Cathode material for use in lithium secondary battery and manufacturing method thereof

Description

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] This invention concerns a cathode material for a lithium secondary battery and, more in particular, it relates to a cathode material for a lithium secondary battery in which an alkaline earth metal or the like is blended in a composite lithium nickelate-cobaltate, as well as a manufacturing method thereof.

[0003] 2. Related Art

[0004] Lithium nickelate as a cathode material for lithium secondary batteries has a feature that the discharging capacity is large. However, when charge/discharge are repeated, lithium nickelate in which lithium ions are deintercalated tends to undergo phase change into a state with no lithium disorder. This trend is remarkable as the working temperature of the battery is higher.

[0005] Since the phase change is an irreversible reaction, the absolute amount of the lithium nickelate that contributes as the cathode material for the cathode active material to result in a problem of lowering the discharging capacity. Further, oxygen evolved tends to react with an electrolyte constituting the battery and, accordingly, it may be even lead to a risk of ignition or bursting of the battery when the working temperature is high.

[0006] In order to solve the problem, Japanese Patent Laid-Open No. 23629/2001, for example, proposes a method of evaluating the thermal stability of the lithium secondary battery by using lithium nickelate as the cathode material to form a lithium secondary battery, conducting charging/discharging operation to the secondary battery thereby causing deintercalation of lithium ions from the lithium nickelate and then conducting thermogravimetry of the lithium nickelate. Further, as a preferred active material for use in the cathode of the lithium ion secondary battery evaluated by the method described above, it discloses a composition containing Co at a ratio of 0.05 to 0.3 mol based on one mol of Ni and further containing one or more of elements selected from B, Al, Mg, Ca, Sr, Ba, Fe, Ti, Zr, Y, La and Ce by 0.001 to 0.1 mol in total.

[0007] However, it has been found as a result of the study made by the present inventors that the safety of the battery can not be evaluated satisfactorily by the existent method described above. An actual example is to be shown below. It is considered that an oxygen gas evolves at a high temperature region near 170° C. or higher on the cathode in a state where the battery is charged, and it causes a worry that the oxygen evolved and the electrolyte constituting the battery should take place a reaction. In a case of evaluating the safety of the battery whose cathode material is exposed to a high temperature by measuring the decrease of the weight of the cathode material in a temperature change from 200 to 300° C. by thermogravimetry, although swelling or ignition of the battery can be estimated based on the decomposition gas from the cathode or the electrolyte, it can not be estimated that abnormality will start in the battery by the starting of reaction between the oxygen evolving from the cathode and the electrolyte. As described above, the safety of the battery can not be recognized well by the existent method described above.

SUMMARY OF THE INVENTION

[0008] This invention intends to propose a cathode material excellent in thermal stability that contributes to the improvement of the safety of the battery, as well as a manufacturing method thereof.

[0009] The cathode material for use in the lithium secondary battery according to this invention comprises a compound represented by the chemical formula: LixNiyCOzMmO2 and a lithium secondary battery having high thermal stability and large discharging capacity can be obtained by using the material. In the chemical formula described above, M is one or more of elements selected from Ba, Sr and B, x, y, z and m represent values for the molar ratio of each element and they are, respectively, 0.9≦x≦1.1, 0.5≦y≦0.95, 0.05≦z≦0.5 and 0.0005≦m≦0.02. The BET specific surface area of the cathode material is 0.8 m2/g or less, and more preferably, less than 0.5 m2/g.

[0010] The compound represented by the chemical formula LixNiyCozMmO2 is a compound represented by the chemical formula LiaNibCocMnO2 in the charged state, and the DTG increase start temperature is preferably 215° C. or higher. In the chemical formula described above, M is one or more of elements selected from Ba, Sr and B, and x, y, z, m, a, b, c and n are a values for the molar ratio of each element and they are, respectively, 0.9≦x≦1.1, 0.5≦y≦0.95, 0.05≦z≦0.5, 0.0005<m<0.02, 0.2≦a≦0.4, 0.5≦b≦0.95, 0.05≦c≦0.5, and 0.0005≦n≦0.02. The DTG increase start temperature is more preferably 230° C. or higher.

[0011] The tap density of the cathode material is preferably 1.5 g/cm3 or more, in which the amount of the cathode material filled in the battery can be increased to further increase the charging/discharging capacity per unit volume of the battery.

