JP6556886B2 - Non-aqueous electrolyte secondary battery, battery pack and car - Google Patents

Non-aqueous electrolyte secondary battery, battery pack and car Download PDF

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JP6556886B2
JP6556886B2 JP2018029799A JP2018029799A JP6556886B2 JP 6556886 B2 JP6556886 B2 JP 6556886B2 JP 2018029799 A JP2018029799 A JP 2018029799A JP 2018029799 A JP2018029799 A JP 2018029799A JP 6556886 B2 JP6556886 B2 JP 6556886B2
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negative electrode
graphite material
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nonaqueous electrolyte
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JP2018088425A (en
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高見 則雄
則雄 高見
文 張
文 張
稲垣 浩貴
浩貴 稲垣
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株式会社東芝
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/122Lithium-ion batteries

Description

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

Non-aqueous electrolyte batteries using a graphite material or a carbonaceous material that occlude and release lithium ions as a negative electrode have been commercialized as high energy density batteries for portable devices. In recent years, in order to further improve the energy density of batteries, lithium metal oxides containing Ni, such as lithium nickel cobalt aluminum oxide and lithium nickel cobalt manganese oxide, can be used instead of LiCoO 2 and LiMn 2 O 4 as positive electrode active materials. Practical use is in progress.

  On the other hand, when mounted on vehicles such as automobiles and trains, the constituent materials of the positive and negative electrodes are chemically and electrochemically stable due to storage performance under high temperature environment, cycle performance, and long-term reliability of high output. Materials with excellent properties, strength and corrosion resistance are required. Furthermore, the constituent materials of the positive electrode and the negative electrode are required to have high performance in a cold region, high output performance in a low temperature environment (−40 ° C.), and long life performance. On the other hand, the development of non-volatile and non-flammable electrolytes as non-aqueous electrolytes is being promoted from the viewpoint of improving safety performance, but they have not been put into practical use due to the decrease in output characteristics, low temperature performance and long life performance.

  As described above, high-temperature durability, cycle life, safety, and output performance are issues for mounting a lithium ion battery on a car or the like.

  Thus, various attempts have been made to improve the negative electrode performance of graphite materials and carbonaceous materials. For example, the cycle life performance is improved by adding an additive to the electrolytic solution to suppress the reductive decomposition of the electrolytic solution of the graphite negative electrode. In addition, in order to improve the output performance, investigations to make the particle shape granular or to reduce the particle size are underway, but since the reductive decomposition of the electrolyte solution at high temperatures proceeds and the life performance decreases, the particle size It is difficult to make (particle diameter) small (for example, 10 μm or less).

Moreover, in order to increase the positive electrode capacity and improve the energy density, practical use of lithium metal oxides containing Ni such as lithium nickel cobalt aluminum oxide and lithium nickel cobalt manganese oxide instead of LiCoO 2 and LiMn 2 O 4 Is being promoted. However, when a lithium metal oxide containing Ni is used for the positive electrode and the graphite material particles are used for the negative electrode, the cycle life and safety (especially internal short circuit) at high temperatures are reduced. It is difficult to put a large-sized secondary battery to practical use.

JP 2001-243950 A JP 2009-252421 A JP 2010-182477 A JP 2011-90876 A JP 2012-89245 A

  An object of the embodiment is to provide a nonaqueous electrolyte battery and a battery pack excellent in high-temperature cycle performance, safety, and output performance.

According to the embodiment, a non-aqueous electrolyte secondary battery including a positive electrode, a negative electrode, and a non-aqueous electrolyte is provided. The positive electrode includes a lithium metal oxide containing Ni. The negative electrode is a layer containing a graphite material particle having a (002) plane spacing d 002 of 0.337 nm or less by X-ray diffraction method and a titanium-containing oxide covering at least a part of the surface of the graphite material particle. Including. The thickness of this coating layer is 10 nm or less. The titanium-containing oxide includes at least one titanium oxide of Li a TiO 2 (0 ≦ a ≦ 2) and Li 4/3 + a Ti 5/3 O 4 (0 ≦ a ≦ 2). The graphite material particles satisfy the following formula (1).
0 ≦ I r / I h ≦ 0.1 (1)
However, I h is the intensity of the (101) diffraction peak of the hexagonal by X-ray diffraction of the graphite material particles, I r is the rhombohedral by X-ray diffraction of the graphite material particles ( 101) The intensity of the diffraction peak.

Further, according to the embodiment, a battery pack including the nonaqueous electrolyte secondary battery according to the embodiment is provided.
According to the embodiment, a vehicle including the battery pack according to the embodiment is provided.

It is a partial notch sectional view of the nonaqueous electrolyte battery of an embodiment. It is a side view about the battery of FIG. It is a perspective view which shows an example of the assembled battery used for the battery pack of embodiment.

(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 lithium metal oxide represented by LiNi x M 1-x O 2 (M is a metal element containing Mn, and x is in a range of 0.5 ≦ x ≦ 1). The negative electrode is a layer containing a graphite material particle having a (002) plane spacing d 002 of 0.337 nm or less by X-ray diffraction method and a titanium-containing oxide covering at least a part of the surface of the graphite material particle. (Hereinafter referred to as a coating layer).

