in the direction to the surface part 220 from the center part 210. The flow channel of the metal ion and the electrolyte is provided between surfaces of the primary particle in parallel with the a-axis such that the secondary battery is enhanced in charging/discharging efficiency. If the a-axis direction length of the primary particle is increasing as going to the surface part 220 from the center part 210, the metal ion and the electrolyte can easily move to the center part 210 from the surface part 220 of the secondary particle E2 such that the positive electrode active material for the secondary battery with enhanced charging/discharging efficiency can be provided.
(146) The primary particle E1 may include a primary particle of the seed region 312, a primary particle of the intermediate region 322 and a primary particle of the maintain region 332. The primary particle of the seed region 312, the primary particle of the intermediate region 322 and the primary particle of the maintain region 332 may be independent crystals, respectively. Therefore, the primary particle of the seed region 312, the primary particle of the intermediate region 322 and the primary particle of the maintain region 332 may be discriminated in SEM images.
(147) The primary particle of the seed region 312, the primary particle of the intermediate region 322 and the primary particle of the maintain region 332 may be arranged in the seed region 310, the intermediate region 320 and the maintain region 330, respectively. In other words, the primary particle of the seed region 312 may be arranged near by the center part 210, the primary particle of the maintain region 332 may be arranged near by the surface part 220, and the primary particle of the intermediate region 322 may be arranged between the primary particle of the maintain region 332 and the primary particle of the seed region 312.
(148) According to an embodiment, a plurality of the primary particle of the seed region 312, the primary particle of the intermediate region 322 and the primary party of the maintain region 332 may be arranged in the seed region 310, the intermediate region 320 and the maintain region 330, respectively.
(149) The primary particle E1 including primary particle of the seed region 312, the primary particle of the intermediate region 322 and the primary particle of the maintain region 332 may be formed of a multiple metals including a first through a third metals. For example, the first metal may be nickel, the second metal may be manganese and the third metal may be cobalt.
(150) According to an embodiment, the primary particle of the seed region 312 may be rod shape as shown in
(151) The first metal may show concentration gradient in the primary particle of the seed region 312. The first metal may show continuous concentration gradient. Specifically, concentration slop of the first metal may be continuous.
(152) According to an embodiment, in the direction 230 from the center part 210 to the surface part 220, the concentration of the first metal in the primary particle of the seed region 312 may be declined, thereby an end 312a of the primary particle of the seed region 312 near by the center part 210 may be higher than the other end 312b of the primary particle of the seed region 312 near by the surface part 220 in the concentration of the first metal.
(153) At least one of the second metal and the third metal may show concentration gradient in the primary particle of the seed region 312. According to an embodiment, in the direction 230 from the center part 210 to the surface part 220, concentration of the second metal may be increased in the primary particle of the seed region 312 and the concentration of the first metal may be constant. In another embodiment, concentrations of the second and third metals may be increased in the direction 230 from the center part 210 to the surface part 230.
(154) The primary particle of the intermediate region 322 may have a gradient portion 332a where the first metal shows concentration gradient and a uniform portion 332b where the first metal shows constant concentration. The uniform portion 322b may extend from an end of the gradient portion 322a. The gradient portion 322a and the uniform portion 322b may be in one body. In other words, the gradient portion 322a and the uniform portion 322b may compose one crystal. Although the gradient portion 322a and the uniform portion 322b were discriminately shown in
(155) The gradient portion 322a may be adjacent to the primary particle of the seed region 321, and the uniform portion 322b may be adjacent to the primary particle of the maintain region 332. The gradient portion 322a may extend form the other end 321b of the primary particle of the seed region 312.
(156) Concentration of the first metal in the gradient portion 322a may be declined as approaching to the uniform portion 322b. In other words, the first metal in the gradient portion 322a may be declined from the center part 210 to the surface part 220. Therefore, the gradient portion 322a near by the uniform portion 322a may have higher than the gradient portion 322a away from the uniform portion 322a in concentration of the first metal.
(157) At least one of the second metal and the third metal may show concentration gradient in the gradient portion 322a. In an embodiment, according to the direction 230 from the center part 210 to the surface part 220, concentration of the second metal in the gradient portion 322a may be increased while the third metal in the gradient portion 322a shows constant concentration. In another embodiment, concentrations of the second metal and the third metal in the gradient portion 322a may be increased according to the direction 230 from the center part 210 to the surface part 220.
(158) According to an embodiment, concentrations of the second metal and the third metal in the uniform portion 322a may be constant according to the direction 230 from the center part 210 to the surface part 220. Alternatively, at least one of the second metal and the third metal in the uniform portion 322a may show gradient concentration according to the direction 230 from the center part 210 to the surface part 220.
(159) According to an embodiment, the uniform portion 322b may be longer than the gradient portion 322a. Alternatively, according to another embodiment, the uniform portion 322b may be shorter than the gradient portion 322a. According to still another embodiment, the uniform portion 322b and the gradient portion 322a may have substantially equal length. The length of the uniform portion 322b and the gradient portion 322a mean length from the center part 210 to the surface part 220.