[0012] The cathode material for use in the lithium secondary battery can be produced by mixing a compound represented by NiyCoz(OH)2, a lithium salt and a salt containing the element M, heating and pulverizing them to obtain a cathode material for use in the lithium secondary battery represented by the chemical formula LixNiyCozMmO2 in which the compound represented by NiyCoz(OH)2, has a tap density of 1.8 g/cm3 or more and an average particle diameter of 5 to 20 μm measured by laser diffraction method. The shape of the powdery particles of the compound represented by NiyCoz(OH)2 is preferably spherical. In this case, the heating is practiced preferably by successively conducting a preliminary heating of keeping temperature at 300 to 500° C. for 2 to 6 hrs in an oxygen atmosphere, a temperature elevation step of elevating the temperature at a rate of 5 to 30° C./min after the preliminary heating and a final heating step keeping temperature at 650 to 900° C. for 2 to 30 hrs succeeding to the temperature elevation step. In this case, the element M is one or more of elements selected from Ba, Sr and B, and x, y, z and m are, respectively, 0.9≦x≦1.1, 0.5≦y≦0.95, 0.05≦z≦0.5 and 0.0005≦m≦0.02.

[0013] Further, this invention provides a lithium secondary battery in which the active cathode material comprises partially or entirely the cathode material described above.

[0014] According to this cathode material for the lithium secondary battery of this invention, safety for the secondary battery can be improved outstandingly and a worry of ignition or bursting of the battery can be avoided even in a case where the secondary battery is exposed to a high temperature state.

BRIEF DESCRIPTION OF THE DRAWINGS

[0015]
FIG. 1 is a graph showing the change of DTG when the temperature of various kinds of cathode materials for use in lithium secondary batteries in a charged state in an argon atmosphere under the condition of 10° C./min; and

[0016]
FIG. 2 is a graph showing a relation between a BET specific surface area and a DTG increase start temperature of a cathode material for use in a lithium secondary battery.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The present inventors have found that a difference is observed for the DTG curves (Derivative Thermogravimetry: primary differentiation curves regarding the temperature of thermogravimetry curves) for the charged cathode material between each of the materials, and a cathode material which starts to DTG change at higher temperature has characteristic of excellent thermostability. Further, it has also been found important that the cathode material has a determined composition and can maintain the specific surface area of the material small for providing such characteristic. This invention has been accomplished based on the findings described above.

[0018]
FIG. 1 shows DTG curves of the cathode materials for lithium secondary battery of Nos. 3, 6, 9, 11 and 14 shown in Table 1. As shown in the graph, DTG of the cathode materials starts to increase at a temperature about from 190° C. and has a peak between 220 to 290° C. The present inventors have measured DTG for a number of cathode materials and investigated a relation between the DTG increase start temperature and the safety of the battery.

1TABLE 2Test result forDTG increaseInitial dischargingHigh temperatureCompositionstart temperaturecapacitystorage left atNail penetrationNo.LixNiyCozMmO2(° C.)(mAh/g)150° C., 5 hrtest1Li102Ni0.9Co0.1Ba0.001O2219194No swelling, noIgnition in someignitionbattery2Li1.02Ni0.7Co0.3Ba0.001O2230180No swelling, noNo ignitionignition3Li1.02Ni0.8Co0.3Ba0.001O2227186No swelling, noIgnition in someignitionbattery4Li1.02Ni0.8Co0.2Ba0.001O2229185No swelling, noIgnition in someignitionbattery5Li0.96Ni0.8Co0.2Sr0.007O2230181No swelling, noNo ignitionignition6Li0.99Ni0.8Co0.2Ba0.002Sr0.001O2230185No swelling, noNo ignitionignition7Li1.06Ni0.8Co0.2B0.02O2223190No swelling, noIgnition in someignitionbattery8Li1.01Ni0.8Co0.2Sr0.002O2224184No swelling, noIgnition in someignitionbattery9Li1.02Ni0.7Co0.3Ba0.005O2248184No swelling, noNo ignitionignition10Li1.06Ni0.8Co0.2Sr0.005O2225185No swelling, noIgnition in someignitionbattery11Li1.02Ni0.8Co0.2Ba0.001O2201177Swelling in someIgnition in allbatterybattery12Li1.02Ni0.8Co0.2Ba0.001O2203175Swelling in someIgnition in allbatterybattery13Li0.96Ni0.8Co0.2Ba0.03O2220150No swelling, noIgnition in someignitionbattery14Li0.96Ni0.8Co0.2O2190190Swelling orIgnition in allbursting in allbatterybattery15Li1.02Ni0.7Co0.3Ba0.005O2203169Swelling in someIgnition in allbatterybattery16Li1.06Ni0.8Co0.2Sr0.001O2207170Swelling in someIgnition in allbatterybattery

