Positive Electrode Active Material for Lithium Ion Battery, Positive Electrode for Secondary Battery, and Lithium Ion Battery

Abstract

Provided is a positive electrode active material for a lithium ion battery positive electrode material made of lithium-containing nickel-manganese-cobalt composite oxide of a layered structure represented with LiaNixMnyCozO 2 (1.0<a<1.3, 0.8<x+y+z<1.1), wherein, in a region with a molar volume Vm that is estimated from a lattice constant calculated from a (018) plane and a (113) plane in a powder X-ray diffraction pattern using CuK alpha rays as a vertical axis and Co ratio z (molar %) in metal components as a horizontal axis, the relationship thereof is within a range of Vm=21.276-0.0117z as an upper limit and Vm=21.164-0.0122z as a lower limit, and a half value width of both the (018) plane and the (113) plane is 0.200° or less. As a result of studying and defining the relationship of the cobalt (Co) ratio and the lattice constant, which are considered to influence the crystal structure, obtained was a positive electrode active material having high crystallinity, high capacity and high security. By using this material, it is possible to obtain a positive electrode active material for a lithium ion battery that is able to further ensure the characteristics and safety of the lithium ion battery.

Claims

1 . A positive electrode active material for a lithium ion battery positive electrode material made of lithium-containing nickel-manganese-cobalt composite oxide of a layered structure represented with LiaNixMnyCozO 2 (1.0<a<1.3, 0.8<x+y+z<1.1), wherein, in a region with a molar volume Vm that is estimated from a lattice constant calculated from a (018) plane and a (113) plane in a powder X-ray diffraction pattern using CuK alpha rays as a vertical axis and Co ratio n (molar %) in metal components as a horizontal axis, the relationship thereof is within a range of Vm=21.276-0.0117n as an upper limit and Vm=21.164-0.0122n as a lower limit, and a half value width of both the (018) plane and the (113) plane is 0.200° (degrees) or less. 2 . The positive electrode active material for a lithium ion battery positive electrode material according to claim 1 , wherein the average particle size of the oxide powder is 5 μm or more and 10 μm or less, the specific surface area is 1.0 m 2 /g or more and 1.6 m 2 /g or less, and the tap density is 1.5 or more and 2.0 or less. 3 . A positive electrode for a lithium ion secondary battery having the positive electrode active material according to claim 1 . 4 . A lithium ion secondary battery having the positive electrode according to claim 3 . 5 . A positive electrode active material for a lithium ion battery positive electrode material according to claim 1 , wherein the Co ratio is 20 molar % or more. 6 . A positive electrode active material for a lithium ion battery positive electrode material according to claim 5 , wherein an average particle size of the oxide powder is 5 μm or more and 10 μm or less, a specific surface area is 1.0 m 2 /g or more and 1.6 m 2 /g or less, and a tap density is 1.5 or more and 2.0 or less. 7 . A positive electrode for a lithium ion secondary battery having the positive electrode active material according to claim 6 . 8 . A lithium ion secondary battery having the positive electrode according to claim 7 .
TECHNICAL FIELD [0001] The present invention generally relates to a positive electrode active material for a lithium ion battery, and particularly relates to a positive electrode active material, a positive electrode for a secondary battery, and a lithium ion battery having high crystallinity and high safety while being able to ensure high capacity. BACKGROUND ART [0002] In recent years, there is a rapidly growing demand for a non-aqueous electrolyte lithium secondary battery as a high energy density battery. This lithium secondary battery is configured from three fundamental components; namely, a positive electrode, a negative electrode, and a separator retaining an electrolyte interposed between these electrodes. [0003] As the positive electrode and negative electrode, a slurry obtained by mixing and dispersing active materials, conductive materials, bonding materials and plasticizing agents (where appropriate) in a dispersion medium is used by being supported by a collector such as a metallic foil or a metallic mesh. [0004] Under the foregoing circumstances, as the positive electrode active material, composite oxide of lithium and transition metal; in particular, cobalt-based composite oxide, nickel-based composite oxide, and manganese-based composite oxide are typical examples. These