JP2018200795A - Inorganic particles for nonaqueous electrolyte battery and nonaqueous electrolyte battery - Google Patents

Abstract

To provide a nonaqueous electrolyte battery having excellent lifetime characteristics or safety.SOLUTION: A layered compound containing a metal element having a smaller electronegativity than manganese in the crystal structure and having an interlayer distance of 0.40 nm or more and 2.0 nm or less and an exchangeable cation other than hydrogen ion between the layers is included in inorganic particles for a nonaqueous electrolyte battery.SELECTED DRAWING: None

Description

  The present invention relates to a non-aqueous electrolyte battery having excellent life characteristics or safety.

  With the recent development of electronic technology or increasing interest in environmental technology, various electrochemical devices are used. In particular, there are many demands for energy saving, and the expectation for electrochemical devices that can contribute to this is increasing.

  Lithium ion secondary batteries, which are typical examples of power storage devices and typical examples of non-aqueous electrolyte batteries, have been used mainly as power sources for small devices, but in recent years, they have also been used as power sources for hybrid vehicles and electric vehicles. It is attracting attention.

  In the lithium ion secondary battery, as the performance of the device is increased, the energy density is increasing, and it is important to ensure the reliability. In addition, in a medium-sized or large-sized lithium ion secondary battery such as a vehicle-mounted power supply, it is necessary to ensure reliability more than a small device.

  In lithium ion secondary batteries, lithium (Li) ions move between the positive electrode and the negative electrode, so that charging and discharging are performed. However, if a small amount of metal ions other than Li ions are present in the battery, they are deposited on the negative electrode surface. However, it is known that the battery life is reduced, or that the deposited metal breaks the separator and reaches the positive electrode, thereby causing a short circuit or reducing the safety. Such metal ions are derived from impurities in the battery constituent material, but other than that, metal contained in the positive electrode active material due to side reactions in the battery (for example, decomposition reaction of the nonaqueous electrolyte). Is derived from elution into the non-aqueous electrolyte. Furthermore, it has been pointed out that this metal elution becomes more prominent when the battery is exposed to high temperatures. For this reason, examination of the trapping agent which traps impurities, such as a metal ion, is made (for example, refer to patent documents 1 and 2).

  In recent years, lithium ion batteries have been required to be charged at a high voltage of 4.35 V or more in order to further improve the energy density. In particular, when used as a power source for an electric vehicle, the use environment temperature of the lithium ion battery may be 50 ° C. or more. In such a high voltage / high temperature environment, it has been pointed out that metal elution from the positive electrode active material described above is promoted and the battery life decreases more significantly. There is a demand for a lithium ion battery capable of maintaining the capacity even when the above is repeated.

JP 2000-77103 A JP 2012-146477 A

  However, known scavengers have not achieved life characteristics or safety that can withstand practical use. Therefore, an object of the present invention is to provide a nonaqueous electrolyte battery that is excellent in life characteristics or safety.

