JP2004047180A - Nonaqueous electrolytic solution battery - Google Patents

Nonaqueous electrolytic solution battery Download PDF

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JP2004047180A
JP2004047180A JP2002200380A JP2002200380A JP2004047180A JP 2004047180 A JP2004047180 A JP 2004047180A JP 2002200380 A JP2002200380 A JP 2002200380A JP 2002200380 A JP2002200380 A JP 2002200380A JP 2004047180 A JP2004047180 A JP 2004047180A
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positive electrode
active material
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Tomohito Okamoto
岡本 朋仁
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Japan Storage Battery Co Ltd
日本電池株式会社
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/122Lithium-ion batteries

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonaqueous electrolytic solution battery whose safety characteristics at the time of overcharging is excellent. <P>SOLUTION: The first anode active material includes compound which is expressed by LiCo<SB>a</SB>Ni<SB>b</SB>M1<SB>1-a-b</SB>O<SB>2</SB>(0≤a<1, 0≤b<1, 0.9≤a+b≤0.99 and M1 is element chosen from B, Mg, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Sn or W) or compound which is expressed by Li<SB>a+b</SB>M<SB>b</SB>Mn<SB>2-a-b</SB>O<SB>4</SB>(0<a≤0.2, 0<b≤0.15 and M is element chosen from elements excluding Mn). The second anode active material includes compound which is expressed by LiCo<SB>c</SB>M2<SB>1-c</SB>PO<SB>4</SB>(0.5≤c≤1 and M2 is element chosen from Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Zr, Nb, Mo, W or Ge), compound which is expressed by LiMn<SB>2-d</SB>M3<SB>d</SB>O<SB>4</SB>(0<d≤0.5 and M3 is element chosen from Cr, Fe, Co, Ni, Cu or Zn) and compound which is chosen from LiNiVO<SB>4</SB>. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a non-aqueous electrolyte battery.
[0002]
[Prior art]
A positive electrode containing a positive electrode active material capable of reversibly electrochemically reacting with lithium ions, a negative electrode containing a negative electrode active material capable of reversibly storing and releasing lithium ions, and a non-aqueous electrolyte containing a solid polymer electrolyte and an organic solvent Non-aqueous electrolyte batteries, such as lithium-ion batteries, comprising high voltage and high energy density, are widely used as power sources for portable electronic and communication devices such as small video cameras, mobile phones, and notebook computers. ing.
[0003]
Since the positive electrode active material has high voltage, high energy density, and excellent charge / discharge cycle characteristics, LiCoO 2 And the like.
[0004]
When the lithium ion battery is overcharged, lithium ions are excessively extracted from the positive electrode active material. As a result, the crystal structure becomes unstable, and there is a possibility that heat is rapidly generated with a change in the crystal structure. Further, there is a possibility that heat is generated due to decomposition of the electrolytic solution.
[0005]
In order to avoid such a problem, at present, a protection circuit for preventing overcharge is always incorporated in a lithium ion battery.
[0006]
[Problems to be solved by the invention]
However, a protection circuit for preventing overcharging requires a complicated control technique, which causes an increase in the total cost of the battery. In addition, since a protection circuit is arranged in a battery pack in a lithium-ion battery that is actually used, the substantial energy density of the battery is reduced due to the occupied volume and mass.
[0007]
Therefore, in order to meet the demands for further downsizing and cost reduction of non-aqueous electrolyte batteries, there is a demand for the development of non-aqueous electrolyte batteries in which safety at the time of overcharge is ensured without a protection circuit.
[0008]
The present invention has been completed based on the above circumstances, and has as its object to provide a nonaqueous electrolyte battery excellent in safety during overcharge.