lithium composite oxides are generally synthesized by mixing the compound of the constitution element (carbonate and oxide of Mn, Fe, Co, Ni and the like) and lithium compound (lithium carbonate and the like) at a predetermined ratio, and performing heat treatment (oxidation treatment) thereto (refer to Patent Document 1, Patent Document 2, and Patent Document 3). [0005] Under the foregoing circumstances, a ternary positive electrode material of Ni:Mn:Co=1:1:1 composition has been proposed (refer to Patent Document 4). In the case of Patent Document 4, the Li/metal ratio is 0.97 to 1.03, and it describes that it is possible to obtain a discharge capacity of 200 mAh/g. Nevertheless, in the foregoing case, since the charge cutoff voltage is a high voltage of 4.7 V, if the voltage is cut at 4.3 V, the initial discharge capacity will be roughly 150 mAh/g. [0006] Generally speaking, the initial performance, cycle life or internal resistance of a battery will differ considerably depending on the crystal structure of the material. Even if the material is of a layered structure, there is a problem in that the battery performance will deteriorate if a spinel structure or the like coexists locally. [0007] Thus, the identification of the crystal structure is important, but the identification of the crystal structure was conventionally based on XRD (X-ray diffraction). Nevertheless, it was difficult to determine the coexistence of phases due to reasons such as the peak positions being close. [0008] In light of the above, a proposal has been made for defining the positive electrode active material based on Raman spectrometry (refer to Patent Document 5). Patent Document 5 defines the peak intensity ratio of the spinel structure and the hexagonal structure in the Raman spectrum analysis based on the chemical formula of LiCoMA 2 (0.95≦Li≦1.0, wherein A contains O, F, S, P). However, since the main peak is the peak of the spinel structure and not a layered structure, it cannot be said that sufficient performance have been obtained. [0009] As described above, a lithium secondary battery material yields superior performance compared to conventional technology, but further improvement is demanded in terms of sinterability and battery performance. [0010] Layered lithium nickel-manganese-cobalt composite oxide as a positive electrode active material for a lithium ion battery has high expectations, since it has high capacity and high safety compared to lithium cobalt oxide and lithium manganese oxide. Nevertheless, there is limited literature regarding its composition and crystallinity, and with respect to the lattice constant in particular, descriptions are provided only in terms of its approximate width. [0011] There are the following Patent Documents (refer to Patent Documents 6 to 9) that define the lattice constant in a positive electrode active material for a lithium ion battery having a composition of LiaNixMnyCozO 2 . [0012] For example, Patent Document 6 describes a lithium-nickel-manganese cobalt-based composite oxide for a lithium secondary battery positive electrode material in which the lattice constant is within the range of 2.855 Å≦a≦2.870 Å, 14.235 Å≦c≦14.265 Å. Patent Document 7 describes a layered lithium nickel-based composite oxide in which the bulk density is 2.0 g/cc or more, the median size of secondary particles is 9 to 20 um, and the BET specific surface area is 0.5 to 1 m 2 /g. Patent Document 8 describes a lithium-containing transition metal composite oxide in which the lattice constant of the a axis is 2.895 to 2.925 Å, and the lattice constant of the c axis is 14.28 to 14.38 Å. Patent Document 9 describes a lithium-containing transition metal composite oxide in which the lattice constant of the a axis is 2.830 to 2.890 Å, and the lattice constant of the c axis is 14.150 to 14.290 Å. [0013] Nevertheless, although the lattice constant of the a axis and the lattice constant of the c axis are defined, there is no in-depth description regarding the composition and molar volume. Thus, there is a problem in that the foregoing Patent Documents are insufficient in terms of ensuring the performance and safety of the lithium ion battery. [0014] Patent Document 1: Japanese Published Unexamined Patent Application No. H1-294364 [0015] Patent Document 2: Japanese Published Unexamined Patent Application No. H11-307094 [0016] Patent Document 3: Japanese Published Unexamined Patent Application No. 2005-285572 [0017] Patent Document 4: Japanese Published Unexamined Patent Application No. 2003-59490 [0018] Patent Document 5: Japanese Published Unexamined Patent Application No. 2005-44785 [0019] Patent Document 6: Japanese Published Unexamined Patent Application No. 2006-253119 [0020] Patent Document 7: Japanese Patent No.4003759 [0021] Patent Document 8: Japanese Published Unexamined Patent Application No. 2002-145623 [0022] Patent Document 9: Japanese Published Unexamined Patent Application No. 2003-068298 DISCLOSURE OF THE INVENTION [0023] As described above, the layered lithium nickel-manganese-cobalt composite oxide as the positive electrode active material for a lithium ion battery is a material that has high expectations since it has high capacity and high safety compared to lithium cobalt oxide and lithium manganese oxide, but its composition and crystallinity have not been sufficiently clarified. In light of this point, an object of the present invention is to study and define the relationship of the cobalt (Co) ratio and the lattice constant, which are considered to primarily influence the crystal structure in the foregoing composition, and thereby obtain a positive electrode active material having high crystallinity, high capacity and high safety. Another object of this invention is to obtain, by using the foregoing material, a positive electrode active material for a lithium ion battery that is able to further ensure the performance and safety of the lithium ion battery. [0024] In order to achieve the foregoing object, the present invention provides the following: [0025] 1) A positive electrode active material for a lithium ion battery positive electrode material made of lithium-containing nickel-manganese-cobalt composite oxide of a layered structure represented with LiaNixMnyCozO 2 (1.0<a<1.3, 0.8<x+y+z<1.1), wherein, in a region with a molar volume Vm that is estimated from a lattice constant calculated from a (018) plane and a (113) plane in a powder X-ray diffraction pattern using CuK alpha rays as a vertical axis and Co ratio z (molar %) in metal components as a horizontal axis, the relationship thereof is within a range of Vm=21.276-0.0117z as an upper limit and Vm=21.164-0.0122z as a lower limit, and a half value width of both the (018) plane and the (113) plane is 0.200° (degrees) or less. [0026] 2) The positive electrode active material for a lithium ion battery positive electrode material according to 1) above, wherein the average particle size of the oxide powder is 5 μm or more and 10 μm or less, the specific surface area is 1.0 m 2 /g or more and 1.6 m 2 /g or less, and the tap density is 1.5 or more and 2.0 or less. [0027] 3) A positive electrode for a lithium ion secondary battery using the positive electrode active material according to 1) or 2) above. [0028] 4) A lithium ion secondary battery using the positive electrode according to 3) above. [0029] As a result of defining the relationship of the cobalt (Co) ratio and the lattice constant, which are considered to primarily influence the crystal structure in the foregoing composition, the present invention is able to obtain a positive electrode active material having high crystallinity, high capacity and high safety. By using this material, the present invention yields a superior effect of being able to obtain a positive electrode active material for a lithium ion battery that is able to further ensure the characteristics and safety of the lithium ion battery. BEST MODE FOR CARRYING OUT THE INVENTION [0030] A lithium-containing transition metal oxide is generally used as a positive electrode active material of a lithium ion battery. Specifically, lithium cobalt oxide (LiNiO 2 ), lithium nickel oxide (LiNiO 2 ), lithium manganese oxide (LiMn 2 O 4 ) or the like is used, and these are compounded in order to improve the performance (high capacity, cycle life, storage performance, reduction of internal resistance, discharge properties) and increase the safety. [0031] As the positive electrode active material of a lithium ion battery according to the present invention, a ternary positive electrode material having a layered structure; namely LiaNixMnyCozO 2 (1.0<a<1.3, 0.8<x+y+z<1.0) is used. [0032] As a result of studying in detail the X-ray diffraction pattern using CuK alpha rays with respect to the foregoing material having a layered structure, the present inventors discovered that, when a material having high capacity and high safety is obtained, there is a certain correlation in the molar volume that is estimated from the lattice constant calculated from the (018) plane and the (113) plane, and the Co ratio of the ternary positive electrode material, and that the average particle size, the specific surface area, and the tap density should be within a predetermined range. [0033] Specifically, the