As a result of diligent investigations on materials that can exclude the adverse effects of metal ions eluted from electrodes or electrode active materials, the present inventors have developed a specific crystal structure and element, and in particular, an inorganic compound having a specific atomic arrangement. It has been found that the adverse effects of metal ions can be efficiently excluded by arranging them appropriately in the battery.
Furthermore, the present inventors have found that inorganic compounds having a specific crystal structure and constituent elements have no effect on Li ions, which are the main components that determine battery performance.
In particular, the fact that the above effects were further enhanced by controlling the surface of the inorganic compound was a major factor for completing the present invention.
That is, the present invention is as follows.
[1]
In the crystal structure, a metal element having an electronegativity smaller than that of manganese is included, and a layered compound having an interlayer distance of 0.40 nm to 2.0 nm and having an exchangeable cation other than a hydrogen ion between the layers is included. Inorganic particles for non-aqueous electrolyte batteries.
[2]
The non-aqueous electrolyte battery inorganic material according to [1], wherein the exchangeable cation is selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, organic cations, and any mixture thereof. particle.
[3]
The inorganic particles are 0.035 parts by mass in an atmosphere of 23 ° C. with respect to 100 parts by mass of a mixed solution of 5 ppm of Mn ²⁺ ions, 1 mol / L LiPF ₆ and cyclic and / or chain carbonate. The inorganic particles for nonaqueous electrolyte batteries according to [1] or [2], wherein the Mn ²⁺ ion adsorption rate when immersed for a period of time is 5% or more.
[4]
The inorganic particles were immersed in 100 parts by mass of a mixture of 800 ppm of HF, 1 mol / L LiPF ₆ and cyclic and / or chain carbonate in an amount of 8 parts by mass in an atmosphere of 23 ° C. for 5 minutes. The inorganic particles for nonaqueous electrolyte batteries according to any one of [1] to [3], wherein the HF concentration at the time decreases by 10% or more.
[5]
Following formula:
Hydrophilic parameter A = BET1 / BET2
{In the formula, BET1 means the specific surface area of the inorganic particles calculated using the BET method from the adsorption isotherm measured by adsorbing water vapor to the inorganic particles, and BET2 represents nitrogen in the inorganic particles. It means the specific surface area of inorganic particles calculated using the BET method from the adsorption isotherm measured by adsorption. }
The inorganic particle for nonaqueous electrolyte batteries according to any one of [1] to [4], wherein the hydrophilic parameter A of the inorganic particle defined by (1) is greater than 0.65 and not more than 2.0.
[6]
The inorganic particles for nonaqueous electrolyte batteries according to any one of [1] to [5], wherein the inorganic particles are surface-modified.
[7]
The BET specific surface area of the inorganic particles calculated by using the BET method from the adsorption isotherm measured by adsorbing nitrogen to the inorganic particles is 3 m ² / g or more and 200 m ² / g or less, [1] to [6] The inorganic particle for a nonaqueous electrolyte battery according to any one of [6].
[8]
The BET specific surface area of the inorganic particles calculated using the BET method from the adsorption isotherm measured by adsorbing nitrogen to the inorganic particles is 3 m ² / g or more and 30 m ² / g or less, [1] to [7] The inorganic particle for a nonaqueous electrolyte battery according to any one of [7].
[9]
The inorganic particles for nonaqueous electrolyte batteries according to any one of [1] to [8], wherein the inorganic particles are zirconium phosphate.
[10]
The battery constituent material containing the inorganic particle for nonaqueous electrolyte batteries as described in any one of [1]-[9].
[11]
A nonaqueous electrolyte battery provided with the adsorption layer comprised by the inorganic particle for nonaqueous electrolyte batteries as described in any one of [1]-[9].
[12]
The non-aqueous electrolyte battery includes a positive electrode, a negative electrode, and a separator as battery constituent materials, and the adsorption layer includes at least one of the inside of the separator, the facing surface of the positive electrode and the separator, and the facing surface of the negative electrode and the separator. The non-aqueous electrolyte according to [11], wherein the adsorbing layer is formed on the whole or a part of the inside of the separator, or on the whole or a part of each facing surface. battery.

  ADVANTAGE OF THE INVENTION According to this invention, the nonaqueous electrolyte battery excellent in a lifetime characteristic or safety | security can be provided.

  Hereinafter, modes for carrying out the present invention (hereinafter simply referred to as “embodiments”) will be described in detail. The following embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

  The inorganic particles for a non-aqueous electrolyte battery according to the present embodiment include a metal element having an electronegativity smaller than that of manganese in the crystal structure, an interlayer distance of 0.40 nm to 2.0 nm, and between the layers. A layered compound having exchangeable cations other than hydrogen ions is included. In the present specification, in the layered compound, the exchangeable cation between layers is other than a hydrogen ion, and therefore, in the zirconium phosphate, the exchangeable cation is preferably substituted with other than hydrogen. The inorganic particles according to this embodiment can be used as a component of a nonaqueous electrolyte battery.

  The components in the embodiment described above will be described below.

[Nonaqueous electrolyte battery]
The non-aqueous electrolyte battery includes battery constituent materials such as a positive electrode, a negative electrode, a separator, a non-aqueous electrolyte, and an outer package, and at least one of the battery constituent materials includes life characteristics or safety of the non-aqueous electrolyte battery. Inorganic particles for non-aqueous electrolyte batteries that adsorb substances that affect performance. The inorganic particles for nonaqueous electrolyte batteries can also be used as an adsorbent capable of adsorbing substances that affect the life characteristics or safety of nonaqueous electrolyte batteries.
As for these electrode constituent materials, for example, aluminum or the like is used for the packaging material or exterior body, nickel, cobalt, manganese, iron, zinc, copper, aluminum, or the like is used for the positive electrode active material, and copper is used for the current collector foil. Aluminum or the like is used.

The inorganic particles for a non-aqueous electrolyte battery contained in the constituent material of the non-aqueous electrolyte battery include a metal element having an electronegativity lower than that of manganese in the crystal structure, and an interlayer distance is 0.40 nm or more and 2.0 nm or less, It is a nonmetallic layered compound having exchangeable cations between layers.
The nonmetallic layered compound has no effect on Li ions, which are main components that determine battery performance.