[0009]
[Means for Solving the Problems and Functions / Effects]
According to a first aspect of the present invention, there is provided a nonaqueous electrolyte battery including a positive electrode including a positive electrode active material, a negative electrode, and a nonaqueous electrolyte, wherein the positive electrode active material is a first positive electrode. An active material and a second positive electrode active material, wherein the first positive electrode active material has a general formula LiCo a Ni b M1 1-ab O 2 (However, 0 ≦ a <1, 0 ≦ b <1, 0.9 ≦ a + b ≦ 0.99, M1 is B, Mg, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, A compound represented by at least one element selected from the group consisting of Zr, Nb, Mo, Sn, and W); a + b M b Mn 2-ab O 4 (Where 0 <a ≦ 0.2, 0 <b ≦ 0.15, M is at least one element other than Mn), and the second positive electrode active material has a general formula LiCo c M2 1-c PO 4 (0.5 ≦ c ≦ 1, M2 is at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Zr, Nb, Mo, W, and Ge) Compound represented by the general formula LiMn 2-d M3 d O 4 (0 <d ≦ 0.5, M3 is at least one element selected from the group consisting of Cr, Fe, Co, Ni, Cu and Zn), and LiNiVO 4 And at least one selected from the group consisting of
[0010]
General formula LiCo used as a first positive electrode active material a Ni b M1 1-ab O 2 (However, 0 ≦ a <1, 0 ≦ b <1, 0.9 ≦ a + b ≦ 0.99, M1 is B, Mg, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, 4.3 V (vs. Li / Li) for a compound represented by Zr, Nb, Mo, Sn, and W). + If charging is performed at the above potential, the crystal structure changes and overcharging occurs. Similarly, Li a + b M b Mn 2-ab O 4 (Provided that 0 <a ≦ 0.2, 0 <b ≦ 0.15, and M is at least one element other than Mn) for a compound represented by 4.5 V (vs. Li / Li + If charging is performed at the above potential, overcharging occurs.
[0011]
On the other hand, a general formula LiCo used as a second positive electrode active material c M2 1-c PO 4 (0.5 ≦ c ≦ 1, M2 is at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Zr, Nb, Mo, W, and Ge) Overcharged potential is 5.2 V (vs. Li / Li + ) And the general formula LiMn 2-d M3 d O 4 (0 <d ≦ 0.5, M3 is at least one element selected from the group consisting of Cr, Fe, Co, Ni, Cu, and Zn) in a compound represented by 5.2 V (vs. Li / Li). + ) Or more, and LiNiVO 4 Then 5.0V (vs. Li / Li + ) That is all. As described above, the potential at which the second positive electrode active material is overcharged is more noble than that of the first positive electrode active material. Therefore, even if the first positive electrode active material is charged beyond the overcharged potential of 4.3 to 5.0 V, the second positive electrode active material is safely charged and consumes the charging current. In addition, the first positive electrode active material is prevented from being decomposed by the current at the time of overcharging. In addition, decomposition of the electrolytic solution is also suppressed. As a result, heat generation due to the decomposition reaction of the positive electrode active material during overcharge is suppressed, and the safety of the nonaqueous electrolyte battery during overcharge is improved.
[0012]
According to a second aspect of the present invention, there is provided the non-aqueous electrolyte battery according to the first aspect, wherein the first positive electrode active material, the second positive electrode active material, a conductive agent, and a binder are mixed. In which the content of the second positive electrode active material is 1% by weight or more and 20% by weight or less.
[0013]
If the content of the second positive electrode active material in the positive electrode mixture is less than 1% by weight, the effect of improving safety due to consumption of the current during overcharge by the second positive electrode active material is not sufficiently exhibited. It is not preferred. On the other hand, if the content of the second positive electrode active material exceeds 20% by weight, the weight ratio of the second positive electrode active material in the positive electrode mixture becomes too large, and the discharge capacity is undesirably reduced. This is because the discharge capacity of the second positive electrode active material is smaller than that of the first positive electrode active material.
[0014]
In the non-aqueous electrolyte battery according to claim 1 or 2, the metal element M1 is preferably at least one element selected from the group consisting of Mg, Mn, and Sn.
[0015]
LiCo a Ni b M1 1-ab O 2 By using the above-mentioned metal element as M1 in the above, a battery having excellent battery characteristics such as discharge capacity and cycle characteristics while maintaining safety at the time of overcharge, and having good performance in safety such as a heating test is provided. A water electrolyte battery can be obtained.
