JP2013152825A - Battery, battery pack, electronic device, electrically-powered vehicle, power storage device and electric power system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress decomposition of an electrolyte near a positive electrode under a high temperature environment.SOLUTION: A battery comprises a positive electrode and an electrolyte, and a phosphorus compound having a P-OH structure is added to at least one of the positive electrode and the electrolyte. As a result of the addition of the phosphorus compound, a protective coating film containing, as a main component, at least one of phosphate derived from the phosphorus compound having the P-OH structure and a metal salt of its derivative is formed on the surface of at least one of the positive electrode and a positive electrode active material as the battery is charged and discharged. The addition of the phosphorus compound having the P-OH structure is particularly effective in a battery which contains, as a negative electrode active material, a lithium transition metal compound having a Spinel structure. The electrolyte is preferably held by a polymer material, thereby making an illiquid electrolyte. This electrolyte is particularly effective in application to a battery having positive and negative electrodes and an electrolyte sheathed by a laminate film.

Description

  The present technology relates to a battery, a battery pack, an electronic device, an electric vehicle, a power storage device, and a power system.

  In recent years, portable electronic devices such as a camera-integrated VTR (Video Tape Recorder), a mobile phone, or a laptop computer have been widely used, and there is a strong demand for miniaturization, weight reduction, thinning, and long life. Along with this, development of secondary batteries that are lightweight and capable of obtaining a high energy density is also being promoted for secondary batteries used as power sources.

  Among them, a secondary battery using a carbon material as a negative electrode active material, a lithium transition metal oxide as a positive electrode active material, and a carbonate ester mixture as an electrolytic solution, and using lithium (Li) occlusion and release for charge / discharge reactions (so-called Lithium ion secondary batteries) are widely used. Lithium ion secondary batteries are widely used because they have higher energy density than lead batteries and nickel cadmium batteries, which are conventional nonaqueous electrolyte secondary batteries. Among them, a laminate film type battery in which an electrode body is sheathed with a laminate film is widely used for weight reduction and thickness reduction.

In recent years, a spinel-structured titanium-containing lithium transition metal oxide, particularly lithium titanate (Li ₄ Ti ₅ O ₁₂ ) has attracted attention as a negative electrode active material as disclosed in Patent Document 1. Since lithium titanate is less reactive with electrolyte than graphite, it has been proposed that decomposition of the electrolyte in the vicinity of the negative electrode is suppressed, and that an increase in DC resistance due to decomposition of the electrolyte can be suppressed. Yes.

JP 2008-84690 A

  However, in the battery as shown in Patent Document 1, although the decomposition of the electrolyte solution in the vicinity of the negative electrode can be suppressed, the positive electrode active material uses a conventional material, and the decomposition of the electrolyte solution in the vicinity of the positive electrode can be suppressed. There wasn't. For this reason, it has been difficult to suppress an increase in DC resistance due to the decomposition of the electrolyte solution in the vicinity of the positive electrode.

  The present technology has been made in view of such problems of the conventional technology, and the object of the present technology is to suppress the decomposition of the electrolyte solution in the vicinity of the positive electrode and to suppress the increase in DC resistance. To provide a battery. In addition, an object of the present technology is to provide a battery pack, an electronic device, an electric vehicle, a power storage device, and a power system using such a battery.

In order to solve the above-described problems, the battery of the present technology includes a positive electrode including a positive electrode active material,
A negative electrode containing a lithium transition metal compound having a spinel structure as a negative electrode active material;
Comprising a solvent and an electrolyte solution containing an electrolyte salt;
At least one of the positive electrode and the electrolytic solution contains a phosphorus compound having a P—OH structure.

In order to solve the above-described problems, the battery of the present technology includes a positive electrode including a positive electrode active material,
A negative electrode containing a lithium transition metal compound having a spinel structure as a negative electrode active material;
Comprising a solvent and an electrolyte solution containing an electrolyte salt;
It is characterized by having a protective film mainly comprising at least one of a phosphate derived from a phosphorus compound having a P—OH structure and a metal salt of a derivative thereof on the surface of at least one of the positive electrode and the positive electrode active material.

  The battery of the present technology preferably includes a titanium-containing lithium transition metal oxide having a spinel structure as the negative electrode active material.

  In the battery of the present technology, the phosphorus compound having a P—OH structure is decomposed, and the phosphate and the derivative metal derived from the phosphorus compound having the P—OH structure are formed on at least one surface of the positive electrode and the positive electrode active material. A protective coating mainly comprising at least one of the salts is formed.

  According to the present technology, it is possible to suppress the decomposition of the electrolytic solution in the vicinity of the positive electrode, and it is possible to suppress an increase in DC resistance caused by the decomposition of the electrolytic solution.

It is the external appearance perspective view and decomposition | disassembly perspective view which show the structure of the lamination film type battery using the laminated electrode body concerning 1st Embodiment of this technique. It is sectional drawing which expands and shows a part of laminated electrode body accommodated in the battery shown in FIG. It is a perspective view of the positive electrode and negative electrode which are used for the laminated electrode body accommodated in the battery shown in FIG. It is a disassembled perspective view which shows the structure of the laminate film type battery using the winding electrode body concerning the 2nd Embodiment of this technique. It is sectional drawing of the winding electrode body accommodated in the battery shown in FIG. It is a mimetic diagram showing the composition of the square battery concerning a 3rd embodiment of this art. It is sectional drawing which shows the structure of the cylindrical battery concerning 4th Embodiment of this technique. It is a block diagram showing an example of circuit composition of a battery pack concerning a 5th embodiment of this art. It is the schematic which shows the example applied to the electrical storage system for houses concerning the 6th Embodiment of this technique. It is a schematic diagram showing roughly an example of composition of a hybrid vehicle which adopts a series hybrid system to which this art is applied.

The best mode for carrying out the present technology (hereinafter referred to as an embodiment) will be described below. The description will be made as follows.
1. First embodiment (first example of a laminate film type battery using an electrolyte of the present technology)
2. Second embodiment (second example of a laminate film type battery using the electrolyte of the present technology)
3. Third embodiment (an example of a prismatic battery using the electrolyte of the present technology)
4). Fourth embodiment (example of cylindrical battery using electrolyte of the present technology)
5. Fifth embodiment (example of battery pack using electrolyte of the present technology)
6). Sixth embodiment (an example of a power storage system using a battery)

1. 1st Embodiment In 1st Embodiment, the 1st example of the battery of this technique is described.

(1-1) Configuration of Battery A first example of the battery of the present technology is a so-called laminate film type battery in which an electrode body including a positive electrode and a negative electrode is packaged with an exterior member made of, for example, a laminate film. The laminate film type battery of the present technology uses a lithium transition metal composite compound having a spinel structure as a negative electrode active material, and contains a phosphorus compound having a P—OH structure in at least one of an electrolytic solution and a positive electrode (positive electrode active material layer). Is. The laminate film type battery is, for example, a lithium ion secondary battery.

[Phosphorus compounds]
The phosphorus compound having a P—OH structure of the present technology decomposes as the battery is charged and discharged, and a phosphate derived from the phosphorus compound having a P—OH structure on at least one surface of the positive electrode and the positive electrode active material, and A protective coating mainly comprising at least one of the metal salts of the derivatives is formed. The protective coating containing phosphorus has high stability and low activity against the electrolytic solution. For this reason, decomposition | disassembly of the electrolyte solution in a positive electrode surface can be suppressed, and the raise of the direct current | flow resistance of a battery resulting from decomposition | disassembly of electrolyte solution can be suppressed. And since gas generation is suppressed, even if it is a case where the exterior member which is easy to deform | transform is used, battery swelling can be suppressed.

  In addition, the protective film mainly comprising at least one of a phosphate and a metal salt of a derivative thereof formed on the surface of at least one of the positive electrode and the positive electrode active material has the surface of the positive electrode or the positive electrode active material subjected to X-ray photoelectron spectroscopy ( X-ray photoelectron spectroscopy (XPS) or time-of-flight secondary ion mass spectrometer (TOF-SIMS) can be used for analysis.

  As the phosphorus compound having a P—OH structure, for example, at least one of the compounds represented by formula (A) and formula (B) can be used.

（式（Ａ）および式（Ｂ）中、Ｒ１〜Ｒ４はそれぞれ独立してＯ_mＣ_nＨ_2n+1またはＯ_mＣ₆Ｈ₅であり、ｍは０または１かつ０≦ｎ≦４である。）

(In Formula (A) and Formula (B), R1 to R4 are each independently O _m C _n H _{2n + 1} or O _m C ₆ H ₅ , and m is 0 or 1, and 0 ≦ n ≦ 4. is there.)

Examples of the phosphorus compound having a P—OH structure represented by formula (A) include phosphonic acid (H ₃ PO ₃ ) represented by formula (A-1) and phosphoric acid (H ₃ PO represented by formula (A-2)). ₄ ), phosphinic acid (H ₃ PO ₂ ), methylphosphonic acid ((CH ₃ ) PO (OH) ₂ ), methyl phosphate ((CH ₃ O) PO (OH) ₂ ), ethylphosphinic acid ((C ₂ H ₅ ) PHOOH), diethylphosphinic acid ((CH ₃ ) ₂ POOH), phenylphosphonic acid represented by formula (A-3) ((C ₆ H ₅ ) PO (OH) ₂ ), represented by formula (A-4) And phenylphosphinic acid ((C ₆ H ₅ ) PHOOH) and diphenyl phosphate ((C ₆ H ₅ ) ₂ HPO ₄ ) represented by formula (A-5). Examples of the phosphorus compound having a P—OH structure represented by formula (A) include phosphonic acid (H ₃ PO ₃ ) represented by formula (A-1) and phosphoric acid (H ₃ PO ₄ ) represented by formula (A-2). Alternatively, it is preferable to use diphenyl phosphate ((C ₆ H ₅ ) ₂ HPO ₄ ) represented by the formula (A-5).

Examples of the phosphorus compound having a P—OH structure represented by the formula (B) include phosphorous acid (H ₃ PO ₃ ) and dimethyl phosphite ((CH ₃ O) ₂ POH) represented by the formula (B-1). And diphenyl phosphite ((C ₆ H ₅ O) ₂ POH). As the phosphorus compound having a P—OH structure represented by the formula (B), it is preferable to use dimethyl phosphite ((CH ₃ O) ₂ POH) represented by the formula (B-1).

Among the compounds represented by formula (A) and formula (B), phosphorus compounds having a P—H bond or a P—C bond are preferred. In addition, trivalent phosphorus compounds are particularly easy to react and are easy to deposit on the surface of the positive electrode. For this reason, it is particularly preferable to use the phosphonic acid (H ₃ PO ₃ ) represented by the formula (A-1).

  Such a phosphorus compound having a P—OH structure may be mixed in an electrolytic solution or may be used by mixing with a positive electrode active material.

  When the phosphorous compound having a P—OH structure is used in combination with a positive electrode active material, it is contained in an amount of 0.0125% by mass to 0.5% by mass with respect to 100% by mass of the positive electrode active material in the battery before the first charge. It is preferable. In addition, when the phosphorus compound having a P—OH structure is used by being mixed in an electrolytic solution, it is preferably contained in the electrolytic solution in an amount of 0.05% by mass or more and 1.5% by mass or less in the battery before the first charge. This is because the effect of suppressing the generation of gas due to the addition of the phosphorus compound can be sufficiently obtained, and the increase in DC resistance after high-temperature storage can be suppressed. The phosphorus compound having a P—OH structure is preferable in that it is easy to obtain the effect in a small amount when mixed with the positive electrode active material. On the other hand, a phosphorus compound having a P—OH structure is preferably used by mixing with an electrolytic solution because the production process is easy.

  The phosphorus compound having a P—OH structure contained in the electrolyte solution or in the mixture of the positive electrode active material and the phosphorus compound is decomposed as the battery is charged and discharged, and is formed on at least one surface of the positive electrode and the positive electrode active material. It becomes a protective film to be formed. This protective film is mainly composed of at least one of a phosphate derived from a phosphorus compound having a P—OH structure and a metal salt of a derivative thereof. For this reason, content of the phosphorus compound which has a P-OH structure reduces with charging / discharging, and may become content below the above-mentioned range.

  Hereinafter, the battery configuration of the laminate film type battery according to the first embodiment will be described.

[Battery structure]
Drawing 1A-Drawing 1C are figures showing the composition of lamination film type battery 1 concerning a 1st embodiment. The laminate film type battery 1 accommodates a laminated electrode body 10 in which a positive electrode 11 and a negative electrode 12 are laminated. FIG. 1A is an external perspective view from one main surface side of the laminated film type battery 1 according to the first embodiment of the present technology, and FIG. 1B is an exploded view from the other main surface side of the laminated film type battery 1. FIG. 1C is an external perspective view from the other main surface side of the laminated film type battery 1. FIG. 2 is an enlarged cross-sectional view of the multilayer structure taken along line II of the multilayer electrode body 10 shown in FIG. 1B.

  In this battery, a laminated electrode body 10 to which a positive electrode lead 2 and a negative electrode lead 3 are attached is packaged on an exterior member 5 made of a laminate film. As shown in FIG. 1B, the laminated electrode body 10 accommodated in the laminated film type battery 1 is obtained by laminating a rectangular positive electrode 11 and a rectangular negative electrode 12 with a separator 13 therebetween, and the outermost periphery thereof. The part is protected by a fixing member 14 made of a protective tape or the like.

  The positive electrode lead 2 and the negative electrode lead 3 are led out from the inside of the laminated film type battery 1 that is packaged by the package member 5. The positive electrode lead 2 is made of a metal material such as aluminum, and the negative electrode lead 3 is made of a metal material such as copper, nickel, or stainless steel. These metal materials are, for example, in a thin plate shape or a mesh shape.

[Positive electrode]
The positive electrode 11 has, for example, a structure in which a positive electrode active material layer 11B is provided on both surfaces of a positive electrode current collector 11A having a pair of opposed surfaces. The positive electrode current collector 11A is made of, for example, a metal foil such as an aluminum foil. As shown in FIG. 3A, a positive electrode tab 11C connected to the positive electrode lead 2 is continuously extended from the positive electrode current collector 11A. The plurality of positive electrode tabs 11C extending from the plurality of stacked positive electrodes 11 are fixed to each other, and the positive electrode current collector 11A is connected thereto. In FIG. 3A, in order to clarify the configuration of the positive electrode tab 11C, the positive electrode active material layer 11B is not formed in part, but actually, the positive electrode active material layer 11B is formed except for the positive electrode tab 11C portion. It is formed.