The lithium metal oxide represented by LiNi x M 1-x O 2 (M is a metal element containing Mn and x is in the range of 0.5 ≦ x ≦ 1) has a high capacity (high energy density). And excellent in thermal stability. On the other hand, graphite material particles having a (002) plane spacing d 002 of 0.337 nm or less by X-ray diffraction method have a high capacity (high energy density) and excellent electron conductivity. Therefore, a non-aqueous electrolyte battery equipped with a positive electrode containing lithium metal oxide and a negative electrode containing graphite material particles can achieve a high energy density, but a large current tends to flow during an internal short circuit, so thermal runaway There is a risk of reaching.

  Therefore, at least a part of the surface of the graphite material particles is coated with a coating layer containing a titanium-containing oxide. When the battery voltage reaches 0 V due to an internal short circuit, a lithium elimination reaction that has been occluded in the titanium-containing oxide occurs, and the titanium-containing oxide changes into an insulator, so that the negative electrode resistance can be increased. As a result, since an exothermic reaction due to a short-circuit current can be suppressed, a rise in battery temperature can be suppressed and thermal runaway can be avoided. Therefore, the safety of the nonaqueous electrolyte battery can be improved.

  Moreover, since the titanium-containing oxide can suppress reductive decomposition due to the non-aqueous electrolyte of the graphite material particles at a high temperature, it can suppress an increase in negative electrode resistance and gas generation at a high temperature, Charge / discharge cycle life performance at high temperatures can be improved.

  Furthermore, since the titanium-containing oxide can exhibit high electronic conductivity in a normal battery operating voltage range (for example, 4.2 to 2.5 V), the nonaqueous electrolyte battery can achieve excellent output performance. .

  From the above, a nonaqueous electrolyte battery excellent in safety, output performance and charge / discharge cycle life performance at high temperature can be obtained.

  The graphite material particles preferably satisfy the following formula (1).

0 ≦ I r / I h ≦ 0.5 (1)
However, I h is the intensity of the (101) diffraction peak of the hexagonal by X-ray diffraction of the graphite material particles, I r is the rhombohedral by X-ray diffraction of the graphite material particles ( 101) The intensity of the diffraction peak.

Graphite material particles satisfying the formula (1) have high reactivity with the non-aqueous electrolyte, but since the coating layer suppresses the reaction with the non-aqueous electrolyte, resistance due to occlusion and release of lithium ions into the negative electrode active material. The input / output performance can be improved. Moreover, since this graphite material particle has a small proportion of rhombohedral system, the thermal stability at high temperature is high, and the safety and charge / discharge cycle life performance at high temperature can be further improved. A more preferable range of the ratio (I r / I h ) is 0 or more and 0.2 or less.

The titanium-containing oxide preferably contains at least one titanium oxide of Li a TiO 2 (0 ≦ a ≦ 2) and Li 4/3 + a Ti 5/3 O 4 (0 ≦ a ≦ 2). Since such a titanium-containing oxide usually exhibits high electronic conductivity in a battery operating voltage range (for example, 4.2 to 2.5 V), output performance can be further improved. Further, this titanium-containing oxide undergoes a desorption reaction of lithium that has been occluded during an internal short circuit and changes to an insulator, so that a rapid increase in resistance of the battery occurs and high safety can be exhibited.

Therefore, the graphite material particles satisfying the formula (1) are used, and the titanium-containing oxides are Li a TiO 2 (0 ≦ a ≦ 2) and Li 4/3 + a Ti 5/3 O 4 (0 ≦ a ≦ 2). ), It is possible to realize a nonaqueous electrolyte battery in which safety, output performance, and charge / discharge cycle life performance at high temperature are further improved.

  The average diameter of the graphite material particles having at least a part of the surface covered with the coating layer is preferably 6 μm or less. Thereby, quick charge performance and output performance can be improved significantly. A more preferable range of the average diameter is 5 μm or less, and a further preferable range is 3 μm or less. If the average diameter is too small, even if a coating layer is present, the negative electrode resistance may increase due to reductive decomposition of the nonaqueous electrolyte at high temperature and gas generation may occur. Therefore, the lower limit of the average diameter is 1 μm. It is desirable to make it.

  The non-aqueous electrolyte is preferably liquid or gel, and a gel or organic electrolyte compounded with a liquid or polymer material in which a lithium salt is dissolved in an organic solvent can be used. Particularly preferred are organic electrolytes having a boiling point of 200 ° C. or higher, or those containing a room temperature molten salt. Organic electrolytes with a boiling point of 200 ° C or higher, or non-aqueous electrolytes containing room temperature molten salts have low vapor pressure and low gas generation in high-temperature environments of 80 ° C or higher, such as in-vehicle applications. The life performance can be improved.

  Furthermore, as the separator, an olefin-based porous film having a porosity of 50% or more or a cellulose fiber separator can be used. In particular, by using a cellulose fiber separator having a porosity of 60% or more, an increase in resistance due to the shrinkage of the separator under a high temperature environment can be suppressed and a decrease in output can be prevented.

