JP4940505B2 - Lithium ion secondary battery - Google Patents

Lithium ion secondary battery Download PDF

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JP4940505B2
JP4940505B2 JP2001102690A JP2001102690A JP4940505B2 JP 4940505 B2 JP4940505 B2 JP 4940505B2 JP 2001102690 A JP2001102690 A JP 2001102690A JP 2001102690 A JP2001102690 A JP 2001102690A JP 4940505 B2 JP4940505 B2 JP 4940505B2
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containing oxide
cobalt
manganese
example
positive electrode
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JP2001345102A (en
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純司 久山
佳克 山本
昌志 熊川
尚 辻本
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ソニー株式会社
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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

Description

[0001]
BACKGROUND OF THE INVENTION
  The present invention includes a positive electrode including a manganese-containing oxide containing lithium (Li) and manganese (Mn) and a cobalt-containing oxide containing lithium and cobalt (Co).lithium ionThe present invention relates to a secondary battery.
[0002]
[Prior art]
In recent years, with the advancement of electronic technology, many small portable electronic devices such as a camera-integrated VTR (video tape recorder), a mobile phone, or a laptop computer have become widespread, and their size and weight have been reduced. Therefore, as a portable power source used for them, development of a small battery, a light battery and a high energy density, in particular, a secondary battery is underway. Among them, lithium ion secondary batteries are highly expected because they can provide a higher energy density than conventional lead batteries or nickel-cadmium batteries using a liquid electrolyte containing water as a solvent.
[0003]
As a negative electrode material for this lithium ion secondary battery, a carbon material capable of inserting and extracting lithium has been put into practical use. Among them, non-graphitizable carbon has a gentle potential shape at the time of discharge and can easily display the remaining capacity. Therefore, it is widely used.
[0004]
On the other hand, lithium-cobalt composite oxide, lithium-manganese composite oxide, lithium-nickel composite oxide, and the like have been put to practical use as positive electrode materials. Of these, lithium-cobalt composite oxides have the best balance in terms of battery capacity, cost, and thermal stability, and are currently widely used. Although lithium-manganese composite oxides have drawbacks such as low battery capacity and slightly poor high-temperature storage characteristics, they are excellent in terms of raw material price and stable supply, and are being researched for future use. .
[0005]
In addition, about these positive electrode materials, since the capacity | capacitance reduction by repetition of charging / discharging was seen, various improvement for improving charging / discharging cycling characteristics was tried until now. For example, regarding lithium-cobalt composite oxide, it has been reported that a part of cobalt is replaced with a transition metal, an alkali metal, aluminum (Al) or boron (JP-A-4-25316, JP-A-7- No. 176302 and Japanese Patent Publication No. 4-24831). Regarding lithium-manganese composite oxides, in addition to a method of substituting a part of manganese with other elements, LiMn2 OFour And Li2 Mn2 OFour A method using a composite with (see JP-A-6-338320) or a method of coating the surface of a lithium / manganese composite oxide with boron (see JP-A-8-73527) has been reported. In addition, a method for suppressing the expansion and contraction of the positive electrode during charge and discharge by using a mixture of lithium / manganese composite oxide and lithium / cobalt composite oxide has also been reported (see Japanese Patent No. 2751624).
[0006]
[Problems to be solved by the invention]
However, in a secondary battery using a lithium-cobalt composite oxide, a lithium-manganese composite oxide or a mixture of these for the positive electrode, the characteristics deteriorate when stored or used in a high temperature environment of 45 ° C. to 60 ° C., for example. There was a problem that. In particular, when used in an information terminal such as a mobile phone, it may be used at a low temperature of about −20 ° C. after high temperature storage, but sufficient battery characteristics cannot be obtained after high temperature storage. In addition, when non-graphitizable carbon is used for the negative electrode, the discharge capacity under heavy load decreases after high temperature use, and it is easy to be exposed to high temperature like a laptop computer, and heavy load discharge capacity is important. For applications, sufficient characteristics could not be obtained. Further, these secondary batteries have a problem that the charge / discharge cycle characteristics cannot be sufficiently improved depending on the particle sizes of the lithium / manganese composite oxide and the lithium / cobalt composite oxide.
[0007]
  The present invention has been made in view of such problems, and its purpose is excellent in high-temperature storage characteristics, and also excellent in load characteristics and charge / discharge cycle characteristics after use at high temperatures.lithium ionIt is to provide a secondary battery.
[0008]
[Means for Solving the Problems]
  The lithium ion secondary battery according to the present invention has LiMn as a manganese-containing oxide.1.8Cr0.2OFour andLiCoO as cobalt-containing oxide2 Positive electrode material consisting ofA positive electrode material mixture layer is provided on the positive electrode current collector layer, and each of the manganese-containing oxide and the cobalt-containing oxide has an average particle size of 30 μm or less.
[0009]
  In the lithium ion secondary battery according to the present invention, the positive electrode is LiMn as a manganese-containing oxide. 1.8 Cr 0.2 O Four LiCoO as a cobalt-containing oxide 2 And the average particle diameter of the manganese-containing oxide and the cobalt-containing oxide is 30 μm or less, respectively.Excellent battery characteristics can be obtained even after high temperature storage.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
[0011]
FIG. 1 shows a cross-sectional configuration of a secondary battery according to an embodiment of the present invention. This secondary battery is a so-called cylindrical type, and a wound electrode body 20 in which a belt-like positive electrode 21 and a negative electrode 22 are wound through a separator 23 inside a substantially hollow cylindrical battery can 11. have. The battery can 11 is made of, for example, iron (Fe) plated with nickel (Ni), and has one end closed and the other end open. Inside the battery can 11, a pair of insulating plates 12 and 13 are arranged perpendicular to the winding peripheral surface so as to sandwich the winding electrode body 20.