[0019] The measuring method for DTG and initial discharging capacity was conducted according to the following procedures. After adding N-methyl-2-pyrrolidone to 90 mass % of a cathode material powder, 5 mass % of acetylene black and 5 mass % of polyvinylidene fluoride and thoroughly kneading them, it was coated to about 150 μm thickness on an aluminum substratum, and, after pressing at about 200 kg/cm2, it was punched into a disk of 14 mm diameter. The disk was vacuum-dried at 150° C. for 15 hrs and used for the cathode. A lithium metal sheet was used for the anode and a porous polypropylene film (CELGARD #2400, trade name of products manufactured by Celgard Inc.) was used for the separator. Further, 1 mol of LiClO4 was dissolved in 1 liter of a mixed solution at a 1:1 by volumic ratio of ethylene carbonate (EC) and dimethyl carbonate (DMC) to prepare a non-aqueous electrolyte.

[0020] They were used and assembled into a test cell in an argon-substituted globe box and charging/discharging were conducted with a current density at a constant value of 1 MA/cm2 and under a voltage within a range from 2.75 to 4.2 V to measure the initial discharging capacity. After conducting the charging/discharging as described above, the cathode was taken out of the test cell in the 4.2 V charged state, the cathode material powder was peeled from the aluminum substratum, which was cleaning with dimethyl carbonate and vacuum-dried at 100° C. When the molar ratio for each of the elements of the cathode material LiaNibCocMnO2 for a lithium secondary battery thus obtained was calculated by chemical analysis, the molar ratio a for Li was within a range from 0.2 to 0.4 mol based on the total amount of Ni and Co. This powder was heated in an argon atmosphere at a rate of 10° C./min by using a thermogravimetric apparatus to measure the DTG and determine the DTG increase start temperature. The DTG increase start temperature means a temperature at which DTG exceeds 0.015%/° C.

[0021] The cathode material or the compound used for the material when the cathode was taken out of the test cell in the charged state of the battery is referred to simply as the cathode material or the compound in the charged state in this specification.

[0022] The safety test for the battery was conducted as described below.

[0023] (1) N-methyl-2-pyrrolidone was added to 90 mass % of lithium nickelate composite oxide, 5 mass % of carbon black and 5 mass % of polyvinylidene fluoride to form a paste, which was coated and dried on an aluminum foil to prepare a cathode.

[0024] (2) A paste comprising a graphite powder and N-methyl-2-pyrrolidone was coated and baked on a copper foil to prepare an anode.

[0025] (3) A separator was put between the cathode and the negative electrode, and one mol of LiPF6 dissolved in 1 liter of a mixed solution at 1:1 volumic ratio of ethylene carbonate (EC) and diethyl carbonate (DEC) was used as the electrolyte, to prepare a cylindrical lithium ion secondary battery of 18 mm diameter and 65 mm length.

[0026] (4) Cylindrical batteries each having an identical cathode material were manufactured by the number of 10 and each five of them was subjected to a high temperature storage test and nail penetration test.

[0027] (5) In the high temperature storage test, deformation or bursting, or absence or presence of ignition accompanying bursting of the batteries was investigated in a case of storage in a 4.2 V charged state at 1500C for 5 hrs in an atmospheric air.

[0028] (6) In the nail penetration test, a nail of 2.5 mm diameter was penetrated through the battery in a 4.4 V charged state in atmospheric air to investigate the absence or presence of ignition from the batteries. This is a severer test than the high temperature storage test as a test regarding the safety of the battery at high temperature.