  The positive electrode active material layer 11B includes, for example, a positive electrode active material, a conductive agent, and a binder. In addition, the positive electrode active material layer 11B may include a phosphorus compound having a P—OH structure together with the positive electrode active material, the conductive agent, the binder, and the like. The positive electrode active material includes one or more of positive electrode materials capable of inserting and extracting lithium, and includes other materials such as a binder and a conductive agent as necessary. You may go out.

As the positive electrode material capable of inserting and extracting lithium, for example, lithium-containing compounds such as lithium oxide, lithium phosphorus oxide, lithium sulfide, or an intercalation compound containing lithium are suitable, and two or more of these are used. May be used in combination. In order to increase the energy density, a lithium-containing compound containing lithium, a transition metal element, and oxygen (O) is preferable. Examples of such a lithium-containing compound include a lithium composite phosphate having an olivine type structure shown in (Chemical Formula I), a lithium composite oxide having a layered rock salt type structure shown in (Chemical Formula II), and the like. Can be mentioned. It is more preferable that the lithium-containing compound includes at least one member selected from the group consisting of cobalt (Co), nickel (Ni), manganese (Mn), and iron (Fe) as a transition metal element. Examples of such lithium-containing compounds include lithium composite phosphates having the olivine type structure shown in (Chemical Formula III), and the layered rock salt type shown in (Chemical IV), (Chemical V), or (Chemical VI). Or a lithium composite oxide having a spinel structure shown in (Chemical Formula VII). Specifically, LiNi _0.50 Co _0.20 Mn _0.30 O ₂ , Li _a CoO ₂ (A≈1), Li _b NiO ₂ (b≈1), Li _c1 Ni _c2 Co _1-c2 O ₂ (c1≈1, 0 <c2 <1), Li _d Mn ₂ O ₄ (d≈1) or Li _e FePO ₄ (e≈1).

(Chemical I)
Li _a M1 _b PO ₄
(In the formula, M1 represents at least one element selected from Groups 2 to 15. a and b are values within the range of 0 ≦ a ≦ 2.0 and 0.5 ≦ b ≦ 2.0. .)

(Chemical II)
Li _c Ni _(1-de) Mn _d M2 _e O _(1-f) X _g
(In the formula, M2 represents at least one element selected from Group 2 to Group 15 excluding nickel (Ni) and manganese (Mn). X represents Group 16 elements and Group 17 elements other than oxygen (O). And c, d, e, f and g are 0 ≦ c ≦ 1.5, 0 ≦ d ≦ 1.0, 0 ≦ e ≦ 1.0, −0.10 ≦ f ≦. 0.20 and 0 ≦ g ≦ 0.2.)

(Chemical III)
Li _h M3PO ₄
(In the formula, M3 is cobalt (Co), manganese (Mn), iron (Fe), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V ), Niobium (Nb), copper (Cu), zinc (Zn), molybdenum (Mo), calcium (Ca), strontium (Sr), tungsten (W) and zirconium (Zr) H is a value in a range of 0.9 ≦ h ≦ 1.1, wherein the composition of lithium varies depending on the state of charge and discharge, and the value of z represents a value in a complete discharge state. )

(Chemical IV)
Li _i Mn _(1-jk) Ni _j M4 _k O _(1-m) F _n
(In the formula, M4 is cobalt (Co), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu ), Zinc (Zn), zirconium (Zr), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W). j, k, m and n are 0.8 ≦ i ≦ 1.2, 0 <j <0.5, 0 ≦ k ≦ 0.5, j + k <1, −0.1 ≦ m ≦ 0.2, (It is a value in the range of 0 ≦ n ≦ 0.1. Note that the composition of lithium varies depending on the state of charge and discharge, and the value of i represents the value in the fully discharged state.)

(Chemical V)
Li _o Ni _(1-p) M5 _p O _(1-q) F _r
(In the formula, M5 represents cobalt (Co), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W). p, q, and r are values within the range of 0.8 ≦ o ≦ 1.2, 0.005 ≦ p ≦ 0.5, −0.1 ≦ q ≦ 0.2, and 0 ≦ r ≦ 0.1. Note that the composition of lithium varies depending on the state of charge and discharge, and the value of o represents the value in a fully discharged state.)

(Chemical VI)
Li _s Co _(1-t) M6 _t O _(1-u) F _v
(In the formula, M6 represents nickel (Ni), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W). t, u, and v are values within the ranges of 0.8 ≦ s ≦ 1.2, 0 ≦ t <0.5, −0.1 ≦ u ≦ 0.2, and 0 ≦ v ≦ 0.1. (Note that the composition of lithium varies depending on the state of charge and discharge, and the value of s represents the value in a fully discharged state.)

(Chemical VII)
Li _w Mn _(1-x) M7 _x O _y F _z
(Wherein M7 is cobalt (Co), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W). x, y, and z are values within a range of 0.9 ≦ w ≦ 1.1, 0 ≦ x ≦ 0.6, 3.7 ≦ y ≦ 4.1, and 0 ≦ g ≦ 0.1. Note that the composition of lithium varies depending on the state of charge and discharge, and the value of w represents a value in a fully discharged state.)

  Furthermore, from the viewpoint that higher electrode filling properties and cycle characteristics can be obtained, the surface of the core particles made of any of the above lithium-containing compounds is coated with fine particles or carbon materials made of any of the other lithium-containing compounds. It is good also as a composite particle.

In addition, examples of the positive electrode material capable of inserting and extracting lithium include oxides, disulfides, chalcogenides, and conductive polymers. Examples of the oxide include vanadium oxide (V ₂ O ₅ ), titanium dioxide (TiO ₂ ), and manganese dioxide (MnO ₂ ). Examples of the disulfide include iron disulfide (FeS ₂ ), titanium disulfide (TiS ₂ ), and molybdenum disulfide (MoS ₂ ). The chalcogenide is particularly preferably a layered compound or a spinel compound, such as niobium selenide (NbSe ₂ ). Examples of the conductive polymer include sulfur, polyaniline, polythiophene, polyacetylene, and polypyrrole. Of course, the positive electrode material may be other than the above. Further, two or more kinds of the series of positive electrode materials described above may be mixed in any combination.

  As the conductive agent, for example, a carbon material such as carbon black or graphite is used. Examples of the binder include resin materials such as polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), styrene butadiene rubber (SBR), and carboxymethyl cellulose (CMC), and these resin materials. At least one selected from copolymers and the like mainly composed of is used.

[Negative electrode]
The negative electrode 12 has, for example, a structure in which a negative electrode active material layer 12B is provided on both surfaces of a negative electrode current collector 12A having a pair of opposed surfaces. The negative electrode current collector 12A is made of, for example, a metal foil such as a copper foil. As shown in FIG. 3C, a negative electrode tab 12C connected to the negative electrode lead 3 is continuously extended from the negative electrode current collector 12A. The plurality of negative electrode tabs 12C extending from the plurality of stacked negative electrodes 12 are fixed to each other, and the negative electrode current collector 12A is connected thereto. In FIG. 3B, in order to clarify the configuration of the negative electrode tab 12C, a part of the negative electrode active material layer 12B is not formed, but actually, the negative electrode active material layer 12B is formed except for the negative electrode tab 12C portion. It is formed.

  The negative electrode active material layer 12B is configured to include any one or more of lithium transition metal composite compounds having a spinel structure as the negative electrode active material, and the same as the positive electrode active material layer 11B as necessary. You may be comprised including other materials, such as a electrically conductive agent and a binder.

  In this laminated film type battery 1, the electrochemical equivalent of the negative electrode material capable of occluding and releasing lithium is larger than the electrochemical equivalent of the positive electrode 11, and theoretically the negative electrode 12 during the charging. Lithium metal is prevented from precipitating.

  As the lithium transition metal composite compound having a spinel structure, at least one of the following formula (1) is used.

Formula (1)
A [B ₂ ] X ₄
(In the formula, A and B are lithium (Li), titanium (Ti), magnesium (Mg), calcium (Ca), copper (Cu), zinc (Zn), strontium (Sr), aluminum (Al), scandium. (Sc), chromium (Cr), manganese (Mn), iron (Fe), gallium (Ga), yttrium (Y), aluminum (Al), scandium (Sc), chromium (Cr), manganese (Mn), iron (At least one metal cation selected from (Fe), gallium (Ga) and yttrium (Y), and X is oxygen (O) or sulfur (S).)

  Among these, it is preferable to use a titanium-containing lithium transition metal composite oxide as the lithium transition metal composite compound having a spinel structure. As the titanium-containing lithium transition metal composite oxide having a spinel structure, at least one of titanium-containing lithium transition metal composite oxides represented by the following formulas (1-1) to (1-3) is used.

Formula (1-1)
Li [Li _x M1 _{(1-3x) / 2} Ti _{(3 + x) / 2} ] O ₄
(In the formula, M1 is at least one of divalent ions of magnesium (Mg), calcium (Ca), copper (Cu), zinc (Zn) and strontium (Sr)), and 0 ≦ x ≦ 1/3 is there.)

Formula (1-2)
Li [Li _y M2 _1-3y Ti _{1 + 2y} ] O ₄
(Wherein M2 is at least one of trivalent ions of aluminum (Al), scandium (Sc), chromium (Cr), manganese (Mn), iron (Fe), gallium (Ga) and yttrium (Y)). Yes, 0 ≦ y ≦ 1/3.)

Formula (1-3)
Li [Li _1/3 M3 _z Ti _{(5/3) -z} ] O ₄
(In the formula, M3 is at least one of tetravalent ions of vanadium (V), zirconium (Zr), and niobium (Nb), and 0 ≦ z ≦ 2/3.)

Equation (1-1) to Formula for (1-3), as the titanium-containing lithium composite oxide containing no transition metal other than titanium (Ti), and lithium titanate (Li ₄ Ti ₅ O ₁₂₎ it is. For the titanium-containing lithium transition metal composite oxide containing a transition metal other than titanium (Ti), examples of the titanium-containing lithium transition metal composite oxide represented by the formula (1-1) include lithium / titanium / magnesium composite oxide. Examples of the titanium-containing lithium transition metal composite oxide (Li _3.75 Ti _4.575 Mg _0.375 O ₁₂ ) and the like represented by the formula (1-2) include lithium-titanium-aluminum composite oxide (Li _3.75 Ti _4.50 Al _0.75 Examples of the titanium-containing lithium transition metal composite oxide in which O ₁₂ ) is represented by the formula (1-3) include lithium / titanium / niobium composite oxide (Li ₄ Ti _4.95 Nb _0.05 O ₁₂ ).

  As the negative electrode active material, a material in which the surface of the negative electrode material described above is coated with an electronic conductive material such as a carbon material may be used. The negative electrode active material whose surface is coated with a carbon material is prepared by mixing a lithium (Li) source, a titanium (Ti) source, and a necessary transition metal source, and adding an electron conductive material or a precursor of the electron conductive material. It is obtained by applying or spraying a solution or suspension containing it and heating it. Further, the negative electrode active material whose surface is coated with a carbon material is electronically conductive with respect to the titanium-containing lithium transition metal composite oxide represented by any one of the above formulas (1-1) to (1-3). It can also be obtained by applying or spraying a solution or suspension containing a conductive material or a precursor of an electronically conductive material to dry or heat.

  Since these materials are less reactive with the electrolyte than graphite, it is difficult for the electrolyte to decompose near the negative electrode, and it is possible to suppress an increase in resistance caused by the decomposition of the electrolyte. preferable.

[Electrolyte]
The electrolytic solution contains a phosphorus compound having a P—OH structure as necessary together with a solvent and an electrolyte salt. Note that the phosphorus compound having the P—OH structure may be mixed in the positive electrode, but even in this case, a part of the phosphorus compound having the P—OH structure is caused by charging / discharging of the battery. May be included. In addition, the electrolytic solution may be a non-flowable electrolyte that is held in a polymer material and made non-flowable, for example, a gel electrolyte.

As an electrolyte salt, you may contain 1 type, or 2 or more types of light metal salts, such as inorganic lithium salt. Examples of the inorganic lithium salt include lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium perchlorate (LiClO ₄ ), and lithium hexafluoroarsenate (LiAsF ₆ ). , Lithium tetraphenylborate (LiB (C ₆ H ₅ ) ₄ ), lithium methanesulfonate (LiCH ₃ SO ₃ ), lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ), lithium tetrachloroaluminate (LiAlCl ₄ ), Examples thereof include dilithium hexafluorosilicate (Li ₂ SiF ₆ ), lithium chloride (LiCl), and lithium bromide (LiBr). Among these, at least one member selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, and lithium hexafluoroarsenate is preferable, lithium hexafluorophosphate, tetrafluoride More preferred is lithium borate.

  Further, as the electrolyte salt, an imide salt compound represented by the following formula (C) or a methide salt compound represented by the formula (D) may be used.

Formula (C)
M ⁺ [(ZY) ₂ N] ⁻
(Wherein M ⁺ is a monovalent cation, Y is SO ₂ or CO, and each substituent Z is independently a fluorine atom or a polymerizable functional group.)

Formula (D)
M ⁺ [(ZY) ₃ C] ⁻
(Wherein M ⁺ is a monovalent cation, Y is SO ₂ or CO, and each substituent Z is independently a fluorine atom or a polymerizable functional group.)

In formulas (C) and (D), examples of the cation constituting M ⁺ include alkali metal ions such as lithium ion (Li ⁺ ), sodium ion (Na ⁺ ), potassium ion (K ⁺ ), and the like. In addition to metal element ions, ammonium cations, phosphonium cations, and the like can be given. Of these, lithium ions are preferred.

  Especially, it is preferable to use the sulfonimide lithium salt shown by following formula (C-1) as an imide salt compound shown by Formula (C).

Formula (C-1)
_{LiN (C m F 2m + 1} SO 2) (C n F 2n + 1 SO 2)
(In the formula, m and n are integers of 1 or more.)

  Examples of the imide salt compound represented by the formula (C-1) include lithium bis (fluorosulfonyl) imide, lithium (fluorosulfonyl) (trifluoromethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, and the like. Can be used alone or in admixture of two or more.

  Moreover, it is preferable to use the sulfonemethide lithium salt shown by following formula (D-1) as a metide salt compound shown by Formula (D).

Formula (D-1)
_{LiC (C P F 2P + 1} SO 2) (C q F 2q + 1 SO 2) (C r F 2r + 1 SO 2)
(In the formula, p, q and r are integers of 1 or more.)

