JP5863849B2 - Nonaqueous electrolyte battery and battery pack - Google Patents

Description

  The present embodiment relates to a nonaqueous electrolyte battery and a battery pack.

Non-aqueous electrolyte batteries using lithium metal, lithium alloys, lithium compounds, or carbonaceous materials as negative electrodes are expected as high energy density batteries and are actively researched and developed. Up to now, a positive electrode containing LiCoO ₂ , LiMn ₂ O ₄ , LiNi _1/3 Co _1/3 Mn _1/3 O ₂ or LiFePO ₄ as an active material, and a negative electrode containing a carbonaceous material that occludes and releases lithium are provided. Such lithium ion batteries have been widely put into practical use. In addition, for the negative electrode, metal oxides or alloys that replace carbonaceous materials have been studied.

  High energy, high output type large-sized batteries for stationary and automobile use are required to have excellent cycle performance, thermal stability and discharge rate performance under high temperature conditions. It is necessary to realize a battery that does this.

Japanese Patent Laid-Open No. 2005-142047 JP 2012-160345 A

  An object of the embodiment is to provide a nonaqueous electrolyte battery and a battery pack that are excellent in cycle performance, thermal stability, and discharge rate performance under a high temperature environment.

According to the embodiment, a nonaqueous electrolyte battery including a positive electrode, a negative electrode, and a nonaqueous electrolyte is provided. The positive electrode includes a first oxide having a spinel structure represented by Li _x Ni _0.5 Mn _1.5 O ₄ (0 <x ≦ 1.1) and Li _x Mn _1-w Fe _w PO ₄ (0 < x ≦ 1.1, 0 ≦ w ≦ 0.5), and at least one of the second oxides having an olivine structure is included. The negative electrode includes a titanium-containing metal oxide. The non-aqueous electrolyte includes a non-aqueous solvent and LiPF ₆ dissolved in the non-aqueous solvent. The non-aqueous solvent is composed of at least one compound selected from the group consisting of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, and tributyl phosphate, and fluorinated phosphate esters of the aforementioned at least one compound. A first solvent comprising at least one selected from the group;
According to the embodiment, a nonaqueous electrolyte battery including a positive electrode, a negative electrode, and a nonaqueous electrolyte is provided. The positive electrode includes a first oxide having a spinel structure represented by Li _x Ni _0.5 Mn _1.5 O ₄ (0 <x ≦ 1.1) and Li _x Mn _1-w Fe _w PO ₄ (0 < x ≦ 1.1, 0 ≦ w ≦ 0.5), and at least one of the second oxides having an olivine structure is included. The negative electrode includes a titanium-containing metal oxide. The non-aqueous electrolyte includes a non-aqueous solvent and LiPF ₆ dissolved in the non-aqueous solvent. The non-aqueous solvent includes a first solvent composed of fluorinated phosphates and a second solvent composed of at least one selected from the group consisting of ethyl methyl sulfone and ethyl isopropyl sulfone.

  Moreover, according to embodiment, the battery pack containing the nonaqueous electrolyte battery which concerns on embodiment is provided.

It is a partial notch perspective view which shows typically the nonaqueous electrolyte battery which concerns on embodiment. It is a disassembled perspective view of the battery pack which concerns on embodiment. It is a block diagram which shows the electric circuit of the battery pack of FIG.

(First embodiment)
According to the first embodiment, a nonaqueous electrolyte battery including a positive electrode, a negative electrode, and a nonaqueous electrolyte is provided. The positive electrode includes a first oxide having a spinel structure represented by Li _x Ni _0.5 Mn _1.5 O ₄ (0 <x ≦ 1.1) and Li _x Mn _1-w Fe _w PO ₄ (0 < x ≦ 1.1, 0 ≦ w ≦ 0.5), which includes at least one of the second oxides having an olivine structure. The negative electrode includes a titanium-containing metal oxide. The non-aqueous electrolyte includes a non-aqueous solvent and LiPF ₆ dissolved in the non-aqueous solvent. Non-aqueous solvents include trimethyl phosphate (PO (OCH ₃ ) ₃ ), triethyl phosphate (PO (OC ₂ H ₅ ) ₃ ), tripropyl phosphate (PO (OC ₃ H ₇ ) ₃ ) and tributyl phosphate ( A first compound comprising at least one compound selected from the group consisting of PO (OC ₄ H ₉ ) ₃ ) and at least one compound selected from the group consisting of fluorinated phosphates of the aforementioned at least one compound. Contains solvent.