[0029] As a result, it has been found that there is a correlation between the DTG increase start temperature of the cathode material and the safety of the battery according to the evaluation standard described above as shown in Table 1 and the battery having higher DTG increase start temperature is more excellent in the safety of the battery. Since DTG is considered as an index of the thermal decomposition rate of the cathode material in the temperature elevation process, it is estimated that those of higher increase start temperature provided improvement for the safety of the battery. As can be seen from Table 1, the results of the high temperature storage test for battery are satisfactory in a case of the cathode material of higher DTG increase start temperature with the temperature of about 215° C. being as the boundary. Further, also in the nail penetration test, the results are different with respect to the DTG increase start temperature at 215° C. being as the boundary and the results are satisfactory at 215° C. or higher. Further, in those having the DTG increase start temperature of 2300C or higher, the results are extremely excellent. As described above, it can be estimated that the safety of the battery is improved more as the DTG increase start temperature is higher.

[0030]
FIG. 2 is a graph showing a relation between the BET specific surface area and the DTG increase start temperature in a charged state of a cathode material for a lithium secondary battery. As shown in the graph, it can be seen that there is a close relation between the DTG increase start temperature of the cathode material for the lithium secondary battery of this type and the specific surface area thereof. When the BET specific surface area is 0.8 m2/g or less, the DTG increase start temperature is 215° C. or higher. In the chemical formula described above, M is one or more of elements selected from Ba, Sr and B, and x, y, z and m are, respectively, 0.9≦x≦1.1, 0.5≦y≦0.95, 0.05≦z≦0.5, and 0.0005≦m≦0.02. The specific surface area was measured by the BET method of determining based on the adsorption amount of a nitrogen gas.

[0031] The reason for defining the chemical formula LixNiyCzMmO2 is explained as below. At first, in this invention, the lithium nickelate of a large discharging capacity is used as a base. LiNiO2 itself has high discharging capacity among cathode materials but, it involves, on the other hand, a problem in view of the safety. Then, 0.05 to 0.5 mol of Ni is substituted for Co to enhance the thermal stability. Improvement of the thermal stability is observed by Co at 0.05 mol or more and, on the other hand, discharging capacity is lowered if it is 0.5 mol or more. Further, B, Sr or Ba is blended at a ratio of 0.0005 to 0.02 mol based on the total amount of Ni and Co to improve the thermal stability and obtain a sufficient discharging capacity. The improvement for the thermal stability by the element is in sufficient when it is less than 0.0005 mol, whereas the discharging capacity is lowered when it is 0.02 mol or more. When Li is insufficient, this results in a crystal structure with many lithium disorder to lower the discharging capacity. Further if Li is excessive, it forms hydrates or carbonates, which are gelled upon manufacture of the electrode, failing to obtain a satisfactory paste state to worsen the handlability. Accordingly, Li is defined within a range from 0.9 to 1.1 mol based on the total amount of Ni and Co.

[0032] In the invention described above, for increasing the discharging capacity per unit volume of the battery by increasing the amount of the cathode material to be filled in the battery, the tap density is preferably 1.5 g/cm3 or more. The tap density was measured by using a powder tester manufactured by Hosokawa Micron Co. and applying tapping for 200 times by using a 100 ml vessel for use in tap density measurement.

[0033] The cathode material for the lithium secondary battery described above can be manufactured as described below. At first, a high density NiyCoz(OH)2 in which the ratio of Co is controlled to 0.05 to 0.5 mol based on the total amount of Ni and Co as the starting material is prepared. Upon preparation thereof, NiyCoz(OH)2 is prepared, for example, by a wet solution synthesis method in which the average particle diameter is controlled to 5-20 μm and the tap density is controlled so as to be 1.8 g/cm3 or more, and each of the particles is desirably a spherical shape. In a case of synthesizing lithium-nickelate composite oxide, since the shape of NiyCoz(OH)2 as the starting material remains as it is, it is desirable to prepare the starting material as described above for obtaining a cathode material of a small specific surface area and a high tap density according to this invention.