[0012]
At the open end of the battery can 11, a battery lid 14, a safety valve mechanism 15 provided inside the battery lid 14 and a heat sensitive resistance element (Positive Temperature Coefficient; PTC element) 16 are interposed via a gasket 17. It is attached by caulking, and the inside of the battery can 11 is sealed. The battery lid 14 is made of, for example, the same material as the battery can 11. The safety valve mechanism 15 is electrically connected to the battery lid 14 via the heat sensitive resistance element 16, and the disk plate 15a is reversed when the internal pressure of the battery exceeds a certain level due to an internal short circuit or external heating. Thus, the electrical connection between the battery lid 14 and the wound electrode body 20 is cut off. When the temperature rises, the heat sensitive resistance element 16 limits the current by increasing the resistance value and prevents abnormal heat generation due to a large current, and is made of, for example, barium titanate semiconductor ceramics. The gasket 17 is made of, for example, an insulating material, and asphalt is applied to the surface.
[0013]
For example, the wound electrode body 20 is wound around the center pin 24. A positive electrode lead 25 made of aluminum (Al) or the like is connected to the positive electrode 21 of the spirally wound electrode body 20, and a negative electrode lead 26 made of nickel or the like is connected to the negative electrode 22. The positive electrode lead 25 is electrically connected to the battery lid 14 by being welded to the safety valve mechanism 15, and the negative electrode lead 26 is welded to and electrically connected to the battery can 11.
[0014]
The positive electrode 21 includes, for example, a positive electrode mixture layer and a positive electrode current collector layer, and has a structure in which a positive electrode mixture layer is provided on both surfaces or one surface of the positive electrode current collector layer. The positive electrode current collector layer is made of, for example, a metal foil such as an aluminum foil, a nickel foil, or a stainless steel foil. The positive electrode mixture layer includes, for example, a manganese-containing oxide and a cobalt-containing oxide described below, and further includes a conductive agent such as graphite and a binder such as polyvinylidene fluoride as necessary. .
[0015]
The manganese-containing oxide contains lithium, manganese, at least one first element selected from the group consisting of metal elements other than manganese and boron, and oxygen. This manganese-containing oxide has, for example, a cubic (spinel) structure or a tetragonal structure, and the first element is present in a part of the site of the manganese atom by being replaced with a manganese atom. Thus, by substituting a part of manganese with the first element, the manganese-containing oxide is considered to stabilize the crystal structure. Thus, in this secondary battery, the capacity retention rate after high-temperature storage and the high-temperature storage It is possible to improve the heavy load discharge capacity maintenance rate after the cycle.
[0016]
The chemical formula of the manganese-containing oxide is Li, where the first element is represented by Ma.xMn2-yMayOFourIndicated by The value of x is preferably in the range of 0.9 ≦ x ≦ 2, and the value of y is preferably in the range of 0.01 ≦ y ≦ 0.5. That is, the composition ratio Ma / Mn of the first element to manganese is preferably in the range of 0.01 / 1.99 to 0.5 / 1.5 in terms of molar ratio. Within this range, the crystal structure is more stable, and if the first element is less than this, a sufficient effect due to substitution cannot be obtained. If the first element is more, the discharge energy at low temperatures after high-temperature storage and This is because the heavy load discharge capacity maintenance rate after use at high temperature is lowered. The more preferable ranges of x and y are 0.9 ≦ x ≦ 1.4 and 0.01 ≦ y ≦ 0.3.
[0017]
Specifically, as the first element, iron, nickel, cobalt, copper (Cu), zinc (Zn), aluminum, tin (Sn), chromium (Cr), vanadium (V), titanium (Ti), At least one member selected from the group consisting of magnesium (Mg), calcium (Ca) and strontium (Sr) is preferable, and among them, iron, nickel, cobalt, zinc, aluminum, tin, chromium, vanadium, titanium, magnesium and strontium. At least one of the group is preferred. This is because manganese-containing oxides containing these as the first element can be obtained relatively easily and are chemically stable.
[0018]
The cobalt-containing oxide contains lithium, at least cobalt in the group consisting of a metal element and boron, and oxygen. This cobalt-containing oxide has, for example, a layered structure, and at least one second element in the group consisting of a metal element other than cobalt and boron is substituted with a cobalt atom in a part of the cobalt atom site. May exist. The chemical formula of this cobalt-containing oxide is typically LiCo when the second element is represented by Mb.1-zMbzO2Indicated by The composition ratio of lithium and oxygen may not be Li: O = 1: 2, and the value of z is preferably in the range of 0 ≦ z ≦ 0.5. That is, the composition ratio Mb / Co of the second element with respect to cobalt is preferably in the range of 0 to 0.5 / 0.5 in terms of molar ratio. This is because, within this range, the crystal structure is stable, and if the amount of the second element is large, the discharge energy at a low temperature after storage at a high temperature becomes low.
[0019]
In addition, for example, when the non-graphitizable carbon described later is used for the negative electrode 22, the cobalt-containing oxide is present by replacing at least one second element with a cobalt atom at a part of the site of the cobalt atom. It is preferable. Thereby, it is considered that the crystal structure of the cobalt-containing oxide is further stabilized, and the heavy load discharge capacity retention rate after the high temperature cycle can be improved. In that case, the value of z is preferably in the range of 0.01 ≦ z ≦ 0.5. That is, the composition ratio Mb / Co of the second element with respect to cobalt is preferably in the range of 0.01 / 0.99 to 0.5 / 0.5 in terms of molar ratio. This is because within this range, the crystal structure is more stable, and the heavy load discharge capacity retention rate after use at high temperatures can be further improved. A more preferable range of z is 0.01 ≦ z ≦ 0.25.
[0020]
Specifically, the second element is selected from the group consisting of iron, nickel, manganese, copper, zinc, aluminum, tin, boron, gallium (Ga), chromium, vanadium, titanium, magnesium, calcium and strontium. Among these, at least one is mentioned, and among them, at least one selected from the group consisting of iron, manganese, zinc, aluminum, tin, boron, gallium, chromium, vanadium, titanium, magnesium and strontium is preferable. This is because cobalt-containing oxides containing these as second elements can be obtained relatively easily and are chemically stable.