crystal structure is a structure that belongs to a layered R3 m. Moreover, the a value representing the ratio of Li in relation to all metals desirably exceeds 1.0 and is less than 1.3. This is because if the ratio is 1.0 or less it is difficult to retain a stable crystal structure, and if it is not less than 1.3 it is impossible to ensure high capacity. [0034] Moreover, the (x+y+z) value representing the molar ratio of all metals shall be a range that exceeds 0.8 and less than 1.1. If the value is 0.8 or less, the amount of oxygen is great and it will be difficult to ensure capacity, and if the value is 1.1 or more, oxygen defect occurs and it will be difficult to ensure safety. [0035] The molar volume (Vm) in this crystal structure can be calculated by employing the following formula based on the X-ray diffraction pattern that is obtained by using CuK alpha rays. Here, a represents the lattice constant of the a axis and c represents the lattice constant of the c axis. [0000] Vm= 0.17906×a×a×c [0036] Moreover, the lattice constant (a, c) can also be obtained from a relational expression of hexagonal spacing and the lattice constant. A more detailed lattice constant will require the use of data on the high-angle side, but here, data of the (018) plane and the (113) plane is used. Note that the (018) plane is positioned at 2θ=64.0 to 64.4° and the (113) plane is positioned at 2θ=67.8 to 68.2°. [0037] The Co ratio z in the metal components can be represented with the following mathematical formula by using x, y, z of the foregoing chemical formula. [0000] z=z× 100/( x+y+z ) [0038] When Vm and z are plotted, the correlation of Vm and z can be found if it is a material capable of ensuring high capacity and high safety, and it was discovered that it will be within a range that is defined according to the following formula in a region when taking Vm as the vertical axis and z as the horizontal axis. [0039] Vm=21.276-0.0117z (upper limit) [0040] Vm=21.164-0.0122z (lower limit) [0041] It is difficult to ensure the capacity in a region that exceeds the upper limit, and it is difficult to ensure the safety in a region that falls below the lower limit. Accordingly, the foregoing range takes on major significance. [0042] With respect to the crystallinity, the half value width of both the (018) plane and the (113) plane is desirably 0.200° or less, preferably, 0.180° or less. Outside the foregoing range, the crystallinity is inferior and it is difficult to ensure high capacity. [0043] Moreover, with the powder characteristics, preferably, the average particle size is 5 μm or more and 10 μm or less, the specific surface area is 1.0 m 2 /g or more and 1.8 m 2 /g or less, and the tap density is 1.5 or more and 2.0 or less. More preferably, the average particle size is 6 μm or more and 9 μm or less, the specific surface area is 1.1 m 2 /g or more and 1.6 m 2 /g or less, and the tap density is 1.6 or more and 2.0 or less. If this range is deviated, the coating properties will deteriorate, it is difficult to ensure high capacity, and safety may be affected. [0044] In addition, the foregoing positive electrode active material can be used to prepare a positive electrode for a lithium ion battery, and such positive electrode can be used to further produce a lithium ion battery. EXAMPLES [0045] The present invention is now explained with reference to the Examples and Comparative Examples. These Examples are merely illustrative, and the present invention shall in no way be limited thereby. In other words, various modifications and other embodiments based on the technical spirit claimed in the claims shall be included in the present invention as a matter of course. Examples 1 to 8 [0046] Carbonate as a precursor was prepared with the wet process using a chloride solution of Fe, Ni, Mn, Co and lithium carbonate. This was dried and subsequently subject to oxidation treatment to prepare the positive electrode material having the composition shown in Table 1. Table 1 shows Sample No. 1 to Sample No. 8 corresponding to Examples 1 to 8. [0047] The Li, Ni, Mn, Co content is measured with ICP, and the Co ratio was obtained as the Co content relative to the total content of the respective metals excluding Li. The lattice constant was obtained from the spacing of the (018) plane and the (113) plane in the powder X-ray diffraction pattern using CuK alpha rays, and by calculating the molar volume. Moreover, the half value width of the (018) plane and the (113) plane was also measured and these results are similarly shown in Table 1. [0048] The conditions shown in Sample No. 1 to Sample No. 8 of Table 1 satisfy