  The nonaqueous electrolyte battery of the embodiment includes a separator disposed between the positive electrode and the negative electrode together with the positive electrode, the negative electrode, and the nonaqueous electrolyte, and a container that stores the positive electrode, the negative electrode, the separator, and the nonaqueous electrolyte. it can. Hereinafter, the positive electrode, the negative electrode, the nonaqueous electrolyte, the separator, and the container will be described.

1) 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 surfaces of the current collector and containing an active material, a conductive agent, and a binder.

In a lithium metal oxide represented by LiNi x M 1-x O 2 (M is a metal element containing Mn, and x is in the range of 0.5 ≦ x ≦ 1), the range of x is 0.5. The reason why ≦ x ≦ 1 is that when x is less than 0.5, a high battery capacity cannot be obtained. When the range of x is 0.5 ≦ x ≦ 1, a high capacity can be obtained, but a thermal decomposition reaction of the positive electrode active material tends to occur. By containing Mn in the element M, the thermal stability of the positive electrode active material is improved, so that the thermal decomposition reaction of the positive electrode active material when 0.5 ≦ x ≦ 1 can be suppressed. The type of the metal constituting the element M can be Mn alone or two or more types including Mn. Examples of metals other than Mn contained in the element M include Co, Al, Zr, Nb, Mo, and W. A more preferable range of x is 0.6 ≦ x ≦ 0.8.

Examples of LiNi x M 1-x O 2 include lithium nickel cobalt manganese oxide (LiNi y Co z Mn 1-yz O 2 , 0 <y <1, 0 <z <1, 0 <(1- yz) <1) and the like.

As the positive electrode active material, only LiNi x M 1-x O 2 or a mixture of LiNi x M 1-x O 2 and another oxide can be used. Examples of other oxides include lithium nickel oxide (LiNiO 2 ), lithium nickel cobalt oxide (LiNi w Co 1-w O 2 , 0 <w <1), lithium nickel cobalt aluminum oxide (LiNi y Co). z Al 1-y-z O 2, 0 <y <1,0 <z <1,0 <(1-y-z) <1) , and the like.

  Examples of the conductive agent include acetylene black, carbon black, graphite, and carbon fiber. The type of the conductive agent can be one type or two or more types.

  The average particle diameter of the positive electrode active material is preferably in the range of 1 μm to 15 μm. A more preferable range is 3 μm or more and 10 μm or less. The positive electrode active material may be in the form of primary particles, the form of secondary particles in which primary particles are aggregated, or the form in which primary particles and secondary particles are mixed.

  Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and fluorine-based rubber. The type of the binder can be one type or two or more types.

  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.

For example, the positive electrode is obtained by suspending a positive electrode active material, a conductive agent and a binder in an appropriate solvent, applying the suspension to a current collector of an aluminum foil or an aluminum alloy foil, drying, and applying a press. Produced. The specific surface area by the BET method of the positive electrode material layer is preferably in the range of 0.1 to 2 m 2 / g.

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

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.

To the plane spacing d 002 of (002) plane measured by X-ray diffraction of the graphite material particles below 0.337 nm, when the plane spacing d 002 exceeding 0.337 nm, the electron conductivity of the graphite material particles This is because the capacity decreases and a high capacity cannot be obtained. A more preferable range is 0.3368 nm or less. Further, the lower limit value of the inter-surface distance d 002 is desirably 0.3355 nm.

  Examples of the graphite material include artificial graphite, natural graphite and the like obtained by heat-treating a carbon precursor such as pitch derived from petroleum or coal, synthetic pitch, mesophase pitch, coke, and resin in an inert atmosphere at 2000 to 3000 ° C. included. Graphite material particles satisfying the formula (1) can be produced, for example, by adjusting the pulverization conditions of the obtained graphite material after heat treatment.

The graphite material particle is a composite containing a metal capable of forming an alloy with lithium such as Si, Al, Sn, Pb, and Zn, and an oxide of the metal such as SiO α (0 <α ≦ 2). There may be. The type of metal and metal oxide can be one type or two or more types. Inclusion of the metal enables higher capacity. Composite particles composed of Si material and the graphite material particles such as Si or SiO alpha is preferred in view of the cycle life performance. The content of the Si component in the composite particles is preferably 10 to 80% by weight.

  Examples of the titanium-containing oxide include titanium oxide, lithium titanium oxide, niobium titanium oxide, and the like. The type of titanium-containing oxide can be one type or two or more types.

Examples of the titanium oxide include monoclinic (bronze structure (B)) titanium oxide and titanium oxide having an anatase structure. As the titanium oxide, TiO 2 (B) having a bronze structure (B) is preferable, and a low crystalline material having a heat treatment temperature of 300 to 600 ° C. is preferable. Titanium oxide can be represented by the general formula Li a TiO 2 (0 ≦ a ≦ 2). In this case, the composition formula before charging is TiO 2 . Examples of the lithium titanium oxide include those having a spinel structure (for example, general formula Li 4/3 + a Ti 5/3 O 4 (0 ≦ a ≦ 2)), those having a ramsdelide structure (for example, general formula Li 2 + a Ti 3 O 7 (0 ≦ a ≦ 1) , Li 1 + b Ti 2 O 4 (0 ≦ b ≦ 1), Li 1.1 + b Ti 1.8 O 4 (0 ≦ b ≦ 1), Li 1.07 + b Ti 1 .86 O 4 (0 ≦ b ≦ 1)), Nb, Mo, W, P, V, Sn, Cu, Ni, and at least one element selected from the group consisting of Fe and lithium-titanium-containing composite oxidation Things are included.