(160) The primary particle of the maintain region 332 may show constant concentration of the first metal according to the direction 230 from the center part 210 to the surface part 220. Concentration of the first metal of the primary particle of the maintain region 332 may be lower than concentration of the first metal of the primary particle of the seed region 312.
(161) According to an embodiment, the concentration of the second metal and the third metal in the primary particle of the maintain region 332 may be constant according to the direction from the center part 210 to the surface part 220. Alternatively, according to another embodiment, at least one of the second metal and the third metal in the primary particle of the maintain region 332 may show concentration gradient according to the direction from the center part 332 to the surface part 220.
(162) According to an embodiment, the primary particle of the maintain region 332 may be longer than the primary particle of the seed region 312 in the direction from the center part 210 to the surface part 220. Alternatively, according to an embodiment, length of the primary particle of the maintain region 332 may be equal or shorter than length of the primary particle of the seed region 312 in the direction from the center part 210 to the surface part 220.
(163) According to an embodiment, the positive electrode active material may include the primary particle E1 and the secondary particle E3 formed by at least one of the primary particles E2, and the seed region where the primary particle of the seed region 312 with concentration gradient of the first metal may have length of at least 1 m. Therefore, the primary particle of the intermediate region 322 and/or the primary particle of the maintain region 332 formed after the primary particle of the seed region 312 may have rod shape extending toward the surface part 220 from the center part 210, thereby providing flow channel into the interior of the secondary particle E2 for metal ions (for example, lithium ions) and electrolyte.
(164) If the seed region 310 where the primary particle of the seed region 312 with concentration gradient of metal is arranged is shorter than 1 m in the direction from the center part 210 to the surface part 220, the primary particle of the intermediate region 322 and/or the primary particle of the maintain region 332 formed after the primary particle of the seed region 312 may not be formed of rod shape. Thus, metal ions and electrolyte flow channel cannot be provided to the interior of the secondary particle 322, thereby the secondary battery may be declined in charge/discharge efficiency and life time characteristic.
(165) As described above, however, according to an embodiment, the length of the seed region 310 may be at least 1 m in the direction from the center part 210 to the surface part 220. Thus, the primary particles E1 including the primary particle of the maintain region 332 may have rod shape extending to radiate direction from the center part 210, thereby providing a secondary battery of high efficiency, high reliability and long life time.
(166) According to an embodiment of the present invention, the primary particle of the seed region 312 of which concentration of the first metal (for example, nickel) is decreasing as going in the direction from the center part 210 to the surface part 220 may be formed followed by forming the rod shaped primary particle of the maintain region 332 of which concentration of the first metal (for example, nickel) is constant. Thus, the primary particle E1 including the primary particle of the seed region 312, the primary particle of the intermediate region 322 and the primary particle of the maintain region 332 may be formed as rod shape, spontaneously with providing a positive electrode active material with maximum concentration of the first metal in the secondary particle E2.
(167) If the concentration of the first metal in the primary particle E1 is gradually decreasing as going to the surface part 220 from the center part 210 for manufacturing the primary particle Elin the form of rod shape, the positive electrode active material including the primary particle E1 and the secondary particle E2 may be declined in characteristics caused by the first metal (for example, capacity and/or safety).
(168) As described above, however, according to an embodiment, a positive electrode active material may be provided with maximum concentration of the first metal while the primary particle E1 maintains the rod shape. Therefore, a secondary battery may be provided with maximum characteristics caused by the first metal (for example, capacity and/or safety).
(169) The above described embodiment of the present invention, it was described that the secondary particle E2 includes the intermediate region 320, the primary particle E1 includes the primary particle of the intermediate region which is arranged in the intermediate region 320, however, the intermediate region 320 and the primary particle of the intermediate region 322 may not be exist in the secondary particle E2 and the primary particle E1.
(170) The characteristics evaluation of the positive electrode active material and the secondary battery including the same according to embodiments of the present invention will be described below.
(171) Manufacturing of the Positive Electrode Active Material According to the Embodiment.
(172) Nickel manganese cobalt hydroxide was manufactured using nickel sulfate, manganese sulfate, cobalt sulfate according to the embodiment of the present invention. Lithium hydroxide was mixed in the nickel manganese cobalt hydroxide followed by heating and firing, thereby a positive electrode active material with a secondary particle including lithium nickel manganese cobalt was manufactured.
(173) In the concrete, a primary particle and a secondary particle was manufactured with including a primary particle of the seed region of which concentrations of nickel, cobalt and manganese are gradient by varying mol ratio of the metal aqueous solution (nickel sulfate, manganese sulfate, cobalt sulfate) and a primary particle of the maintain region of which concentrations of nickel, cobalt and manganese are constant by maintaining mol ratio of the metal aqueous solution.