In order to realize a high-performance, long-life and high-safety battery, it is considered to use a non-aqueous electrolyte containing LiBF ₄ as an electrolyte and a mixed solvent composed of phosphate ester and γ-butyrolactone (GBL) as a non-aqueous solvent. Has been. GBL is excellent in ionic conductivity, but LiBF ₄ is difficult to dissociate in phosphate ester, so this non-aqueous electrolyte is inferior in ionic conductivity. In addition, when LiPF ₆ is used instead of LiBF ₄ , hydrogen fluoride (HF) generated from LiPF ₆ reacts with GBL to cause GBL ring-opening polymerization reaction, and the decomposition of the nonaqueous electrolyte is accelerated. Furthermore, GBL is highly viscous and easily reacts with the positive electrode.

Nonaqueous solvent containing phosphoric acid ester such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate or tributyl phosphate, or fluorinated phosphate esters of these compounds, and LiPF ₆ dissolved in the non-aqueous solvent The nonaqueous electrolyte contained has a high degree of dissociation of the lithium salt, so that it has excellent ion conductivity and is useful for improving the discharge rate performance. However, when a graphite material, lithium, or a lithium alloy is used for the negative electrode, the reductive decomposition reaction of the nonaqueous electrolyte is promoted, so that the life performance is deteriorated and gas is generated, which makes it difficult to put it to practical use.

By using a negative electrode including a titanium-containing metal oxide as in the embodiment, reduction side reaction at the negative electrode in a high temperature environment such as 45 ° C. can be suppressed, and gas generation can be suppressed. Excellent charge / discharge cycle performance can be obtained even underneath. _{Moreover, Li x Ni 0.5 Mn 1.5 O} 4 first oxide having a spinel structure represented by _{(0 <x ≦ 1.1),} Li x Mn 1-w Fe w PO 4 (0 <x ≦ 1.1, 0 ≦ w ≦ 0.5), each of the second oxides having an olivine structure can take out a high capacity up to a high voltage of 4 V or more, thereby increasing the battery capacity. Can do. This can be combined with the non-aqueous electrolyte of the embodiment to suppress oxidative decomposition of the non-aqueous electrolyte even in a high-temperature and high-voltage environment, so that the positive electrode can be charged to a high-voltage region of 4 V or higher, and the positive electrode capacity This is because it can be increased. Furthermore, each of the first oxide and the second oxide is a layer having at least one selected from the group consisting of Mn, Fe, Co, Ti, and Cu and a transition metal containing Ni as a metal element. Compared to the lithium metal composite oxide with a structure, it has higher thermal stability, so it can suppress the oxidation reaction of non-aqueous electrolyte accompanied by heat generation at a high temperature of 150 ° C or higher, and suppress the rise in battery temperature. It is possible to improve safety.

  From the above, according to the first embodiment, it is possible to provide a nonaqueous electrolyte battery having high safety under a high temperature environment, excellent charge / discharge cycle performance even under a high temperature environment, and high discharge rate performance and capacity. Can do.

  The non-aqueous solvent is at least one selected from the group consisting of propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), ethyl methyl sulfone (EMS), and ethyl isopropyl sulfone (EiPS). 2 solvent further, and by setting the content of the first solvent in the non-aqueous solvent to 30 to 90% by volume, safety under high temperature environment and charge / discharge cycle performance, discharge rate performance, The capacity can be further improved.

  Since the titanium-containing metal oxide contains at least one selected from the group consisting of lithium titanium oxide, titanium oxide, and niobium titanium composite oxide, the reductive decomposition of the non-aqueous electrolyte can be further suppressed, so that the high temperature The amount of gas generated in the environment can be further reduced, and the cycle life performance in a high temperature environment can be further improved.

  The battery according to the embodiment may include a separator between the positive electrode and the negative electrode, and may further include a container for housing these and the nonaqueous electrolyte.

  Hereinafter, the nonaqueous electrolyte, the negative electrode, the positive electrode, the separator, and the container will be described.

(1) Non-aqueous electrolyte The non-aqueous electrolyte contains a non-aqueous solvent and LiPF ₆ dissolved in the non-aqueous solvent. Non-aqueous solvents are trimethyl phosphate (PO (OCH ₃ ) ₃ ), triethyl phosphate (PO (OC ₂ H ₅ ) ₃ ), tripropyl phosphate (PO (OC ₃ H ₇ ) ₃ ) and tributyl phosphate ( A first compound comprising at least one compound selected from the group consisting of PO (OC ₄ H ₉ ) ₃ ) and at least one compound selected from the group consisting of fluorinated phosphates of the aforementioned at least one compound. Contains solvent. The boiling point of this non-aqueous electrolyte is 200 ° C. or higher. More preferred first solvents are those containing trimethyl phosphate or triethyl phosphate. Thereby, the oxidation resistance of the nonaqueous electrolyte under high temperature and high voltage can be improved.

  The content of the first solvent in the non-aqueous solvent is desirably in the range of 30 to 90% by volume. Thereby, the thermal stability and cycle life performance of the battery can be made excellent. A more preferable range is 40% by volume or more and 80% by volume or less.