About the crystal structure of the inorganic particle for nonaqueous electrolyte batteries, a trace amount of eluted metal ions other than lithium ions can be selectively and efficiently adsorbed by having a layered structure. The specific mechanism is beyond the scope of inference, but it is thought that the layered structure increases the specific surface area for metal ions and increases the adsorption sites of metal ions. Moreover, it is thought that it has contributed to stabilization of the adsorbed ion by having a layered structure. In addition, since the eluted ions to be adsorbed are divalent or higher metal ions, while the Li ions that determine the battery performance are monovalent, the Li ions are relatively smaller than the eluted ions of interest. It is considered that it is difficult to adsorb to the layered compound, and the layered compound can selectively adsorb eluted ions.
In particular, the interlayer distance of a layered compound is defined as the interplanar distance measured by X-ray diffraction or electron beam diffraction, and when the distance is 0.40 nm or more and 2.0 nm or less, metal ions can be adsorbed efficiently. I found out that The lower limit is preferably 0.50 nm or more, more preferably 0.80 nm or more, from the viewpoint of making it difficult to adsorb Li ions. The upper limit is preferably 1.8 nm or less and more preferably 1.5 nm or less from the viewpoint of adsorption of eluted ions. The surface spacing does not need to have a uniform surface spacing in the above range, and may have fluctuations. That is, the peak corresponding to the interlayer distance in X-ray diffraction or electron beam diffraction is preferably broad, and may be a double peak or a triple peak. For such a layered compound having fluctuations in interplanar spacing, for example, the interlayer distance can be measured from a TEM (transmission electron microscope) image.

The layered structure of the layered compound is a structure in which exchangeable cations are held between a plurality of layers in the crystal structure. Examples of the exchangeable cation element include hydrogen ions, ammonium ions, and metal ions. As the metal ions, metal ions diffusing from the adsorbent are preferably stable, more preferably elements belonging to alkali metal ions and alkaline earth metal ions, and alkali metals and alkaline earth metals include Be, Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs and the like can be mentioned.
A part of the exchangeable cation held between the plurality of layers in these crystal structures may be substituted with water, or may be substituted with non-ionized organic molecules.
When the exchangeable cation is the above element, the exchangeable cation diffuses into the electrolyte as a cation, and the vacant site formed in the adsorbent is negatively charged, and the positive electrode active material or the current collector foil The metal ions eluted from the battery constituent materials such as The exchangeable cation, which has a relatively negative electronegativity compared to the eluted metal ion, diffuses into the electrolyte, and ion exchange occurs in which the eluted metal ion is adsorbed, thereby maintaining the charge balance of the entire system inside the battery. It is. Then, the potential of the entire system inside the battery becomes more stable after adsorption. As a result, metal ions eluted from the battery constituent material are reduced.

  Furthermore, the layered compound only needs to contain in advance in the crystal structure of the adsorbent a metal element having a smaller electronegativity than metal ions eluted from the battery constituent material. Thereby, even if the layered compound consumes all the exchangeable cations, it is preferable in that the metal eluted from other battery constituent materials can be efficiently reduced. This is because the metal element contained in the crystal structure of the layered compound is more stable as a cation than the metal ion eluted from other battery constituent materials, and thus easily diffuses into the electrolyte. This is presumed.

As the metal element having a small electronegativity, an element having an electronegativity smaller than that of manganese having the smallest electronegativity among battery constituent materials is preferable. Among them, the element contained in the crystal structure of the inorganic particles is preferably divalent or higher when it becomes an ion. Accordingly, a metal element having an electronegativity smaller than that of manganese is more likely to remain in the crystal structure of the inorganic particles than monovalent lithium. As a result, only exchangeable cations cause adsorption based on ion exchange, and only the eluted metal ions from the battery constituent material can be effectively adsorbed.
Examples of the metal element having an electronegativity smaller than that of manganese include Nb, Ta, Ti, Zr, Hf, Sc, Y, lanthanoid, Be, Mg, Ca, Sr, and Ba.

  Here, the electronegativity means that defined by Pauling's electronegativity.

In a nonaqueous electrolyte battery, 0.035 parts by mass in a 23 ° C. atmosphere with respect to 100 parts by mass of a mixed solution of 5 ppm of Mn ²⁺ ions, 1 mol / L LiPF ₆ and cyclic and / or chain carbonate. It is preferable to include inorganic particles for non-aqueous electrolyte batteries that have an Mn ²⁺ ion adsorption rate of 5% or more when immersed for 6 hours.