Examples of the metide salt compound represented by the formula (D-1) include lithium tris (pentafluoroethanesulfonyl) methide and lithium tris (trifluoromethanesulfonyl) methide (LiC (CF ₃ SO ₂ ) ₃ ).

  Here, the imide salt compound of the formula (C) and the methide salt compound of the formula (D) are not limited to these.

  As the solvent, for example, a non-aqueous solvent can be used. Examples of the non-aqueous solvent include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and methyl propyl carbonate (MPC). ), Γ-butyrolactone, γ-valerolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, tetramethylene sulfone, 3-methyl-2-oxazolidone, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethyl acetate, trimethyl Ethyl acetate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, N, N-dimethylacetamide, methyl N, N-diethylcarbamate, ethyl N, N-diethylcarbamate, N, N- Dimethylformamide, N-methylpyrrolidinone, N-methyloxazolidinone, N, N′-dimethylimidazolidinone, nitromethane, nitroethane, sulfolane, trimethyl phosphate, dimethyl sulfoxide, or the like can be used. These may be used alone or in combination of two or more.

  Among them, as the non-aqueous solvent, at least one of propylene carbonate, butylene carbonate and γ-butyrolactone, which is a high dielectric constant solvent (for example, relative dielectric constant ε ≧ 30), and a low viscosity solvent (for example, viscosity ≦ 1 mPa · s) It is preferable to use a mixture of at least one of dimethyl carbonate and ethyl methyl carbonate. In this case, it is particularly preferable that propylene carbonate as a high dielectric constant solvent and both dimethyl carbonate and ethyl methyl carbonate as a low viscosity solvent are mixed and contained. This is because the dissociation property of the electrolyte salt and the ion mobility are improved, and thus higher effects can be obtained.

  In addition, when using the lithium transition metal complex compound which has a spinel structure as a negative electrode active material, at least 1 type in the cyclic carbonate shown by the following formula (E) can be used.

（式中、Ｒ１１〜Ｒ１６はそれぞれ独立してＣ_nＨ_2n+1であり、０≦ｎ≦４である。）

(Wherein, R11 to R16 is C _n H _{2n + 1} each independently is 0 ≦ n ≦ 4.)

  The cyclic carbonate represented by the formula (E) does not contain ethylene carbonate (EC). As a solvent for a battery using a conventional carbon-based negative electrode active material, although it was almost essential to contain ethylene carbonate (EC), for example, it has a higher reactivity than propylene carbonate (PC) and is relatively a gas. Occurrence was easy to occur. In the present technology, unlike a battery using a conventional carbon-based negative electrode active material, the inclusion of ethylene carbonate (EC) in a solvent is not essential, which is preferable because the gas generation suppression effect is improved.

  Further, the electrolytic solution may contain a carboxylic acid ester represented by the following formula (F). This is because the carboxylic acid ester has a lower viscosity than carbonic acid esters such as ethylene carbonate (EC) and propylene carbonate (PC), and the mobility of ions in the electrolytic solution in which the carboxylic acid ester is mixed becomes larger. In particular, it is preferable to include ethyl acetate represented by the formula (F-1), methyl propionate represented by the formula (F-2), and the like.

（式中、Ｒ２１〜Ｒ２６はそれぞれ独立してＣ_nＨ_2n+1であり、０≦ｎ≦４である。）

(Wherein, R21 to R26 is C _n H _{2n + 1} each independently is 0 ≦ n ≦ 4.)

  Furthermore, you may contain the unsaturated cyclic carbonate shown by Formula (G), and the halogenated ethylene carbonate shown by Formula (H) in electrolyte solution. Since these also form a protective film on the electrode surface, a higher gas generation suppression effect can be obtained by including them in the electrolyte together with the phosphorus compound having the P—OH structure.

（式（Ｇ）および式（Ｈ）中、Ｒ３１〜Ｒ３５はそれぞれ独立してＣ_mＨ_2m+1-nＸ_nであり、Ｘはハロゲン原子であり、０≦ｍ≦４かつ０≦ｎ≦２ｍ＋１である。）

(In the formula (G) and formula (H), R31~R35 is _{C m H 2m + 1-n} X n independently, X is a halogen atom, 0 ≦ m ≦ 4 and 0 ≦ n ≦ 2m + 1.)

  As the unsaturated cyclic carbonate represented by the formula (G), for example, a vinylene carbonate compound can be used. Examples of vinylene carbonate compounds include vinylene carbonate (1,3-dioxol-2-one), methyl vinylene carbonate (4-methyl-1,3-dioxol-2-one), ethyl vinylene carbonate (4-ethyl- 1,3-dioxol-2-one), 4,5-dimethyl-1,3-dioxol-2-one, 4,5-diethyl-1,3-dioxol-2-one, 4-fluoro-1,3 -Dioxol-2-one, 4-trifluoromethyl-1,3-dioxol-2-one, etc. are mentioned. These may be used alone or in combination. Among these, vinylene carbonate represented by the formula (G-1) is preferable. This is because they can be easily obtained and a high gas generation suppression effect can be obtained by forming a protective film.

  Examples of the halogenated ethylene carbonate represented by the formula (H) include fluoroethylene carbonate (4-fluoro-1,3-dioxolan-2-one, FEC), difluoroethylene carbonate (4,5-difluoro-1,3-dioxolane- 2-one, DFEC), 4-chloro-1,3-dioxolan-2-one, tetrafluoro-1,3-dioxolan-2-one, 4-chloro-5-fluoro-1,3-dioxolane-2- ON, 4,5-dichloro-1,3-oxolan-2-one, tetrachloro-1,3-dioxolan-2-one, 4,5-bistrifluoromethyl-1,3-dioxolan-2-one, 4 -Trifluoromethyl-1,3-dioxolan-2-one, 4,5-difluoro-4,5-dimethyl-1,3-dioxolan-2-one 4,4-difluoro-5-methyl-1,3-dioxolan-2-one, 4-ethyl-5,5-difluoro-1,3-dioxolan-2-one, 4-fluoro-5-trifluoromethyl -1,3-dioxolan-2-one, 4-methyl-5-trifluoromethyl-1,3-dioxolan-2-one, 4-fluoro-4,5-dimethyl-1,3-dioxolan-2-one 5- (1,1-difluoroethyl) -4,4-difluoro-1,3-dioxolan-2-one, 4,5-dichloro-4,5-dimethyl-1,3-dioxolan-2-one, 4-ethyl-5-fluoro-1,3-dioxolan-2-one, 4-ethyl-4,5-difluoro-1,3-dioxolan-2-one, 4-ethyl-4,5,5-trifluoro -1,3-dioxola 2-one, 4-methyl-1,3-dioxolan-2-one can be used. These may be single and multiple types may be mixed.

  Especially, the fluoroethylene carbonate shown by Formula (H-1) or the difluoroethylene carbonate shown by Formula (H-2) is preferable, and the fluoroethylene carbonate shown by Formula (H-1) is more preferable. In particular, as difluoroethylene carbonate, a trans isomer is preferable to a cis isomer. This is because they can be easily obtained and a high gas generation suppression effect can be obtained by forming a protective film.

  Alternatively, the electrolytic solution may contain a nitrile compound. Since the nitrile compound also forms a protective film on the electrode surface, the effect of suppressing gas generation can be obtained by including it in the electrolyte together with the phosphorus compound having the P—OH structure.

  Among the nitrile compounds, examples of the dinitrile compound include malononitrile, succinonitrile (SN) represented by the formula (I-1), glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, azeronitrile, sebaconitrile, dodecandinitrile, phthalonitrile, and the like. Can be used. These may be single and multiple types may be mixed.

  Among the nitrile compounds, for example, acetonitrile, propionitrile, butanenitrile, valeronitrile, dodecanenitrile, acrylonitrile, benzonitrile and the like can be used as the mononitrile compound. These may be single and multiple types may be mixed.

  When a gel electrolyte is used, the electrolytic solution is held by the polymer material. The polymer material may be any material that absorbs a non-aqueous solvent and gels. For example, polyvinylidene fluoride (PVdF) or vinylidene fluoride (VdF) and hexafluoropropylene (HFP) are included in a repeating unit. Fluorine-based polymer materials such as polymers, ether-based polymer materials such as polyethylene oxide (PEO) or cross-linked products containing polyethylene oxide (PEO), polyacrylonitrile (PAN), polypropylene oxide (PPO), or polymethyl methacrylate (PMMA) ) As a repeating unit. Any one of these polymer materials may be used alone, or two or more thereof may be mixed and used.

  In particular, from the viewpoint of redox stability, a fluorine-based polymer material is desirable, and among them, a copolymer containing polyvinylidene fluoride (PVdF) or vinylidene fluoride and hexafluoropropylene as components is preferable. Furthermore, this copolymer is composed of unsaturated dibasic acid monoesters such as maleic acid monomethyl ester (MMM), halogenated ethylenes such as ethylene trifluorochloride (PCTFE), or epoxy group-containing acrylic vinyl monomers. May be included. This is because higher characteristics can be obtained.

  As a polymer material, a polymerizable gelling agent may be included in the electrolytic solution, and a gel electrolyte layer may be formed by performing a polymerization treatment such as ultraviolet curing or heat curing. Examples of the polymerizable gelling agent include those having an unsaturated double bond such as acryloyl group, methacryloyl group, vinyl group or allyl group. Specifically, acrylic acid, methyl acrylate, ethyl acrylate, ethoxyethyl acrylate, methoxyethyl acrylate, ethoxyethoxyethyl acrylate, polyethylene glycol monoacrylate, ethoxyethyl methacrylate, methoxyethyl methacrylate, ethoxyethoxyethyl methacrylate, polyethylene glycol mono Methacrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate, allyl acrylate, acrylonitrile, N-vinyl pyrrolidone, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol Diacrylate, diethylene glycol Dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polyalkylene glycol diacrylate, polyalkylene glycol dimethacrylate, etc. can be used, and trimethylolpropane alkoxylate triacrylate or pentaerythritol alkoxylate Trifunctional monomers such as triacrylate, tetrafunctional or higher functional monomers such as pentaerythritol alkoxylate tetraacrylate or ditrimethylolpropane alkoxylate tetraacrylate can also be used. Especially, it is preferable to use the oxyalkylene glycol type compound which has an acryloyl group or a methacryloyl group. Any one of the polymerizable gelling agents may be used alone, or two or more thereof may be mixed and used.

  Instead of using the separator 13, the gel electrolyte layer may be used in place of the separator 13 that insulates the positive electrode 11 and the negative electrode 12 and prevents physical contact between the positive electrode 11 and the negative electrode 12. In this case, the gel electrolyte layer is provided between the positive electrode 11 and the negative electrode 12.

[Separator]
The separator 13 separates the positive electrode 11 and the negative electrode 12 and allows lithium ions to pass through while preventing a short circuit of current due to contact between the two electrodes. The separator 13 is made of, for example, a porous film made of synthetic resin made of polytetrafluoroethylene (PTFE), polypropylene (PP), polyethylene (PE), polyvinylidene fluoride (PVdF), or the like, or a ceramic porous film. It may be configured to have a structure in which these two or more porous films are mixed or laminated. In particular, a polyolefin porous membrane is preferable because it is excellent in short-circuit prevention effect and can improve battery safety by a shutdown effect. The separator 13 is impregnated with a part of the electrolytic solution.

Furthermore, the separator 13 may apply or deposit a polymer material such as polyvinylidene fluoride (PVdF) on the surface of the porous film. In this case, the electrolyte solution is held on the polymer material on the surface of the separator 13 to form a gel electrolyte. The polymer material on the surface of the separator 13 may be mixed with an inorganic oxide such as alumina (Al ₂ O ₃ ) or silica (SiO ₂ ).

[Exterior material]
The exterior member 5 is made of, for example, a laminate film in which resin layers are formed on both surfaces of a metal layer. In the laminate film, an outer resin layer is formed on the surface of the metal layer that is exposed to the outside of the battery, and an inner resin layer is formed on the inner surface of the battery facing the power generation element such as the laminated electrode body 10.

  The metal layer plays the most important role in protecting the contents by preventing the ingress of moisture, oxygen and light, and aluminum (Al) is most often used because of its lightness, extensibility, price and ease of processing. The outer resin layer has a beautiful appearance, toughness, flexibility, and the like, and a resin material such as nylon or polyethylene terephthalate (PET) is used. Since the inner resin layer is a portion that melts and fuses with heat or ultrasonic waves, polyolefin is suitable, and unstretched polypropylene (CPP) is often used. As the resin material constituting the inner resin layer, a resin material having a melting point lower than that of the outer resin layer is used. This is because only the inner resin layer can be melted by heat-sealing at a temperature between the melting point of the resin material constituting the inner resin layer and the melting point of the resin material constituting the outer resin layer. An adhesive layer may be provided between the metal layer, the outer resin layer, and the inner resin layer as necessary.

  The exterior member 5 is provided with, for example, a recessed portion 5a that accommodates the laminated electrode body 10 formed by deep drawing from the inner resin layer side to the outer resin layer side. It arrange | positions so that it may oppose. The inner resin layers facing each other of the exterior member 5 are in close contact with each other by fusion or the like at the outer edge of the recess 5a. Between the exterior member 5 and the positive electrode lead 2 and the negative electrode lead 3, there is an adhesive film 4 for improving the adhesion between the inner resin layer of the exterior member 5 and the positive electrode lead 2 and the negative electrode lead 3 made of a metal material. Has been placed. The adhesion film 4 is made of a resin material having high adhesion to a metal material, and is made of, for example, polyethylene, polypropylene, or a polyolefin resin such as modified polyethylene or modified polypropylene obtained by modifying these materials.

  The exterior member 5 may be made of a laminate film having another structure, a polymer film such as polypropylene, or a metal film, instead of the aluminum laminate film whose metal layer is made of aluminum (Al).

  An adhesive film 4 is inserted between the exterior member 5 and the positive electrode lead 2 and the negative electrode lead 3 to prevent intrusion of outside air and infiltration of moisture. The adhesion film 4 is made of a material having adhesion to the positive electrode lead 2 and the negative electrode lead 3. Examples of such a material include polyolefin resins such as polyethylene, polypropylene, modified polyethylene, and modified polypropylene.

(1-2) Battery Manufacturing Method The laminated film type battery 1 according to the first embodiment is manufactured by, for example, the following manufacturing method.

