NICKEL-LITHIUM METAL COMPOSITE OXIDE POWDER AND METHOD FOR PRODUCING SAME

Abstract

To show an LNCAO-type positive electrode active material for a lithium ion battery having a high discharge capacity per unit volume and excellent discharging capacity-holding properties.

Nickel-lithium metal composite oxide powder includes a nickel-lithium metal composite oxide represented by General Formula (1) described below:

Li.sub.xNi.sub.1-y-zM.sub.yN.sub.zO.sub.1.7-2.2   (1), in which the breakdown strength of secondary particles is in a range of 80 MPa or less, the density is 3.30 g/cm.sup.3 or higher when compressed at a pressure of 192 MPa, and the density is 3.46 g/cm.sup.3 or higher when compressed at a pressure of 240 MPa. A method for producing the nickel-lithium metal composite oxide powder includes a water washing step after a firing step for producing a nickel-lithium metal composite oxide powder precursor.

Claims

1. Nickel-lithium metal composite oxide powder comprising: a nickel-lithium metal composite oxide represented by General Formula (1) described below:
Li.sub.xNi.sub.1-y-zM.sub.yN.sub.zO.sub.1.7-2.2   (1) in Formula (1), M represents one or more metal elements selected from a group consisting of Co, Mn, Fe, and Cu, N represents one or more metal elements selected from a group consisting of Al, W, Ta, and B, 0.90<x<1.10, 0.01<y<0.15, and 0.005<z<0.10, wherein the breakdown strength of secondary particles is in a range of 80 MPa or less, the density is 3.30 g/cm.sup.3 or higher when compressed at a pressure of 192 MPa, and the density is 3.46 g/cm.sup.3 or higher when compressed at a pressure of 240 MPa.

2. The nickel-lithium metal composite oxide powder according to claim 1, wherein, when 2 g of the nickel-lithium metal composite oxide represented by General Formula (1) is dispersed in 100 g of water, a supernatant has a hydrogen ion concentration of 11.0 or lower in terms of pH and has a content of LiOH of 0.1% by weight or less.

3. The nickel-lithium metal composite oxide powder according to claim 1, wherein M in General Formula (1) is Co.

4. The nickel-lithium metal composite oxide powder according to claim 1, wherein N in General Formula (1) is Al.

5. The nickel-lithium metal composite oxide powder according to claim 1, wherein, in General Formula (1), M is Co, and N is Al.

6. A positive electrode active material for a lithium ion battery, comprising: the nickel-lithium metal composite oxide powder according to claim 1.

7. A positive electrode for a lithium ion battery, wherein the positive electrode active material for a lithium ion battery according to claim 6 is used.

8. A lithium ion battery, wherein the positive electrode for a lithium ion battery according to claim 7 is used.

9. A method for producing nickel-lithium metal composite oxide powder including a nickel-lithium metal composite oxide represented by General Formula (1) described below:
Li.sub.xNi.sub.1-y-zM.sub.yN.sub.zO.sub.1.7-2.2   (1) in Formula (1), M represents one or more metal elements selected from a group consisting of Co, Mn, Fe, and Cu, N represents one or more metal elements selected from a group consisting of Al, W, Ta, and B, 0.90<x<1.10, 0.01<y<0.15, and 0.005<z<0.10, wherein the breakdown strength of secondary particles is in a range of 80 MPa or less, the density is 3.30 g/cm.sup.3 or higher when compressed at a pressure of 192 MPa, and the density is 3.46 g/cm.sup.3 or higher when compressed at a pressure of 240 MPa, comprising: a water washing step after a firing step for producing a nickel-lithium metal composite oxide powder precursor.

10. The method for producing nickel-lithium metal composite oxide powder according to claim 9, wherein, when 2 g of the obtained nickel-lithium metal composite oxide powder is dispersed in 100 g of water, a supernatant has a hydrogen ion concentration of 11.0 or lower in terms of pH and has a content of LiOH of 0.1% by weight or less.

11. The method for producing nickel-lithium metal composite oxide powder according to claim 9, wherein M in General Formula (1) is Co.

12. The method for producing nickel-lithium metal composite oxide powder according to claim 9, wherein N in General Formula (1) is Al.

13. The method for producing nickel-lithium metal composite oxide powder according to claim 9, wherein, in General Formula (1), M is Co, and N is Al.