The adsorption rate of Mn ²⁺ ions is the difference between the initial Mn concentration in the mixed solution and the Mn concentration in the filtrate obtained by filtering the inorganic particles for nonaqueous electrolyte batteries in the mixed solution after the above-mentioned conditions and filtering. This value is obtained by dividing by the initial Mn concentration and multiplying by 100.

The structure of the nonaqueous electrolyte battery having excellent life characteristics or safety is extremely small (for example, on the order of ppm) even in the situation where Li ions are excessively present, such as the inorganic particles for nonaqueous electrolyte batteries described above. It is specified by including inorganic particles for a non-aqueous electrolyte battery that can selectively adsorb ⁽ concentration) Mn ²⁺ ions in the battery.

When 0.035 parts by mass is immersed for 6 hours in an atmosphere of 23 ° C. with respect to 100 parts by mass of a mixed solution of 5 ppm of Mn ²⁺ ions, 1 mol / L LiPF ₆ and cyclic and / or chain carbonate. Examples of inorganic particles for nonaqueous electrolyte batteries having an Mn ²⁺ adsorption rate of 5% or more include Nb, Ta, Ti, Zr, Hf, Sc, Y, lanthanoids, Be, Mg, Ca, Sr, and Ba. A material containing an element such as Among these, calcium silicate hydrate or zirconium phosphate is particularly preferable.

  The cyclic and / or chain carbonate is as described as a non-aqueous solvent used in the non-aqueous electrolyte described later.

The liquid mixture for measuring the adsorption rate of Mn ²⁺ ions is such that LiPF ₆ is 1 mol / L in a mixed solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) are mixed at a volume ratio of 1: 2. It is preferably formed by dissolving manganese trifluoromethanesulfonate [Mn (CF ₃ SO ₃ ) ₂ ] so that the Mn concentration is 5 ppm.

The conditions for measuring the adsorption rate of Mn ²⁺ ions of the inorganic particles for nonaqueous electrolyte batteries will be described in detail in Examples.

  In addition, it is more preferable that the inorganic particles for nonaqueous electrolyte batteries can remove hydrogen fluoride (HF), which is a decomposition product of the nonaqueous electrolyte. By effectively removing HF, elution of metal from battery constituent materials such as a positive electrode active material and current collector foil by HF can be suppressed. In order for the adsorbent to effectively remove HF, among the metal elements having an electronegativity smaller than that of manganese, an element that forms a stable fluoride is more preferable. Specific elements include Ti, Zr, and Hf. , Sc, Y, lanthanides, Be, Mg, Ca, Sr, and Ba.

  In order to stably adsorb metal ions and remove HF in the electrolytic solution, the non-aqueous electrolyte battery inorganic particles preferably contain an oxygen atom in the crystal structure, more than manganese contained in the crystal structure. More preferably, a metal element having a low electronegativity is bonded to an oxygen atom.

From such a point of view, 8 parts by mass of inorganic particles in an atmosphere of 23 ° C. is 5 parts by mass with respect to 100 parts by mass of a mixture of 800 ppm of HF, 1 mol / L LiPF ₆ and cyclic and / or chain carbonate. When immersed for a minute, the HF concentration in the mixed solution is preferably reduced by 10% or more.

The cyclic and / or chain carbonate is as described as a non-aqueous solvent used in the non-aqueous electrolyte described later. The liquid mixture used for the measurement of the HF concentration was prepared by dissolving LiPF ₆ at 1 mol / L in a mixed solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 1: 2. In addition, it is preferable to form the HF by dissolving the HF so as to have a concentration of 800 ppm. The conditions for measuring the HF concentration when the inorganic particles for nonaqueous electrolyte batteries are immersed in the mixed solution will be described in detail in Examples.

  The element having an electronegativity lower than that of manganese is preferably contained in a molar ratio of 0.2 to 0.8 with respect to 1 mol of inorganic particles. The lower limit is more preferably 0.25 or more, and still more preferably 0.3 or more. The upper limit is preferably 0.75 or less, and more preferably 0.7 or less.

The inorganic particles for a non-aqueous electrolyte battery are preferably non-metallic, that is, a semiconductor or an insulator. In particular, the electrical resistivity is preferably 10 ³ Ω · m or more. A semiconductor or insulator having an electrical resistivity of 10 ³ Ω · m or more is preferable because it does not deteriorate charge / discharge characteristics or safety in the battery.