(1-2-1) First Production Method [Production of Positive Electrode]
First, the positive electrode 11 is produced. For example, if necessary, a positive electrode material mixed with a phosphorus compound having a P—OH structure, a binder, and a conductive agent are mixed to form a positive electrode mixture, which is then dispersed in an organic solvent and pasted into a positive electrode A mixture slurry is obtained. Next, the positive electrode mixture slurry is uniformly applied to both surfaces of the belt-like positive electrode current collector 11A by a doctor blade or a bar coater and dried. At this time, the positive electrode mixture slurry is applied except for the end portion of the long side of the positive electrode current collector 11A. Subsequently, the positive electrode active material layer 11B is formed by compression-molding the coating film with a roll press or the like while heating as necessary. In this case, compression molding may be repeated a plurality of times. Finally, the strip-shaped positive electrode current collector 11A on which the positive electrode active material layer 11B is formed is cut into a rectangular shape, and the exposed portion of the positive electrode current collector 11A is cut to form a positive electrode tab 11C. Form.

[Manufacture of negative electrode]
Next, the negative electrode 12 is produced. For example, a negative electrode material comprising a titanium-containing lithium transition metal composite oxide having a spinel structure of the present technology, a binder, and a conductive agent as necessary are mixed to form a negative electrode mixture, which is then used as an organic solvent. To make a paste-like negative electrode mixture slurry. Next, the negative electrode mixture slurry is uniformly applied to both surfaces of the strip-shaped negative electrode current collector 12A by a doctor blade or a bar coater and dried. At this time, the negative electrode mixture slurry is applied except for the end portion of the long side of the negative electrode current collector 12A. Subsequently, the coating film is compression-molded by a roll press machine or the like while being heated as necessary to form the negative electrode active material layer 12B. Finally, the strip-shaped negative electrode current collector 12A on which the negative electrode active material layer 12B is formed is cut into a rectangular shape, and the exposed portion of the negative electrode current collector 12A is cut so as to form a negative electrode tab 12C. Form.

[Preparation of electrolyte]
A phosphorus compound having a P—OH structure represented by formula (A) or formula (B) is mixed with a solvent and an electrolyte salt as necessary to prepare an electrolytic solution.

[Battery assembly]
After laminating the positive electrode 11 and the negative electrode 12 via the separator 13, the fixing member 14 is stuck and the laminated structure is fixed to produce the laminated electrode body 10. Subsequently, the positive electrode lead 2 is attached to a portion where a plurality of the positive electrode current collectors 11 </ b> A extending from the positive electrode 11 are fixed to each other by wearing for ultrasonic waves or the like. Similarly, the negative electrode lead 3 is attached to a portion where a plurality of the negative electrode current collectors 12 </ b> A extending from the negative electrode 12 are fixed to each other by wearing for ultrasonic waves or the like.

  Subsequently, after the laminated electrode body 10 is accommodated in the recess 5a provided in the exterior member 5, the exterior member 5 is heat-sealed so as to have a bag shape. Subsequently, after injecting the electrolyte into the bag-shaped exterior member 5, the opening of the exterior member 5 is sealed by, for example, heat sealing in a reduced pressure environment. Thereby, the laminated film type battery 1 of this technique is obtained.

(1-2-2) Second Manufacturing Method In the second manufacturing method, a manufacturing method of the laminate film type battery 1 on which the gel electrolyte layer is formed will be described.

[Battery assembly]
A polymer material such as polyvinylidene fluoride (PVdF) is deposited on both surfaces of the positive electrode 11 and the negative electrode 12 or both surfaces of the separator 13. The polymer material is mixed with a solvent and applied to both surfaces of the positive electrode 11 and the negative electrode 12 or the separator 13 or is sprayed to adhere the solvent by volatilizing the solvent.

  Next, the laminated electrode body 10 is manufactured using the separator 13 described above, a plurality of positive electrode current collectors 11A extending from the positive electrode 11 are fixed to each other, the positive electrode lead 2 is attached, and the negative electrode 12 is extended. The plurality of negative electrode current collectors 12A are fixed to each other and the negative electrode lead 3 is attached.

  Subsequently, the laminated electrode body 10 is accommodated in the bag-shaped exterior member 5, and the electrolyte is injected into the bag-shaped exterior member 5, and then the opening of the exterior member 5 is heat-sealed in a reduced pressure environment, for example. Seal with etc. Finally, by pressing and heating the sealed exterior member 5 containing the laminated electrode body 10 and the electrolytic solution, and impregnating the electrolytic solution with the polymer material, a gel electrolyte layer is formed. A laminate film type battery 1 is obtained. At this time, a predetermined amount of the phosphorus compound having the P—OH structure of the present technology is mixed with at least one of the electrolytic solution and the positive electrode active material layer 21 </ b> B of the positive electrode 21.

(1-2-3) Third Manufacturing Method In the third embodiment, a polymerizable gelling agent is added to the electrolytic solution of the first manufacturing method, and the opening of the exterior member 5 is heat-sealed. Seal with. Thereafter, the sealed exterior member 5 containing the laminated electrode body 10 and the electrolytic solution is pressurized and heated to form a gel electrolyte layer, and the laminate film type battery 1 of the present technology is obtained. At this time, a predetermined amount of the phosphorus compound having the P—OH structure of the present technology is mixed with at least one of the electrolytic solution and the positive electrode active material layer 21 </ b> B of the positive electrode 21.

<Effect>
In the battery according to the first embodiment, even after being stored in a high temperature environment, gas generation inside the battery is suppressed, and battery swelling is also suppressed in a laminate film type battery using a laminate film as an exterior member. can do. In addition, it is possible to suppress an increase in DC resistance after storage at a high temperature environment due to gas generation inside the battery.

2. 2nd Embodiment 2nd Embodiment demonstrates the 2nd example of the battery of this technique. A second example of the battery according to the present technology is a laminated film battery in which the electrode body is a wound electrode body that is wound in a flat shape after a belt-like positive electrode and a belt-like negative electrode are stacked.

(2-1) Configuration of Laminate Film Type Battery In the battery of the second embodiment, a belt-like electrode is laminated instead of the laminated electrode body 10 in the first embodiment, and is further wound in a flat shape. A laminated film type battery in which a wound electrode body is covered with a laminated film.

  FIG. 4 is an exploded perspective view of the laminate film type battery 1 that houses the wound electrode body 20 according to the second embodiment of the present technology, and FIG. 5 is the wound electrode body 20 shown in FIG. This represents a cross-sectional structure along the line II-II. Since the laminated film type battery 1 according to the second embodiment is the same as the first embodiment except that the laminated electrode body 10 includes a wound electrode body 20 instead of the laminated electrode body 10, the common portions are the same. The symbol is attached.

  The wound electrode body 20 is formed by laminating and winding a belt-like positive electrode 21 and a belt-like negative electrode 22 via a belt-like separator 23, and a winding terminal portion is fixed by a fixing member 14 as necessary. The A gel electrolyte layer 25 is formed between the positive electrode 21 and the negative electrode 22 and the separator 23.

  The positive electrode 21 is obtained by providing a positive electrode active material layer 21B on, for example, both surfaces of a positive electrode current collector 21A having a pair of surfaces. Part of the positive electrode current collector 21A is provided with a positive electrode current collector exposed portion where the positive electrode active material layer 21B is not formed, and the positive electrode lead 2 is connected to the positive electrode current collector exposed portion.

  The negative electrode 22 is obtained by providing a negative electrode active material layer 22B on, for example, both surfaces of a negative electrode current collector 22A having a pair of surfaces. A part of the negative electrode current collector 22A is provided with a negative electrode current collector exposed portion where the negative electrode active material layer 22B is not formed, and the negative electrode lead 3 is connected to the negative electrode current collector exposed portion.

(2-2) Manufacturing Method of Laminated Film Type Battery The laminated film type battery 1 of the second embodiment is manufactured by, for example, the following four types of manufacturing methods (first to fourth manufacturing methods).

(2-2-1) First Manufacturing Method to Third Manufacturing Method The laminated film type battery 1 according to the second embodiment is a first manufacturing method to a third manufacturing method according to the first embodiment. It can be manufactured by the same method.

(2-2-2) Fourth Manufacturing Method In the fourth manufacturing method, first, the electrolytic solution, the polymer material used in the second manufacturing method, or the polymerizable gelation used in the third manufacturing method. A gel electrolyte layer 25 is formed by applying a precursor solution mixed with an agent to the surfaces of the strip-like positive electrode 21 and the strip-like negative electrode 22 and subjecting it to a heat treatment. When an ultraviolet curable polymerizable gelling agent is used, an ultraviolet curing treatment is performed instead of the heat treatment. At this time, a predetermined amount of the phosphorus compound having the P—OH structure of the present technology is mixed with at least one of the electrolytic solution and the positive electrode active material layer 21 </ b> B of the positive electrode 21.

  Thereafter, the positive electrode 21 and the negative electrode 22 are laminated via the separator 23 and wound in a flat shape, and the fixing member 14 is adhered to the winding terminal portion to produce the wound electrode body 20.

  Subsequently, the wound electrode body 20 is accommodated in the bag-shaped exterior member 5, and the opening of the exterior member 5 is sealed by, for example, heat sealing in a reduced pressure environment. Thereby, the laminated film type battery 1 of this technique is obtained.

<Effect>
The laminated film type battery 1 of the second embodiment has the same effect as the laminated film type battery 1 of the first embodiment.

3. 3rd Embodiment 3rd Embodiment demonstrates the 3rd example of the battery of this technique. A third example of the battery of the present technology is a prismatic battery in which an electrode body including a positive electrode and a negative electrode is accommodated in a rectangular outer can.

(3-1) Configuration of Square Battery FIG. 6 shows the configuration of the square battery 30 according to the third embodiment of the present technology, and the laminated electrode body 40 is placed in the rectangular outer can 31. It is what was contained. Instead of the laminated electrode body 40, the rectangular battery 30 may be assembled using a wound electrode body.

  The rectangular battery 30 includes a rectangular tube-shaped outer can 31, a laminated electrode body 40 that is a power generation element housed in the outer can 31, a battery lid 32 that closes an opening of the outer can 31, and a battery lid 32. It is comprised by the electrode pin 33 etc. which were provided in the approximate center part.

  The outer can 31 is formed as a hollow, bottomed rectangular tube with a conductive metal such as iron (Fe), for example. The inner surface of the outer can 31 is preferably configured to increase the conductivity of the outer can 31 by, for example, applying nickel plating or applying a conductive paint. The outer peripheral surface of the outer can 31 may be covered with an outer label formed of, for example, a plastic sheet or paper, or may be protected by applying an insulating paint. The battery lid 32 is formed of a conductive metal such as iron (Fe), for example, like the outer can 31.

  The laminated electrode body 40 has the same configuration as that of the first embodiment, and is obtained by laminating a positive electrode and a negative electrode via a separator. Since the positive electrode, the negative electrode, and the separator are the same as those in the first embodiment or the second embodiment, detailed description thereof is omitted.

  The laminated electrode body 40 having such a configuration is provided with a positive terminal 41 connected to a plurality of positive electrodes and a negative terminal connected to a plurality of negative current collectors. The positive electrode terminal 41 and the negative electrode terminal are led out to one end of the laminated electrode body 40 in the axial direction. The positive terminal 41 is connected to the lower end of the electrode pin 33 by fixing means such as welding. Further, the negative electrode terminal is connected to the inner surface of the outer can 31 by fixing means such as welding.

  The electrode pin 33 is made of a conductive shaft member, and is held by an insulator 34 with its head protruding to the upper end. The electrode pin 33 is fixed to a substantially central portion of the battery lid 32 through the insulator 34. The insulator 34 is made of a highly insulating material and is fitted into a through hole 35 provided on the surface side of the battery lid 32. Further, the electrode pin 33 is passed through the through hole 35, and the tip end portion of the positive electrode terminal 41 is fixed to the lower end surface thereof.

  The battery lid 32 provided with such electrode pins 33 and the like is fitted into the opening of the outer can 31, and the contact surface between the outer can 31 and the battery lid 32 is joined by a fixing means such as welding. Yes. Thereby, the opening part of the armored can 31 is sealed by the battery cover 32, and is comprised airtight and liquid-tight. The battery lid 32 is provided with an internal pressure release mechanism 36 that breaks a part of the battery lid 32 to release (release) the internal pressure to the outside when the pressure in the outer can 31 rises above a predetermined value. ing.

  The internal pressure release mechanism 36 includes two first opening grooves 36a (one first opening groove 36a not shown) linearly extending in the longitudinal direction on the inner surface of the battery lid 32, and the battery The inner surface of the lid 32 includes a second opening groove 36b extending in the width direction orthogonal to the longitudinal direction and having both ends communicating with the two first opening grooves 36a. The two first opening grooves 36 a are provided in parallel to each other along the outer edge of the long side of the battery lid 32 in the vicinity of the inner side of the two long sides positioned so as to face the width direction of the battery lid 32. ing. Further, the second opening groove 36 b is provided so as to be positioned at a substantially central portion between one short side outer edge and the electrode pin 33 on one side in the longitudinal direction of the electrode pin 33.

  Both the first opening groove 36a and the second opening groove 36b have, for example, a V-shape in which the cross-sectional shape is opened on the lower surface side. The shapes of the first opening groove 36a and the second opening groove 36b are not limited to the V shape shown in this embodiment. For example, the shapes of the first opening groove 36a and the second opening groove 36b may be U-shaped or semicircular.

  The electrolyte injection port 37 is provided so as to penetrate the battery lid 32. The electrolyte solution injection port 37 is used to inject the electrolyte solution after the battery lid 32 and the outer can 31 are caulked, and is sealed by the sealing member 38 after the electrolyte solution injection. When the gel electrolyte layer is formed in advance and the electrolytic solution is not injected, the electrolytic solution injection port 37 may not be provided.

(3-2) Manufacturing Method of Square Battery The laminated electrode body 40 of the third embodiment is manufactured by each manufacturing method described in the first embodiment. Even when a wound electrode body is used, it can be manufactured by the same method as in the second embodiment.

[Assembly of square battery]
The laminated electrode body 40 produced by previously forming a gel electrolyte layer on the surfaces of the positive electrode and the negative electrode is accommodated in an outer can 31 that is a square can made of a metal such as aluminum (Al) or iron (Fe).