Examples of niobium titanium oxide include those represented by the general formula Li c Nb d TiO 7 (0 ≦ c ≦ 5, 1 ≦ d ≦ 4).

  The thickness of the coating layer is preferably 10 nm or less. Thereby, since the diffusion resistance of lithium ions can be reduced, the output performance can be improved. A more preferable range is 5 to 1 nm.

  When the total of the graphite material particles and the coating layer is 100% by weight, the weight ratio of the coating layer is desirably in the range of 0.1% by weight to 5% by weight. By setting this range, it is possible to realize a high capacity (high energy density) negative electrode while suppressing reductive decomposition of the graphite material particles by the nonaqueous electrolyte.

  The coating of the graphite material particles can be performed, for example, by the following process. A titanium alkoxide is dissolved in ethanol, and lithium is added to the titanium alkoxide and brought into contact with the graphite material particles to coat the surface of the graphite material particles with a precursor of lithium titanium oxide. Then, the graphite material particle coat | covered with the thin film of lithium titanium oxide is obtained by heat-processing at appropriate temperature. Examples of the contact method (coating method) include a spray method and a hydrothermal synthesis method.

An example of covering will be described. The graphite material particles were added to ethanol in which a predetermined amount of titanium tetrapropoxide (Ti (OC 3 H 7 ) 4 ) was dissolved, and these were sufficiently stirred. Then, a predetermined amount of an aqueous lithium hydroxide solution was added, and 70 ° C. Stir at. Next, hydrothermal synthesis (temperature 100 to 200 ° C.) treatment is performed, and the obtained product is dried, and then subjected to heat treatment at a temperature of 300 to 800 ° C. in an air atmosphere or an inert atmosphere. Graphite material particles coated with a layer of 4/3 Ti 5/3 O 4 or a layer of Li a TiO 2 (0 ≦ a ≦ 2) can be obtained. The heat treatment temperature is desirably 500 ° C. or lower in order to suppress surface oxidation of the graphite material particles.

  The thickness of the coating layer is measured, for example, from a transmission electron micrograph (TEM photograph) of the cross section of the sample.

  The porosity of the negative electrode (excluding the current collector) 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 50%.

  The negative electrode current collector is desirably a metal foil such as a copper foil, a stainless steel foil, a nickel foil, or a carbon coated metal foil.

  The thickness of the metal foil is 20 μm or less, more preferably 15 μm or less.

  Examples of the conductive agent include acetylene black, carbon black, coke, carbon fiber, graphite, metal compound powder, and metal powder. The type of the conductive agent can be one type or two or more types.

  Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine-based rubber, styrene butadiene rubber, and core-shell binder. The type of the binder can be one type or two or more types.

  The compounding ratio of the negative electrode active material, the conductive agent and the binder is preferably in the range of 90 to 99% by weight of the negative electrode active material, 0 to 5% 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) Non-aqueous electrolyte As the non-aqueous electrolyte, a liquid organic electrolyte prepared by dissolving an electrolyte in an organic solvent, a gel organic electrolyte obtained by combining a liquid organic solvent and a polymer material, or a lithium salt electrolyte And a solid non-aqueous electrolyte in which a polymer material is combined. Moreover, you may use the normal temperature molten salt (ionic melt) containing lithium ion as a non-aqueous electrolyte. Examples of the polymer material include polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyethylene oxide (PEO), and the like.

  The liquid organic electrolyte is prepared by dissolving the electrolyte in an organic solvent at a concentration of 0.5 to 2.5 mol / L. Thereby, a high output can be taken out even in a low temperature environment. A more preferable range is a range of 1.5 to 2.5 mol / L.

Examples of the electrolyte include LiBF 4 , LiPF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 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. Among these, it is preferable to contain lithium tetrafluoroborate (LiBF 4 ). As a result, the chemical stability of the organic solvent is increased, the film resistance on the negative electrode can be reduced, and the low temperature performance and cycle life performance can be greatly improved.

  Examples of the organic solvent include cyclic carbonates such as propylene carbonate (PC) and ethylene carbonate (EC), chain carbonates such as diethyl carbonate (DEC), dimethyl carbonate (DMC), and methyl ethyl carbonate (MEC), dimethoxyethane ( Examples thereof include chain ethers such as DME) and dietoethane (DEE), cyclic ethers such as tetrahydrofuran (THF) and dioxolane (DOX), γ-butyrolactone (GBL), acetonitrile (AN) and sulfolane (SL). These organic solvents can be used alone or in the form of a mixture of two or more. By containing at least one selected from the group consisting of propylene carbonate (PC), ethylene carbonate (EC) and γ-butyrolactone (GBL), the boiling point becomes 200 ° C. or higher, so that thermal stability is improved. Can do. In particular, a non-aqueous solvent containing γ-butyrolactone (GBL) can dissolve a high-concentration lithium salt, so that output performance in a low-temperature environment can be improved.