  Moreover, it is preferable that it is 0.05 micrometer-4.0 micrometers about the average secondary particle diameter (D50) of the inorganic particle for nonaqueous electrolyte batteries. The lower limit is more preferably 0.1 μm or more, and further preferably 0.2 μm or more. Further, the upper limit is more preferably 3.5 μm or less, and further preferably 3.0 μm or less. When the average secondary particle diameter is adjusted within the above range, the energy density of the nonaqueous electrolyte battery tends to increase. In addition, although it does not restrict | limit especially about a primary particle diameter, 10 nm-2.0 micrometers are preferable.

  The inorganic particles for non-aqueous electrolyte battery preferably have a swelling power of 10 ml / 2 g or less when brought into contact with water. Swelling force is evaluated as an undisturbed sedimentation volume occupied by 2 g of sample in 100 ml of purified water. When the swelling force is 10 ml / 2 g or less, the inorganic particles for non-aqueous electrolyte batteries can be used without absorbing and swelling the water or electrolyte present in the battery and causing deterioration in battery characteristics. .

  The method for controlling the average secondary particle diameter (D50) of the inorganic particles for nonaqueous electrolyte batteries within the range of 0.05 μm to 4.0 μm is not particularly limited, but a conventionally known method such as an axial flow mill Method, an annular mill method, a roll mill method, a ball mill method, a jet mill method, a container rotary compression shearing mill method, a method of pulverizing with a porcelain mortar, and the like.

  The shape of the inorganic particles for a non-aqueous electrolyte battery may be spherical, plate-like, or needle-like, and is preferably plate-like or needle-like, but the aspect ratio does not matter.

The BET specific surface area of the inorganic particles for non-aqueous electrolyte batteries is preferably 3 m ² / g or more. When the BET specific surface area is 3 m ² / g or more, the life characteristics or safety of the nonaqueous electrolyte battery can be further improved. The BET specific surface area is more preferably 3 m ² / g or more and 200 m ² / g or less. When the BET specific surface area exceeds 200 m ² / g, gas is generated and the battery tends to swell. The BET specific surface area is further preferably 30 m ² / g or less, more preferably 20 m ² / g or less, and particularly preferably 15 m ² / g or less. By controlling the BET specific surface area within the above range, swelling can be further suppressed, and the life characteristics or safety of the nonaqueous electrolyte battery can be further improved.

  Inorganic particles for nonaqueous electrolyte batteries must have a certain level of hardness so that they do not deform or crush due to external force such as battery compression in order to exhibit stable adsorption performance when used as a material for nonaqueous electrolyte batteries. is there. From the above viewpoint, the Mohs hardness of the inorganic particles for nonaqueous electrolyte batteries is preferably more than 1.

  Specific inorganic particles for non-aqueous electrolyte batteries that can be used as an adsorbent, that is, a metal element having an electronegativity smaller than that of manganese in the crystal structure, and an interlayer distance of 0.40 nm to 2.0 nm The non-metallic layered compound having an exchangeable cation between layers is not particularly limited. For example, a material that selectively adsorbs a trace amount of metal ions other than lithium ions, such as hydrogen fluoride (HF) A material having an adsorbing ability is preferable, and more specifically, calcium silicate hydrate, zirconium phosphate, titanium phosphate, titanate, niobate, niobium titanate, and the like can be given.

  The inorganic particles for non-aqueous electrolyte batteries described above may be used alone or in combination of two or more.

The inorganic particles for nonaqueous electrolyte batteries described above are more preferably chemically modified on the surface in order to improve the characteristics of the nonaqueous electrolyte battery. When surface modification is carried out, the lipophilicity of the surface can be changed and the adsorption of metal ions can be enhanced. Moreover, since the adhesiveness of moisture is also changed, not only can the life characteristics or safety of the nonaqueous electrolyte battery be improved, but also swelling due to gas generation can be suppressed.
Although it does not specifically limit as a surface modification method, For example, the method of coat | covering the surface of an inorganic particle with an inorganic compound, an organic compound, etc., the method of immersing in liquids, such as water and an organic solvent, the method of heat processing, etc. are mentioned.