the conditions claimed in claim 1 ; specifically, “within a range of Vm=21.276-0.0117z as an upper limit and Vm=21.164-0.0122z as a lower limit, and a half value width of both the (018) plane and the (113) plane is 0.200° or less.” For ease of understanding, the foregoing “within a range of Vm=21.276-0.0117z as an upper limit and Vm=21.164-0.0122z as a lower limit” is shown in FIG. 1 . The horizontal axis of FIG. 1 is the z: Co ratio (molar %) and the vertical axis is the Vm: molar volume (CC/mole). The range between the two lines; namely, the upper and lower lines in FIG. 1 shows the range of the conditions of the present invention, and eight circles (∘) corresponding to Example 1 to Example 8 are plotted. [0000] TABLE 1 Molar Half Value Half Value Sample Ni Mn Co a c Volume Width (018) Width (113) No. Molar % Molar % Molar % Å Å cc/mole Degrees (°) Degrees (°) 1 70 20 10 2.878 14.231 21.105 0.165 0.176 2 60 25 15 2.874 14.236 21.051 0.165 0.188 3 70 10 20 2.869 14.205 20.941 0.153 0.188 4 50 20 30 2.863 14.210 20.853 0.176 0.153 5 33 33 34 2.858 14.226 20.802 0.176 0.165 6 25 25 50 2.852 14.205 20.685 0.141 0.141 7 16.5 25 58.5 2.842 14.192 20.521 0.153 0.129 8 8 25 67 2.837 14.152 20.395 0.153 0.165 [0049] In addition, the average particle size was obtained as the 50% diameter in the particle size distribution based on the laser diffraction method, the specific surface area was obtained as the BET value, and the tap density was obtained as the density after tapping 200 times. The positive electrode material, the conductive material, and the binder were weighed at a ratio of 85:8:7. The binder was dissolved in an organic solvent (N-methylpyrrolidone), a material and a conductive material were mixed to form a slurry, and this was applied on an Al foil and dried and pressed to form a positive electrode. Note that well-known standard materials may be used as the conductive material and the binder, and are not specified herein. [0050] Subsequently, a 2032-type coin cell for evaluation having Li as the counter electrode was prepared, and, upon dissolving 1M-LiPF 6 in EC-DMC (1:1) as the electrolytic solution, this was used to perform charging and discharging at a charging condition of 4.3 V and a discharging condition of 3.0 V. The initial discharge capacity was confirmed by confirming the discharge capacity of the charge/discharge at 0.1 C. [0051] The results are summarized in Table 2. The safety shown in Table 2 was evaluated by charging a coin cell prepared as described above to 4.3 V, thereafter extracting the positive electrode material from the cell, performing analysis with a DSC (differential scanning calorimeter), and comparing the exothermic onset temperature. [0052] The results upon comparison with LiCoO 2 having a conventional layered structure are similarly shown in Table 1. The evaluation results shown in Table 1 are as follows: ∘ (safer), Δ (same as before), × (inferior). [0000] TABLE 2 Average Specific Tap Sample Ni Mn Co Grain Size Surface area Density Capacity No. Molar % Molar % Molar % μm m 2 /g g/cc mAh/g Safety 1 70 20 10 5.5 1.52 1.7 186 ∘ 2 60 25 15 5.5 1.47 1.6 180 ∘ 3 70 10 20 6.2 1.36 1.8 190 ∘ 4 50 20 30 6.8 1.36 1.7 170 ∘ 5 33 33 34 5.8 1.36 2.0 155 ∘ 6 25 25 50 6.3 1.47 1.6 156 ∘ 7 16.5 25 58.5 5.8 1.16 1.7 148 ∘ 8 8 25 67 7.5 1.12 1.6 148 ∘ [0053] As evident from the results of Table 2, Example 1 to Example 8 (Sample No. 1 to Sample No. 8) all showed a safety of o, and the safety had improved compared to conventional technology. In addition, the capacity in all Examples was 148 mAh/g or more, and in certain cases reached 190 mAh/g. Even in the foregoing case, the safety had improved compared to conventional technology. Accordingly, all materials shown in the Examples are superior as a positive electrode active material for a lithium ion battery positive electrode material. [0054] Note that the Samples shown in Table 2 were selected on the condition that the average particle size, the specific surface area, and the tap density all satisfied the conditions claimed in claim 2 , but if the deviation is approximately ±20% from the conditions of claim 2 , changes in the capacity and safety were not significant. Specifically, the discharge capacity exceeded 140 mAh/g, and the safety was (∘) which improved than before, or (Δ) which was the same as before. [0055] Accordingly, it is easy to understand that the primary requirement is to satisfy the condition of “within a range of Vm=21.276-0.0117z as an upper limit and Vm=21.164-0.0122z as a lower limit, and a half value width of both the (018) plane and the (113) plane is 0.200° or less” claimed in claim 1 . [0056] Nevertheless, needless to say, the conditions claimed in claim 2 , specifically, “the average particle size of the oxide powder is 5 μm or more and 10 μm or less, the specific surface area is 1.0 m 2 /g or more and 1.6 m 2 /g or less, and the tap density is 1.5 or more and 2.0 or less” are more favorable conditions. Comparative Examples 1 to 9 [0057] Oxides of Ni, Mn, Co and lithium carbonate were used and the respective raw materials were mixed and pulverized, thereafter subject to spray drying and oxidation treatment to obtain a positive electrode material. This positive electrode material was subject to the same treatment as the Examples and evaluated similarly. The molar volume, the half value width (018), and the half value width (113) are shown in Table 3. All conditions described in Table 3 are the same as the conditions described in Examples 1 to 8. [0058] Sample No. 9 to Sample No. 17 shown in Table 3 and Table 4 described later respectively correspond to Comparative Example 1 to Comparative Example 9. [0059] In addition, Table 4 shows the average particle size, the specific surface area, and the tap density of Sample No. 9 to Sample No. 17. The capacity and safety are also similarly shown. [0060] Note that Comparative Examples 1 to 9 (Sample No. 9 to Sample No. 17) exist outside of the “range of Vm=21.276-0.0117z as an upper limit and Vm=21.164-0.0122z as a lower limit” shown in FIG. 1 , and nine squares (□) corresponding to Comparative Example 1 to Comparative Example 9 are plotted. [0000] TABLE 3 Molar Half Value Half Value Sample Ni Mn Co a c Volume Width (018) Width(113) No. Molar % Molar % Molar % Å Å cc/mole Degrees (°) Degrees (°) 9 45 45 10 2.903 14.340 21.639 0.188 0.188 10 30 50 20 2.858 14.239 20.826 0.165 0.144 11 37.5 37.5 25 2.877 14.248 21.117 0.188 0.188 12 33 33 34 2.850 14.233 20.701 0.165 0.165 13 33 33 34 2.865 14.245 20.937 0.153 0.188 14 27 27 46 2.842 14.218 20.563 0.165 0.165 15 25 25 50 2.855 14.224 20.760 0.188 0.165 16 15 15 60 2.852 14.152 20.612 0.165 0.188 17 15 15 60 2.841 14.120 20.407 0.144 0.165 [0000] TABLE 4 Average Specific Tap Sample Ni Mn Co Grain Size Surface Area Density Capacity No. Molar % Molar % Molar % μm m 2 /g g/cc mAh/g Safety 9 45 45 10 11.8 0.94 2.0 140 Δ 10 30 50 20 12.5 0.88 2.2 130 Δ 11 37.5 37.5 25 12.2 0.85 1.8 150 x 12 33 33 34 12.8 0.92 2.1 145 x 13 33 33 34 12.8 0.92 2.1 135 Δ 14 27 27 46 12.5 0.88 2.1 142 x 15 25 25 50 12.6 0.90 2.0 135 Δ 16 15 15 60 12.8 0.88 2.2 130 Δ 17 15 15 60 12.9 0.85 2.2 135 x [0061] As evident from Table 3, Table 4 and FIG. 1 , certain Samples showed high discharge capacity at 150 mAh/g (Sample No. 11) and 145 mAh/g (Sample No. 12), but in these cases the safety was inferior. The other Samples were all 140 mAh/g or less, had low capacity, or had safety that was the same as before or inferior than conventional technology. [0062] Accordingly, the safety of Comparative Example 1 to Comparative Example 9 (Sample No. 9 to No. 17) was or x in all cases, and the safety was the same as before or inferior than conventional technology. In addition, the capacity was also the same as before or inferior than conventional technology. [0063] Based on the foregoing comparison of the Examples and the Comparative Examples, it is evident that the materials shown in the Examples are all superior as a positive electrode active material for a lithium ion battery positive electrode material. INDUSTRIAL APPLICABILITY [0064] Since the positive electrode active material for a lithium ion battery positive electrode material according to the present invention is in a region with a molar volume Vm that is estimated from a lattice constant calculated from a (018) plane and a (113) plane in a powder X-ray diffraction pattern using CuK alpha rays as a vertical axis and Co ratio z (molar %) in metal components as a horizontal axis, the relationship thereof is within a range of Vm=21.276-0.0117z as an upper limit and Vm=21.164-0.0122z as a lower limit, and a half value width of both the (018) plane and the (113) plane is 0.200° or less, it yields a superior effect of being able to obtain a positive electrode active material having high crystallinity, high capacity and high safety. Thus, the present invention is effective as a lithium secondary battery material. BRIEF DESCRIPTION OF DRAWINGS [0065] [ FIG. 1 ] A diagram showing a range in which Vm=21.276-0.0117z is the upper limit and Vm=21.164-0.0122z is the lower limit in a region with the molar volume Vm as the vertical axis and the Co ratio z (molar %) as the horizontal axis, and which additionally plots the conditions of the Examples and the Comparative Examples.