  The room temperature molten salt (ionic melt) is preferably composed of lithium ions, organic cations and organic anions. The room temperature molten salt is preferably liquid at room temperature or lower.

  Hereinafter, an electrolyte containing a room temperature molten salt will be described.

  The room temperature molten salt refers to a salt that is at least partially in a liquid state at room temperature, and the room temperature refers to a temperature range in which a power supply is assumed to normally operate. The temperature range in which the power supply is assumed to normally operate has an upper limit of about 120 ° C. and in some cases about 60 ° C., and a lower limit of about −40 ° C. and in some cases about −20 ° C. Especially, the range of -20 degreeC or more and 60 degrees C or less is suitable.

  For room temperature molten salts containing lithium ions, it is desirable to use an ionic melt composed of lithium ions, organic cations and anions. The ionic melt is preferably in a liquid state even at room temperature or lower.

  Examples of the organic cation include alkyl imidazolium ions and quaternary ammonium ions having a skeleton shown in Chemical Formula 1 below.

As the alkyl imidazolium ion, a dialkyl imidazolium ion, a trialkyl imidazolium ion, a tetraalkyl imidazolium ion and the like are preferable. As dialkylimidazolium, 1-methyl-3-ethylimidazolium ion (MEI + ), as trialkylimidazolium ion, 1,2-diethyl-3-propylimidazolium ion (DMPI + ), as tetraalkylimidazolium ion 1,2-diethyl-3,4 (5) -dimethylimidazolium ion is preferred.

  As the quaternary ammonium ion, a tetraalkylammonium ion or a cyclic ammonium ion is preferable. As the tetraalkylammonium ion, dimethylethylmethoxyethylammonium ion, dimethylethylmethoxymethylammonium ion, dimethylethylethoxyethylammonium ion, and trimethylpropylammonium ion are preferable.

  By using the alkylimidazolium ion or quaternary ammonium ion (particularly tetraalkylammonium ion), the melting point can be made 100 ° C. or lower, more preferably 20 ° C. or lower. Furthermore, the reactivity with the negative electrode can be lowered.

  The concentration of lithium ions is preferably 20 mol% or less. A more preferred range is in the range of 1 to 10 mol%. By setting it within this range, a liquid room temperature molten salt can be easily formed even at a low temperature of 20 ° C. or lower. Further, the viscosity can be lowered even at room temperature or lower, and the ionic conductivity can be increased.

As anions, BF 4 , PF 6 , AsF 6 , ClO 4 , CF 3 SO 3 , CF 3 COO , CH 3 COO , CO 3 2− , (FSO 2 ) 2 N , N (CF 3 SO 2) 2 - , N (C 2 F 5 SO 2) 2 -, (CF 3 SO 2) 3 C - to coexist one or more anions selected from such preferred. By coexisting a plurality of anions, a room temperature molten salt having a melting point of 20 ° C. or lower can be easily formed. More preferable anions include BF 4 , (FSO 2 ) 2 N , CF 3 SO 3 , CF 3 COO , CH 3 COO , CO 3 2− , N (CF 3 SO 2 ) 2 , N ( C 2 F 5 SO 2) 2 -, (CF 3 SO 2) 3 C - and the like. These anions make it easier to form a room temperature molten salt at 0 ° C. or lower.

4) Separator
A separator can be disposed between the positive electrode and the negative electrode. Examples of the separator include olefinic porous membranes such as polyethylene (PE) and polypropylene (PP), and cellulose fiber separators. Examples of the separator include non-woven fabric, film, and paper. The porosity of the separator is preferably 50% or more. Cellulose fiber separators having a porosity of 60% or more have good electrolyte impregnation properties, and can provide high output performance from low to high temperatures. A more preferable range is 62% to 80%.

  By setting the diameter of the fibers constituting the separator to 10 μm or less, the affinity between the nonaqueous electrolyte and the separator can be improved, and the battery resistance can be reduced. More preferably, it is 3 μm or less.

The separator preferably has a thickness of 20 to 100 μm and a density of 0.2 to 0.9 g / cm 3 . Within this range, it is possible to balance the mechanical strength and the reduction of battery resistance, and it is possible to provide a battery that is high in output and hardly shorts internally. Moreover, there is little heat shrinkage in a high temperature environment, and good high temperature storage performance can be obtained.

5) Container A metal container or a laminate film container can be used as a container for accommodating the positive electrode, the negative electrode, and the nonaqueous electrolyte.

  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.