  And after connecting the electrode pin 33 provided in the battery cover 32 and the positive electrode terminal 41 connected with the laminated electrode body 40, it seals with the battery cover 32, for example, it electrolyzes from the electrolyte solution injection port 37 under pressure reduction. Inject liquid. Finally, the electrolyte solution inlet 37 is sealed with a sealing member 38. At this time, a predetermined amount of the phosphorus compound having the P—OH structure of the present technology is mixed with at least one of the electrolytic solution and the positive electrode constituting the laminated electrode body 40. Thus, the square battery 30 of the present technology shown in FIG. 6 is obtained.

<Effect>
The square battery 30 of the third embodiment has the same effects as the laminate film battery 1 of the first embodiment and the laminate film battery 1 of the second embodiment.

4). 4th Embodiment 4th Embodiment demonstrates the 4th example of the battery of this technique. A fourth example of the battery of the present technology is a cylindrical battery in which an electrode body including a positive electrode and a negative electrode is accommodated in a cylindrical outer can. Unlike the laminated film type battery 1 of the first embodiment or the second embodiment, the outer shape of the cylindrical battery is not greatly changed by gas generation inside the battery. However, the internal pressure of the battery rises due to the generation of gas inside the battery, and the gas may be ejected to the outside of the battery, which may reduce safety. For this reason, it is effective in the point that a safety improvement effect is acquired by applying the electrolyte of this art to a cylindrical battery, and suppressing gas generation.

(4-1) Configuration of cylindrical battery [battery structure]
FIG. 7 is a cross-sectional view showing an example of the cylindrical battery 50 according to the fourth embodiment. The cylindrical battery 50 includes a wound electrode body 60 in which a strip-shaped positive electrode 61 and a strip-shaped negative electrode 62 are wound through a strip-shaped separator 63 inside a substantially hollow cylindrical battery can 51, and a book (not shown). With technical electrolytes. The electrolyte is an electrolytic solution or a gel electrolyte.

  The battery can 51 is made of, for example, iron plated with nickel, and has one end closed and the other end open. Inside the battery can 51, a pair of insulating plates 52 a and 52 b are respectively arranged perpendicular to the winding peripheral surface so as to sandwich the winding electrode body 60.

  Examples of the material of the battery can 51 include iron (Fe), nickel (Ni), stainless steel (SUS), aluminum (Al), titanium (Ti), and the like. The battery can 51 may be plated with, for example, nickel in order to prevent corrosion due to the electrochemical electrolyte accompanying charging / discharging of the cylindrical battery 50. At the open end of the battery can 51, a battery lid 53, which is a positive electrode lead plate, and a safety valve mechanism and a thermal resistance element (PTC element: Positive Temperature Coefficient) 57 provided inside the battery lid 53 are insulated and sealed. It is attached by caulking through a gasket 58 for

  The battery lid 53 is made of, for example, the same material as that of the battery can 51, and is provided with an opening for discharging gas generated inside the battery. In the safety valve mechanism, a safety valve 54, a disk holder 55, and a shut-off disk 56 are sequentially stacked. The protruding portion 54a of the safety valve 54 is connected to the positive electrode lead 65 led out from the wound electrode body 60 through a sub disk 59 disposed so as to cover a hole 56a provided in the central portion of the cutoff disk 56. . By connecting the safety valve 54 and the positive electrode lead 65 via the sub disk 59, the positive electrode lead 65 is prevented from being drawn from the hole 56a when the safety valve 54 is reversed. Further, the safety valve mechanism is electrically connected to the battery lid 53 via the heat sensitive resistance element 57.

  In the safety valve mechanism, when the internal pressure of the cylindrical battery 50 exceeds a certain level due to internal short circuit or heating from the outside of the battery, the safety valve 54 is reversed, and the protrusion 54a, the battery lid 53, the wound electrode body 60, This disconnects the electrical connection. That is, when the safety valve 54 is reversed, the positive electrode lead 65 is pressed by the shut-off disk 56 and the connection between the safety valve 54 and the positive electrode lead 65 is released. The disc holder 55 is made of an insulating material, and when the safety valve 54 is reversed, the safety valve 54 and the shut-off disc 56 are insulated.

  Further, when further gas is generated inside the battery and the internal pressure of the battery further increases, a part of the safety valve 54 is broken and the gas can be discharged to the battery lid 53 side.

  Further, for example, a plurality of gas vent holes (not shown) are provided around the hole portion 56a of the shut-off disk 56, and when gas is generated from the wound electrode body 60, the gas is effectively removed from the battery lid. It is set as the structure which can discharge | emit to 53 side.

  The resistance element 57 increases in resistance when the temperature rises, cuts off the electrical connection between the battery lid 53 and the wound electrode body 60 and cuts off the current, thereby generating abnormal heat generation due to an excessive current. To prevent. The gasket 58 is made of, for example, an insulating material, and asphalt is applied to the surface.

  The wound electrode body 60 accommodated in the cylindrical battery 50 is wound around a center pin 64. The wound electrode body 60 has the same configuration as that of the second embodiment, and is obtained by sequentially laminating the positive electrode 61 and the negative electrode 62 via the separator 63 and winding in the longitudinal direction. Since the positive electrode 61, the negative electrode 62, the separator 63, and the electrolytic solution are the same as those in the first embodiment, detailed description thereof is omitted.

  A positive electrode lead 65 is connected to the positive electrode 61, and a negative electrode lead 66 is connected to the negative electrode 62. As described above, the positive electrode lead 65 is welded to the safety valve 54 and electrically connected to the battery lid 53, and the negative electrode lead 66 is welded to and electrically connected to the battery can 51.

(4-2) Cylindrical battery manufacturing method [Positive electrode and negative electrode manufacturing method]
The positive electrode and the negative electrode can be manufactured in the same manner as in the first embodiment.

[Battery assembly]
A positive electrode lead 65 is attached to the positive electrode 61 by welding or the like, and a negative electrode lead 66 is attached to the negative electrode 62 by welding or the like. Thereafter, the positive electrode 61 and the negative electrode 62 are wound through a separator 63 to form a wound electrode body 60.

  Subsequently, the tip of the positive electrode lead 65 is welded to the safety valve mechanism, and the tip of the negative electrode lead 66 is welded to the battery can 51. Thereafter, the wound surface of the wound electrode body 60 is sandwiched between the pair of insulating plates 52 a and 52 b and housed inside the battery can 51. After the wound electrode body 60 is accommodated in the battery can 51, the electrolytic solution is injected into the battery can 51.

  When forming the gel electrolyte layer, the wound electrode body 60 is manufactured by the fourth manufacturing method of the second embodiment. That is, the wound electrode body 60 is formed using the positive electrode 61 and the negative electrode 62 on which the gel electrolyte layer is formed in advance. In the cylindrical battery 50, unlike the laminated film battery 1 in the first embodiment, it is difficult to form a gel electrolyte layer by sealing and heating from the outside of the battery after sealing. For this reason, it is necessary to prepare the wound electrode body 60 after assembling the gel electrolyte layer on the surfaces of the positive electrode 61 and the negative electrode 62 in advance and assemble the cylindrical battery 50. Then, the tip of the positive electrode lead 65 is welded to the safety valve mechanism, and the tip of the negative electrode lead 66 is welded to the battery can 51. Thereafter, the wound surface of the wound electrode body 60 is sandwiched between the pair of insulating plates 52 a and 52 b and housed inside the battery can 51. The wound electrode body 60 is housed inside the battery can 51. If necessary, an electrolytic solution may be further injected into the battery can 51.

  Subsequently, the safety valve mechanism including the battery lid 53 and the safety valve 54 and the heat sensitive resistance element 57 are fixed to the opening end of the battery can 51 by caulking through the gasket 58. At this time, a predetermined amount of a phosphorus compound having a P—OH structure of the present technology is mixed with at least one of the electrolytic solution and the positive electrode 61 constituting the wound electrode body 60. Thereby, the cylindrical battery 50 of this technique shown in FIG. 7 is obtained.

<Effect>
The cylindrical battery 50 according to the fourth embodiment is arranged inside the battery similarly to the laminated film battery 1 according to the first embodiment and the second embodiment and the prismatic battery 30 according to the third embodiment. It has the effect of suppressing gas generation.

5. Fifth Embodiment In the fifth embodiment, a battery pack provided with a battery (laminated film battery 1, prismatic battery 30, or cylindrical battery 50) using the electrolyte of the present technology will be described.

  FIG. 8 is a block diagram illustrating a circuit configuration example when the battery of the present technology (laminate film battery 1, square battery 30 or cylindrical battery 50) is applied to a battery pack. The battery pack includes a switch unit 104 including an assembled battery 101, an exterior, a charge control switch 102a, and a discharge control switch 103a, a current detection resistor 107, a temperature detection element 108, and a control unit 110.

  In addition, the battery pack includes a positive electrode terminal 121 and a negative electrode terminal 122. When charging, the positive electrode terminal 121 and the negative electrode terminal 122 are connected to the positive electrode terminal and the negative electrode terminal of the charger, respectively, and charging is performed. Further, when the electronic device is used, the positive electrode terminal 121 and the negative electrode terminal 122 are connected to the positive electrode terminal and the negative electrode terminal of the electronic device, respectively, and discharge is performed.

  The assembled battery 101 is formed by connecting a plurality of batteries 101a in series and / or in parallel. The battery 101a is a battery according to the present technology. In addition, in FIG. 8, although the case where the six batteries 101a are connected to 2 parallel 3 series (2P3S) is shown as an example, other than n parallel m series (n and m are integers), Any connection method may be used.

  The switch unit 104 includes a charge control switch 102a and a diode 102b, and a discharge control switch 103a and a diode 103b, and is controlled by the control unit 110. The diode 102b has a reverse polarity with respect to a charging current flowing from the positive electrode terminal 121 in the direction of the assembled battery 101 and a forward polarity with respect to a discharging current flowing from the negative electrode terminal 122 in the direction of the assembled battery 101. The diode 103b has a polarity in the forward direction with respect to the charging current and in the reverse direction with respect to the discharging current. In the example, the switch portion is provided on the + side, but may be provided on the − side.

  The charge control switch 102a is turned off when the battery voltage becomes the overcharge detection voltage, and is controlled by the charge / discharge control unit so that the charge current does not flow in the current path of the assembled battery 101. After the charging control switch is turned off, only discharging is possible via the diode 102b. Further, it is turned off when a large current flows during charging, and is controlled by the control unit 110 so as to cut off the charging current flowing in the current path of the assembled battery 101.

  The discharge control switch 103a is turned off when the battery voltage becomes the overdischarge detection voltage, and is controlled by the control unit 110 so that the discharge current does not flow in the current path of the assembled battery 101. After the discharge control switch 103a is turned off, only charging is possible via the diode 103b. Further, it is turned off when a large current flows during discharging, and is controlled by the control unit 110 so as to cut off the discharging current flowing through the current path of the assembled battery 101.

  The temperature detection element 108 is, for example, a thermistor, is provided in the vicinity of the assembled battery 101, measures the temperature of the assembled battery 101, and supplies the measured temperature to the control unit 110. The voltage detection unit 111 measures the voltage of the assembled battery 101 and each of the batteries 101a constituting the assembled battery 101, A / D converts this measurement voltage, and supplies the voltage to the control unit 110. The current measurement unit 113 measures current using the current detection resistor 107 and supplies this measurement current to the control unit 110.

  The switch control unit 114 controls the charge control switch 102a and the discharge control switch 103a of the switch unit 104 based on the voltage and current input from the voltage detection unit 111 and the current measurement unit 113. The switch control unit 114 sends a control signal to the switch unit 104 when any voltage of the battery 101a becomes equal to or lower than the overcharge detection voltage or the overdischarge detection voltage, or when a large current suddenly flows. Prevents overcharge, overdischarge, and overcurrent charge / discharge.

  As the charge / discharge switch, for example, a semiconductor switch such as a MOSFET can be used. In this case, the parasitic diode of the MOSFET functions as the diodes 102b and 103b. When a P-channel FET is used as the charge / discharge switch, the switch control unit 114 supplies control signals DO and CO to the gates of the charge control switch 102a and the discharge control switch 103a, respectively. When the charge control switch 102a and the discharge control switch 103a are P-channel type, they are turned on by a gate potential that is lower than the source potential by a predetermined value or more. That is, in normal charging and discharging operations, the control signals CO and DO are set to a low level, and the charging control switch 102a and the discharging control switch 103a are turned on.

  For example, in the case of overcharge or overdischarge, the control signals CO and DO are set to a high level, and the charge control switch 102a and the discharge control switch 103a are turned off.

  The memory 117 includes a RAM and a ROM, and includes, for example, an EPROM (Erasable Programmable Read Only Memory) that is a nonvolatile memory. In the memory 117, the numerical value calculated by the control unit 110, the internal resistance value of the battery in the initial state of each battery 101a measured in the manufacturing process, and the like are stored in advance, and can be appropriately rewritten. (In addition, by storing the full charge capacity of the battery 101a, for example, the remaining capacity can be calculated together with the control unit 110.

  The temperature detection unit 118 measures the temperature using the temperature detection element 108, performs charge / discharge control during abnormal heat generation, and performs correction in the calculation of the remaining capacity.

6). Sixth Embodiment In the sixth embodiment, an electronic device, an electric vehicle, a power storage device, or the like equipped with the battery according to the second to fourth embodiments or the battery pack according to the fifth embodiment. The device will be described. The batteries and battery packs described in the second to fifth embodiments can be used to supply power to devices such as electronic devices, electric vehicles, and power storage devices.

  Examples of electronic devices include notebook computers, PDAs (personal digital assistants), mobile phones, cordless phones, video movies, digital still cameras, electronic books, electronic dictionaries, music players, radios, headphones, game consoles, navigation systems, Memory cards, pacemakers, hearing aids, power tools, electric shavers, refrigerators, air conditioners, TVs, stereos, water heaters, microwave ovens, dishwashers, washing machines, dryers, lighting equipment, toys, medical equipment, robots, road conditioners, traffic lights Etc.

  Further, examples of the electric vehicle include a railway vehicle, a golf cart, an electric cart, an electric vehicle (including a hybrid vehicle), and the like, and these are used as a driving power source or an auxiliary power source.

  Examples of the power storage device include a power storage power source for buildings such as houses or power generation facilities.

  Below, the specific example of the electrical storage system using the electrical storage apparatus to which the battery of this technique is applied among the application examples mentioned above is demonstrated.