[0021]
The mixing ratio of the manganese-containing oxide and the cobalt-containing oxide in the positive electrode 21 is a mass ratio, and is preferably a cobalt-containing oxide 90-20 with respect to the manganese-containing oxide 10-80. Since manganese-containing oxides deteriorate significantly in the electrolyte described later in a high-temperature atmosphere, if there is more manganese-containing oxide content than this, the internal resistance increases after high-temperature storage, and the capacity decreases. Because it ends up. Conversely, if the content of the cobalt-containing oxide is higher than this, the discharge energy at low temperatures after high-temperature storage will be low. Moreover, it is because the heavy load discharge capacity after high temperature use cannot be improved sufficiently outside this range. In particular, when it is desired to improve the heavy load discharge capacity after high temperature use, the cobalt-containing oxide 60 to 20 can be obtained in a mass ratio with respect to the manganese-containing oxide 40 to 80, so that a higher effect can be obtained. preferable.
[0022]
The average particle diameters of the manganese-containing oxide and the cobalt-containing oxide are each preferably 30 μm or less. This is because if the average particle size is larger than this, expansion and contraction of the positive electrode 21 accompanying charge / discharge cannot be sufficiently suppressed, and sufficient charge / discharge cycle characteristics cannot be obtained at room temperature. These average particle diameters are obtained by, for example, a laser diffraction method. For example, when non-graphitizable carbon is used for the negative electrode 22, heavy duty cycle characteristics under a high temperature environment can be improved by defining specific surface areas of the manganese-containing oxide and the cobalt-containing oxide.
[0023]
The manganese-containing oxide and the cobalt-containing oxide are, for example, a lithium compound, a manganese compound, and a compound containing the first element, or a lithium compound, a cobalt compound, and a compound containing the second element as necessary, respectively. It can be obtained by preparing and mixing them at a desired ratio, followed by heating and firing at a temperature of 600 ° C. to 1000 ° C. in an oxygen-existing atmosphere. At that time, carbonates, hydroxides, oxides, nitrates, or organic acid salts are used as raw material compounds.
[0024]
The negative electrode 22 has, for example, a structure in which a negative electrode mixture layer is provided on both surfaces or one surface of the negative electrode current collector layer, similarly to the positive electrode 21. The negative electrode current collector layer is made of, for example, a metal foil such as a copper foil, a nickel foil, or a stainless steel foil. The negative electrode mixture layer includes, for example, lithium metal or any one or more of negative electrode materials capable of inserting and extracting lithium at a potential of 2 V or less with reference to the lithium metal potential. In addition, a binder such as polyvinylidene fluoride is further included as necessary.
[0025]
Examples of the anode material capable of inserting and extracting lithium include metals and semiconductors capable of forming an alloy or compound with lithium, or alloys or compounds thereof. These metals, alloys or compounds can be represented, for example, by the chemical formula DsEtLiuIt is represented by In this chemical formula, D represents at least one of a metal element and a semiconductor element capable of forming an alloy or compound with lithium, and E represents at least one of a metal element and a semiconductor element other than lithium and D. The values of s, t, and u are s> 0, t ≧ 0, and u ≧ 0, respectively.
[0026]
Among them, the metal element or semiconductor element capable of forming an alloy or compound with lithium is preferably a group 4B metal element or semiconductor element, particularly preferably silicon or tin, and most preferably silicon. These alloys or compounds are also preferable, specifically, SiBFour, SiB6, Mg2Si, Mg2Sn, Ni2Si, TiSi2, MoSi2CoSi2NiSi2, CaSi2, CrSi2, CuFiveSi, FeSi2, MnSi2, NbSi2, TaSi2, VSi2, WSi2Or ZnSi2Etc.
[0027]
Examples of the negative electrode material capable of absorbing and desorbing lithium include carbon materials, metal oxides, and polymer materials. Examples of the carbon material include non-graphitizable carbon, artificial graphite, cokes, graphites, glassy carbons, organic polymer compound fired bodies, carbon fibers, activated carbon, and carbon blacks. Of these, coke includes pitch coke, needle coke, and petroleum coke. Organic polymer compound fired bodies are carbonized by firing polymer materials such as phenol resin and furan resin at an appropriate temperature. What you did. In addition, examples of the metal oxide include iron oxide, ruthenium oxide, molybdenum oxide, and tin oxide, and examples of the polymer material include polyacetylene and polypyrrole.
[0028]
In particular, a carbon material is preferable because an excellent discharge capacity and cycle characteristics can be obtained. Among these, graphite is preferable because a high discharge capacity can be obtained, and non-graphitizable carbon is preferable because the discharge potential shape is gentle, the capacity residual display is easy, and cycle characteristics are excellent. Graphite has a true density of 2.1 g / cm.ThreeOr more, more preferably 2.18 g / cmThreeThe thickness of the C-axis crystallite on the (002) plane is 14.0 nm or more and the plane spacing of the (002) plane is less than 0.34 nm, more preferably 0.335 nm or more and 0.337 nm or less. Non-graphitizable carbon has a (002) plane spacing of 0.372 nm or more and a true density of 1.70 g / cm, among carbon materials with almost no developed graphite structure.ThreeLess than N which is an inert gas2The thing which does not have the exothermic peak in airflow in 700 degreeC or more is said.
[0029]
For example, the separator 23 is composed of a porous film made of a polyolefin-based material such as polypropylene or polyethylene, or a porous film made of an inorganic material such as a ceramic nonwoven fabric. A laminated structure may be used.