  Examples of the fluorinated phosphate esters include trifluoromethyl phosphate, trifluoroethyl phosphate, trifluoropropyl phosphate, and trifluorobutyl phosphate. Preference is given to containing trifluoromethyl phosphate or trifluoroethyl phosphate. Thereby, the oxidation resistance of the nonaqueous electrolyte under high temperature and high voltage can be improved.

  A second non-aqueous solvent comprising at least one selected from the group consisting of propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), ethyl methyl sulfone (EMS), and ethyl isopropyl sulfone (EiPS); It is desirable to further contain a solvent. Thereby, the ion conductivity of a non-aqueous electrolyte can be made high. Preferred second solvents are those containing propylene carbonate (PC) or ethyl methyl sulfone (EiPS). Thereby, since the ion conductivity of a nonaqueous electrolyte can be improved, the discharge rate performance and low-temperature performance of a battery can be improved.

The electrolyte dissolved in the non-aqueous solvent may be composed of only lithium hexafluorophosphate (LiPF ₆ ) or a mixture of LiPF ₆ and a lithium salt other than LiPF ₆ . Examples of lithium salts other than LiPF ₆ include lithium perchlorate (LiClO ₄ ), lithium hexafluoroarsenide (LiAsF ₆ ), lithium trifluorometasulfonate (LiCF ₃ SO ₃ ), lithium bistrifluoromethylsulfonylimide [ LiN (CF ₃ SO ₂ ) ₂ ], LiN (C ₂ F ₅ SO ₂ ) ₂ , LiN (FSO ₂ ) ₂ , Li (CF ₃ SO ₂ ) ₃ C, LiB [(OCO) ₂ ] _{2 and the} like. . The type of electrolyte used can be one type or two or more types. The electrolyte composed of LiPF ₆ and LiB [(OCO) ₂ ] ₂ can increase the chemical stability of the first solvent and reduce the film resistance on the negative electrode. Therefore, low temperature performance and cycle life performance Can be greatly improved.

  Since the first solvent has a high dielectric constant despite its low viscosity, a high concentration lithium salt can be dissolved in a non-aqueous solvent. The electrolyte concentration in the non-aqueous solvent is preferably in the range of 1 to 2.5 mol / L. By setting the electrolyte concentration to 1 mol / L or more, it is possible to suppress a decrease in the lithium ion concentration at the interface between the positive electrode and the nonaqueous electrolyte that is being discharged with a large current. Moreover, the viscosity rise of a nonaqueous electrolyte can be suppressed by making electrolyte concentration into 2.5 mol / L or less. Therefore, by setting the electrolyte concentration in the range of 1 to 2.5 mol / L, a high output can be taken out even in a low temperature environment.

  The non-aqueous electrolyte may contain a polymer material or a room temperature molten salt made of a non-volatile and non-flammable ionic liquid. Examples of the polymer material include polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyethylene oxide (PEO), and the like. When a polymer material is combined with a liquid non-aqueous electrolyte (non-aqueous electrolyte) made of a non-aqueous solvent in which an electrolyte (for example, a lithium salt) is dissolved, a gel electrolyte is obtained.

(2) Negative Electrode This negative electrode has a negative electrode current collector and a negative electrode material layer (negative electrode active material-containing layer) supported on one or both sides of the current collector and containing an active material, a conductive agent, and a binder.

  The negative electrode active material includes titanium-containing metal oxide particles. Examples of the titanium-containing metal oxide include lithium titanium oxide, titanium oxide, and niobium titanium composite oxide.

Examples of the lithium titanium oxide include spinel structure Li _{4 + x} Ti ₅ O ₁₂ (x is −1 ≦ x ≦ 3), ramsteride structure Li _{2 + x} Ti ₃ O ₇ (x is −1 ≦ x). ≦ 3) is included.

Examples of the titanium oxide include anatase-structure TiO ₂ and monoclinic TiO ₂ (B). TiO ₂ (B) is preferably heat-treated in the range of 300 to 500 ° C. TiO ₂ (B) preferably contains 0.5 to 10% by weight of Nb. As a result, the negative electrode capacity can be increased. Since irreversible lithium may remain in the titanium oxide after the battery is charged / discharged, the titanium oxide after the battery is charged / discharged is Li _d TiO ₂ (0 <d ≦ 1).

Examples of the niobium titanium composite oxide include Li _x Nb _a Ti _b O _C (0 ≦ x ≦ 3, 0 <a ≦ 3, 0 <b ≦ 3, 5 ≦ c ≦ 10). Examples of Li _x Nb _a Ti _b O _C include Li _x Nb ₂ TiO ₇ , Li _x Nb ₂ Ti ₂ O ₉ , and Li _x NbTiO ₅ . Li _x Ti _1-y Nb _y Nb ₂ O _{7 + σ} (0 ≦ x ≦ 3, 0 ≦ y ≦ 1, 0 ≦ σ ≦ 0.3) heat-treated at 800 ° C. to 1200 ° C. has high true density and volume. The specific capacity can be increased. Li _x Nb ₂ TiO ₇ is preferred because of its high density and high capacity. As a result, the negative electrode capacity can be increased. Further, a part of Nb or Ti in the above oxide is selected from the group consisting of V, Zr, Ta, Cr, Mo, W, Ca, Mg, Al, Fe, Si, B, P, K, and Na. At least one element may be substituted.