14. The method for producing nickel-lithium metal composite oxide powder according to claim 9, wherein, in the water washing step, the nickel-lithium metal composite oxide is washed with water having a weight that is 10% to 300% of the weight of the nickel-lithium metal composite oxide.

15. The method for producing nickel-lithium metal composite oxide powder according to claim 9, wherein, in the water washing step, the nickel-lithium metal composite oxide is washed with water having a weight that is 50% to 100% of the weight of the nickel-lithium metal composite oxide.

16. The method for producing nickel-lithium metal composite oxide powder according to claim 9, further comprising: a dehydration step after the water washing step.

17. The method for producing nickel-lithium metal composite oxide powder according to claim 16, wherein, in the dehydration step, dehydration through filtration is carried out.

18. The method for producing nickel-lithium metal composite oxide powder according to claim 16, wherein, in the dehydration step, dehydration through filtration and vacuum drying are carried out.

19. The method for producing nickel-lithium metal composite oxide powder according to claim 9, further comprising: the dehydration step after the water washing step and a firing step after the dehydration step.

20. The method for producing nickel-lithium metal composite oxide powder according to claim 9, wherein the firing step for producing a nickel-lithium metal composite oxide powder precursor is carried out after a powder-mixing step coming after a dissolution step, a precipitation step, a filtration and washing step, and a drying step of a raw material.

Description

BEST MODE FOR CARRYING OUT THE INVENTION

[0038] A nickel-lithium metal composite oxide included in nickel-lithium metal composite oxide powder of the present invention is a compound represented by General Formula (1) described below:

Li.sub.xNi.sub.1-y-zM.sub.yN.sub.zO.sub.1.7-2.2   (1)

[0039] (in Formula (1), M represents one or more metal elements selected from a group consisting of Co, Mn, Fe, and Cu, N represents one or more metal elements selected from a group consisting of Al, W, Ta, and B, 0.90<x<1.10, 0.01<y<0.15, and 0.005<z<0.10).

[0040] The nickel-lithium metal composite oxide included in the nickel-lithium metal composite oxide powder of the present invention is preferably an oxide represented by General Formula (2) described below in which M is Co and N is Al in General Formula (1):

Li.sub.xNi.sub.1-y-zCo.sub.yAl.sub.zO.sub.1.7-2.2   (2)

[0041] (in Formula (2), 0.90<x<1.10, 0.01<y<0.15, and 0.005<z<0.10).

[0042] The nickel-lithium metal composite oxide powder of the present invention can be produced using the following method.

[0043] (1. Dissolution of raw materials) As raw materials, soluble metal salts such as hydrosulfates and nitrates of the metals included in General Formula (1) can be used. In a case in which nitrate is used, a costly treatment is required for a waste liquid containing nitrate-nitrogen, and thus the use of nitrates is not preferable in an industrial sense. Generally, a hydrosulfate of a metal included in General Formula (1) is used. In a method for producing the nickel-lithium metal composite oxide powder of the present invention, first, nickel sulfate and cobalt sulfate, which are raw materials, are respectively dissolved in water.

[0044] (2. Precipitation) An aqueous solution of nickel sulfate, an aqueous solution of cobalt sulfate, and sodium hydroxide and ammonia water as a precipitating agent are mixed together in a precipitation tank. A co-precipitate of nickel hydroxide and cobalt hydroxide is generated.

[0045] (3. Filtration and washing) The precipitate is filtered, and moisture is removed, thereby separating out a hydroxide cake. The hydroxide cake is washed with an aqueous solution of sodium hydroxide, thereby removing sulfate ions. Furthermore, the hydroxide cake is washed with pure water, thereby removing sodium hydroxide. A precursor cake including nickel hydroxide and cobalt hydroxide is obtained in the above-described manner.

[0046] (4. Drying) The precursor cake is dried. As a drying method, any of hot-air drying at atmospheric pressure, infrared drying, vacuum drying, and the like may be used. When vacuum drying is used, it is possible to dry the precursor cake within a short period of time. The drying is continued until the content of moisture in the precursor reaches approximately 1% by weight.

[0047] (5. Powder mixing) Aluminum hydroxide and lithium hydroxide powder are added to the dried precursor powder, and the components are mixed together by applying a shear force.

[0048] (6. Firing) The mixture is fired in the presence of oxygen. The firing causes the following reactions.