[0030]
The separator 23 is impregnated with an electrolytic solution that is a liquid electrolyte. This electrolytic solution is obtained by dissolving, for example, a lithium salt as an electrolyte salt in a solvent. Examples of the solvent include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, γ-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, Non-aqueous solvents such as 4-methyl-1,3-dioxolane, diethyl ether, sulfolane, methyl sulfolane, acetonitrile, propionitrile, anisole, acetate ester, butyrate ester or propionate ester are preferred, and any one of these A seed or a mixture of two or more is used.
[0031]
Examples of the lithium salt include LiClO.Four, LiAsF6, LiPF6, LiBFFour, LiB (C6HFive)Four, CHThreeSOThreeLi, CFThreeSOThreeThere are Li, LiCl, LiBr, etc., and any one or more of these are used in combination. Among them, LiPF6 Is preferable because it can obtain high conductivity and is excellent in oxidation stability.Four Is preferable because it is excellent in thermal stability and oxidation stability.
[0032]
For example, the secondary battery can be manufactured as follows.
[0033]
First, for example, a positive electrode mixture is prepared by mixing a manganese-containing oxide, a cobalt-containing oxide, and, if necessary, a conductive agent and a binder, and this positive electrode mixture is mixed with N-methyl-2-pyrrolidone. A paste-like positive electrode mixture slurry is dispersed in such a solvent. After applying this positive electrode mixture slurry to the positive electrode current collector layer and drying the solvent, the positive electrode mixture layer is formed by compression molding with a roller press or the like, and the positive electrode 21 is produced.
[0034]
Next, for example, a negative electrode material and, if necessary, a binder are mixed to prepare a negative electrode mixture, and the negative electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to obtain a paste-like negative electrode A mixture slurry is obtained. After applying this negative electrode mixture slurry to the negative electrode current collector layer and drying the solvent, the negative electrode mixture layer is formed by compression molding using a roller press or the like, and the negative electrode 22 is produced.
[0035]
Subsequently, the positive electrode lead 25 is attached to the positive electrode current collector layer by welding or the like, and the negative electrode lead 26 is attached to the negative electrode current collector layer by welding or the like. After that, the positive electrode 21 and the negative electrode 22 are wound through the separator 23, and the tip portion of the positive electrode lead 26 is welded to the safety valve mechanism 15, and the tip portion of the negative electrode lead 27 is welded to the battery can 11. The positive electrode 21 and the negative electrode 22 are sandwiched between a pair of insulating plates 12 and 13 and stored in the battery can 11. After the positive electrode 21 and the negative electrode 22 are accommodated in the battery can 11, an electrolyte is injected into the battery can 11 and impregnated in the separator 23. After that, the battery lid 14, the safety valve mechanism 15, and the heat sensitive resistance element 16 are fixed to the opening end of the battery can 11 by caulking through a gasket 17. Thereby, the secondary battery shown in FIG. 1 is formed.
[0036]
This secondary battery operates as follows.
[0037]
In the secondary battery, when charged, for example, lithium ions are released from the positive electrode 21 and inserted in the negative electrode 22 through the electrolyte impregnated in the separator 23. When the discharge is performed, for example, lithium ions are released from the negative electrode 22 and inserted into the positive electrode 21 through the electrolyte impregnated in the separator 23. Here, since the positive electrode 21 contains the manganese-containing oxide containing the first element and the cobalt-containing oxide, the battery capacity does not decrease even after high-temperature storage, and a high capacity retention rate is obtained. In addition, a high heavy load discharge capacity retention rate can be obtained even after high temperature use.
[0038]
Thus, according to the secondary battery in accordance with the present embodiment, positive electrode 21 contains a manganese-containing oxide containing lithium, manganese, and the first element, and a cobalt-containing oxide containing lithium and cobalt. Therefore, even when stored at a high temperature, the battery capacity does not decrease, and the capacity retention rate can be improved. Therefore, for example, when used in a mobile phone or a laptop computer, even if it is left in a car or the temperature rises during use, it is exposed to a high temperature environment of about 40 ° C to 60 ° C. Excellent battery characteristics can be maintained.
[0039]
In particular, if the cobalt-containing oxide contains the second element in addition to lithium and cobalt, the heavy load discharge capacity retention rate after high temperature use can also be improved. Therefore, particularly when used in a laptop computer or the like, an excellent heavy load discharge capacity can be obtained even when exposed to a high temperature environment.
[0040]
Moreover, if the molar ratio of the first element to manganese in the manganese-containing oxide is 0.01 / 1.99 or more, the capacity retention rate after high-temperature storage can be further improved, and further the manganese-containing oxide When the molar ratio of the first element to manganese is 0.01 / 1.99 or more and the molar ratio of the second element to cobalt in the cobalt-containing oxide is 0.01 / 0.99 or more, high temperature use is possible. The subsequent heavy load discharge capacity maintenance rate can be further improved.
[0041]
In addition, the molar ratio of the first element to manganese in the manganese-containing oxide is 0.5 / 1.5 or less, or the molar ratio of the second element to cobalt in the cobalt-containing oxide is 0.5 / 1.5. If it is 0.5 or less, sufficient discharge energy can be obtained even when used at a low temperature of, for example, about −20 ° C. after high-temperature storage. Therefore, for example, when used in a mobile phone or a laptop computer, excellent battery characteristics can be maintained even when placed in an environment where the temperature fluctuates severely.
[0042]
Furthermore, if the mixing ratio of the manganese-containing oxide and the cobalt-containing oxide is set to the cobalt-containing oxide 90 to 20 with respect to the manganese-containing oxide 10 to 80 by mass ratio, the battery after high-temperature storage is obtained. The characteristics can be further improved.
[0043]
In addition, if the average particle diameters of the manganese-containing oxide and the cobalt-containing oxide are each 30 μm or less, the expansion and contraction of the positive electrode 21 accompanying charge / discharge can be suppressed, and sufficient charge / discharge cycle characteristics at room temperature. Can be obtained.
[0044]
【Example】
Further, a specific embodiment of the present invention will be described in detail with reference to FIG.