[0034] After mixing the spherical and dense NiyCoz(OH)2, a lithium salt and an M-containing salt, they are heated and pulverized to obtain a cathode material for use in the lithium secondary battery represented by the chemical formula LixNiyCozMmO2 in which it is preferred to set the heating conditions so as to conduct a preliminary heating of keeping at a temperature of 300 to 500° C. for 2 to 6 hrs in an oxygen atmosphere, a temperature elevation process of elevating the temperature at 5 to 30° C./min after the preliminary heating and a final heating process of keeping at a temperature of 650 to 900° C. for 2 to 30 hrs succeeding to the temperature elevation process, successively. M is one or more of elements selected from Ba, Sr and B.

[0035] Since the preliminary heating is applied with an aim of completely removing the water content of the water of crystallization in the starting material while suppressing reaction between lithium and nickel, it is preferred to keep the temperature at 300 to 500° C. for 2 hrs or more. Since it was confirmed that water content can be removed thoroughly at 6 hrs or less, it is not necessary that the process exceeds 6 hrs in view of the productivity. The temperature elevation rate in the temperature elevation process is preferably 5 to 30° C./min in view of the protection of the heating crucible or refractory for heating and in view of productivity. Further, the temperature for the final heating is preferably from 650° C. to 900° C. Reaction less proceeds at a temperature lower than 650° C., whereas scattering of lithium is caused at a temperature in excess of 900° C. The retention time is preferably from 2 to 30 hrs in view of the reactivity and the productivity.

EXAMPLE

[0036] A cathode materials having the composition of the general formula LixNiyCozMmO2 shown in Table 2 were prepared and specific surface area, tap density, discharging capacity and DTG increase start temperature thereof were measured. In the manufacture, finely powderous reagents were used as the starting material for Nos. 11, 12, 15 and 16. Dense spherical NiyCoz(OH)2 with the tap density of 1.9 to 2.1 g/cm3 was used for other sample numbers as starting materials. As the heating condition, short time heating or long time heating described below in an oxygen atmosphere was adopted. The result of measurement is shown in Table 2.

2Short Time HeatingPreliminary heatingkept at 400° C. for 4 hrsTemperature elevation rate10° C./minFinal heatingkept at 800° C. for 4 hrsLong Time HeatingPreliminary heatingkept at 500° C. for 6 hrsTemperature elevation rate20° C./minFinal heatingkept at 750° C. for 12 hrsThe specific surface area was measured by the so-called BET method.

[0037]

3

TABLE 2

Ni-Co hydrates

Average

Specific

Discharge
DTG increase

Tap density
particle diameter
Composition

surface area
Tap density
capacity
start temperature

No.
(g/cm3)
(μm)
LixNiyCozMmO2
Heating time
(m2/g)
(g/cm3)
(mAh/g)
(° C.)

1
2.0
11.3
Li1.02Ni0.9Co0.1Ba0.001O2
Short time
0.42
2.1
194
219

2
1.9
11.8
Li1.02Ni0.7Co0.3Ba0.001O2
Short time
0.41
2.0
180
230

3
2.1
10.2
Li1.02Ni0.8Co0.2Ba0.001O2
Short time
0.39
2.1
186
227

4
2.1
10.2
Li1.02Ni0.8Co0.2Ba0.001O2
Long time
0.37
2.1
185
229

5
2.1
10.2
Li0.96Ni0.8Co0.2Sr0.007O2
Short time
0.45
2.1
181
230

6
2.1
10.2
Li0.99Ni0.8Co0.2Ba0.002Sr0.001O2
Short time
0.41
2.1
185
230

7
2.1
10.2
Li1.06Ni0.8Co0.2B0.002O2
Short time
0.37
2.2
190
223

8
2.1
10.2
Li1.01Ni0.8Co0.2Sr0.002O2
Short time
0.44
2.1
184
224

9
2.1
10.2
Li1.02Ni0.7Co0.3Ba0.005O2
Long time
0.32
2.2
184
248

10
2.1
10.2
Li1.06Ni0.8Co0.2Sr0.005O2
Longtime
0.78
2.1
185
225

11
1.6
27.2
Li1.02Ni0.8Co0.2Ba0.001O2
Short time
1.21
1.4
177
201

12
1.7
25.6
Li1.02Ni0.8Co0.2Ba0.001O2
Long time
1.14
1.5
175
203

13
2.1
10.2
Li0.96Ni0.8Co0.2Ba0.03O2
Short time
0.58
1.7
150
220

14
2.1
10.2
Li0.96Ni0.8Co0.2O2
Short time
0.38
2.1
190
190

15
1.6
27.2
Li1.02Ni0.7Co0.3Ba0.005O2
Long time
0.85
1.5
169
203

16
1.6
27.2
Li1.06Ni0.8Co0.2Sr0.001O2
Long time
0.92
1.5
170
207

[0038] As shown in the table, the cathode materials having the composition of the invention and having the determined specific surface area have large discharging capacity and high DTG increase start temperature. Further, when the tap density is large, the amount of the cathode material that can be filled in the battery can be increased and the charging/discharging capacity per unit volume of the battery can be increased by so much.