4Co(OH).sub.2+4LiOH+O.sub.2.fwdarw.4LiCoO.sub.2+6H.sub.2O

Al(OH).sub.3+LiOH.fwdarw.LiAlO.sub.2+2H.sub.2O

4Ni(OH).sub.2+4LiOH+O.sub.2.fwdarw.4LiNiO.sub.2+6H.sub.2O

[0049] (7. Water washing) In the production of the nickel-lithium metal composite oxide powder of the present invention, the fired nickel-lithium metal composite oxide is washed with water. The fired nickel-lithium metal composite oxide is washed with water having a weight that is 10% by weight to 300% by weight, preferably 20% by weight to 300% by weight, and more preferably 50% by weight to 100% by weight of the weight of the nickel-lithium metal composite oxide. When the amount of water being used is within the above-described range, the effect of the water washing is sufficient, a desired particle breakdown strength can be obtained, and the battery performance becomes favorable.

[0050] (8. Dehydration) The washed nickel-lithium metal composite oxide contains a large amount of moisture. In a dehydration step after the water washing step, moisture in the nickel-lithium metal composite oxide is removed. Dehydration is carried out through filtration. Alternately, dehydration is carried out through a combination of filtration and subsequent vacuum drying. Through the dehydration step, a majority of moisture in the nickel-lithium metal composite oxide is removed. The content of water in the dried nickel-lithium metal composite oxide needs to be suitable for the efficiency of the following firing step, and is generally 1.0% by weight or less, preferably 0.5% by weight or less, and more preferably 0.1% by weight or less. The moisture value after rough finishing is preferably within the above-described range since the battery performance becomes favorable and there is no waste in the production efficiency in the drying step.

[0051] (9. Firing) After the dehydration step, the nickel-lithium metal composite oxide is fired. The firing temperature is in a range of 300° C. to 800° C. When the firing temperature is in the above-described range at this time, moisture is sufficiently removed, the crystal structure of the active material does not break, and the battery performance becomes favorable.

[0052] The nickel-lithium metal composite oxide powder of the present invention is completed through the above-described steps 1 to 9. In the present invention, the use of the production method including the above-described water washing step enables the obtainment of nickel-lithium metal composite oxide powder having the controlled breakdown strength and compressive strength of secondary particles. When the nickel-lithium metal composite oxide powder of the present invention is used as a lithium ion battery positive electrode active material, the active material can be disposed on an electrode in a high density, and the battery performance improves.

[0053] The excellent properties of the nickel-lithium metal composite oxide powder of the present invention are considered to result from the fact that the above-described step (7. Water washing) is provided in the production method. The discharge characteristics of the nickel-lithium metal composite oxide powder of the present invention do not deteriorate compared with those of nickel-lithium metal composite oxide powder that is not subjected to the water washing. That is, it can be assumed that the above-described water washing does not cause any phenomenon deteriorating the discharge characteristics such as the desorption of lithium ions from between crystal layers. Furthermore, the particle size distribution of the nickel-lithium metal composite oxide powder of the present invention does not significantly change compared with nickel-lithium metal composite oxide powder that is not subjected to the water washing. That is, it can be assumed that the above-described water washing does not cause any undesirable phenomenon such as the agglomeration of the nickel-lithium metal composite oxide powder or particle breakage.

[0054] As described above, in the present invention, the discharge characteristics or the particle characteristics are not deteriorated, and the breakdown strength or compressive strength of the positive electrode active material is successfully controlled. It is an astonishing fact that the above-described achievements can be obtained in the present invention although there has been a concern of a variety of adverse effects caused by the water washing of the lithium ion battery positive electrode active material in the related art.

[0055] Furthermore, in the present invention, undesirable components for the battery performance, which are included in the nickel-lithium metal composite oxide powder, are decreased. Examples of the undesirable components include alkaline Li compounds such as LiOH which cause the gelation of a positive electrode slurry, and the like. As a result of measuring the amount of LiOH included in the nickel-lithium metal composite oxide powder of the present invention through titration, it is confirmed that the amount of LiOH is decreased to less than 0.1% by weight. The pH of a supernatant generated when 2 g of the nickel-lithium metal composite oxide powder of the present invention is dispersed in 100 g of water is decreased to less than 11.0.