  This power storage system has the following configuration, for example. The first power storage system is a power storage system in which a power storage device is charged by a power generation device that generates power from renewable energy. The second power storage system is a power storage system that includes a power storage device and supplies power to an electronic device connected to the power storage device. The third power storage system is an electronic device that receives power supply from the power storage device. These power storage systems are implemented as a system for efficiently supplying power in cooperation with an external power supply network.

  Further, the fourth power storage system includes an electric vehicle having a conversion device that receives power supplied from the power storage device and converts the power into a driving force of the vehicle, and a control device that performs information processing related to vehicle control based on information related to the power storage device. It is. The fifth power storage system is a power system that includes a power information transmission / reception unit that transmits / receives signals to / from other devices via a network, and performs charge / discharge control of the power storage device described above based on information received by the transmission / reception unit. . The sixth power storage system is a power system that receives power from the power storage device described above or supplies power from the power generation device or the power network to the power storage device. Hereinafter, the power storage system will be described.

(6-1) Residential Power Storage System as an Application Example An example in which a power storage device using a battery of the present technology is applied to a residential power storage system will be described with reference to FIG. For example, in a power storage system 200 for a house 201, power is stored from a centralized power system 202 such as a thermal power generation 202a, a nuclear power generation 202b, and a hydropower generation 202c through a power network 209, an information network 212, a smart meter 207, a power hub 208, and the like. Supplied to the device 203. At the same time, power is supplied to the power storage device 203 from an independent power source such as the home power generation device 204. The electric power supplied to the power storage device 203 is stored. Electric power used in the house 201 is supplied using the power storage device 203. The same power storage system can be used not only for the house 201 but also for buildings.

  The house 201 is provided with a home power generation device 204, a power consumption device 205, a power storage device 203, a control device 210 that controls each device, a smart meter 207, and a sensor 211 that acquires various types of information. Each device is connected by a power network 209 and an information network 212. A solar cell, a fuel cell, or the like is used as the home power generation device 204, and the generated power is supplied to the power consumption device 205 and / or the power storage device 203. The power consuming device 205 is a refrigerator 205a, an air conditioner 205b, a television receiver 205c, a bath 205d, or the like. Furthermore, the electric power consumption device 205 includes an electric vehicle 206. The electric vehicle 206 is an electric vehicle 206a, a hybrid car 206b, and an electric motorcycle 206c.

  The battery of the present technology is applied to the power storage device 203. The battery of the present technology may be configured by, for example, the above-described lithium ion secondary battery. The smart meter 207 has a function of measuring the usage amount of commercial power and transmitting the measured usage amount to an electric power company. The power network 209 may be any one or a combination of DC power supply, AC power supply, and non-contact power supply.

  The various sensors 211 are, for example, human sensors, illuminance sensors, object detection sensors, power consumption sensors, vibration sensors, contact sensors, temperature sensors, infrared sensors, and the like. Information acquired by the various sensors 211 is transmitted to the control device 210. Based on the information from the sensor 211, the weather condition, the condition of the person, and the like can be grasped, and the power consumption device 205 can be automatically controlled to minimize the energy consumption. Furthermore, the control apparatus 210 can transmit the information regarding the house 201 to an external electric power company etc. via the internet.

  The power hub 208 performs processing such as branching of power lines and DC / AC conversion. As a communication method of the information network 212 connected to the control device 210, a method using a communication interface such as UART (Universal Asynchronous Receiver-Transceiver), Bluetooth (registered trademark of Bluetooth SIG), ZigBee, There is a method of using a sensor network based on a wireless communication standard such as Wi-Fi. The Bluetooth method is applied to multimedia communication and can perform one-to-many connection communication. ZigBee uses the physical layer of IEEE (Institute of Electrical and Electronics Engineers) 802.15.4. IEEE 802.15.4 is the name of a short-range wireless network standard called PAN (Personal Area Network) or W (Wireless) PAN.

  The control device 210 is connected to an external server 213. The server 213 may be managed by any one of the house 201, the power company, and the service provider. The information transmitted and received by the server 213 is, for example, information related to power consumption information, life pattern information, power charges, weather information, natural disaster information, and power transactions. These pieces of information may be transmitted / received from a power consuming device in the home (for example, a television receiver) or may be transmitted / received from a device outside the home (for example, a mobile phone). Such information may be displayed on a device having a display function, such as a television receiver, a mobile phone, or a PDA (Personal Digital Assistants).

  The control device 210 that controls each unit includes a CPU (Central Processing Unit), a RAM (Random Access Memory), a ROM (Read Only Memory), and the like, and is stored in the power storage device 203 in this example. The control device 210 is connected to the power storage device 203, the home power generation device 204, the power consumption device 205, the various sensors 211, the server 213 and the information network 212, and adjusts, for example, the amount of commercial power used and the amount of power generation. It has a function. In addition, you may provide the function etc. which carry out an electric power transaction in an electric power market.

  As described above, the electric power can be stored not only in the centralized power system 202 such as the thermal power 202a, the nuclear power 202b, and the hydropower 202c but also in the power storage device 203 in the power generation device 204 (solar power generation, wind power generation). it can. Therefore, even if the generated power of the home power generator 204 fluctuates, it is possible to perform control such that the amount of power sent to the outside is constant or discharge is performed as necessary. For example, the power obtained by solar power generation is stored in the power storage device 203, and midnight power with a low charge is stored in the power storage device 203 at night, and the power stored by the power storage device 203 is discharged during a high daytime charge. You can also use it.

  In this example, the example in which the control device 210 is stored in the power storage device 203 has been described. However, the control device 210 may be stored in the smart meter 207 or may be configured independently. Furthermore, the power storage system 200 may be used for a plurality of homes in an apartment house, or may be used for a plurality of detached houses.

(6-2) Power Storage System in Vehicle as Application Example An example in which the present technology is applied to a power storage system for a vehicle will be described with reference to FIG. FIG. 10 schematically shows an example of the configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied. A series hybrid system is a car that runs on an electric power driving force conversion device using electric power generated by a generator driven by an engine or electric power once stored in a battery.

  The hybrid vehicle 300 includes an engine 301, a generator 302, a power driving force conversion device 303, driving wheels 304a, driving wheels 304b, wheels 305a, wheels 305b, a battery 308, a vehicle control device 309, various sensors 310, and a charging port 311. Is installed. The battery of the present technology described above is applied to the battery 308.

  The hybrid vehicle 300 travels using the power driving force conversion device 303 as a power source. An example of the power driving force conversion device 303 is a motor. The electric power / driving force converter 303 is operated by the electric power of the battery 308, and the rotational force of the electric power / driving force converter 303 is transmitted to the driving wheels 304a and 304b. In addition, by using a direct current-alternating current (DC-AC) or reverse conversion (AC-DC conversion) in a necessary place, the power driving force conversion device 303 can be applied to either an alternating current motor or a direct current motor. The various sensors 310 control the engine speed via the vehicle control device 309 and control the opening (throttle opening) of a throttle valve (not shown). The various sensors 310 include a speed sensor, an acceleration sensor, an engine speed sensor, and the like.

  The rotational force of the engine 301 is transmitted to the generator 302, and the electric power generated by the generator 302 by the rotational force can be stored in the battery 308.

  When the hybrid vehicle 300 decelerates by a braking mechanism (not shown), the resistance force at the time of deceleration is applied as a rotational force to the power driving force conversion device 303, and the regenerative power generated by the power driving force conversion device 303 by this rotational force is used as the battery 308. Accumulated in.

  The battery 308 is connected to a power source external to the hybrid vehicle 300, so that power can be supplied from the external power source using the charging port 311 as an input port, and the received power can be stored.

  Although not shown, an information processing apparatus that performs information processing related to vehicle control based on information related to the battery may be provided. As such an information processing apparatus, for example, there is an information processing apparatus that displays a remaining battery level based on information on the remaining battery level.

  In addition, the above demonstrated as an example the series hybrid vehicle which drive | works with a motor using the electric power generated with the generator driven by an engine, or the electric power once stored in the battery. However, the present technology is also effective for a parallel hybrid vehicle in which the engine and motor outputs are both driving sources, and the system is switched between the three modes of driving with only the engine, driving with the motor, and engine and motor. Applicable. Furthermore, the present technology can be effectively applied to a so-called electric vehicle that travels only by a drive motor without using an engine.

  Hereinafter, the present technology will be specifically described by way of examples. However, the present technology is not limited only to these examples.

  In addition, the following Example 1-1 to Example 1-23 and Comparative Example 1-1 to Comparative Example 1-6, and Example 2-1 to Example 2-23 and Comparative Example 2-1 to Comparative Example 2 Additive A and additive B, and the solvent used in -6 are as follows.

Additive A
H ₃ PO ₃ : phosphonic acid H ₃ PO ₄ : phosphoric acid PhPO (OH) ₂ : phenylphosphonic acid PhPHOOH: phenylphosphinic acid Ph ₂ HPO ₄ : diphenyl phosphate (CH ₃ O) ₂ POH: dimethyl phosphite

Additive B
VC: vinylene carbonate FEC: fluoroethylene carbonate SN: succinonitrile

Solvent PC: Propylene carbonate EC: Ethylene carbonate DMC: Dimethyl carbonate EMC: Ethyl methyl carbonate EA: Ethyl acetate MP: Methyl propionate

<Example 1-1> to <Example 1-23>, <Comparative Example 1-1> to <Comparative Example 1-6>
In Example 1-1 to Example 1-23 and Comparative Example 1-1 to Comparative Example 1-6, additive A, which is a phosphorus compound having a P—OH structure, and halogenated ethylene carbonate or The battery characteristics were evaluated by changing the positive electrode active material, the negative electrode active material, and the solvent composition using an electrolytic solution to which an additive B that is either a saturated cyclic carbonate or a nitrile compound was added.

<Example 1-1>
[Production of positive electrode]
First, 94 parts by mass of lithium-manganese composite oxide (LiMn ₂ O ₄ ) as a positive electrode active material, 3 parts by mass of amorphous carbon as a conductive agent, and 3 parts by mass of polyvinylidene fluoride (PVdF) as a binder. After homogeneous mixing, N-methylpyrrolidone was added to obtain a positive electrode mixture coating solution. Next, the obtained positive electrode mixture coating liquid was uniformly applied to both surfaces on a 15 μm thick aluminum foil and dried to form a positive electrode active material layer having a thickness of 75 μm per one surface. This was cut into a shape having a width of 60 mm and a length of 80 mm to produce a rectangular positive electrode.

[Production of negative electrode]
96 parts by mass of lithium-titanium composite oxide (Li ₄ Ti ₅ O ₁₂ ) as a negative electrode active material, 1 part by mass of amorphous carbon as a conductive agent, and 3 parts by mass of polyvinylidene fluoride (PVdF) as a binder Homogeneously mixed and N-methylpyrrolidone was added to obtain a negative electrode mixture coating solution. Next, the obtained negative electrode mixture coating liquid was uniformly applied on both surfaces of a 15 μm-thick aluminum foil serving as a negative electrode current collector and dried to form a negative electrode active material layer having a thickness of 100 μm per side. This was cut into a shape having a width of 60 mm and a length of 80 mm to produce a rectangular negative electrode.

Note that the potential of the lithium / titanium composite oxide (Li ₄ Ti ₅ O ₁₂ ) used as the negative electrode active material at the time of full charge is about 1.55 V as a counter electrode lithium potential.

[Preparation of electrolyte]
As the solvent, propylene carbonate (PC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) were mixed at a mass ratio of 4: 3: 3. To this solvent, lithium hexafluorophosphate (LiPF ₆ ) as an electrolyte salt and phosphonic acid (H ₃ PO ₃ ) as an additive A were mixed to obtain an electrolytic solution. The electrolyte was added so that the concentration of lithium hexafluorophosphate was 16.5% by mass and the concentration of phosphoric acid was 0.2% by mass in the electrolyte. That is, the composition in the electrolytic solution was propylene carbonate 33.3 mass%, dimethyl carbonate 25.0 mass%, ethyl methyl carbonate 25.0 mass%, phosphonic acid 0.2 mass%, lithium hexafluorophosphate 16. The amount was 5% by mass.

[Battery assembly]
The positive electrode and the negative electrode are laminated through a separator made of a microporous polyethylene film having a thickness of 16 μm, and a positive electrode, a negative electrode, a positive electrode,... And a laminated electrode body was produced. Subsequently, the laminated electrode body was inserted into an aluminum laminate film formed into a bag shape by heat-sealing except for one side. Finally, 3 g of the electrolyte solution was poured into the bag-shaped aluminum laminate film, and then one side of the bag-shaped aluminum laminate film was heat-sealed and sealed under a reduced pressure environment to produce a laminated film type battery. This laminated film type battery had a battery capacity of 600 mAh.

<Example 1-2>
In the electrolyte solution, vinylene carbonate (VC), which is an unsaturated cyclic carbonate, was added as additive B, and the concentration of vinylene carbonate (VC) in the electrolyte solution was adjusted to 1.0% by mass, A laminated film type battery was produced in the same manner as in Example 1-2. At this time, according to the addition amount of vinylene carbonate (VC), propylene carbonate (PC) was reduced and the electrolyte solution was prepared.

<Example 1-3> to <Example 1-4>
In the same manner as in Example 1-2, except that the concentration of phosphonic acid (H ₃ PO ₃ ) in the electrolytic solution was 0.05% by mass and 0.5% by mass, Examples 1-3 and The laminate film type battery of Example 1-4 was produced.

<Example 1-5>
A laminate film type battery was prepared in the same manner as in Example 1-2, except that phosphoric acid (H ₃ PO ₄ ) was used instead of phosphonic acid (H ₃ PO ₃ ) as additive A added to the electrolyte. Produced.

<Example 1-6> to <Example 1-8>
As an additive A to be added to the electrolytic solution, phenylphosphonic acid (PhPO (OH) ₂ ), phenylphosphinic acid (PhPHOOH) or diphenyl phosphate (Ph ₂ HPO ₄ ) is used instead of phosphonic acid (H ₃ PO ₃ ). The laminated film batteries of Examples 1-6 to 1-8 were produced in the same manner as in Example 1-2, except that each was used and the concentration was changed to 0.5% by mass.

<Example 1-9>
As in Example 1-2, except that dimethyl phosphite ((CH ₃ O) ₂ POH) was used instead of phosphonic acid (H ₃ PO ₃ ) as additive A to be added to the electrolytic solution. A laminate film type battery was produced.