[0039] While this invention has been described with reference to several embodiments, it should be construed that such embodiments are only for the purpose of specifically explaining the invention and do not restrict the invention. After studying the present specification, various modifications equivalent materials or substitution of technique will occur to those skilled in the art. All such modifications and substitutions are considered to fall within the scope of the present claims.

Claims

1. A cathode material for use in a lithium secondary battery comprising a compound represented by the chemical formula: LixNiyCozMmO2, having high thermal stability and large discharging capacity in which M is one or more of elements selected from Ba, Sr and B, and x, y, z and m are values for the molar ratio of each element: 0.9≦x≦1.1, 0.5≦y≦0.95, 0.05≦z≦0.5 and 0.0005≦m≦0.02, wherein the material is powdery and the BET specific surface area is 0.8 m2/g or less.
2. A cathode material as defined in claim 1, wherein the BET specific surface area is less than 0.5 m2/g.
3. A cathode material as defined in claim 1 or 2, wherein the compound represented by the chemical formula: LixNiyCozMmO2 is a compound represented by the chemical formula: LiaNibCocMnO2 in the charged state, and the DTG increase start temperature is at 215° C. or higher wherein M is one or more of elements selected from Ba, Sr and B, x, y, z, m, a, b, c and n are values for the molar ratio of each element and they are, respectively, 0.9≦x≦1.1, 0.5≦y≦0.95, 0.05≦z≦0.5 and 0.0005≦m≦0.02, 0.2≦a≦0.4, 0.5≦b≦0.95, 0.05≦c≦0.5, and 0.0005≦n≦0.02.
4. A cathode material as defined in claim 3, wherein the DTG increase start temperature is at 230° C. or higher.
5. A cathode material as defined in any one of claims 1 to 4, wherein the compound represented by the chemical formula: LixNiyCozMmO2 is powdery and the tap density is 1.5 g/cm3 or more.
6. A method of manufacturing a cathode material for use in a lithium secondary battery of high thermal stability and large discharging capacity as defined in any one of claims 1 to 5, by mixing a powder of a compound represented by NiyCoz(OH)2, a lithium salt and a salt containing the element M, and then heating and pulverizing them to prepare a cathode material for use in the lithium secondary battery represented by the chemical formula: LixNiyCozMmO2, wherein the powder of the compound represented by NiyCoz(OH)2 has a tap density 1.8 g/cm3 or more and an average particle diameter of 5 to 20 μm, and wherein the element M is one or more or elements selected from Ba, Sr and B, and x, y, z and m are, respectively; 0.9≦x≦1.1, 0.5 ≦y≦0.95, 0.05≦z≦0.5, and 0.0005≦m≦0.02.
7. A manufacturing method of a cathode material as defined in claim 6, wherein the powdery particle of the compound represented by NiyCoz(OH)2 has a spherical shape.
8. A manufacturing method of a cathode material as defined in claim 6, wherein heating includes conducting successively preliminary heating of keeping temperature at 300 to 500° C. for 2 to 6 hrs in an oxygen atmosphere, a temperature elevation process of elevating the temperature at a rate of 5 to 300C/min after the preliminary heating and final heating process for keeping temperature at 650 to 900° C. for 2 to 30 hrs succeeding to the temperature elevation process.
9. A lithium secondary battery in which the cathode active material contains the cathode material as defined in any one of claims 1 to 5.
10. A lithium secondary battery in which the cathode material is a cathode material as defined in any one of claims 1 to 5.

Priority Claims (1)

Number	Date	Country	Kind
2001-173285	Jul 2001	JP

Cathode material for use in lithium secondary battery and manufacturing method thereof

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Priority Claims (1)