  It is preferable that at least a part of the surface of the titanium-containing metal oxide particles is coated with a carbon material. This increases the electron conduction network inside the electrode, reduces the electrode resistance, and improves the high current performance.

The specific surface area according to the BET method by N ₂ adsorption of the negative electrode active material particles is desirably 3 m ² / g or more and 50 m ² / g or less. By setting the specific surface area to 3 m ² / g or more, particle aggregation can be reduced, so that the affinity between the negative electrode and the nonaqueous electrolyte can be increased, and the interface resistance of the negative electrode can be reduced. Therefore, output characteristics and charge / discharge cycle characteristics can be improved. Further, by setting the specific surface area to 50 m ² / g or less, the non-aqueous electrolyte can be uniformly dispersed in the positive electrode and the negative electrode, so that the output characteristics and the charge / discharge cycle characteristics can be improved. A more preferable range of the specific surface area is 5 to 50 m ² / g.

  The negative electrode active material particles preferably have an average secondary particle diameter of 10 μm or less and a primary particle diameter (diameter) of 1 μm or less. Thereby, the affinity between the negative electrode and the non-aqueous electrolyte can be further increased. Further, the reduction side reaction of the nonaqueous electrolyte in a high temperature environment is suppressed, and the high temperature cycle life performance and the thermal stability are improved.

  The negative electrode material layer is preferably a porous layer. The porosity of the negative electrode material layer is desirably in the range of 20 to 50%. Thereby, it is possible to obtain a negative electrode having excellent affinity between the negative electrode and the non-aqueous electrolyte and a high density. A more preferable range of the porosity is 25 to 40%.

  The negative electrode current collector is preferably an aluminum foil or an aluminum alloy foil. The thickness of the aluminum foil and aluminum alloy foil is preferably 20 μm or less, more preferably 15 μm or less. The purity of the aluminum foil is preferably 99.99% or more. The aluminum alloy is preferably an aluminum alloy containing at least one element selected from the group consisting of magnesium, zinc and silicon. On the other hand, the content of transition metals such as iron, copper, nickel and chromium is preferably 100 ppm or less.

As the conductive agent, for example, a carbon material can be used. Examples of the carbon material include acetylene black, carbon black, coke, carbon fiber, graphite, aluminum powder, and TiO. More preferably, coke, graphite, TiO powder having an average particle diameter of 10 μm or less, and carbon fiber having an average fiber diameter of 1 μm or less that has been heat-treated at a temperature of 800 ° C. to 2000 ° C. are preferable. The BET specific surface area by N ₂ adsorption of the carbon material is preferably 10 m ² / g or more.

  Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine-based rubber, styrene butadiene rubber, and core-shell binder.

  The compounding ratio of the negative electrode active material, the conductive agent and the binder is preferably in the range of 80 to 95% by weight of the negative electrode active material, 3 to 18% by weight of the conductive agent, and 2 to 7% by weight of the binder.

  The negative electrode is produced, for example, by suspending a negative electrode active material, a conductive agent, and a binder in a suitable solvent, applying the suspension to a current collector, drying, and applying a hot press.

(3) Positive electrode This positive electrode has a positive electrode current collector and a positive electrode material layer (positive electrode active material-containing layer) supported on one or both sides of the current collector and containing an active material, a conductive agent, and a binder.

The positive electrode active material particles include first oxide particles having a spinel structure represented by Li _x Ni _0.5 Mn _1.5 O ₄ (0 <x ≦ 1.1) and Li _x Mn _1-w Fe _w PO. ₄ (0 <x ≦ 1.1, 0 ≦ w ≦ 0.5), which includes at least one of the second oxide particles having an olivine structure. In the second oxide, the lower limit value of w is preferably larger than 0 (not including 0), and the upper limit value is preferably 0.2 or less. Preferable examples of the second oxide include LiMn _0.85 Fe _0.15 PO _{4 and the} like.

The specific surface area of the positive electrode active material particles by the BET method is preferably in the range of 0.1 to ⁵ m ² / g.

  Examples of the conductive agent include acetylene black, carbon black, and graphite.

  Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and fluorine-based rubber.

  The compounding ratio of the positive electrode active material, the conductive agent and the binder is preferably in the range of 80 to 95% by weight of the positive electrode active material, 3 to 19% by weight of the conductive agent, and 1 to 7% by weight of the binder.