[0045]
  (Example 1-1, Reference Examples 1-2 to 1-10)
  First, lithium carbonate (Li2COThree) And manganese dioxide (MnO)2) And dichromium trioxide (Cr2OThreeManganese-containing oxide Li containing lithium, manganese, and chromium as the first element (Ma) by firing at 850 ° C. for 5 hours in the air.xMn2-yCryOFourWas made. that time,Example 1-1, Reference Examples 1-2 to 1-10Then, the mixing ratio of the raw materials was changed so that the composition of the manganese-containing oxide was as shown in Table 1. Next, the obtained manganese-containing oxide was pulverized to have an average particle size of 20 μm. The average particle size was measured by a laser diffraction method.
[0046]
[Table 1]
[0047]
  Also, lithium carbonate and cobalt monoxide (CoO) and depending on the embodiment dialuminum trioxide (Al2OThreeAnd a cobalt-containing oxide LiCo containing lithium, cobalt, and aluminum as the second element (Mb) according to the embodiment.1-zAlzO2Was made. even here,Example 1-1, Reference Examples 1-2 to 1-10Then, the mixing ratio of the raw materials was changed so that the composition of the cobalt-containing oxide was as shown in Table 1. Next, the obtained cobalt-containing oxide was pulverized to have an average particle size of 10 μm. The measurement of the average particle diameter was similarly performed by a laser diffraction method.
[0048]
Subsequently, after mixing 10 parts by mass of the obtained manganese-containing oxide and 90 parts by mass of the cobalt-containing oxide, 7 parts by mass of graphite as a conductive agent and polyfluorination as a binder with respect to 90 parts by mass of the mixed powder. A positive electrode mixture was prepared by mixing 3 parts by mass of vinylidene. After preparing the positive electrode mixture, the positive electrode mixture is dispersed in N-methylpyrrolidone as a solvent to form a positive electrode mixture slurry, and uniformly formed on both surfaces of the positive electrode current collector layer made of a 20 μm-thick strip-shaped aluminum foil. It was applied, dried, and compression molded to form a positive electrode mixture layer, and a positive electrode 21 was produced. After that, an aluminum positive electrode lead 25 was attached to one end of the positive electrode current collector layer.
[0049]
Next, 30 parts by mass of coal tar coke as a binder is added to 100 parts by mass of coal-based coke as a filler, mixed at about 100 ° C., then compression molded by a press machine, and heat-treated at a temperature of 1000 ° C. or less. Thus, a carbon molded body was produced. Subsequently, the carbon impregnated body was impregnated with coal tar pitch melted at 200 ° C. or lower and heat-treated at 1000 ° C. or lower, and the pitch impregnation / heat treatment step was repeated several times, and then in an inert atmosphere at 2700 ° C. A graphitized molded body was produced by heat treatment. After that, the graphitized molded body was pulverized and classified into powder.
[0050]
The obtained graphitized powder was subjected to structural analysis by X-ray diffraction. As a result, the (002) plane spacing was 0.337 nm, and the (002) plane C-axis crystallite thickness was 50.0 nm. It was. The true density determined by the pycnometer method is 2.23 g / cm.ThreeThe bulk density is 0.83 g / cmThreeThe average shape parameter was 10. Furthermore, the specific surface area determined by the BET (Brunauer, Emmett, Teller) method is 4.4 m.2The average particle size is 31.2 μm, the cumulative 10% particle size is 12.3 μm, the cumulative 50% particle size is 29.5 μm, and the cumulative 90% particle size is 53. 0.7 μm. In addition, the fracture strength of graphitized particles determined using a Shimadzu micro-compression tester (manufactured by Shimadzu Corporation) is 7.0 × 10 on average.7Pa.
[0051]
  blackAfter obtaining the leaded powder, 90 parts by mass of this graphitized powder and 10 parts by mass of polyvinylidene fluoride as a binder are mixed to prepare a negative electrode mixture, which is dispersed in N-methylpyrrolidone as a solvent. A negative electrode mixture slurry was obtained. After preparing the negative electrode mixture slurry, the negative electrode mixture slurry was uniformly applied to both sides of the negative electrode current collector layer made of a strip-shaped copper foil having a thickness of 10 μm, dried, and compression molded to form the negative electrode mixture layer. Thus, a negative electrode 22 was produced. After that, a copper negative electrode lead 26 was attached to one end of the negative electrode current collector layer.
[0052]
After each of the positive electrode 21 and the negative electrode 22 was prepared, a separator 23 made of a microporous polypropylene film having a thickness of 25 μm was prepared, and the negative electrode 22, the separator 23, the positive electrode 21, and the separator 23 were laminated in this order. A spirally wound electrode body 20 was manufactured by winding a large number in a spiral shape and fixing the outermost periphery with an adhesive tape.
[0053]
  After producing the wound electrode body 20, the wound electrode body 20 is sandwiched between the pair of insulating plates 12 and 13, the negative electrode lead 26 is welded to the battery can 11, and the positive electrode lead 25 is welded to the safety valve mechanism 15. The wound electrode body 20 was housed inside a nickel-plated iron battery can 11. The battery can 11 used had an outer diameter of 18.0 mm, an inner diameter of 17.38 mm, a can thickness of 0.31 mm, and a height of 65 mm. After the wound electrode body 20 was accommodated in the battery can 11, an electrolyte solution was injected into the battery can 11. The electrolytic solution includes LiPF as an electrolyte salt in a solvent in which equal volumes of propylene carbonate and 1,2-dimethoxyethane are mixed.6Was dissolved at a rate of 1.0 mol / l. Thereafter, the battery lid 14 is caulked to the battery can 11 through the gasket 17 whose surface is coated with asphalt, whereby the cylindrical secondary battery shown in FIG. Produced. In addition,Example 1-1, Reference Examples 1-2 to 1-10The other secondary batteries are the same except that the composition of the manganese-containing oxide or the cobalt-containing oxide is different.