[0016]
In the nonaqueous electrolyte battery according to claim 1 or 2, it is preferable that the transition metal element M2 is Fe.
[0017]
LiCo c M2 1-c PO 4 By using Fe as M2 in the above, the balance of battery characteristics such as discharge capacity and cycle characteristics can be variously changed according to the application and purpose while maintaining the safety of the nonaqueous electrolyte battery during overcharge. .
[0018]
Furthermore, in the nonaqueous electrolyte battery according to any one of claims 1 and 2, it is preferable that the transition metal element M3 is at least one element selected from the group consisting of Ni, Fe, and Zn.
[0019]
LiMn 2-d M3 d O 4 By using the above metal element as M3 in the above, the balance of battery characteristics such as discharge capacity and cycle characteristics is variously changed according to the use and purpose while maintaining the safety of the nonaqueous electrolyte battery during overcharge. be able to.
[0020]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.
FIG. 1 is a schematic sectional view of a prismatic nonaqueous electrolyte battery according to one embodiment of the present invention. The prismatic nonaqueous electrolyte battery 1 includes a positive electrode 3 formed by applying a positive electrode mixture to a positive electrode current collector made of aluminum foil, and a negative electrode 4 formed by applying a negative electrode mixture to a negative electrode current collector formed of copper foil. Are stored in the battery case 6 with the flat wound electrode group 2 wound through the separator 5 and the non-aqueous electrolyte.
[0021]
A battery lid 7 provided with a safety valve 8 is attached to the battery case 6 by laser welding, a negative electrode terminal 9 is connected to the negative electrode 4 via a negative electrode lead 11, and the positive electrode 3 is connected to the battery lid 7 via a positive electrode lead 10. It is connected.
[0022]
In the present invention, a first positive electrode active material and a second positive electrode active material can be used as the positive electrode active material.
[0023]
As the first positive electrode active material according to the present invention, a general formula LiCo a Ni b M1 1-ab O 2 (However, 0 ≦ a <1, 0 ≦ b <1, 0.9 ≦ a + b ≦ 0.99, M1 is M1, B, Mg, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga , Ge, Zr, Nb, Mo, Sn, W, at least one element selected from the group consisting of). LiCo a Ni b M1 1-ab O 2 Has an excellent ability to insert and extract lithium ions, has a high discharge potential, and has an excellent cycle life. LiCo a Ni b M1 1-ab O 2 Adds at least one metal element selected from the group consisting of B, Mg, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Sn and W as M1 By doing so, the crystal structure can be stabilized. When the crystal structure is stabilized, the potential at which the crystal structure changes becomes noble, so that charging can be performed safely even at a more noble potential.
[0024]
The first positive electrode active material according to the present invention has a general formula Li a + b M b Mn 2-ab O 4 (Where 0 <a ≦ 0.2, 0 <b ≦ 0.15, M is at least one element other than Mn, and M is particularly preferably Al, Co, or Cr). it can. Li a + b M b Mn 2-ab O 4 Mn, which is a raw material of LiCo, is cheaper than Co and Ni and has abundant reserves. a Ni b M1 1-ab O 2 As compared with the case, the cost can be easily reduced. The charge potential at which the crystal structure changes is LiCo a Ni b M1 1-ab O 2 As compared with, it is excellent in safety when fully charged.
[0025]
As the second positive electrode active material according to the present invention, a general formula LiCo c M2 1-c PO 4 (0 ≦ c ≦ 1, M2 is at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Zr, Nb, Mo, W, and Ge). A compound having an olivine-type crystal structure can be used. LiCo c M2 1-c PO 4 In this case, the overcharge potential is 5.2 V (vs. Li / Li + ), The first positive electrode active material becomes overcharged at 4.5 V to 5.2 V (vs. Li / Li). + LiCo) even when charged at a potential nobler than c M2 1-c PO 4 Is safely charged and consumes the overcharge current, so that the decomposition of the first positive electrode active material and the decomposition of the electrolytic solution are suppressed, so that a non-aqueous electrolyte battery excellent in safety at the time of overcharge is obtained. Can be. LiCo c M2 1-c PO 4 Has a crystal structure by adding at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Zr, Nb, Mo, W, and Ge as M2. Can be stabilized. When the crystal structure is stabilized, the potential at which the crystal structure changes becomes noble, so that charging can be performed safely even at a more noble potential.