  The positive electrode current collector is preferably an aluminum foil or an aluminum alloy foil. The thickness of the positive electrode current collector is preferably 20 μm or less, and more preferably 15 μm or less.

  The positive electrode is produced, for example, by suspending a positive electrode active material, a conductive agent, and a binder in an appropriate solvent, applying the suspension to a positive electrode current collector, drying, and pressing.

(4) Separator Examples of the separator include a synthetic resin nonwoven fabric, a polyethylene porous film, a polypropylene porous film, and a cellulose nonwoven fabric.

(5) Container As the container, a metal container or a laminate film container can be used.

  As the metal container, a metal can made of aluminum, aluminum alloy, iron, stainless steel or the like having a square or cylindrical shape can be used. Further, the plate thickness of the container is desirably 0.5 mm or less, and a more preferable range is 0.3 mm or less.

  Examples of the laminate film include a multilayer film in which an aluminum foil is covered with a resin film. As the resin, polymers such as polypropylene (PP), polyethylene (PE), nylon, polyethylene terephthalate (PET) can be used. The thickness of the laminate film is preferably 0.2 mm or less. The purity of the aluminum foil is preferably 99.5% or more.

  The metal can made of an aluminum alloy is preferably an alloy containing an element such as manganese, magnesium, zinc, or silicon and having an aluminum purity of 99.8% or less. The strength of the metal can made of an aluminum alloy is dramatically increased, and thus the thickness of the can can be reduced. As a result, a thin, lightweight, high output and excellent heat dissipation battery can be realized.

  An example of the nonaqueous electrolyte battery according to the first embodiment is shown in FIG. A flat or thin non-aqueous electrolyte battery shown in FIG. 1 is a rectangular parallelepiped aluminum alloy container 1, an electrode group 2 housed in the container 1, and housed in the container 1 and held by the electrode group 2. Non-aqueous electrolyte (not shown). The electrode group 2 has a structure in which the positive electrode 3 and the negative electrode 4 are wound in a spiral shape so that a flat shape is formed with a separator 5 interposed therebetween. The electrode group 2 is produced by, for example, winding the positive electrode 3 and the negative electrode 4 in a spiral shape with a separator 5 interposed therebetween, and then applying a heat press. The strip-like positive electrode lead 6 is electrically connected to the positive electrode 3. On the other hand, the strip-like negative electrode lead 7 is electrically connected to the negative electrode 4. The positive electrode lead 6 is electrically connected to the container 1, and the negative electrode lead 7 is electrically connected to a negative electrode terminal 8 that is insulated from the container 1.

According to the nonaqueous electrolyte battery of the first embodiment, a positive electrode including at least one of the first oxide and the second oxide, a negative electrode including a titanium-containing metal oxide, LiPF _6, and the first Therefore, it is possible to provide a non-aqueous electrolyte battery having high safety under a high temperature environment, excellent charge / discharge cycle performance even under a high temperature environment, and high discharge rate performance and capacity. .

(Second Embodiment)
According to the second embodiment, a battery pack including the nonaqueous electrolyte battery of the first embodiment as a unit cell is provided. The number of single cells used in the battery pack can be one or more. When a plurality of single cells are included, the single cells may be connected in series or in parallel.

  A battery pack according to a second embodiment will be described with reference to the drawings. 2 and 3 show an example of a battery pack including a plurality of flat batteries.

  The plurality of single cells 21 are stacked such that the positive electrode terminal 18 and the negative electrode terminal 19 extending to the outside are aligned in the same direction, and are fastened with an adhesive tape 22 to constitute an assembled battery 23. These unit cells 21 are electrically connected to each other in series as shown in FIG.

  The printed wiring board 24 is disposed to face the side surface of the unit cell 21 from which the positive electrode terminal 18 and the negative electrode terminal 19 extend. As shown in FIG. 3, a thermistor 25, a protection circuit 26, and a terminal 27 for energizing external devices are mounted on the printed wiring board 24. An insulating plate (not shown) is attached to the surface of the printed wiring board 24 facing the assembled battery 23 in order to avoid unnecessary connection with the wiring of the assembled battery 23.

  The positive electrode side lead 28 is connected to the positive electrode terminal 18 located in the lowermost layer of the assembled battery 23, and the tip thereof is inserted into the positive electrode side connector 29 of the printed wiring board 24 and electrically connected thereto. The negative electrode side lead 30 is connected to the negative electrode terminal 19 located in the uppermost layer of the assembled battery 23, and the tip thereof is inserted into and electrically connected to the negative electrode side connector 31 of the printed wiring board 24. These connectors 29 and 31 are connected to the protection circuit 26 through wirings 32 and 33 formed on the printed wiring board 24.

  The thermistor 25 is used to detect the temperature of the unit cell 21, and the detection signal is transmitted to the protection circuit 26.