[0054]
The obtained secondary battery was examined for high-temperature storage characteristics and charge / discharge cycle characteristics at room temperature. As the high temperature storage characteristics, the room temperature discharge capacity retention rate and the low temperature discharge energy after high temperature storage were determined, respectively. The results are shown in Table 1, respectively.
[0055]
In addition, the room temperature discharge capacity maintenance rate after high temperature storage was calculated | required as follows. First, charge and discharge were performed in a 23 ° C. constant temperature bath to obtain an initial discharge capacity. At that time, charging is performed at a constant current of 1 A until the battery voltage reaches 4.2 V, and then charging is performed at a constant voltage of 4.2 V until the total charging time reaches 3 hours, and discharging is performed at a constant current of 0.5 A. The final voltage was 3.0V. Next, after charging again under these charging conditions, it was stored in an oven at 60 ° C. for 2 weeks. Subsequently, after discharging to a final voltage of 3.0 V once in a constant temperature bath at 23 ° C., charging / discharging is performed for 10 cycles under the above-described charging / discharging conditions, and the highest value in 10 cycles is the discharge capacity after high-temperature storage. The ratio to the initial discharge capacity was defined as the room temperature discharge capacity retention rate after high-temperature storage.
[0056]
The low-temperature discharge energy after high-temperature storage is stored at 60 ° C. for 2 weeks, and then discharged to a final voltage of 3.0 V in a thermostatic bath at 23 ° C., then charged under the above-mentioned charging conditions, and −20 ° C. It calculated | required from the result of having discharged on the above-mentioned discharge conditions in a thermostat.
[0057]
Furthermore, as charge / discharge cycle characteristics at normal temperature, 200 cycles of charge / discharge were performed in a constant temperature bath at 23 ° C. under the above-mentioned charge / discharge conditions, and the ratio of the discharge capacity at the 200th cycle to the discharge capacity at the second cycle (capacity maintenance rate). )
[0058]
  Example 1-1, Reference Examples 1-2 to 1-10As Comparative Example 1-1, except that the compositions of the manganese-containing oxide and the cobalt-containing oxide were changed as shown in Table 1,Example 1-1, Reference Examples 1-2 to 1-10A secondary battery was fabricated in the same manner as described above. Also for Comparative Example 1-1,Example 1-1, Reference Examples 1-2 to 1-10Similarly, the high temperature storage characteristics and the charge / discharge cycle characteristics at room temperature were examined. The obtained results are shown in Table 1, respectively.
[0059]
  As can be seen from Table 1,Example 1-1, Reference Examples 1-2 to 1-10In both cases, a high value of 95% or more was obtained for the room temperature discharge capacity retention ratio after high-temperature storage, whereas in Comparative Example 1-1 using manganese-containing oxide in which manganese was not substituted with chromium, 89 Only a low value of% was obtained. That is, it was found that if the manganese-containing oxide contains chromium, the room temperature discharge capacity retention rate after high temperature storage can be improved.
[0060]
Further, Example 1-4 in which the molar ratio of aluminum to cobalt in the cobalt-containing oxide (Al / Co) is greater than 0.5 / 0.5, and the molar ratio of chromium to manganese in the manganese-containing oxide (Cr / In Example 1-7 where Mn) is larger than 0.5 / 1.5, the low-temperature discharge energy after high-temperature storage was only 2.4 Wh or less, whereas in other examples A high value of 3.0 Wh or more was obtained. That is, the molar ratio of chromium to manganese in the manganese-containing oxide (Cr / Mn) is 0.5 / 1.5 or less, and the molar ratio of aluminum to cobalt in the cobalt-containing oxide (Al / Co) is 0.5 / 1.5. It was found that if it is 0.5 or less, the low temperature discharge energy after high temperature storage can be increased. Good results were obtained for the charge / discharge cycle characteristics at room temperature.
[0061]
  (referenceExamples 1-11 to 1-22)
  referenceIn Examples 1-11 to 1-16, except that the first element (Ma) was changed as shown in Table 2 to produce a manganese-containing oxide, the same procedure as in Example 1-1 was performed. A secondary battery was produced. When producing the manganese-containing oxide, diiron trioxide (Fe) was used in Example 1-11 instead of dichromium trioxide in Example 1-1.2OThree)referenceExample 1-12 uses dialuminum trioxide,referenceIn Example 1-13, magnesium monoxide (MgO) was used.referenceIn Example 1-14, zinc monoxide (ZnO) was used.referenceIn Example 1-15, tin monoxide (SnO) was used.referenceIn Examples 1-16, cobalt monoxide and dichromium trioxide were used.
[0062]
[Table 2]
[0063]
  Also,referenceIn Examples 1-17 to 1-22, except that the cobalt-containing oxide was produced by changing the second element (Mb) so that the composition shown in Table 2 was obtained, the others were the same as in Example 1-1. Similarly, a secondary battery was produced. When preparing cobalt-containing oxides, in addition to lithium carbonate and cobalt monoxidereferenceIn Example 1-17, nickel monoxide (NiO) was mixed,referenceIn Example 1-18, digallium trioxide (Ga2OThree)referenceIn Example 1-19, magnesium monoxide was mixed,referenceIn Example 1-20, zinc monoxide is mixed,referenceIn Example 1-21, tin monoxide was mixed,referenceIn Example 1-22, nickel monoxide and dialuminum trioxide were mixed.
[0064]
  referenceFor Examples 1-11 to 1-22, the high-temperature storage characteristics and the charge / discharge cycle characteristics at room temperature were examined in the same manner as in Example 1-1. The obtained results are shown in Table 2 together with the results of Example 1-1.