Description

Topics

Download Full PDF Version (Non-Commercial Use)

Patent Citations (26)

    Publication numberPublication dateAssigneeTitle
    JP-2005310421-ANovember 04, 2005Nikko Materials Co Ltd, 株式会社日鉱マテリアルズリチウムイオン二次電池用正極材料
    US-2002150820-A1October 17, 2002Hideyuki Kanai, Motoya Kanda, Koichi KuboPositive electrode active material and lithium ion secondary battery
    US-2004241084-A1December 02, 2004Yoshio Kajiya, Hiroshi TakasakiManganese oxide producing method
    US-2005019661-A1January 27, 2005Samsung Sdi Co., Ltd.Cathode active material and lithium secondary battery using the same
    US-2005142440-A1June 30, 2005Takahiro Yamaki, Juichi AraiLithium ion secondary battery
    US-2005265909-A1December 01, 2005Yoshio Kajiya, Hiroshi TasakiMethod for producing positive plate material for lithium secondary cell
    US-2006121350-A1June 08, 2006Yoshio Kajiya, Hiroshi TasakiCathode material for lithium secondary battery and method of producing same
    US-2007027015-A1February 01, 2007National Institute Of Advanced Industrial Science And TechnologyNanocrystal oxide/glass composite mesoporous powder or thin film, process for producing the same, and utilizing the powder or thin film, various devices, secondary battery and lithium storing device
    US-2007202405-A1August 30, 2007Mitsubishi Chemical CorporationLayered Lithium Nickel Manganese Cobalt Composite Oxide Powder For Material Of Positive Electrode Of Lithium Secondary Battery, Process For Producing The Same, Positive Electrode Of Lithium Secondary Battery Therefrom, And Lithium Secondary Battery
    US-2008182169-A1July 31, 2008Mitsubishi Chemical CorporationLayered lithium-nickel-based compound oxide powder and its prodution process
    US-2009011334-A1January 08, 2009Mitsubishi Chemical CorporationLithium secondary battery and positive electrode material thereof
    US-2009166187-A1July 02, 2009Nippon Mining & Metals Co., Ltd.Lithium-Containing Transition Metal Oxide Target, Process for Producing the same and Lithium Ion Thin Film Secondary Battery
    US-2009200508-A1August 13, 2009Nippon Mining & Metals Co., Ltd.Lithium Nickel Manganese Cobalt Composite Oxide and Lithium Rechargeable Battery
    US-2010209771-A1August 19, 2010Mitsubishi Chemical CorporationLithium transition metal-based compound powder, method for manufacturing the same, spray-dried substance serving as firing precursor thereof, and lithium secondary battery positive electrode and lithium secondary battery using the same
    US-2011065002-A1March 17, 2011Jx Nippon Mining & Metals CorporationPositive Electrode Active Material for Lithium Ion Battery, Positive Electrode for Secondary Battery using said Positive Electrode Active Material, and Lithium Ion Secondary Battery using Secondary Battery Positive Electrode
    US-6395250-B2May 28, 2002Fuji Chemical Industry Co., Ltd.Lithium/nickel/cobalt composite oxide, process for preparing the same, and cathode active material for rechargeable battery
    US-6497854-B2December 24, 2002Nikko Materials Company, LimitedCathode material for a lithium secondary battery and method for manufacturing same
    US-6677082-B2January 13, 2004The University Of ChicagoLithium metal oxide electrodes for lithium cells and batteries
    US-6811923-B1November 02, 2004Kabushiki Kaisha ToshibaActive material for anode of secondary cell and method for production thereof and non-aqueous electrolyte secondary cell, and recycled electronic functional material and method for recycling electronic functional material
    US-6964828-B2November 15, 20053M Innovative Properties CompanyCathode compositions for lithium-ion batteries
    US-7078128-B2July 18, 20063M Innovative Properties CompanyCathode compositions for lithium-ion batteries
    US-7226698-B2June 05, 2007Samsung Sdi Co., LtdPositive active material for rechargeable lithium battery, method of preparing same, and rechargeable lithium battery comprising same
    US-7288242-B2October 30, 2007Nikko Materials Co., Ltd.Lithium-containing complex oxide and method of producing same
    US-7309543-B2December 18, 2007Mitsubishi Chemical CorporationLayered lithium-nickel-based compound oxide powder and its production process
    US-7563540-B2July 21, 2009Samsung Sdi Co., Ltd.Cathode active material and lithium secondary battery using the same
    US-7799301-B2September 21, 2010Nippon Mining & Metals Co., Ltd.Cathode material for lithium secondary battery and manufacturing method thereof

NO-Patent Citations (0)

    Title

Cited By (26)

    Publication numberPublication dateAssigneeTitle