[0026]
As the second positive electrode active material according to the present invention, a general formula LiMn 2-d M3 d O 4 (0 <d ≦ 0.5, M3 is at least one element selected from the group consisting of Cr, Fe, Co, Ni, Cu, Zn) Lithium-manganese composite oxide having a spinel-type crystal structure represented by Can be used. LiMn 2-d M3 d O 4 In this case, the overcharge potential is 5.2 V (vs. Li / Li + ), The first positive electrode active material becomes overcharged at 4.5 V to 5.2 V (vs. Li / Li). + LiMn even when charged at a nobleer potential than 2-d M3 d O 4 Is safely charged and consumes the overcharge current, so that the decomposition of the first positive electrode active material and the decomposition of the electrolytic solution are suppressed, so that a non-aqueous electrolyte battery excellent in safety at the time of overcharge is obtained. Can be. LiMn 2-d M3 d O 4 By adding at least one element selected from the group consisting of Cr, Fe, Co, Ni, Cu, and Zn as M3, the crystal structure can be stabilized. When the crystal structure is stabilized, the potential at which the crystal structure changes becomes noble, so that charging can be performed safely even at a more noble potential.
[0027]
As the second positive electrode active material according to the present invention, LiNiVO having an inverse spinel type crystal structure is used. 4 Can be used. LiNiVO 4 In this case, the overcharge potential is 5.0 V (vs. Li / Li + ), The first positive electrode active material is overcharged at 4.5 V to 5.0 V (vs. Li / Li). + LiNiVO even when charged at a potential higher than that of LiNiVO 4 Is safely charged and consumes the overcharge current, so that the decomposition of the first positive electrode active material and the decomposition of the electrolytic solution are suppressed, so that a non-aqueous electrolyte battery excellent in safety at the time of overcharge is obtained. Can be.
[0028]
As the negative electrode active material, any substance capable of inserting and extracting lithium ions can be used. Among them, cokes, glassy carbons, graphites, non-graphitizable carbons, pyrolytic carbons, carbon fibers, or metallic lithium, lithium alloy, polyacene, etc. are used alone or in combination of two or more. can do. In particular, it is preferable to use a carbon material from the viewpoint of high safety.
[0029]
As the solvent of the non-aqueous electrolyte, ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, trifluoropropylene carbonate, γ-butyrolactone, 2-methyl-γ-butyrolactone, acetyl-γ-butyrolactone, γ-valerolactone, sulfolane, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyl-1,3-dioxolan, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, dimethyl carbonate, diethyl Carbonate, methyl ethyl carbonate, methyl propyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl isopropyl carbonate, dibutyl carbonate It can be used alone or as a mixture of two or more.
[0030]
The electrolyte salt as a solute of the non-aqueous electrolyte is LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiCF 3 CF 2 SO 3 , LiCF 3 CF 2 CF 2 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 6 SO 2 ) 2 And the like can be used alone or in combination of two or more. Among them, LiPF 6 It is preferable to use
[0031]
Further, a solid ion-conductive polymer electrolyte can be used instead of or in addition to the above-mentioned electrolyte salt. In this case, the configuration of the nonaqueous electrolyte battery includes the following combinations. A positive electrode, a negative electrode, a separator, an organic or inorganic solid electrolyte, a combination of a solvent alone or a non-aqueous electrolytic solution composed of a solvent and an electrolyte salt, or a positive electrode, a negative electrode, and an organic or inorganic separator as a separator Examples include a combination of a solid electrolyte membrane and a non-aqueous electrolyte composed of only a solvent or a solvent and an electrolyte salt. Polyethylene oxide, polyacrylonitrile, polyethylene glycol, and their modified products have low density and flexibility, and are therefore preferably used when they are used as a polymer electrolyte membrane in a wound electrode plate. Further, as the electrolyte, other than the polymer electrolyte, an inorganic solid electrolyte, a mixed material of an organic polymer electrolyte and an inorganic solid electrolyte, or the like can be used.