  The protection circuit 26 can cut off the plus side wiring 34a and the minus side wiring 34b between the protection circuit 26 and the energization terminal 27 to the external device under a predetermined condition. The predetermined condition is, for example, when the temperature detected by the thermistor 25 is equal to or higher than a predetermined temperature. Alternatively, the predetermined condition is when an overcharge, overdischarge, overcurrent, or the like of the cell 21 is detected. The detection of overcharge or the like may be performed for each unit cell 21 or may be performed for the plurality of unit cells 21 as a whole. When detecting each single cell 21, the battery voltage may be detected, or the positive electrode potential or the negative electrode potential may be detected. In the latter case, a lithium electrode used as a reference electrode is inserted into each unit cell 21. In the case of FIG. 2 and FIG. 3, a wiring 35 for voltage detection is connected to each single cell 21, and a detection signal is transmitted to the protection circuit 26 through these wirings 35. Since the battery provided in the battery pack of the present embodiment is excellent in controlling the potential of the positive electrode or the negative electrode by detecting the battery voltage, a protection circuit for detecting the battery voltage is preferably used.

  Protective sheets 36 made of rubber or resin are disposed on the three side surfaces of the assembled battery 23 excluding the side surfaces from which the positive electrode terminal 18 and the negative electrode terminal 19 protrude.

  The assembled battery 23 is stored in a storage container 37 together with each protective sheet 36 and the printed wiring board 24. That is, the protection sheet 36 is disposed on each of the inner side surfaces of the storage container 37 in the long side direction and one inner side surface in the short side direction, and the printed wiring board 24 is disposed on the other inner side surface in the short side direction. The assembled battery 23 is located in a space surrounded by the protective sheet 36 and the printed wiring board 24. The lid 38 is attached to the upper surface of the storage container 37.

  In addition, instead of the adhesive tape 22, a heat shrink tape may be used for fixing the assembled battery 23. In this case, protective sheets are arranged on both side surfaces of the assembled battery, the heat shrinkable tape is circulated, and then the heat shrinkable tape is heat shrunk to bind the assembled battery.

  2 and 3 show the configuration in which the single cells 21 are connected in series, but in order to increase the battery capacity, they may be connected in parallel, or a combination of serial connection and parallel connection may be used. The assembled battery packs can be further connected in series and in parallel.

  The mode of the battery pack is appropriately changed depending on the application. The battery pack is preferably one that exhibits excellent cycle characteristics when a large current is taken out. Specific examples include a power source for a digital camera, a vehicle for a two- to four-wheel hybrid electric vehicle, a two- to four-wheel electric vehicle, an assist bicycle, and the like. In particular, the vehicle-mounted one is suitable.

  According to the battery pack of the second embodiment, since the non-aqueous electrolyte battery of the first embodiment is included, the safety in a high temperature environment is high, the charge / discharge cycle performance is excellent even in a high temperature environment, and the discharge rate performance. In addition, a battery pack having a high capacity can be realized.

[Example]
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the embodiments described below.

Example 1
As the positive electrode active material, LiMn _0.85 Fe _0.15 PO ₄ particles having an olivine structure having an average particle diameter of 3 μm and a specific surface area of 0.8 m ² / g by BET method using N ₂ adsorption were used. This was mixed with 8% by weight of graphite powder as a conductive material and 5% by weight of PVdF as a binder, and dispersed in an n-methylpyrrolidone (NMP) solvent. After the preparation, both sides are applied to an aluminum alloy foil (purity 99%) having a thickness of 15 μm, dried, and subjected to a pressing process. The coating amount on one side is 12.8 mg / cm ² , and the thickness of the positive electrode material layer on one side is A positive electrode having a thickness of 43 μm and an electrode density of 3.2 g / cm ³ was produced. The specific surface area of the positive electrode material layer was 0.5 m ² / g.

Monoclinic TiO ₂ (B) particles having an average secondary particle diameter of 5 μm, an average primary particle diameter of 0.3 μm, and a BET specific surface area of 20 m ² / g were used as the negative electrode active material. A negative active material particle, a graphite powder having an average particle diameter of 5 μm and a BET specific surface area of 10 m ² / g, and PVdF as a binder were blended in a weight ratio of 90: 6: 4, and n-methylpyrrolidone ( NMP) was dispersed in a solvent, and a slurry was prepared using stirring with a ball mill at a rotation speed of 1000 rpm and a stirring time of 2 hours. The obtained slurry was applied to an aluminum alloy foil (purity: 99.3%) having a thickness of 15 μm, dried, and subjected to a heat press process, whereby the coating amount on one side was 13 mg / cm ² and the negative electrode material layer on one side A negative electrode having a thickness of 59 μm and an electrode density of 2.2 g / cm ³ was produced. The negative electrode porosity excluding the current collector was 35%. Further, the BET specific surface area (surface area per 1 g of the negative electrode material layer) of the negative electrode material layer was 10 m ² / g.