<Example 1-10> to <Example 1-11>
Examples 1 to 10 were carried out in the same manner as Example 1-2 except that the concentration of vinylene carbonate (VC) as additive B was adjusted to 0.1% by mass and 5.0% by mass. The laminate film type battery of Example 1-11 was produced. At this time, according to the addition amount of vinylene carbonate (VC), propylene carbonate (PC) was increased / decreased and the electrolyte solution was prepared.

<Example 1-12> to <Example 1-13>
As Example 1-2, except that fluoroethylene carbonate (FEC) or succinonitrile (SN) was used instead of vinylene carbonate (VC) as additive B to be added to the electrolytic solution, respectively. Examples 1-12 to 1-13 were produced.

<Example 1-14>
Example 1 except that lithium-nickel-cobalt-aluminum composite oxide (LiNi _0.77 Co _0.20 Al _0.03 O ₂ ) was used as the positive electrode active material instead of lithium-manganese composite oxide (LiMn ₂ O ₄ ). In the same manner as in Example 2, a laminate film type battery was produced.

<Example 1-15>
Example 1 except that lithium-nickel-cobalt-manganese composite oxide (LiNi _0.5 Co _0.2 Mn _0.3 O ₂ ) was used as the positive electrode active material instead of lithium-manganese composite oxide (LiMn ₂ O ₄ ). In the same manner as in Example 2, a laminate film type battery was produced.

<Example 1-16>
Except that lithium / nickel / manganese composite oxide (LiNi _0.5 Mn _1.5 O ₂ ) was used instead of lithium / manganese composite oxide (LiMn ₂ O ₄ ) as the positive electrode active material, the same as Example 1-2. Thus, a laminated film type battery was produced. This laminated film type battery had a battery capacity of 700 mAh.

<Example 1-17>
Example 1 except that lithium / titanium / niobium composite oxide (Li ₄ Ti _4.95 Nb _0.05 O ₁₂ ) was used as the negative electrode active material instead of lithium / titanium composite oxide (Li ₄ Ti ₅ O ₁₂ ). In the same manner as in Example 2, a laminate film type battery was produced. This laminated film type battery had a battery capacity of 700 mAh.

<Example 1-18>
Example 1 except that lithium / titanium / magnesium composite oxide (Li _3.75 Ti _4.875 Mg _0.375 O ₁₂ ) was used instead of lithium / titanium composite oxide (Li ₄ Ti ₅ O ₁₂ ) as the negative electrode active material. In the same manner as in Example 2, a laminate film type battery was produced. This laminated film type battery had a battery capacity of 700 mAh.

<Example 1-19>
Example 1-2 except that carbon-coated lithium / titanium composite oxide (Li ₄ Ti ₅ O ₁₂ ) was used instead of lithium / titanium composite oxide (Li ₄ Ti ₅ O ₁₂ ) as the negative electrode active material. In the same manner, a laminated film type battery was produced. The negative electrode active material was obtained by applying and drying a solution containing lithium / titanium composite oxide (Li ₄ Ti ₅ O ₁₂ ) and a carbon material. This laminated film type battery had a battery capacity of 700 mAh.

<Example 1-20>
A laminate film type battery was produced in the same manner as in Example 1-2 except that ethylene carbonate (EC) was used instead of propylene carbonate (PC) as a solvent used in the electrolytic solution.

<Example 1-21> to <Example 1-22>
Example 1-21 was carried out in the same manner as Example 1-2 except that ethyl acetate (EA) or methyl propionate (MP) was used instead of ethyl methyl carbonate (EMC) as the solvent used in the electrolytic solution. -A laminated film type battery of Example 1-22 was produced.

<Example 1-23>
A laminate film type battery was produced in the same manner as in Example 1-2, except that phosphonic acid (H ₃ PO ₃ ) as additive A was mixed with the positive electrode active material instead of being added to the electrolytic solution. Additive A is mixed at a concentration of 0.1% by mass with respect to lithium-manganese composite oxide (LiMn ₂ O ₄ ) which is a positive electrode active material, and lithium-manganese composite oxidation is performed according to the amount of additive A added. The weight was reduced.

<Comparative Example 1-1>
A laminated film type battery was produced in the same manner as in Example 1-2 except that additive A was not mixed with the electrolytic solution.

<Comparative Example 1-2>
A laminated film type battery was produced in the same manner as in Example 1-2, except that amorphous carbon was used in place of lithium / titanium composite oxide (Li ₄ Ti ₅ O ₁₂ ) as the negative electrode active material.

<Comparative Example 1-3>
As the negative electrode active material, amorphous carbon was used instead of lithium-titanium composite oxide (Li ₄ Ti ₅ O ₁₂ ), and the concentration of phosphonic acid (H ₃ PO ₃ ) in the electrolytic solution was 2.0 mass%. Except for the above, a laminated film type battery was produced in the same manner as in Example 1-2.

<Comparative Example 1-4>
As the positive electrode active material, lithium / nickel / cobalt / aluminum composite oxide (LiNi _0.77 Co _0.20 Al _0.03 O ₂ ) is used in place of lithium / manganese composite oxide (LiMn ₂ O ₄ ), and phosphone is added to the electrolyte. A laminated film type battery was produced in the same manner as in Example 1-2, except that the acid (H ₃ PO ₃ ) was not mixed and dimethyl carbonate and ethyl methyl carbonate were increased by the same amount.

<Comparative Example 1-5>
As the positive electrode active material, lithium / nickel / cobalt / manganese composite oxide (LiNi _0.5 Co _0.2 Mn _0.3 O ₂ ) is used instead of lithium / manganese composite oxide (LiMn ₂ O ₄ ), and phosphone is used for the electrolyte. A laminated film type battery was produced in the same manner as in Example 1-2, except that the acid (H ₃ PO ₃ ) was not mixed and dimethyl carbonate and ethyl methyl carbonate were increased by the same amount. This laminated film type battery had a battery capacity of 750 mAh.

<Comparative Example 1-6>
As the negative electrode active material, lithium / titanium / niobium composite oxide (Li ₄ Ti _4.95 Nb _0.05 O ₁₂ ) is used instead of lithium / titanium composite oxide (Li ₄ Ti ₅ O ₁₂ ), and phosphone is used for the electrolyte. A laminated film type battery was produced in the same manner as in Example 1-2, except that the acid (H ₃ PO ₃ ) was not mixed and dimethyl carbonate and ethyl methyl carbonate were increased by the same amount.

[Battery evaluation]
The laminated film type batteries of each Example and Comparative Example were charged with a constant current at a constant current of 700 mA under a 23 ° C. environment until the battery voltage reached 2.7 V (3.3 V in Example 1-16). Thereafter, the battery was charged at a constant voltage of 2.7 V (3.3 V in Example 1-16) until the total charge time was 2 hours. Thereafter, the battery thickness (initial thickness) and DC resistance (initial resistance) were measured. Then, it preserve | saved under the environment of 60 degreeC for 6 weeks. The battery thickness after storage at high temperature (thickness after storage) and DC resistance (resistance after storage) were measured, and the rate of increase in battery thickness after storage at high temperature and the DC resistance ratio before and after storage at high temperature were calculated from the following formula. In addition, DC resistance measured the voltage drop at the time of charging / discharging, and computed resistance from there. A measuring device manufactured by Nippon Steel Elex Co., Ltd. was used.

Battery thickness increase rate after storage at high temperature [%] = {(thickness after storage−initial thickness) / initial thickness} × 100
DC resistance ratio before and after storage at high temperature [%] = (resistance after storage / initial resistance) × 100

  The evaluation results are shown in Table 1.

As shown in Table 1, Example 1-2 to Example 1-4 was added phosphonic acid (H ₃ PO ₃₎ to the electrolytic solution, without the addition of phosphonic acid (H ₃ PO ₃₎ to the electrolytic solution in Comparative Example Compared with 1-1, it was possible to remarkably suppress an increase in DC resistance while maintaining the increase rate of the battery thickness after high-temperature storage substantially equal. Further, as additive A which is a phosphorus compound having a P—OH structure, phosphonic acid (H ₃ PO ₄ ), phenylphosphonic acid (PhPO (OH) ₂ ), phenylphosphinic acid (PhPHOOH), diphenyl phosphate (Ph ₂₎ Similarly, in Examples 1-5 to 1-9 using HPO ₄ ) or dimethyl phosphite ((CH ₃ O) ₂ POH), the rate of increase in battery thickness after high-temperature storage was maintained substantially the same. However, the increase in DC resistance could be remarkably suppressed.

  Moreover, from Example 1-1, Example 1-2, and Examples 1-10, Example 1-11, by adding vinylene carbonate (VC) to the electrolytic solution, battery swelling and DC resistance after high-temperature storage However, the DC resistance slightly increases as the amount added increases. In addition, Example 1-12 using fluoroethylene carbonate (FEC), which is a halogenated ethylene carbonate, instead of vinylene carbonate (VC) gave almost the same result as Example 1-2. Further, in Example 1-13 using succinonitrile (SN) instead of vinylene carbonate (VC), battery swelling and direct current resistance after high temperature storage were reduced as compared with Comparative Example 1-1. However, higher effects were obtained in Example 1-2 and Example 1-12 to which vinylene carbonate (VC) and fluoroethylene carbonate (FEC) were added.

  When a lithium / nickel / cobalt / aluminum composite oxide having a layered structure or a lithium / nickel / cobalt / manganese composite oxide was used as the positive electrode active material, Example 1-14, Comparative Example 1-4, and Example 1 were used. From −15 and Comparative Example 1-5, it was possible to confirm the suppression of battery swelling and the increase in DC resistance after high-temperature storage.

  Further, in Example 1-16 using a lithium-nickel-manganese composite oxide having a spinel structure as the positive electrode active material, the same effect could be confirmed.

  Even when lithium-titanium-niobium composite oxide is used as the negative electrode active material, the comparison between Example 1-17 and Comparative Example 1-6 shows that suppression of battery swelling after storage at high temperatures and increase in DC resistance are suppressed. I was able to confirm. Also in the case of Example 1-18 using a lithium / titanium / magnesium composite oxide as a negative electrode active material and Example 1-19 using a carbon-coated lithium / titanium composite oxide, Example 1-19 The effect equivalent to 17 was confirmed.

  Furthermore, Example 1-20 in which propylene carbonate in the solvent was changed to ethylene carbonate, Example 1-21 to Example 1-22 in which ethyl methyl carbonate was changed to ethyl acetate or methyl propionate were also the same as Example 1-20. The swelling suppression effect substantially equivalent to 2 was confirmed. As the cyclic carbonate, Example 1-2 using propylene carbonate was more effective in suppressing battery swelling and DC resistance increase than Example 1-20 using ethylene carbonate.

  From Example 1-23, the same effect could be confirmed even when the additive A, which is a phosphorus compound having a P—OH structure, was mixed in the positive electrode instead of the electrolytic solution.

On the other hand, from Comparative Examples 1-2 and 1-3, even when phosphonic acid (H ₃ PO ₃ ) is added, when the negative electrode active material is a carbon material, the swelling suppression effect is remarkably small. It was. As the amount of phosphonic acid (H ₃ PO ₃ ) is increased, the increase in the direct current resistance can be suppressed, but the increase in the battery thickness has increased.

  From the above results, by using a lithium transition metal compound having a spinel structure as a negative electrode active material and mixing a phosphorus compound having a P—OH structure in an electrolytic solution or in a positive electrode, suppression of battery swelling after high-temperature storage and It was confirmed that the increase in DC resistance was suppressed.

<Example 2-1> to <Example 2-23>, <Comparative Example 2-1> to <Comparative Example 2-6>
In Example 2-1 to Example 2-23 and Comparative Example 2-1 to Comparative Example 2-6, in a battery in which the same electrolyte solution as in Example 1-1 was held in a polymer material to form a gel electrolyte Battery characteristics were evaluated.

  Example 1 except that instead of a separator made of a microporous polyethylene film having a thickness of 16 μm, a separator in which 2 μm of polyvinylidene fluoride (PVdF) was applied to both sides of a microporous polyethylene film having a thickness of 12 μm was used. -1 to Example 1-19 and Comparative Example 1-1 to Comparative Example 1-6 were each used in the same manner to produce a laminate film type battery.

  At this time, after 4 g of the electrolyte solution was injected into the bag-shaped aluminum laminate film, sealing was performed while applying pressure and heating in a reduced pressure environment when heat-sealing one side of the bag-shaped aluminum laminate film. . As a result, the electrolytic solution was held on the polyvinylidene fluoride on the separator surface and gelled to produce a laminate film type battery on which a gel electrolyte layer was formed.

[Battery evaluation]
About the laminated film type battery of each Example and Comparative Example, the battery thickness after high-temperature storage under the same charging conditions and storage conditions as in Example 1-1 (for the upper limit voltage, only Example 2-16 is 3.3V) The rate of increase was calculated.

  The evaluation results are shown in Table 2.

  As shown in Table 2, by using a lithium transition metal compound having a spinel structure as a negative electrode active material and mixing an additive composed of a phosphorus compound having a P-OH structure into a gel electrolyte, the battery swells even after high temperature storage Inhibition could be confirmed. And by making electrolyte solution hold | maintain to a polymeric material and making it gel, the battery thickness increase rate and direct current | flow resistance ratio after high-temperature storage became still smaller than the case where electrolyte solution was used.

  While the present technology has been described with reference to the embodiment and examples, the present technology is not limited to the above-described embodiment and examples, and various modifications can be made.

  In addition, the battery of this technique can also be set as the following structures.