As the coupling agent, for example, a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, a phosphonic acid coupling agent, or the like can be used, and these coupling agents are combined. May be used. When a silane coupling agent is used, a surface treatment layer is formed of a compound containing silicon (Si) on the surface of the inorganic particles. When an aluminate coupling agent is used, a surface treatment layer is formed of a compound containing aluminum (Al) on the surface of the inorganic particles. When a titanate coupling agent or the like is used, a surface treatment layer is formed of a compound containing titanium (Ti) on the surface of the inorganic particles. When a phosphonic acid coupling agent or the like is used, a surface treatment layer is formed on the surface of the inorganic particles with a compound containing phosphorus (P). The surface modification with a coupling agent can be appropriately performed according to a known treatment method. For example, as the surface modification with a silane coupling agent, a direct treatment method (dry and / or wet), an integral blend method, There are primer-type treatment methods. In addition, inorganic particles having a surface modified from commercially available powder products may be appropriately selected and used. The same surface treatment is possible when an aluminate coupling agent, titanate coupling agent, phosphonic acid coupling agent, or the like is used as a coupling agent other than the silane coupling agent. In addition, the inorganic particles for non-aqueous electrolyte batteries may be subjected to a surface treatment such as a resin surface treatment with a silicone-modified resin, a fluorine-modified resin, a modified polyethylene resin, a silica treatment, a SiO ₂ -Al ₂ O ₃ treatment, or the like. The same effect as a coupling agent is provided. Among these, from the viewpoint of increasing the affinity with the non-aqueous electrolyte, increasing the adsorption of metal ions, and improving the life characteristics or safety of the non-aqueous electrolyte battery more effectively, the coupling agent is used for inorganic particles. It is more preferable to modify the surface.

<Silane coupling agent>
The silane coupling agent is not particularly limited, but a vinyl silane coupling agent, an alkyl silane coupling agent, an epoxy silane coupling agent, a styryl silane coupling agent, a (meth) acryloxy silane coupling agent. , Amino silane coupling agents, ureido silane coupling agents, chloropropyl silane coupling agents, polysulfide silane coupling agents, isocyanate silane coupling agents, mercapto silane coupling agents, triazine silane coupling agents And at least one selected from the group consisting of an epoxy silane coupling agent, an amino silane coupling agent, and a (meth) acryloxy silane coupling agent. It is preferably a compound. A silane coupling agent can be used individually by 1 type or in mixture of 2 or more types.

  As such a silane coupling agent, what was manufactured by the conventionally well-known method may be used, or a commercial item may be used.

<Titanate coupling agent>
Examples of the titanate coupling agent include titanium tetraisopropoxide, titanium tetranormal butoxide, butyl titanate dimer, titanium tetra-2-ethylhexoxide, titanium dioctyloxybis (octylene glycolate), tetramethyl titanate, titanium. Acetylacetonate, titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium diisopropoxybis (ethylacetoacetate), titanium ethylacetoacetate, titanium octanediolate, titanium diisopropoxybis (triethanol) Aminate), titanium triethanolamate, titanium lactate ammonium salt, titanium lactate, polyhydroxytitanium stearate and the like. 38S, KR44, KR46B, KR55, KR9SA, KRTTS, KR41B, KR138S, KR238S, KR338X (all manufactured by Ajinomoto Fine-Techno Co.), and the like.

  As such a titanate coupling agent, what was manufactured by the conventionally well-known method may be used, or a commercial item may be used.

<Aluminate coupling agent>
Examples of the aluminate coupling agent include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum diisopropylene. Propoxymonooleyl acetoacetate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate), aluminum monoisopropoxymonooleoxyethyl acetoacetate, cyclic aluminum oxide isopropylate, cyclic aluminum oxide octylate, cyclic Aluminum oxide stearate , PLENACT AL-M (manufactured by alkyl acetoacetate aluminum diisopropylate (Ajinomoto Fine-Techno Co.), and the like.

  As such an aluminate coupling agent, what was manufactured by the conventionally well-known method may be used, or a commercial item may be used.

<Phosphonic acid coupling agent>
Specific examples of the phosphonic acid coupling agent include butylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, decylphosphonic acid, tetradecylphosphonic acid, hexadecylphosphonic acid, octadecylphosphonic acid, 6-phosphonohexanoic acid, 11 -Acetylmercaptoundecylphosphonic acid, 11-hydroxyundecylphosphonic acid, 11-mercaptoundecylphosphonic acid, 1H, 1H, 2H, 2H-perfluorooctanephosphonic acid, 11-phosphonoundecylphosphonic acid, 16-phosphono Hexadecanoic acid, 1,8-octanediphosphonic acid, 1,10-decyldiphosphonic acid, 1,12-dodecyldiphosphonic acid, benzylphosphonic acid, 4-fluorobenzylphosphonic acid, 2,3,4,5,6 -Pentafluorobenzylphosphonic acid, 4-nitrate Benzyl phosphonic acid, 12 pentafluorophenoxy dodecyl phosphonic acid, and (12 Hosuhonododeshiru) phosphonate, 16 phosphonomethylglycine hexadecanoic acid, 11-phosphono undecanoic acid. In addition, compounds such as [2- [2- (2-methoxyethoxy) ethoxy] ethyl] phosphonic acid can also be applied to the target surface.