[0032]
As the separator, a porous polymer such as porous polyvinyl chloride, porous polyethylene, and porous polypropylene, or an ion-conductive polymer electrolyte membrane can be used alone or in combination.
[0033]
Hereinafter, the present invention will be described in detail based on examples. The present invention is not limited by the following examples.
<Example 1>
LiCo as the first positive electrode active material 0.8 Ni 0.15 B 0.05 O 2 5 parts by weight, 5 parts by weight of acetylene black as a conductive agent, and LiCo as a second positive electrode active material 0.75 Fe 0.25 PO 4 5 parts by weight and 5 parts by weight of polyvinylidene fluoride as a binder were mixed, and N-methyl-2-pyrrolidone was appropriately added and dispersed to prepare a positive electrode mixture slurry. This slurry was uniformly applied to an aluminum current collector having a thickness of 20 μm, dried, and then compression molded to a thickness of 180 μm by a roll press to produce a positive electrode.
[0034]
90 parts by weight of a carbon material that absorbs and releases lithium ions and 10 parts by weight of polyvinylidene fluoride were mixed, and N-methyl-2-pyrrolidone was appropriately added and dispersed to prepare a negative electrode mixture slurry. This slurry was uniformly applied to a 10 μm-thick copper current collector, dried, and then compression-molded to a thickness of 180 μm by a roll press to produce a negative electrode.
[0035]
A microporous polyethylene film having a thickness of 25 μm was used for the separator. As the non-aqueous electrolyte, ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 1: 1 and LiPF was used as an electrolyte salt. 6 Was used at a concentration of 1.0 mol / l.
[0036]
A prismatic nonaqueous electrolyte battery was manufactured using the above-described components.
[0037]
<Examples 2 to 16>
LiCo as the first positive electrode active material 0.8 Ni 0.15 B 0.05 O 2 The prismatic nonaqueous electrolyte batteries of Examples 2 to 16 were produced in the same manner as in Example 1 except that the compounds shown in Table 1 were used instead of
[0038]
<Example 17>
LiCo as the first positive electrode active material 0.8 Ni 0.15 B 0.05 O 2 Instead of using LiMn 1.9 Al 0.1 O 4 A prismatic nonaqueous electrolyte battery of Example 17 was produced in the same manner as in Example 1, except for using.
[0039]
<Comparative Example 1>
Instead of using 85 parts by weight of the first positive electrode active material and 5 parts by weight of the second positive electrode active material, LiCo was used as the positive electrode active material. 0.8 Ni 0.15 Mg 0.05 O 2 A prismatic nonaqueous electrolyte battery of Comparative Example 1 was produced in the same manner as in Example 1 except that 90 parts by weight was used.
[0040]
<Comparative Example 2>
LiCo as positive electrode active material 0.8 Ni 0.15 Mg 0.05 O 2 Instead of LiMn 2 O 4 A prismatic nonaqueous electrolyte battery of Comparative Example 2 was produced in the same manner as in Comparative Example 1 except for using.
[0041]
<Measurement>
(Discharge capacity)
Ten batteries of each of Examples 1 to 17 and Comparative Examples 1 and 2 were prepared, and charged and discharged at a temperature of 25 ° C. and a current of 600 mA at a charge end voltage of 4.2 V and a discharge end voltage of 2.5 V. The discharge capacities were determined and are summarized in Table 1.
[0042]
(Safety test)
Using the above battery, the battery was overcharged to a final charge voltage of 10.0 V at a current of 25 mA and a current of 1200 mA. The state of the battery at that time was observed.