  The prismatic secondary battery according to the first embodiment is shown in FIGS. As shown in FIG. 1, the electrode group 1 is housed in a rectangular cylindrical metal container 2. The electrode group 1 has a structure in which a positive electrode 3 and a negative electrode 4 are wound in a spiral shape so as to have a flat shape with a separator 5 interposed therebetween. A nonaqueous electrolyte (not shown) is held in the electrode group 1. As shown in FIG. 2, a strip-like positive electrode lead 6 is electrically connected to each of a plurality of locations at the end of the positive electrode 3 located on the end surface of the electrode group 1. In addition, a strip-like negative electrode lead 7 is electrically connected to each of a plurality of locations at the end of the negative electrode 4 located on this end face. The plurality of positive electrode leads 6 are electrically connected to the positive electrode conductive tab 8 in a bundled state. The positive electrode lead 6 and the positive electrode conductive tab 8 constitute a positive electrode terminal. The negative electrode lead 7 is connected to the negative electrode conductive tab 9 in a bundled state. The negative electrode lead 7 and the negative electrode conductive tab 9 constitute a negative electrode terminal. The metal sealing plate 10 is fixed to the opening of the metal container 2 by welding or the like. The positive electrode conductive tab 8 and the negative electrode conductive tab 9 are each drawn out from an extraction hole provided in the sealing plate 10. The inner peripheral surface of each extraction hole of the sealing plate 10 is covered with an insulating member 11 in order to avoid a short circuit due to contact with the positive electrode conductive tab 8 and the negative electrode conductive tab 9.

  Note that the type of battery is not limited to a rectangular shape, and various types such as a cylindrical shape, a thin shape, and a coin shape can be used. In addition, the shape of the electrode group is not limited to a flat shape, and may be, for example, a cylindrical shape or a laminated shape.

According to the nonaqueous electrolyte battery of the first embodiment described above, LiNi x M 1-x O 2 (M is a metal element containing Mn, and x is in the range of 0.5 ≦ x ≦ 1). And a layer containing a titanium-containing oxide that covers at least a part of the surface of the graphite material particles having a surface spacing d 002 of 0.337 nm or less and a surface of the graphite material particles. Since the negative electrode is provided, a nonaqueous electrolyte battery excellent in safety, output performance, and charge / discharge cycle life performance at high temperature can be provided.

(Second Embodiment)
The battery pack according to the second embodiment includes one or more non-aqueous electrolyte batteries according to the first embodiment. The battery pack may include an assembled battery composed of a plurality of batteries. The connection between the batteries may be in series or in parallel, but in particular, it is preferable to connect in series and connect 6 series n multiples (n is an integer of 1 or more).

One embodiment of the assembled battery used in the battery pack is shown in FIG. Battery pack 21 shown in FIG. 3 includes a plurality of prismatic type secondary battery 22 1-22 5 according to the second embodiment. Positive electrode conductive tab 8 of the rechargeable battery 22 1, a negative electrode conductive tab 9 of the rechargeable battery 22 2 located next to it, are electrically connected by a lead 23. Furthermore, a positive electrode conductive tab 8 of the secondary battery 22 2 and the negative electrode conductive tab 9 of the rechargeable battery 22 3 located next to it, are electrically connected by a lead 23. In this way, the secondary batteries 22 1 to 22 5 are connected in series.

  A metal can, a plastic container, or the like made of aluminum alloy, iron, stainless steel, or the like can be used for a housing in which the assembled battery is stored. Further, the plate thickness of the container is desirably 0.5 mm or more.

  The mode of the battery pack is appropriately changed depending on the application. As a use of the battery pack, one in which cycle performance with a large current characteristic is desired is preferable. 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-vehicle use is suitable.

  According to the second embodiment, since the nonaqueous electrolyte battery according to the first embodiment is provided, a battery pack excellent in safety, output performance, and charge / discharge cycle life performance at high temperature can be realized.

  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, lithium nickel cobalt manganese oxide (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) having a layered structure with an average primary particle size of 1 μm was used. This was mixed with 5% by weight of PVDF as a conductive agent and 5% by weight of PVdF with respect to the whole positive electrode as a binder, and dispersed in an n-methylpyrrolidone (NMP) solvent. After preparing the slurry, the slurry was applied to both sides of an aluminum alloy foil (purity 99%) having a thickness of 15 μm, dried and subjected to a pressing process. The thickness of the positive electrode material layer on one side was 38 μm, and the electrode density was 3.3 g. A positive electrode of / cm 3 was produced.

An artificial graphite powder having a (002) plane spacing d 002 of 0.3358 nm and (I r / I h ) of 0.1 by X-ray diffraction as an anode active material is dissolved in Ti (OC 3 H 7 ) 4. In addition to ethanol, the mixture was sufficiently stirred, and then an aqueous lithium hydroxide solution was added and stirred at 70 ° C. Next, hydrothermal synthesis treatment is performed at 150 ° C., and the resulting product is dried and then heated at 500 ° C. in an air atmosphere to cover the surface with a layer of Li 4/3 Ti 5/3 O 4. An artificial graphite powder was obtained. The coating amount was 1% by weight. Moreover, the thickness of the coating layer was 10 nm.