  On the other hand, a cellulose non-woven separator having a thickness of 20 μm is closely attached to the positive electrode, and the positive electrode is covered with the separator, and then the negative electrode is superimposed on the negative electrode, and the negative electrode is opposed to the positive electrode through the separator, and these are wound in a spiral shape. Thus, an electrode group was produced. This electrode group was further pressed into a flat shape. The electrode group was housed in a thin metal can (container) made of an aluminum alloy (Al purity 99%) having a thickness of 0.3 mm.

As a non-aqueous electrolyte, a liquid non-aqueous electrolyte (non-aqueous electrolyte) is prepared by dissolving 1.0 mol / L of LiPF ₆ as an electrolyte in a mixed solvent of trimethyl phosphate and propylene carbonate (PC) (volume ratio 80:20). Prepared. This nonaqueous electrolyte was poured into an electrode group in a container, and a thin nonaqueous electrolyte battery having the structure shown in FIG. 1 and having a thickness of 4 mm, a width of 30 mm, and a height of 60 mm was produced.

(Examples 2 to 20)
Except for setting the non-aqueous solvent composition, the type and concentration of the electrolyte, the negative electrode active material, the specific surface area of the negative electrode active material, and the positive electrode active material as shown in Tables 1 and 2, described in Example 1 above. In the same manner as described above, a thin nonaqueous electrolyte battery was produced.

(Comparative Examples 1-7)
Except for setting the non-aqueous solvent composition, the type and concentration of the electrolyte, the negative electrode active material, the specific surface area of the negative electrode active material, and the positive electrode active material as shown in Tables 1 and 2, described in Example 1 above. In the same manner as described above, a thin nonaqueous electrolyte battery was produced.

  A method for measuring particles of the negative electrode active material is shown below.

  To measure the particles of the negative electrode active material, use a laser diffraction distribution analyzer (Shimadzu SALD-300). First, add approximately 0.1 g of the sample, a surfactant, and 1 to 2 mL of distilled water to a beaker. After stirring, the mixture was poured into a stirred water tank, and the light intensity distribution was measured 64 times at intervals of 2 seconds, and the particle size distribution data was analyzed.

Positive electrode active material particles, the positive electrode material layer, BET specific surface area by N ₂ adsorption of the anode active material particles and the negative electrode material layer was measured under the following conditions.

In the case of the active material particles of each of the positive electrode and the negative electrode, the amount of sample used for the measurement was 1 g. In the case of the positive electrode and the negative electrode, 2 pieces of 2 × 2 cm ² pieces were cut from each electrode to prepare samples. A BET specific surface area measuring apparatus manufactured by Yuasa Ionics was used, and nitrogen gas was used as an adsorption gas.

  The porosity of the negative electrode is determined by comparing the volume of the negative electrode material layer with the volume of the negative electrode material layer when the porosity is 0%, and the increase from the volume of the negative electrode material layer when the porosity is 0% as the pore volume. It is calculated by considering. Note that the volume of the negative electrode material layer is the sum of the volumes of the negative electrode material layers on both sides when the negative electrode material layers are formed on both sides of the current collector.

  The battery performance of Examples and Comparative Examples was measured under the conditions described below, and the results are shown in Tables 3 and 4.

  About the nonaqueous electrolyte battery, after charging in 1 hour to 2.8V at a constant current of 1A at 25 ° C., the discharge capacity when discharged to 1.5V at 0.6A (equivalent to 1C) was measured. Moreover, after charging at 2.8V for 1 hour at a constant current of 1 A at 25 ° C., the discharge capacity was measured when discharged to 1.5 V at a current value of 5 C. The discharge capacity at 0.6A (equivalent to 1C) was defined as 100%, and the obtained discharge capacity at the time of 5C discharge was expressed, and the 5C discharge capacity retention rate was obtained. As a high-temperature cycle test, a cycle test was repeated at 45 ° C. with a constant current of 1 A up to 2.8 V in 1 hour and then a 0.6 A constant-current discharge up to 1.5 V. The cycle life at the cycle test at 45 ° C. was defined as the number of cycles at a capacity maintenance rate of 80% of the initial capacity.

  In Examples 18 to 21 and Comparative Examples 1 and 6, the charge end voltage was changed from 2.8 V to 3.3 V, and the discharge end voltage was changed from 1.5 V to 2.5 V. Other Examples and Comparative Examples The discharge capacity, 5C discharge capacity retention rate, and high temperature cycle life were measured under the same conditions as the nonaqueous electrolyte battery.

The 150 ° C. oven test was performed by allowing the non-aqueous electrolyte battery after full charge to stand in a thermostatic bath at 150 ° C. for 30 minutes and measuring the maximum temperature of the battery surface.