[0065]
  As can be seen from Table 2,referenceIn Examples 1-11 to 1-22, a high value was obtained as in Example 1-1 together with a normal temperature discharge capacity retention rate of 96% or higher after high-temperature storage and a low-temperature discharge energy after high-temperature storage of 3.1 Wh or higher. It was. Moreover, the favorable result was obtained also about the charge / discharge cycling characteristic in normal temperature. That is, even when a manganese-containing oxide obtained by changing the first element to another element other than chromium or a cobalt-containing oxide containing a second element other than aluminum is used, Example 1-1 It was found that excellent high-temperature storage characteristics can be obtained as well.
[0066]
(Examples 1-23 to 1-26)
A secondary battery was fabricated in the same manner as in Example 1-1 except that the mixing ratio of the manganese-containing oxide and the cobalt-containing oxide was changed as shown in Table 3. Further, as Comparative Example 1-2 with respect to Example 1-1 and Examples 1-23 to 1-26, a secondary battery was manufactured in the same manner as Example 1-1 except that the manganese-containing oxide was not mixed. Produced. Further, as Comparative Example 1-3 for Example 1-1 and Examples 1-23 to 1-26, a secondary battery was obtained in the same manner as Example 1-1 except that no cobalt-containing oxide was mixed. Was made. For Examples 1-23 to 1-26 and Comparative Examples 1-2 and 1-3, the high-temperature storage characteristics and the charge / discharge cycle characteristics at normal temperatures were examined in the same manner as in Example 1-1. The obtained results are shown in Table 3 together with the results of Example 1-1.
[0067]
[Table 3]
[0068]
As can be seen from Table 3, when the mixing ratio of the manganese-containing oxide is high, the low-temperature discharge energy after high-temperature storage is large, and when the mixing ratio of the cobalt-containing oxide is high, the room temperature discharge capacity retention rate after high-temperature storage tends to be high. It was seen. Especially, Example 1-1 and Examples 1-23 to 1-26 were excellent with the normal temperature discharge capacity maintenance factor after high temperature preservation | save 93% or more, and the low temperature discharge energy after high temperature preservation | save with 3.1 Wh or more. On the other hand, Comparative Example 1-2 containing no manganese-containing oxide has a low low-temperature discharge energy after high-temperature storage, and Comparative Example 1-3 containing no cobalt-containing oxide is normal-temperature discharge capacity after high-temperature storage. The maintenance rate was low.
[0069]
That is, if the mixing ratio of the manganese-containing oxide and the cobalt-containing oxide is 90 to 20 cobalt-containing oxide with respect to the manganese-containing oxide 10 to 80 by mass ratio, excellent high-temperature storage characteristics can be obtained. I understood. Good results were obtained for the charge / discharge cycle characteristics at room temperature.
[0070]
  (Examples 1-27 to 1-31, Reference Examples 1-32, 1-33)
  A secondary battery was fabricated in the same manner as in Example 1-1, except that the average particle diameter of the manganese-containing oxide or cobalt-containing oxide was changed as shown in Table 4.Examples 1-27 to 1-31, Reference Examples 1-32, 1-33Also, in the same manner as in Example 1-1, the high temperature storage characteristics and the charge / discharge cycle characteristics at room temperature were examined. The obtained results are shown in Table 4 together with the results of Example 1-1.
[0071]
[Table 4]
[0072]
  As can be seen from Table 4, in Example 1-1 and Examples 1-27 to 1-31, excellent results were obtained both in terms of high-temperature storage characteristics and capacity retention at room temperature. On the contrary,referenceIn Examples 1-32 and 1-33, excellent results were obtained with respect to high-temperature storage characteristics, but sufficient results were not obtained with a capacity retention rate of 79% or less at room temperature. That is, it was found that if the average particle size of the manganese-containing oxide and the cobalt-containing oxide is 30 μm or less, the charge / discharge cycle characteristics at room temperature can be improved.
[0073]
(Examples 2-1 and 2-2)
As Example 2-1, a secondary battery using non-graphitizable carbon instead of graphite as a negative electrode material was produced. The non-graphitizable carbon was produced as follows. First, petroleum pitch is used as a starting material, 10% by mass to 20% by mass of oxygen-containing functional groups are introduced into this (so-called oxygen crosslinking), and then calcined at 1000 ° C. in an inert gas stream to produce non-graphitizable carbon. Got. When the obtained non-graphitizable carbon was subjected to X-ray diffraction measurement, the (002) plane spacing was 0.376 nm. Moreover, when the true density was measured by the pycnometer method, it was 1.50 g / cm.ThreeMet.
[0074]
The positive electrode material includes manganese-containing oxide (LiMn1.8Cr0.2OFour) 30% by mass and cobalt-containing oxide (LiCo0.9Al0.1O2) A mixture of 70% by mass was used. Others were the same as Example 1-1.
[0075]
[Table 5]
[0076]
Further, as Example 2-2, a manganese-containing oxide (LiMn1.8Cr0.2OFour) 30% by mass and cobalt-containing oxide (LiCo0.9Al0.1O2) A secondary battery was fabricated in the same manner as in Example 1-1 except that a positive electrode material mixed with 70% by mass was used.
[0077]
  Further, as Comparative Examples 2-1 and 2-2 for this example, lithium-cobalt composite oxide (LiCoO instead of cobalt-containing oxide)2) Or in place of manganese-containing oxides, lithium-manganese composite oxides (LiMn)2OFour)RespectivelyExample2-1A secondary battery was fabricated in the same manner as described above.
[0078]
For the obtained secondary batteries of Examples 2-1 and 2-2 and Comparative examples 2-1 and 2-2, the heavy load discharge capacity retention ratio after a high-temperature cycle was determined. The results are shown in Table 5.