[0043]
[Table 1]
[0044]
In the batteries of Examples 1 to 17 containing the second positive electrode active material, the number of batteries in which the safety valve was activated was 0, whereas in Comparative Examples 1 and 2 not containing the second positive electrode active material, 7 to 8 were used. Thus, it was found that the batteries of Examples 1 to 17 exhibited high safety during overcharge. This can be considered as follows. The potential of the positive electrode is 4.3 to 4.5 V (vs. Li / Li + ), The first positive electrode active material becomes overcharged. However, LiCo added as the second positive electrode active material 0.75 Fe 0.25 PO 4 Is overcharged at 5.2 V (vs. Li / Li + ), The potential of the positive electrode is 4.5 V (vs. Li / Li + ) Even when it is near, LiCo 0.75 Fe 0.25 PO 4 It is considered that since the overcharge current is consumed by safely charging the battery, the decomposition of the first positive electrode active material and the decomposition of the electrolytic solution are suppressed, so that the thermal escape of the battery is prevented. .
[0045]
<Examples 18 to 23>
LiCo as the first positive electrode active material 0.8 Ni 0.15 B 0.05 O 2 Instead of using LiCo 0.8 Ni 0.15 Mg 0.05 O 2 With the exception that the ratio of the total amount of the first positive electrode active material and the second positive electrode active material to the positive electrode mixture was kept constant while the contents of both were changed as shown in Table 2, In the same manner as in Example 1, the prismatic nonaqueous electrolyte batteries of Examples 18 to 23 were produced. These batteries were subjected to a discharge capacity test and a safety test in the same manner as described above. The results are summarized in Table 2.
[0046]
[Table 2]
[0047]
LiCo for positive electrode mixture 0.75 Fe 0.25 PO 4 In the batteries of Example 18 having a content of 0.5 wt%, the safety valves of five batteries operated, whereas in the batteries of Examples 19 to 23 having 1 wt% or more, the batteries operated with the safety valves Did not. However, in the battery of Example 23, although the safety valve did not operate, LiCo in the positive electrode mixture was not used. 0.75 Fe 0.25 PO 4 , The discharge capacity of the battery during normal use was reduced. From this, LiCo in the positive electrode mixture was 0.75 Fe 0.25 PO 4 Is preferably 20 wt% or less.
[0048]
<Examples 24 to 30, and Comparative Examples 3 to 6>
LiCo as the first positive electrode active material 0.8 Ni 0.15 B 0.05 O 2 Instead of using the compounds shown in Table 3, rectangular non-aqueous electrolyte batteries of Examples 24 to 30 and Comparative Examples 3 to 6 were produced in the same manner as in Example 1. These batteries were subjected to a discharge capacity test and a safety test in the same manner as described above. The results are summarized in Table 3.
[0049]
[Table 3]
[0050]
General formula LiCo a Ni b M1 1-ab O 2 In the first positive electrode active material represented by the formula, in Examples 24 to 28 in which 0.9 ≦ a + b ≦ 0.99, there was no battery in which the safety valve was operated, whereas in the case of LiCo in which a + b = 1, 0.8 Ni 0.2 O 2 In Comparative Example 3 in which was used as the first positive electrode active material, the safety valve operated for one battery. This is considered to be because the crystal structure is stabilized by adding Mg as M1 into the crystal. It is considered that the stable crystal structure results in a noble potential at which the crystal structure changes, so that charging can be performed safely even at a more noble potential.
[0051]
On the other hand, LiCo with a + b = 0.89 0.8 Ni 0.09 Mg 0.11 O 2 In Comparative Example 4 in which was used as the first positive electrode active material, the discharge capacity was significantly reduced to 587 mAh. This is considered to be because the discharge capacity was reduced by adding Mg as M1 to the crystal.
[0052]
From the above, the general formula LiCo a Ni b M1 1-ab O 2 In the first positive electrode active material represented by the formula, it is preferable that 0.9 ≦ a + b ≦ 0.99.
[0053]
General formula LiCo a Ni b M1 1-ab O 2 In the first positive electrode active material represented by, LiCo with a = 0.95 and b = 0 0.95 Mg 0.05 O 2 In Example 29 in which was used as the first positive electrode active material, there was no battery in which the safety valve was activated, whereas LiCoO with a = 1 and b = 0 2 In Comparative Example 5 in which was used as the first positive electrode active material, the safety valve operated with three batteries. This is considered to be because, as described above, the crystal structure was stabilized by adding Mg as M1 into the crystal.