  As is clear from Tables 1 to 4, the nonaqueous electrolyte batteries of Comparative Examples 2 to 6 have a higher battery maximum temperature at the time of the oven test than the nonaqueous electrolyte batteries of Examples 1 to 20, resulting in thermal stability. Inferior. Moreover, although the nonaqueous electrolyte battery of Comparative Examples 1 and 7 has a maximum battery temperature of 150 ° C. during the oven test, the discharge capacity, the capacity retention rate at 5 C high current discharge, and the cycle life are the same as in Examples 1 to 20. It is inferior in comparison. According to Examples 1-20, the battery maximum temperature at the time of an oven test is 150-155 degreeC, and the discharge capacity of 600 mAh or more, the capacity maintenance rate at the time of 5 C discharge of 50% or more, and the cycle life of 1500 or more can be realized. .

According to the nonaqueous electrolyte battery of at least one embodiment and example described above, the first spinel structure represented by Li _x Ni _0.5 Mn _1.5 O ₄ (0 <x ≦ 1.1). And at least one of a second oxide having an olivine structure represented by Li _x Mn _1-w Fe _w PO ₄ (0 <x ≦ 1.1, 0 ≦ w ≦ 0.5) A non-aqueous electrolyte excellent in cycle performance, thermal stability and discharge rate performance in a high-temperature environment because it includes a positive electrode, a negative electrode containing a titanium-containing metal oxide, and a non-aqueous electrolyte containing a first solvent and LiPF ₆ A battery can be realized.

Although several embodiments of the present invention have been described, these embodiments are presented by way of example and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.
Hereinafter, the invention described in the scope of claims of the present application will be appended.
[1] a positive electrode;
A negative electrode comprising a titanium-containing metal oxide;
A non-aqueous electrolyte containing a first solvent comprising a fluorinated phosphate ester, and LiPF ₆ dissolved in the non-aqueous solvent ;
A non-aqueous electrolyte battery comprising:
[2] The non-aqueous solvent further contains a second solvent consisting of at least one selected from the group consisting of propylene carbonate, ethylene carbonate, butylene carbonate, ethyl methyl sulfone, and ethyl isopropyl sulfone, in the non-aqueous solvent. The nonaqueous electrolyte battery according to [1], wherein the content of the first solvent is 30 to 90% by volume.
[3] The non-metal according to [1] or [2], wherein the titanium-containing metal oxide includes at least one selected from the group consisting of lithium titanium oxide, titanium oxide, and niobium titanium composite oxide. Water electrolyte battery.
[4] The fluorinated phosphate esters include at least one selected from the group consisting of trifluoromethyl phosphate, trifluoroethyl phosphate, trifluoropropyl phosphate, and trifluorobutyl phosphate. The nonaqueous electrolyte battery according to any one of [1] to [3], which is characterized.
[5] A battery pack comprising the nonaqueous electrolyte battery according to any one of [1] to [4].

  DESCRIPTION OF SYMBOLS 1 ... Container, 2 ... Electrode group, 3 ... Positive electrode, 4 ... Negative electrode, 5 ... Separator, 6 ... Positive electrode lead, 7 ... Negative electrode terminal, 8 ... Negative electrode terminal, 21 ... Single cell, 23 ... Assembly battery, 24 ... Printed wiring Substrate, 25 ... thermistor, 26 ... protection circuit.

Claims (5)

Li _x Ni _0.5 Mn _1.5 O ₄ first oxide having a spinel structure represented by (0 <x ≦ 1.1) and _{Li x Mn 1-w Fe w} PO 4 (0 <x ≦ 1 .1, 0 ≦ w ≦ 0.5) a positive electrode including at least one of the second oxides having an olivine structure represented by :
A negative electrode comprising a titanium-containing metal oxide;
A first solvent comprising a fluorinated phosphate ester, and a non-aqueous solvent comprising a second solvent selected from the group consisting of ethyl methyl sulfone and ethyl isopropyl sulfone, and dissolved in the non-aqueous solvent A non-aqueous electrolyte battery comprising a non-aqueous electrolyte containing LiPF ₆ formed.   The nonaqueous electrolyte battery according to claim 1, wherein the content of the first solvent in the nonaqueous solvent is 30 to 90% by volume.   The non-aqueous electrolyte battery according to claim 1, wherein the titanium-containing metal oxide includes at least one selected from the group consisting of lithium titanium oxide, titanium oxide, and niobium titanium composite oxide.   The fluorinated phosphate ester includes at least one selected from the group consisting of trifluoromethyl phosphate, trifluoroethyl phosphate, trifluoropropyl phosphate, and trifluorobutyl phosphate. Item 4. The nonaqueous electrolyte battery according to any one of Items 1 to 3.   A battery pack comprising the nonaqueous electrolyte battery according to claim 1.

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