[0056] The nickel-lithium metal composite oxide powder of the present invention can be used as a positive electrode active material for a lithium ion battery. The positive electrode active material for a lithium ion battery may be constituted only with the nickel-lithium metal composite oxide powder of the present invention or may be obtained by mixing the nickel-lithium metal composite oxide powder of the present invention with another nickel-lithium metal composite oxide powder in an amount at which the advantages of the nickel-lithium metal composite oxide powder are exhibited. For example, it is possible to use a mixture of 50 parts by weight of the nickel-lithium metal composite oxide of the present invention and 50 parts by weight of a positive electrode active material for a lithium ion secondary battery, which is not the present invention, as the positive electrode active material. In the case of producing a positive electrode of a lithium ion battery, a positive electrode active material including the above-described nickel-lithium metal composite oxide of the present invention, a conductive aid, a binder, and an organic solvent for dispersion are added so as to prepare a mixed slurry for a positive electrode, and the slurry is applied to the electrode.

EXAMPLES

Example 1

[0057] An aqueous solution of sodium hydroxide was added to an aqueous solution obtained by dissolving nickel sulfate and cobalt sulfate, and the generated precipitate was filtered, washed, and dried. A nickel hydroxide-cobalt hydroxide co-precipitate was obtained. Lithium hydroxide and aluminum hydroxide were mixed into the obtained nickel hydroxide-cobalt hydroxide co-precipitate in a powder form, thereby obtaining a firing raw material. This firing raw material was fired at 780° C. in an oxygen stream. The fired substance was subsequently subjected to a water washing step.

[0058] In the water washing step, 150 g (100% by weight of the fired substance) of water was added to 150 g of the fired substance, the fired substance and water were stirred, and the fired substance was filtered. A separated cake was vacuum-dried at 100° C. until the content of moisture in the cake reached 1% by weight or less. The obtained dried cake was fired in a muffle furnace at 500° C. for five hours in an oxygen stream, thereby obtaining nickel-lithium metal composite oxide powder.

Example 2

[0059] Nickel-lithium metal composite oxide powder was produced under the same conditions as in Example 1 except for the fact that, in the water washing step, 75 g (50% by weight of the fired substance) of water was added to 150 g of the fired substance, and was stirred and filtered.

Example 3

[0060] Nickel-lithium metal composite oxide powder was produced under the same conditions as in Example 1 except for the fact that, in the water washing step, 50 g (33% by weight of the fired substance) of water was added to 150 g of the fired substance, and was stirred and filtered.

Example 4

[0061] Nickel-lithium metal composite oxide powder was produced under the same conditions as in Example 1 except for the fact that, in the water washing step, 30 g (20% by weight of the fired substance) of water was added to 150 g of the fired substance, and was stirred and filtered.

Example 5

[0062] Nickel-lithium metal composite oxide powder was produced under the same conditions as in Example 1 except for the fact that, in the water washing step, 200 g (133% by weight of the fired substance) of water was added to 150 g of the fired substance, and was stirred and filtered.

Example 6

[0063] Nickel-lithium metal composite oxide powder was produced under the same conditions as in Example 1 except for the fact that, in the water washing step, 250 g (167% by weight of the fired substance) of water was added to 150 g of the fired substance, and was stirred and filtered.

Comparative Example 1

[0064] The water washing step of Example 1 was not carried out, and the fired nickel-lithium metal composite oxide powder was used as a comparative product.

Comparative Example 2

[0065] Nickel-lithium metal composite oxide powder for comparison was produced under the same conditions as in Example 1 except for the fact that, in the water washing step, 7.5 g (5% by weight of the fired substance) of water was added to 150 g of the fired substance, and was stirred and filtered.

Example 7

[0066] Nickel-lithium metal composite oxide powder was produced in a larger scale. In the water washing step, 2000 g (100% by weight of the fired substance) of water was added to 2000 g of the fired substance, and was stirred and filtered. A separated cake was not vacuum-dried and was fired using a muffle furnace at 500° C. for five hours in an oxygen stream. Other conditions were set in the same manner as in Example 1. Nickel-lithium metal composite oxide powder was produced as described above.

Example 8

[0067] Nickel-lithium metal composite oxide powder was produced under the same conditions as in Example 7 except for the fact that a separated cake was fired using a large-sized electric furnace at 500° C. in an oxygen stream.

Example 9

[0068] Nickel-lithium metal composite oxide powder was produced under the same conditions as in Example 7 except for the fact that a separated cake was fired using an actual production electric furnace at 500° C. in an oxygen stream.