[0054]
Similarly, LiNi with a = 0 and b = 0.95 0.95 Mg 0.05 O 2 Was used as the first positive electrode active material in Example 30, while no battery operated the safety valve, whereas LiNiO with a = 0 and b = 1 2 In Comparative Example 6 in which was used as the first positive electrode active material, the safety valve operated with two batteries.
[0055]
From the above, the general formula LiCo a Ni b M1 1-ab O 2 In the first positive electrode active material represented by the following formula, it is preferable that 0 ≦ a <1 and 0 ≦ b <1.
[0056]
<Examples 31 to 49>
LiCo as the first positive electrode active material 0.8 Ni 0.15 B 0.05 O 2 Instead of using LiCo 0.8 Ni 0.15 Mg 0.05 O 2 And LiCo as the second positive electrode active material 0.75 Fe 0.25 PO 4 A prismatic nonaqueous electrolyte battery was produced in the same manner as in Example 1 except that the compounds shown in Table 4 were used instead of the above. For these, discharge capacity and safety tests were performed in the same manner as described above. The results are summarized in Table 4.
[0057]
[Table 4]
[0058]
In Examples 31 to 49, the safety valves did not operate in all the batteries, indicating that the batteries had excellent overcharge characteristics. That is, as the second positive electrode active material, the general formula LiCo c M2 1-c PO 4 (0.5 ≦ c ≦ 1, M2 is at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Zr, Nb, Mo, W, and Ge) Compound represented by the general formula LiMn 2-d M3 d A compound represented by O4 (0 <d ≦ 0.5, M3 is at least one element selected from the group consisting of Cr, Fe, Co, Ni, Cu and Zn); and LiNiVO 4 It was found that a non-aqueous electrolyte battery having excellent overcharge characteristics can be obtained by using a battery containing at least one selected from the group consisting of:
[0059]
<Examples 50 to 56 and Comparative Examples 7 to 11>
LiCo as the first positive electrode active material 0.8 Ni 0.15 B 0.05 O 2 Instead of LiCo 0.8 Ni 0.15 Mg 0.05 O 2 And LiCo as the second positive electrode active material 0.75 Fe 0.25 PO 4 A prismatic nonaqueous electrolyte battery was produced in the same manner as in Example 1 except that the compounds shown in Table 5 were used instead of. These batteries were subjected to discharge capacity and safety tests in the same manner as described above. The results are summarized in Table 5.
[0060]
[Table 5]
[0061]
General formula LiCo c M2 1-c PO 4 (0.5 ≦ c ≦ 1, M2 is at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Zr, Nb, Mo, W, and Ge) In Examples 50 to 52 using the compound to be used as the second positive electrode active material, the safety valves did not operate in all the batteries. From this, the general formula LiCo c M2 1-c PO 4 (0.5 ≦ c ≦ 1, M2 is at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Zr, Nb, Mo, W, and Ge) It was found that a nonaqueous electrolyte battery having excellent overcharge characteristics can be obtained by using the compound to be used as the second positive electrode active material. However, in Comparative Example 7 in which the value of c is 0.4 and in Comparative Example 8 in which the value of c is 0.2, the safety valve operates with two batteries, and in Comparative Example 9 in which the value of c is 0, The safety valve was activated by five batteries. Thus, it was found that when the value of c was smaller than 0.5, the safety was poor.
[0062]
General formula LiMn 2-d M3 d O 4 (0 <d ≦ 0.5, M3 is at least one element selected from the group consisting of Cr, Fe, Co, Ni, Cu, and Zn) using a compound represented as the second positive electrode active material. In Examples 53 to 56, the safety valves did not operate in all batteries. On the other hand, LiMn with d = 0 2 O 4 In Comparative Example 10 in which was used as the second positive electrode active material, the safety valve operated with eight batteries. LiMn with d = 0.6 1.4 CrO 4 Was used as the second positive electrode active material, the safety valve was operated with two batteries in Comparative Example 11. From this, the general formula LiMn 2-d M3 d O 4 (0 <d ≦ 0.5, M3 is at least one element selected from the group consisting of Cr, Fe, Co, Ni, Cu, and Zn) by using a compound represented as the second positive electrode active material. It was found that a nonaqueous electrolyte battery having excellent overcharge characteristics could be obtained.