A negative active material particle made of artificial graphite powder (average diameter 3 μm) coated with a layer of Li 4/3 Ti 5/3 O 4 and PVdF as a binder were blended in a weight ratio of 96: 4. A slurry was prepared by dispersing in an n-methylpyrrolidone (NMP) solvent and using a ball mill with stirring at a rotational speed of 1000 rpm and a stirring time of 2 hours. The obtained slurry was applied to a copper foil (purity 99.3%) having a thickness of 15 μm, dried, and subjected to a heating press process, whereby the thickness of the negative electrode material layer on one side was 50 μm, and the electrode density was 1.4 g / A cm 3 negative electrode was produced. The negative electrode porosity excluding the current collector was 38%. Moreover, the BET specific surface area (surface area per 1 g of negative electrode material layer) of the negative electrode material layer was 5 m 2 / g.

  A method for measuring the average diameter of the negative electrode active material particles is shown below. Using a laser diffraction distribution measuring device (Shimadzu SALD-300), first add about 0.1 g of a sample, a surfactant and 1 to 2 mL of distilled water to a beaker, stir well, and then inject into a stirred water tank. The luminous intensity distribution was measured 64 times at intervals of 2 seconds, and the average diameter of D50 was determined from the particle size distribution data.

Electrode active material, and a BET specific surface area by N 2 adsorption of the negative electrode was measured under the following conditions.

Two pieces of a negative electrode active material 1 g or 2 × 2 cm 2 negative electrode were cut out and used as a sample. 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% It is calculated by regarding it as a volume. 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.

  On the other hand, a regenerated cellulose fiber having a thickness of 20 μm, a porosity of 65%, and an average fiber diameter of 1 μm, which is a raw material for pulp, is closely attached to the positive electrode, and the negative electrode active material layer is arranged so as to cover the positive electrode active material layer through a separator. The electrodes were stacked so as to face the positive electrode through a separator, wound in a spiral shape, and then formed into a flat shape by a press to produce an electrode group.

  The electrode group was housed in a thin metal can made of an aluminum alloy (Al purity 99%) having a thickness of 0.3 mm.

On the other hand, lithium hexafluoroborate (LiPF 6 ) as a lithium salt in a mixed solvent (volume ratio 25:25:50) of propylene carbonate (PC), ethylene carbonate (EC), and diethyl carbonate (DEC) as an organic solvent. Was dissolved at 1 mol / L to prepare a liquid organic electrolyte (non-aqueous electrolyte). A nonaqueous electrolyte is injected into the electrode group in the container, and has the structure shown in FIG. 1 described above. The thin nonaqueous solution has a thickness of 14 mm, a width of 62 mm, a height of 94 mm, a capacity of 5 Ah, and an average voltage of 3.7 V. An electrolyte battery was produced.

(Examples 3, 4, 6-11, Reference Examples 2, 5 and Comparative Examples 1-6)
A thin nonaqueous electrolyte battery was produced in the same manner as described in Example 1 except that the negative electrode active material and the positive electrode active material shown in Table 1 below were used.

The negative electrode active material coated with artificial graphite particles of Example 6 in the TiO 2 layer was synthesized by the method described below.

As an anode active material, artificial graphite powder having d 002 of 0.3358 nm and (I r / I h ) of 0.1 by X-ray diffraction method was added to ethanol in which Ti (OC 3 H 7 ) 4 was dissolved, and 70 ° C. Was stirred. Next, hydrothermal synthesis treatment was performed at 150 ° C., and the obtained product was dried and then heat treatment was performed at 500 ° C. in an air atmosphere to obtain artificial graphite powder whose surface was covered with a TiO 2 layer. The coating amount was 1% by weight. Moreover, the thickness of the coating layer was 10 nm.

In addition, the negative electrode active material which coat | covered the artificial graphite particle | grains of the comparative example 5 with the carbonaceous material was synthesize | combined by the method demonstrated below. As a negative electrode active material, an artificial graphite powder having a d 002 of 0.3358 nm and (I r / I h ) of 0.1 by an X-ray diffraction method was heat treated at 1000 ° C. in an argon atmosphere at a surface of a pitch-based carbonaceous material. A coated artificial graphite powder was obtained. The coating amount was 3% by weight. Moreover, the thickness of the coating layer was 10 nm.

The negative electrode active material obtained by coating the hard carbon of Comparative Example 6 with a layer of Li 4/3 Ti 5/3 O 4 was synthesized by the method described below. As a negative electrode active material, a hard carbon powder having d 002 of 0.380 nm and (I r / I h ) of 0 by X-ray diffraction is added to ethanol in which Ti (OC 3 H 7 ) 4 is dissolved, and sufficiently stirred. Then, an aqueous lithium hydroxide solution was added and stirred at 70 ° C. Next, hydrothermal synthesis treatment is performed at 150 ° C., and the resulting product is dried and then heated at 500 ° C. in an air atmosphere to cover the surface with a layer of Li 4/3 Ti 5/3 O 4. Hard carbon powder was obtained. The coating amount was 10% by weight. Moreover, the thickness of the coating layer was 10 nm.