  As such a phosphonic acid coupling agent, what was manufactured by the conventionally well-known method may be used, or a commercial item may be used.

<Silicone-modified resin>
The silicone-modified resin is not particularly limited and can be appropriately selected depending on the purpose. For example, silicone-modified polyimide, silicone-modified polyamideimide, silicone-modified polyamide, silicone-modified polycarbonate, silicone-modified acrylic, silicone-modified epoxy, Examples include silicone-modified urethane, silicone-modified polyester, silicone-modified olefin, silicone-modified vinyl, and silicone-modified phenoxy.

<Fluorine-modified resin>
The fluorine-modified resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer (ETFE), and polychlorotrifluoroethylene. (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene chlorotrifluoroethylene (ECTFE), polyvinyl fluoride ether (PFVE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), Examples thereof include tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) and tetrafluoroethylene / hexafluoropropylene copolymer (FEP). These may be used individually by 1 type and may use 2 or more types together.

<Modified polyolefin>
Examples of the modified polyolefin include maleic anhydride-modified propylene polymer and its chloride, maleic anhydride-modified ethylene-propylene copolymer and its chlorinated product, maleic anhydride-modified propylene-butene copolymer and its chloride, anhydrous Maleic acid-modified ethylene-propylene-butene copolymer and its chloride, acrylic acid-modified propylene polymer and its chloride, acrylic acid-modified ethylene-propylene copolymer and its chloride, acrylic acid-modified propylene-butene copolymer Examples thereof include a coalescence and a chloride thereof.

[Hydrophilic parameter A]
The inorganic particles for nonaqueous electrolyte batteries and the inorganic particles for nonaqueous electrolyte batteries subjected to surface treatment of the present embodiment are represented by the following formula:
Hydrophilic parameter A = BET1 / BET2
{In the formula, BET1 means the specific surface area of an inorganic particle calculated from the adsorption isotherm measured by adsorbing water vapor to the inorganic particle, and BET2 adsorbs nitrogen to the inorganic particle. It means the specific surface area of the inorganic particles calculated from the adsorption isotherm measured using the BET method. }
Is preferably greater than 0.65 and not greater than 2.0. The hydrophilicity parameter A is more preferably larger than 0.65 and not larger than 1.8, further preferably larger than 0.65 and not larger than 1.6. When the hydrophilic parameter A is larger than 0.65 and not larger than 2.0, the adsorption performance of metal ions as described above can be obtained.

  BET1 is a value reflecting the amount of chemical adsorption of water on the inorganic particles. Specifically, water vapor is adsorbed on the inorganic particles by supplying water vapor to the inorganic particles while changing the partial pressure at a predetermined temperature. By measuring the amount of water vapor adsorbed on the inorganic particles during this operation, an adsorption isotherm is obtained. The adsorption isotherm is considered to reflect the amount of water chemically adsorbed to the inorganic particles, and is considered to contain information on the hydrophilicity of the inorganic particles.

  BET2 is the BET specific surface area of inorganic particles measured by a commonly used nitrogen adsorption method. Specifically, nitrogen is adsorbed on the inorganic particles by supplying nitrogen to the inorganic particles at a predetermined temperature while changing the partial pressure thereof. An adsorption isotherm is obtained by measuring the amount of nitrogen adsorbed on the inorganic particles during this operation.

  By dividing BET1 by BET2, a value reflecting the amount of chemical adsorption of water per unit specific surface area of inorganic particles can be obtained. The larger the value of the hydrophilicity parameter A, the higher the hydrophilicity of the inorganic particle surface.

  The inorganic particles of the present embodiment are included in the inorganic particles for nonaqueous electrolyte batteries and the inorganic particles for nonaqueous electrolyte batteries subjected to surface treatment, and the hydrophilic parameter A (= BET1 / BET2) is larger than 0.65 and 2 The material is not limited as long as it satisfies 0.0 or less. When the value of the hydrophilic parameter A (= BET1 / BET2) is larger than the lower limit (0.65), the inorganic particles exhibit a good interaction with the metal ions, and the metal ions are effectively effective on the surface of the particles. Can be adsorbed. Further, when the hydrophilic parameter A is not more than the upper limit (2.0), swelling of the battery can be suppressed.