[0063]
<Summary>
As described above, the first positive electrode active material has the general formula LiCo a Ni b M1 1-ab O 2 (However, 0 ≦ a <1, 0 ≦ b <1, 0.9 ≦ a + b ≦ 0.99, M1 is B, Mg, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, A compound represented by at least one element selected from the group consisting of Zr, Nb, Mo, Sn, and W); a + b M b Mn 2-ab O 4 (Where 0 <a ≦ 0.2, 0 <b ≦ 0.15, M is at least one element other than Mn), and the second positive electrode active material is represented by the general formula LiCo c M2 1-c PO 4 (0.5 ≦ c ≦ 1, M2 is at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Zr, Nb, Mo, W, and Ge) Compound represented by the general formula LiMn 2-d M3 d O 4 (0 <d ≦ 0.5, M3 is at least one element selected from the group consisting of Cr, Fe, Co, Ni, Cu and Zn), and LiNiVO 4 By including at least one selected from the group consisting of, a nonaqueous electrolyte battery excellent in safety during overcharge can be obtained.
[0064]
<Other embodiments>
The present invention is not limited to the embodiments described with reference to the above description and drawings. For example, the following embodiments are also included in the technical scope of the present invention, and furthermore, besides the following, within the scope not departing from the gist. Can be implemented with various modifications.
[0065]
In the above embodiment, the rectangular nonaqueous electrolyte battery 1 has been described. However, the battery structure is not particularly limited, and may be a cylindrical shape, a bag shape, a lithium polymer battery, or the like.
[0066]
【The invention's effect】
According to the present invention, a non-aqueous electrolyte battery having excellent overcharge characteristics can be obtained.
[Brief description of the drawings]
FIG. 1 is a longitudinal sectional view of a prismatic nonaqueous electrolyte battery according to one embodiment of the present invention.
[Explanation of symbols]
1: Square non-aqueous electrolyte battery
2 ... Electrode group
3: Positive electrode
4: Negative electrode
5 ... Separator
6 ... Battery case
7 Battery cover
8. Safety valve
9 ... negative electrode terminal
10 Positive electrode lead
11 ... Negative electrode lead

Claims (2)

  1. In a non-aqueous electrolyte battery including a positive electrode including a positive electrode active material, a negative electrode, and a non-aqueous electrolyte, the positive electrode active material includes a first positive electrode active material and a second positive electrode active material; The active material has a general formula LiCo a Ni b M 1 1-ab O 2 (where 0 ≦ a <1, 0 ≦ b <1, 0.9 ≦ a + b ≦ 0.99, M1 is B, Mg, A compound represented by at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Sn and W), or a general formula Li a + b M b Mn 2- a-b O 4 ( provided that, 0 <a ≦ 0.2,0 <b ≦ 0.15, M is at least one element other than Mn) comprise represented by compounds, wherein the The positive electrode active material of No. 2 has a general formula LiCo c M2 1-c PO 4 (0.5 ≦ c ≦ 1, M2 is Ti , V, Cr, Mn, at least one element selected from the group consisting of Fe, Ni, Cu, Zn, Zr, Nb, Mo, W, and Ge), a general formula LiMn 2-d M3 d A compound represented by O 4 (0 <d ≦ 0.5, M3 is at least one element selected from the group consisting of Cr, Fe, Co, Ni, Cu, Zn) and a group consisting of LiNiVO 4 A non-aqueous electrolyte battery comprising at least one of the following.
  2. The content of the second positive electrode active material in the positive electrode mixture obtained by mixing the first positive electrode active material, the second positive electrode active material, the conductive agent, and the binder is 1% by weight or more. The non-aqueous electrolyte battery according to claim 1, wherein the content is 20% by weight or less.
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