(174) As shown in [Table 15], secondary particles were manufactured according to Example 1 through Example 9. The lengths of seed regions, where the primary particle of the seed region with decreasing nickel concentration was arranged, were 5.5 m, 5 m, 4.5 m, 4 m, 3 m, 2.5 m, 2 m, 1.5 m and 1 m in Example 1 through Example 9, respectively. The lengths of maintain regions, where the primary particle of the maintain region with constant nickel concentration is arranged were 0.5 m, 1 m, 1.5 m, 2 m, 3 m, 3.5 m, 4 m, 4.5 m and 5 m in Example 1 through Example 9, respectively.
(175) TABLE-US-00015 TABLE 15 length length of of seed maintain region region class (m) (m) Example 1 5.5 0.5 Example 2 5 1 Example 3 4.5 1.5 Example 4 4 2 Example 5 3 3 Example 6 2.5 3.5 Example 7 2 4 Example 8 1.5 4.5 Example 9 1 5
(176) Comparison of SEM Images
(177)
(178) Referring to
(179) As shown in
(180) Result of EPMA (Electron Probe Micro-Analysis)
(181)
(182) Referring to
(183) As shown in
(184) Evaluating Discharge Capacity Properties and Life Time Characteristics
(185)
(186) As shown in
(187) As shown in
(188) Evaluating Thermal Safety
(189)
(190) As shown in
(191) According to embodiments of the present invention, it can be confirmed that the efficient method for improving thermal safety of the secondary batteries is forming of the secondary battery using the positive electrode active material with rod shaped primary particle which includes the primary particle of the seed region having concentration gradient of nickel, cobalt and manganese and the primary particle of the maintain region having constant concentration of nickel, cobalt and manganese.
(192) The above-described secondary battery according to the embodiments of the present invention may be applicable to the variety of applications, for example electric vehicles described hereinafter.
(193)
(194) An electric vehicle 1000 according to an embodiment of the present invention may have at least one of a motor 1010, a transmission, an accelerator 1030, a battery pack 1040, a power controller 1050 and a charger 1060.
(195) The motor 1010 can transform electric energy of the battery pack 1040 into kinetic energy. The motor 1010 may provide the transformed kinetic energy with the accelerator 1020 through the transmission 1020. The motor 1010 may be composed of a single motor or a plurality of motors. For example, the motor 1010 may be composed of a front-wheel motor supplying kinetic energy to a front-wheel accelerator and a rear-wheel motor supplying kinetic energy to a rear-wheel accelerator if the motor 1010 is composed of a plurality of motors.
(196) The transmission 1020 may be located between the motor 1010 and the accelerator 1030, change the kinetic energy from the motor 1010 followed by supplying to the accelerator 1030 so as to be adequate for drive circumstance of drivers' demand.
(197) The battery pack 1040 may store electric energy from the charger 1060 and supply the stored electric energy to the motor 1010. The battery pack 1040 may supply electric energy to the motor 1010 directly, or supply electric energy to the motor 1010 through the power controller 1050.
(198) The battery pack 1040 may formed of at least one battery cell. The battery cell may include the lithium air secondary battery, however, it is not limit to the above and the battery cell may include various secondary batteries such as a lithium based secondary battery. The battery cell may be referred to a discrete battery, and the battery pack may be referred to a battery group which is composed of discrete batteries interconnected each other in order to possess required voltage and/or capacity.
(199) The power controller 1050 may control the battery pack 1040. Namely, the power controller 1050 may control at least one of voltage, current, waveform and etc. from the battery pack 1040 in accordance with demand of the motor 1010. Therefore, the power controller 1050 may include at least one of passive power device and an active power device.
(200) The charger 1060 may receive power from an external power supplier 10710 as shown in
(201) According to the embodiment of the present invention, the positive electrode active material includes a secondary particle composed of the primary particle and at least one of the primary particles. The secondary particle may include the seed region where the primary particle having concentration gradient of the first metal is disposed and the maintain region where the primary particle having constant concentration of the first metal is disposed. The seed region has length of 1 m. Therefore, the primary particle can be formed of rod shape extending toward surface part from the center part of the secondary particle while concentration of the first metal is maximized. Thereby, the secondary battery can be provided with high performance, high capacity and long life time.
(202) In the positive electrode active material precursor for a lithium secondary battery of the present invention and a positive electrode active material manufactured by using thereof, the a-axis direction length to c-axis direction length ratio is changed primary particle from the center part to the surface part in the interior of the secondary particle, and the a-axis orientation of the primary particle is headed to the center part of the positive electrode active material as a secondary particle, and the particles are adjoining each other and grow to a fixed route. Accordingly, it has effects that insertion and secession of a lithium ion may become easier, and high capacity can be obtained by reduced electric resistance between particles.
(203) While the invention has been described with respect to the above specific embodiments, it should be recognized that various modifications and changes may be made and also fall within the scope of the invention as defined by the claims that follow.