    US-2009166187-A1July 02, 2009Nippon Mining & Metals Co., Ltd.Lithium-Containing Transition Metal Oxide Target, Process for Producing the same and Lithium Ion Thin Film Secondary Battery
    US-2012231343-A1September 13, 2012Jx Nippon Mining & Metals CorporationPositive Electrode Active Material For A Lithium-Ion Battery, Positive Electrode For A Lithium-Ion Battery, Lithium-Ion Battery Using Same, And Precursor To A Positive Electrode Active Material For A Lithium-Ion Battery
    US-2015024272-A1January 22, 2015Asahi Glass Company, LimitedCathode active material for lithium ion secondary battery
    US-2015111105-A1April 23, 2015Tdk CorporationActive material, electrode using same, and lithium ion secondary battery
    US-8062486-B2November 22, 2011Jx Nippon Mining & Metals CorporationLithium-containing transition metal oxide target, process for producing the same and lithium ion thin film secondary battery
    US-8623551-B2January 07, 2014Jx Nippon Mining & Metals CorporationPositive-electrode active material for lithium ion battery, positive electrode for lithium ion battery, and lithium ion battery
    US-8748041-B2June 10, 2014Jx Nippon Mining & Metals CorporationPositive electrode active material for lithium ion battery
    US-8900757-B2December 02, 2014Hitachi Automotive Systems, Ltd.Lithium ion secondary battery
    US-8993160-B2March 31, 2015Jx Nippon Mining & Metals CorporationPositive electrode for lithium ion battery, method for producing said positive electrode, and lithium ion battery
    US-9090481-B2July 28, 2015Jx Nippon Mining & Metals CorporationPositive electrode active material for lithium-ion battery, positive electrode for lithium-ion battery, and lithium-ion battery
    US-9093712-B2July 28, 2015Tdk CorporationActive material, manufacturing method for active material, and lithium ion secondary battery
    US-9118076-B2August 25, 2015Jx Nippon Mining & Metals CorporationPositive electrode active material for lithium ion battery, positive electrode for lithium ion battery and lithium ion battery
    US-9136533-B2September 15, 2015Jx Nippon Mining & Metals CorporationLithium nickel manganese cobalt composite oxide and lithium rechargeable battery
    US-9214676-B2December 15, 2015Jx Nippon Mining & Metals CorporationPositive electrode active material for lithium ion batteries, positive electrode for lithium ion batteries, and lithium ion battery
    US-9216913-B2December 22, 2015Jx Nippon Mining & Metals CorporationPositive electrode active substance for lithium ion batteries, positive electrode for lithium ion batteries, and lithium ion battery
    US-9221693-B2December 29, 2015Jx Nippon Mining & Metals CorporationMethod for producing positive electrode active material for lithium ion batteries and positive electrode active material for lithium ion batteries
    US-9224514-B2December 29, 2015Jx Nippon Mining & Metals CorporationCathode active material for lithium ion battery, cathode for lithium ion battery, and lithium ion battery
    US-9224515-B2December 29, 2015Jx Nippon Mining & Metals CoporationCathode active material for lithium ion battery, cathode for lithium ion battery, and lithium ion battery
    US-9225020-B2December 29, 2015Jx Nippon Mining & Metals CorporationPositive electrode active substance for lithium ion batteries, positive electrode for lithium ion batteries, and lithium ion battery
    US-9231249-B2January 05, 2016Jx Nippon Mining & Metals CorporationPositive electrode active material for lithium ion battery, positive electrode for lithium ion battery, and lithium ion battery
    US-9240594-B2January 19, 2016Jx Nippon Mining & Metals CorporationPositive electrode active substance for lithium ion batteries, positive electrode for lithium ion batteries, and lithium ion battery
    US-9263732-B2February 16, 2016Jx Nippon Mining & Metals CorporationPositive electrode active material for lithium-ion battery, positive electrode for a lithium-ion battery, lithium-ion battery using same, and precursor to a positive electrode active material for a lithium-ion battery
    US-9327996-B2May 03, 2016Jx Nippon Mining & Metals CorporationMethod for producing positive electrode active material for lithium ion battery and positive electrode active material for lithium ion battery
    US-9559352-B2January 31, 2017Tdk CorporationActive material, electrode using same, and lithium ion secondary battery
    US-9716265-B2July 25, 2017Apple Inc.High-density precursor for manufacture of composite metal oxide cathodes for Li-ion batteries