  Among the obtained secondary batteries of Examples 1, 3, 4, 6-11, Reference Examples 2, 5 and Comparative Examples 1-6, 1.5 hours to 4.2 V at a constant current of 1 C rate at 25 ° C. After charging, the discharge capacity when discharged at a 1C rate up to 3V was measured. As a high-temperature cycle test, the above-mentioned charge / discharge cycle was repeated at 45 ° C., and the cycle number at which the capacity decrease width was 20% was defined as the cycle life number. As the output performance, the maximum output density for 10 seconds at 25 ° C. and −30 ° C. was measured at a charging rate of 50%. As a safety test, the maximum temperature of the battery in the internal short circuit test of crushing (crushing rate 50%) was measured. The measurement results are shown in Table 2 below.

  As is clear from Tables 1 and 2, the batteries of Examples 1, 3, 4, 6 to 11 have a cycle life at 45 ° C. and power densities of 25 ° C. and −30 ° C. compared to Comparative Examples 1 to 6. It can be seen that the maximum temperature of the internal short circuit test by crushing is low. In particular, in the output performance of 25 ° C. and −30 ° C., Examples 7 and 8 obtained excellent performance. Moreover, in the internal short circuit test by crushing, the maximum temperature of Examples 3, 6, and 9 to 11 is low and excellent in safety.

According to the nonaqueous electrolyte battery of at least one embodiment and example described above, LiNi x M 1-x O 2 (M is a metal element containing Mn, and x is in the range of 0.5 ≦ x ≦ 1. And a titanium-containing oxide that covers at least a part of the surface of the graphite material particles and the graphite material particles having an interplanar spacing d 002 of 0.337 nm or less. Since the negative electrode including the included layer is provided, a nonaqueous electrolyte battery excellent in safety, output performance, and charge / discharge cycle life performance at high temperature can be provided.

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 at the beginning of the application of the present application will be added.
[1] a positive electrode containing a lithium metal oxide represented by LiNi x M 1-x O 2 (M is a metal element containing Mn, and x is in a range of 0.5 ≦ x ≦ 1);
Graphite material particles having a (002) plane spacing d 002 of 0.337 nm or less by X-ray diffraction and a layer containing a titanium-containing oxide covering at least a part of the surface of the graphite material particles. A negative electrode containing,
A non-aqueous electrolyte battery comprising a non-aqueous electrolyte.
[2] The nonaqueous electrolyte battery according to [1], wherein the graphite material particles satisfy the following formula (1).
0 ≦ I r / I h ≦ 0.5 (1)
However, the I h, the graphite material (101) of the hexagonal by X-ray diffractometry of the particles is the intensity of the diffraction peak, the I r is rhombohedral by X-ray diffraction of the graphite material particles It is the intensity of the crystal system (101) diffraction peak.
[3] The titanium-containing oxide includes at least one titanium oxide selected from Li a TiO 2 (0 ≦ a ≦ 2) and Li 4/3 + a Ti 5/3 O 4 (0 ≦ a ≦ 2). The nonaqueous electrolyte battery according to [1] or [2], wherein
[4] The nonaqueous electrolyte battery according to any one of [1] to [3], wherein an average diameter of the graphite material particles is 6 μm or less.
[5] A battery pack comprising the nonaqueous electrolyte battery according to any one of [1] to [4].

DESCRIPTION OF SYMBOLS 1 ... Electrode group, 2 ... Container, 3 ... Positive electrode, 4 ... Negative electrode, 5 ... Separator, 6 ... Positive electrode lead, 7 ... Negative electrode lead, 8 ... Positive electrode conductive tab, 9 ... Negative electrode conductive tab, 10 ... Sealing plate, 11 ... Insulating member, 21 ... assembled battery, 22 1 to 22 5 ... single cell, 23 ... lead.

Claims (6)

  1. A positive electrode comprising a lithium metal oxide containing Ni ;
    Graphite material particles having a (002) plane spacing d 002 of 0.337 nm or less by X-ray diffraction and a layer containing a titanium-containing oxide covering at least a part of the surface of the graphite material particles. A negative electrode containing,
    Including non-aqueous electrolyte,
    The titanium-containing oxide includes at least one titanium oxide of Li a TiO 2 (0 ≦ a ≦ 2) and Li 4/3 + a Ti 5/3 O 4 (0 ≦ a ≦ 2),
    The coating layer has a thickness of 10 nm or less,
    The graphite material particles satisfy the following formula (1): a nonaqueous electrolyte secondary battery.
    0 ≦ I r / I h ≦ 0.1 (1)
    However, the I h, the graphite material (101) of the hexagonal by X-ray diffractometry of the particles is the intensity of the diffraction peak, the I r is rhombohedral by X-ray diffraction of the graphite material particles It is the intensity of the crystal system (101) diffraction peak.
  2.   The nonaqueous electrolyte secondary battery according to claim 1, wherein an average diameter of the graphite material particles is 6 μm or less.
  3. The nonaqueous electrolyte secondary battery according to claim 1 or 2 , wherein the battery operating voltage range is 2.5 V or more and 4.2 V or less.
  4. The battery pack containing the nonaqueous electrolyte secondary battery of any one of Claims 1-3 .
  5. The battery pack according to claim 4 , comprising a plurality of the nonaqueous electrolyte secondary batteries, wherein the plurality of nonaqueous electrolyte secondary batteries are connected in series or in parallel.
  6. To any one of claims 4 or 5 comprising a battery pack according, Car.
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