[0079]
In addition, the heavy load discharge capacity maintenance factor after high temperature use was calculated | required as follows. First, charge and discharge were performed under a heavy load discharge condition in a 23 ° C. constant temperature bath, and an initial heavy load discharge capacity was obtained. Next, after 200 cycles of charge and discharge were performed under a low load discharge condition in a 45 ° C. constant temperature bath, charge and discharge were performed again under a heavy load discharge condition in a 23 ° C. constant temperature bath to obtain a heavy load discharge capacity after high temperature use. It was. At that time, charging was performed until the battery voltage reached 4.2 V at a constant current of 0.5 A under both heavy load discharge conditions and low load discharge conditions, and then the total charging time was 3 at a constant voltage of 4.2 V. Went until time was reached. Discharge was performed at a constant current of 2.0 A to a final voltage of 3.0 V under heavy load discharge conditions, and to a final voltage of 3.0 V at a constant current of 0.5 A under low load discharge conditions. The ratio of the heavy load discharge capacity after high temperature use to the first heavy load discharge capacity obtained as described above was defined as the heavy load discharge capacity maintenance ratio after high temperature use.
[0080]
As can be seen from Table 5, if a manganese-containing oxide and a cobalt-containing oxide are used for the positive electrode material and non-graphitizable carbon is used for the negative electrode material, the heavy load discharge capacity retention rate after a high-temperature cycle is improved. Can be made.
[0081]
In addition, in the said Example, although the example was given and demonstrated about the composition of manganese containing oxide and cobalt containing oxide, the other manganese containing oxide and other cobalt containing oxide demonstrated in the said embodiment were mentioned. Even if is used, the same result as in the above embodiment can be obtained.
[0082]
Although the present invention has been described with reference to the embodiments and examples, the present invention is not limited to the above embodiments and examples, and various modifications can be made. For example, in the above embodiments and examples, a secondary battery using an electrolytic solution in which a lithium salt is dissolved in a solvent has been described. However, instead of the electrolytic solution, an electrolytic solution containing a lithium salt is used as the polymer compound. Other electrolytes such as a retained gel electrolyte, a solid electrolyte in which a lithium salt is dispersed in a polymer compound having ionic conductivity, or an electrolyte made of a solid inorganic conductor may be used.
[0083]
At that time, various polymer compounds can be used for the gel electrolyte as long as it absorbs the electrolyte and gels. Examples of such a high molecular compound include a fluorine-based high molecular compound such as polyvinylidene fluoride or a copolymer of vinylidene fluoride and hexafluoropropylene, an ether-based high compound such as polyethylene oxide or a crosslinked product containing polyethylene oxide. A molecular compound or polyacrylonitrile is mentioned. Among these, a fluorine-based polymer compound is preferable because of its high redox stability.
[0084]
For the solid electrolyte, for example, an ether polymer compound such as polyethylene oxide or a crosslinked product containing polyethylene oxide, an ester polymer compound such as polymethacrylate, or an acrylate polymer compound may be used alone or in combination. Or copolymerized in the molecule. In addition, as the inorganic conductor, lithium nitride, lithium iodide or lithium hydroxide polycrystal, a mixture of lithium iodide and aluminum trioxide, or a mixture of lithium iodide, lithium sulfide and phosphorous disulfide is used. Can be used.
[0085]
In the above-described embodiments and examples, a specific example of a cylindrical secondary battery having a winding structure has been described. However, the present invention also relates to a cylindrical secondary battery having another configuration. Can be applied. In addition, the present invention can be similarly applied to secondary batteries having other shapes such as a coin type other than a cylindrical type, a button type, a square type, or a type in which an electrode element is enclosed in a laminate film.
[0086]
【The invention's effect】
  As described above, claims 1 to3Of any one oflithium ionAccording to the secondary batteryLiMn 1.8 Cr 0.2 O Four And LiCoO 2 AndSince the positive electrode is provided, the battery capacity does not decrease even when stored at a high temperature, and the capacity retention rate can be improved. Therefore, for example, when used in a mobile phone or a laptop computer, even if it is left in a car or the temperature rises during use, it is exposed to a high temperature environment of about 40 ° C to 60 ° C. There exists an effect that the outstanding battery characteristic can be hold | maintained.
[0088]
  Claims2Describedlithium ionAccording to the secondary battery, since the mixing ratio of the manganese-containing oxide and the cobalt-containing oxide is set to the cobalt-containing oxide 90 to 20 with respect to the manganese-containing oxide 10 to 80 by mass ratio, The battery characteristics after storage and after use at high temperature can be further improved.
[0090]
  In addition, the claims3Describedlithium ionAccording to the secondary battery, since the negative electrode contains non-graphitizable carbon, it is possible to improve the heavy load discharge capacity retention rate after high temperature use. Therefore, for example, when used in a laptop computer, an excellent battery characteristic can be exhibited even when exposed to a high temperature environment.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view illustrating a configuration of a secondary battery according to an embodiment of the invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 11 ... Battery can, 12, 13 ... Insulation board, 14 ... Battery cover, 15 ... Safety valve mechanism, 15a ... Disc board, 16 ... Heat sensitive resistance element, 17 ... Gasket, 20 ... Winding electrode body, 21 ... Positive electrode, 22 ... Negative electrode, 23 ... Separator, 24 ... Center pin, 25 ... Positive electrode lead, 26 ... Negative electrode lead

Claims (3)

  1. Provided with a positive electrode in which a positive electrode mixture layer containing a positive electrode material composed of LiMn 1.8 Cr 0.2 O 4 as a manganese-containing oxide and LiCoO 2 as a cobalt-containing oxide is provided on the positive electrode current collector layer,
    The manganese-containing oxide and the mean particle size of lithium ion secondary batteries is 30μm or less each of said cobalt-containing oxide.
  2. The lithium ion secondary according to claim 1, wherein a mixing ratio of the manganese-containing oxide and the cobalt-containing oxide in the positive electrode is a cobalt-containing oxide 90 to 20 with respect to the manganese-containing oxide 10 to 80 in terms of mass ratio. battery.
  3. The lithium ion secondary battery according to claim 1, comprising a negative electrode containing non-graphitizable carbon as a negative electrode material .
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