（式（Ａ）および式（Ｂ）中、Ｒ１〜Ｒ４はそれぞれ独立してＯ_mＣ_nＨ_2n+1またはＯ_mＣ₆Ｈ₅であり、ｍは０または１かつ０≦ｎ≦４である。）
［４］
上記Ｐ−ＯＨ構造を有するリン化合物が、ホスホン酸およびリン酸の少なくとも一種を含む［３］に記載の電池。
［５］
上記負極活物質が、式（１）で示すスピネル構造を有するリチウム遷移金属化合物を含む［１］〜［４］のいずれかに記載の電池。
式（１）
Ａ［Ｂ₂］Ｘ₄
（式中、ＡおよびＢは、リチウム（Ｌｉ）、チタン（Ｔｉ）、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、ストロンチウム（Ｓｒ）、アルミニウム（Ａｌ）、スカンジウム（Ｓｃ）、クロム（Ｃｒ）、マンガン（Ｍｎ）、鉄（Ｆｅ）、ガリウム（Ｇａ）、イットリウム（Ｙ）、アルミニウム（Ａｌ）、スカンジウム（Ｓｃ）、クロム（Ｃｒ）、マンガン（Ｍｎ）、鉄（Ｆｅ）、ガリウム（Ｇａ）およびイットリウム（Ｙ）から選択される金属カチオンの少なくとも一種であり、Ｘは、酸素（Ｏ）または硫黄（Ｓ）である。）
［６］
上記負極活物質が、上記チタン含有リチウム遷移金属酸化物を含む［１］〜［５］のいずれかに記載の電池。
［７］
上記チタン含有リチウム遷移金属酸化物が、リチウム・チタン複合酸化物、リチウム・チタン・ニオブ複合酸化物、またはリチウム・チタン・マグネシウム複合酸化物、もしくは表面が炭素被覆されたリチウム・チタン複合酸化物のいずれかを含む［１］〜［６］のいずれかに記載の電池。
［８］
上記電解液が、式（Ｅ）で示す環状カーボネートのうちの少なくとも一種を含む［１］〜［７］のいずれかに記載の電池。

（式中、Ｒ１１〜Ｒ１６はそれぞれ独立してＣ_nＨ_2n+1であり、０≦ｎ≦４である。）
［９］
上記電解液が、ハロゲン化エチレンカーボネートまたは不飽和環状カーボネートを含む［１］〜［８］のいずれかに記載の電池。
［１０］
上記電解液が、高分子材料に保持されて非流動性電解質とされた［１］〜［９］のいずれかに記載の電池。
［１１］
上記高分子材料が、ポリフッ化ビニリデンを含む［１０］に記載の電池。
［１２］
上記正極、上記負極および上記電解液が、ラミネートフィルムで外装された［１］〜［１１］のいずれかに記載の電池。
［１３］
正極活物質を含む正極と、
負極活物質としてスピネル構造を有するリチウム遷移金属化合物を含む負極と、
溶媒と、電解質塩とを含む電解液と
を備え、
上記正極および上記正極活物質の少なくとも一方の表面に、Ｐ−ＯＨ構造を有するリン化合物に由来するリン酸塩およびその誘導体の金属塩の少なくとも一方を主成分とする保護被膜を有する
電池。
［１４］
［１］に記載の電池と、
上記電池を制御する制御部と、
上記電池を内包する外装とを有する
電池パック。
［１５］
［１］に記載の電池を備え、
上記電池から電力の供給を受ける
電子機器。
［１６］
［１］に記載の電池と、
上記電池から電力の供給を受けて車両の駆動力に変換する変換装置と、
上記電池に関する情報に基づいて車両制御に関する情報処理を行う制御装置とを有する
電動車両。
［１７］
［１］に記載の電池を備え、
上記電池に接続される電子機器に電力を供給する蓄電装置。
［１８］
他の機器とネットワークを介して信号を送受信する電力情報制御装置を備え、
上記電力情報制御装置が受信した情報に基づき、上記電池の充放電制御を行う［１７］に記載の蓄電装置。
［１９］
［１］に記載の電池から電力の供給を受け、または、発電装置もしくは電力網から上記電池に電力が供給される
電力システム。 [1]
A positive electrode including a positive electrode active material;
A negative electrode containing a lithium transition metal compound having a spinel structure as a negative electrode active material;
Comprising a solvent and an electrolyte solution containing an electrolyte salt;
A battery containing a phosphorus compound having a P—OH structure in at least one of the positive electrode and the electrolytic solution.
[2]
On the surface of at least one of the positive electrode and the positive electrode active material, a protective film composed mainly of at least one of a phosphate derived from the phosphorus compound having the P-OH structure and a metal salt of a derivative thereof was formed. 1].
[3]
The battery according to [1], wherein the phosphorus compound having the P—OH structure includes at least one of the compounds represented by formula (A) and formula (B).

(In Formula (A) and Formula (B), R1 to R4 are each independently O _m C _n H _{2n + 1} or O _m C ₆ H ₅ , and m is 0 or 1, and 0 ≦ n ≦ 4. is there.)
[4]
The battery according to [3], wherein the phosphorus compound having the P—OH structure includes at least one of phosphonic acid and phosphoric acid.
[5]
The battery according to any one of [1] to [4], wherein the negative electrode active material includes a lithium transition metal compound having a spinel structure represented by Formula (1).
Formula (1)
A [B ₂ ] X ₄
(In the formula, A and B are lithium (Li), titanium (Ti), magnesium (Mg), calcium (Ca), copper (Cu), zinc (Zn), strontium (Sr), aluminum (Al), scandium. (Sc), chromium (Cr), manganese (Mn), iron (Fe), gallium (Ga), yttrium (Y), aluminum (Al), scandium (Sc), chromium (Cr), manganese (Mn), iron (At least one metal cation selected from (Fe), gallium (Ga) and yttrium (Y), and X is oxygen (O) or sulfur (S).)
[6]
The battery according to any one of [1] to [5], wherein the negative electrode active material includes the titanium-containing lithium transition metal oxide.
[7]
The titanium-containing lithium transition metal oxide is a lithium / titanium composite oxide, a lithium / titanium / niobium composite oxide, or a lithium / titanium / magnesium composite oxide, or a lithium / titanium composite oxide whose surface is coated with carbon. The battery according to any one of [1] to [6], including any of them.
[8]
The battery according to any one of [1] to [7], wherein the electrolytic solution contains at least one of cyclic carbonates represented by formula (E).

(Wherein, R11 to R16 is C _n H _{2n + 1} each independently is 0 ≦ n ≦ 4.)
[9]
The battery according to any one of [1] to [8], wherein the electrolytic solution contains halogenated ethylene carbonate or unsaturated cyclic carbonate.
[10]
The battery according to any one of [1] to [9], wherein the electrolytic solution is held in a polymer material to be a non-fluidic electrolyte.
[11]
The battery according to [10], wherein the polymer material includes polyvinylidene fluoride.
[12]
The battery according to any one of [1] to [11], wherein the positive electrode, the negative electrode, and the electrolytic solution are packaged with a laminate film.
[13]
A positive electrode including a positive electrode active material;
A negative electrode containing a lithium transition metal compound having a spinel structure as a negative electrode active material;
Comprising a solvent and an electrolyte solution containing an electrolyte salt;
A battery having a protective coating mainly comprising at least one of a phosphate derived from a phosphorus compound having a P—OH structure and a metal salt of a derivative thereof on the surface of at least one of the positive electrode and the positive electrode active material.
[14]
The battery according to [1],
A control unit for controlling the battery;
A battery pack having an exterior housing the battery.
[15]
Comprising the battery according to [1],
An electronic device that receives power from the battery.
[16]
The battery according to [1],
A conversion device that receives supply of electric power from the battery and converts it into driving force of the vehicle;
An electric vehicle having a control device that performs information processing related to vehicle control based on the information related to the battery.
[17]
Comprising the battery according to [1],
A power storage device that supplies electric power to an electronic device connected to the battery.
[18]
A power information control device that transmits and receives signals to and from other devices via a network,
The power storage device according to [17], wherein charge / discharge control of the battery is performed based on information received by the power information control device.
[19]
The electric power system which receives supply of electric power from the battery as described in [1], or supplies electric power to the said battery from a generator or a power network.

DESCRIPTION OF SYMBOLS 1 ... Laminate film type battery, 2 ... Positive electrode lead, 3 ... Negative electrode lead, 4 ... Adhesion film, 5 ... Exterior member, 5a ... Recessed part, 10 ... Laminated electrode body, 11 ... Positive electrode, 11A ... Positive electrode collector, 11B ... Positive electrode active material layer, 11C ... positive electrode tab, 12 ... negative electrode, 12A ... negative electrode current collector, 12B ... negative electrode active material layer, 12C ... negative electrode tab, 13 ... separator, 14 ... fixing member, 20 ... wound electrode body, 21 ... Positive electrode, 21A ... Positive electrode current collector, 21B ... Positive electrode active material layer, 22 ... Negative electrode, 22A ... Negative electrode current collector, 22B ... Negative electrode active material layer, 23 ... Separator, 25 ... Gel electrolyte layer, 30 ... Square battery 31 ... Exterior can, 32 ... Battery cover, 33 ... Electrode pin, 34 ... Insulator, 35 ... Through hole, 36 ... Internal pressure release mechanism, 36a ... First opening groove, 36b ... Second opening groove, 37 ... Electrolyte injection port, 38 ... sealing member, 40 ... laminated electricity Body, 41 ... positive electrode terminal, 50 ... cylindrical battery, 51 ... battery can, 52a, 52b ... insulating plate, 53 ... battery lid, 54 ... safety valve, 54a ... protrusion, 55 ... disc holder, 56 ... shut-off disc, 56a DESCRIPTION OF SYMBOLS ... Hole part, 57 ... Heat sensitive resistance element, 58 ... Gasket, 59 ... Sub disk, 60 ... Winding electrode body, 61 ... Positive electrode, 62 ... Negative electrode, 63 ... Separator, 64 ... Center pin, 65 ... Positive electrode lead, 66 DESCRIPTION OF SYMBOLS ... Negative electrode lead, 101 ... Assembly battery, 101a ... Each battery, 101a ... Battery, 102a ... Charge control switch, 102b ... Diode, 103a ... Discharge control switch, 103b ... Diode, 104 ... Switch part, 107 ... Current detection resistor, 108 DESCRIPTION OF SYMBOLS ... Temperature detection element 110 ... Control part 111 ... Voltage detection part 113 ... Current measurement part 114 ... Switch control part 117 ... Memory 11 DESCRIPTION OF SYMBOLS ... Temperature detection part 121 ... Positive electrode terminal, 122 ... Negative electrode terminal, 200 ... Power storage system, 201 ... Housing, 202 ... Centralized power system, 202a ... Thermal power generation, 202b ... Nuclear power generation, 202c ... Hydroelectric power generation, 203 ... Power storage device 204 ... Home power generation device, 205 ... Power consumption device, 205a ... Refrigerator, 205b ... Air conditioner, 205c ... Television receiver, 205d ... Bath, 206 ... Electric vehicle, 206a ... Electric car, 206b ... Hybrid car, 206c DESCRIPTION OF SYMBOLS: Electric motorcycle, 207 ... Smart meter, 208 ... Power hub, 209 ... Power network, 210 ... Control device, 211 ... Sensor, 212 ... Information network, 213 ... Server, 300 ... Hybrid vehicle, 301 ... Engine, 302 ... Generator, 303 ... Electric power / driving force conversion device, 304a ... Driving wheel, 304b ... Driving wheel, 305 a ... wheel, 305b ... wheel, 308 ... battery, 309 ... vehicle control device, 310 ... various sensors, 311 ... charging port

Claims (19)

A positive electrode including a positive electrode active material;
A negative electrode containing a lithium transition metal compound having a spinel structure as a negative electrode active material;
Comprising a solvent and an electrolyte solution containing an electrolyte salt;
A battery containing a phosphorus compound having a P—OH structure in at least one of the positive electrode and the electrolytic solution. Claims wherein at least one surface of the positive electrode and the positive electrode active material is formed with a protective film mainly composed of at least one of a phosphate derived from the phosphorus compound having the P-OH structure and a metal salt of a derivative thereof. Item 6. The battery according to Item 1. The battery according to claim 1, wherein the phosphorus compound having a P—OH structure includes at least one of the compounds represented by formula (A) and formula (B).

(In Formula (A) and Formula (B), R1 to R4 are each independently O _m C _n H _{2n + 1} or O _m C ₆ H ₅ , and m is 0 or 1, and 0 ≦ n ≦ 4. is there.) The battery according to claim 3, wherein the phosphorus compound having a P—OH structure contains at least one of phosphonic acid and phosphoric acid. The battery according to claim 1, wherein the negative electrode active material includes a lithium transition metal compound having a spinel structure represented by Formula (1).
Formula (1)
A [B ₂ ] X ₄
(In the formula, A and B are lithium (Li), titanium (Ti), magnesium (Mg), calcium (Ca), copper (Cu), zinc (Zn), strontium (Sr), aluminum (Al), scandium. (Sc), chromium (Cr), manganese (Mn), iron (Fe), gallium (Ga), yttrium (Y), aluminum (Al), scandium (Sc), chromium (Cr), manganese (Mn), iron (At least one metal cation selected from (Fe), gallium (Ga) and yttrium (Y), and X is oxygen (O) or sulfur (S).) The battery according to claim 5, wherein the negative electrode active material contains the titanium-containing lithium transition metal oxide. The titanium-containing lithium transition metal oxide is a lithium / titanium composite oxide, a lithium / titanium / niobium composite oxide, or a lithium / titanium / magnesium composite oxide, or a lithium / titanium composite oxide whose surface is coated with carbon. The battery according to claim 6, comprising any of them. The battery according to claim 1, wherein the electrolytic solution contains at least one of cyclic carbonates represented by the formula (E).

(Wherein, R11 to R16 is C _n H _{2n + 1} each independently is 0 ≦ n ≦ 4.) The battery according to claim 1, wherein the electrolytic solution contains halogenated ethylene carbonate or unsaturated cyclic carbonate. The battery according to claim 1, wherein the electrolytic solution is held in a polymer material to be a non-fluidic electrolyte. The battery according to claim 10, wherein the polymer material includes polyvinylidene fluoride. The battery according to claim 1, wherein the positive electrode, the negative electrode, and the electrolytic solution are covered with a laminate film. A positive electrode including a positive electrode active material;
A negative electrode containing a lithium transition metal compound having a spinel structure as a negative electrode active material;
Comprising a solvent and an electrolyte solution containing an electrolyte salt;
A battery having a protective coating mainly comprising at least one of a phosphate derived from a phosphorus compound having a P—OH structure and a metal salt of a derivative thereof on the surface of at least one of the positive electrode and the positive electrode active material. A battery according to claim 1;
A control unit for controlling the battery;
A battery pack having an exterior housing the battery. A battery according to claim 1,
An electronic device that receives power from the battery. A battery according to claim 1;
A conversion device that receives supply of electric power from the battery and converts it into driving force of the vehicle;
An electric vehicle having a control device that performs information processing related to vehicle control based on the information related to the battery. A battery according to claim 1,
A power storage device that supplies electric power to an electronic device connected to the battery. A power information control device that transmits and receives signals to and from other devices via a network,
The power storage device according to claim 16, wherein charge / discharge control of the battery is performed based on information received by the power information control device. The electric power system which receives supply of electric power from the battery of Claim 1, or supplies electric power to the said battery from an electric power generating apparatus or an electric power network.

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