Comparative Example 3

[0069] A positive electrode active material for a lithium ion battery produced by ShenZhen TianJiao Technology Co., Ltd. (trade name: NCA1301-1ZS) was used as a comparative product and was evaluated.

[0070] The following evaluations were carried out on the nickel-lithium metal composite oxide powders of the present invention obtained in the examples and the nickel-lithium metal composite oxide powders for comparison obtained in the comparative examples.

[0071] (Breakdown strength of secondary particles) A small amount of the nickel-lithium metal composite oxide powder was scattered on a lower pressurization plate in a micro compression tester (Shimadzu's micro compression tester MCT-510), and a compression test was carried out on every particle under microscopic observation, thereby measuring the breakdown strengths of the particles. The measurement results are shown in Table 1.

[0072] (Pressurized density) As a powder pressing machine, a P-16B pressing machine manufactured by Riken Seiki Co., Ltd. was used. As a powder pressing die, a die manufactured by International Crystal Laboratories (13 mm KBR Die, inner diameter of 13 mm) was used. 1.00 g of nickel-lithium metal composite oxide powder was accurately weighed and was installed in the powder pressing die. The powder was pressurized in the powder pressing machine for five minutes. The heights of the pressing die before and after the pressurization were measured, and the density of the nickel-lithium metal composite oxide powder after pressing was computed. The computation results are shown in Table 1.

TABLE-US-00001 TABLE 1 Water washing Evaluation conditions Density Density Amount of under under water pressur- pressur- (% by Break- ization ization weight in Execution down at at relation of vacuum strength 192 MPa 240 MPa to powder) drying (MPa) (g/cm.sup.3) (g/cm.sup.3) Example 1 100 Yes 62.4 3.5 3.6 Example 2 50 Yes 67.8 3.4 3.5 Example 3 33 Yes 73.9 3.3 3.5 Example 4 20 Yes 79.7 3.3 3.5 Example 5 133 Yes 51.8 3.5 3.6 Example 6 167 Yes 51.3 3.6 3.6 Example 7 100 No 62.0 3.4 3.5 Example 8 100 No 61.8 3.3 3.5 Example 9 100 No 61.8 3.3 3.4 Comparative 0 No 81.8 3.3 3.4 Example 1 (No water washing) Comparative 5 Yes 81.0 3.3 3.4 Example 2 Comparative 0 No 26.0 3.2 3.3 Example 3 (No water washing)

[0073] In addition, the pH values and other analysis results of the nickel-lithium metal composite oxide powders obtained in the examples and the comparative examples are shown in Table 2.

TABLE-US-00002 TABLE 2 Water washing conditions Amount of Analysis results water Content Content Content (% by of of of Content weight in Execution LiOH Li.sub.2CO.sub.3 LiAlO.sub.2 of Li relation of vacuum pH at (% by (% by (% by (% by to powder) drying 25° C. weight) weight) weight) weight) Example 1 100 Yes 10.70 0.09 0.07 0.06 0.05 Example 2 50 Yes 10.90 0.09 0.12 0.05 0.05 Example 3 33 Yes 11.00 0.15 0.20 0.07 0.09 Example 4 20 Yes 11.30 0.20 0.30 0.19 0.16 Example 5 133 Yes 10.60 0.05 0.05 0.06 0.04 Example 6 167 Yes 10.50 0.04 0.06 0.06 0.04 Example 7 100 No 10.80 0.09 0.11 0.05 0.05 Example 8 100 No 10.90 0.10 0.14 0.07 0.06 Example 9 100 No 10.70 0.08 0.05 0.04 0.04 Comparative 0 No 11.70 0.61 0.31 0.29 0.27 Example 1 (No water washing) Comparative 5 Yes 11.60 0.65 0.34 0.25 0.25 Example 2 Comparative 0 No 11.50 0.59 2.10 0.25 1.04 Example 3 (No water washing)

INDUSTRIAL APPLICABILITY

[0074] Nickel-lithium metal composite oxide powder and a positive electrode active material for a lithium ion secondary battery including the same satisfy the recent requirement of an increase in the capacity of a secondary battery for small electronic devices and the like, also satisfy an increase in the capacity and a decrease in the size which are required for a power supply used in a large secondary battery for an electric vehicle and a stationary storage battery, and are extremely meaningful in an industrial sense.