  There is no particular method for controlling the hydrophilic parameter A within the above range. By controlling the number of hydrophilic groups in the inorganic particles, particularly the number of surface hydroxyl groups, the above-mentioned value can be generally controlled. That is, a substance that is below the lower limit in the above range can be contained in the above range by, for example, grinding in a state of contact with water. Moreover, about a substance exceeding the upper limit in said range, it can carry out by reducing a hydroxyl group by performing surface treatments, such as a coupling agent shown above. Further, for example, when inorganic particles are treated at a high temperature of 800 ° C. or higher, surface hydroxyl groups can be reduced.

[Adsorbent]
Inorganic particles for nonaqueous electrolyte batteries used as adsorbents are more effectively present in nonaqueous electrolyte batteries at any position between the positive electrode and the negative electrode including the outer package, the positive electrode, the negative electrode, and the separator. The adverse effect of the eluted metal ions can be reduced. Therefore, the adsorbent containing inorganic particles for nonaqueous electrolyte batteries is preferably contained in the positive electrode, the negative electrode, and the separator, and since it is excellent in versatility in the manufacturing process of the nonaqueous electrolyte battery, it may be contained in the separator. More preferred.

  Among the inorganic particles for nonaqueous electrolyte batteries listed above, the nonaqueous electrolyte battery contains calcium silicate hydrate or zirconium phosphate in the battery from the viewpoint of further improving the life characteristics or safety. It is more preferable.

  Moreover, as for a nonaqueous electrolyte battery, it is more preferable that at least one of a positive electrode, a negative electrode, a nonaqueous electrolyte, a separator, and an exterior body contains the inorganic particle for nonaqueous electrolyte batteries as an adsorbent or an adsorption layer.

  The inorganic particles for a nonaqueous electrolyte battery may be contained in only one of these battery constituent materials, or may be contained in two or more.

[Calcium silicate hydrate]
Calcium silicate hydrate is a group of materials called CaO—SiO ₂ —H ₂ O based compounds.

  About 25 kinds of calcium silicate hydrates are known as crystalline, including a high-temperature phase. More preferably, the calcium silicate hydrate has a layered structure. Specific examples include calcium silicate hydrates such as tobermorite and gyrolite.

Examples of the tobermorite system include tobermorite (9%, 11%, 14%, etc.), takaranite, prombierite, low crystalline calcium silicate hydrate (hereinafter referred to as “CSH”), which is also known as a tobermorite precursor, and the like. Examples of the gyrolite include gyrolite, trusscotite, Z-phase generated as an intermediate phase during the synthesis of gyrolite, etc. Among these, the layered calcium silicate hydrate includes tobermorite. A system is preferred.
The fact that calcium silicate hydrate is a tobermorite system can be identified from the fact that a diffraction peak of (220) plane is shown at 28 to 30 ° (2θ) in a powder X-ray diffraction pattern.

  Of the tobermorite systems, those having low interlayer distance order (low crystallinity) are more preferable. Such layered calcium silicate hydrate is not particularly limited, and examples thereof include low crystalline calcium silicate hydrate (CSH). CSH is a diffraction pattern of powder X-ray diffraction and shows a relatively broad diffraction peak in the vicinity of 29.1 to 29.6 ° (2θ), so the presence or absence can be identified. The reason why layered calcium silicate hydrate with low ordering of interlayer distance (low crystallinity) such as CSH can reduce the adverse effects of the aforementioned metal ions is not clear, but the interlayer distance has a certain distribution. This is presumed to act on various types of metal ions. Interlayer distance order (crystallinity) appears, for example, as the intensity of a diffraction peak derived from the (002) plane in powder X-ray diffraction. More specifically, the higher the order of the interlayer distance (the higher the crystallinity), the clearer the diffraction peak. That is, in the layered calcium silicate hydrate, it is more preferable that the diffraction peak derived from the (002) plane appearing at 6 to 9 ° (2θ) is more unclear in powder X-ray diffraction.

  More specifically, in powder X-ray diffraction, the diffraction peak of (002) plane appearing at 6-9 ° (2θ) with respect to the diffraction peak intensity I (220) of (220) plane appearing at 28-30 ° (2θ). The ratio I (002) ratio [I (002) / I (220)] is preferably 1 or less, more preferably 0.5 or less, and still more preferably 0.35 or less. By setting the ratio [I (002) / I (220)] of the diffraction peak intensity I (002) of the (002) plane to the diffraction peak intensity I (220) to such values, the lifetime of the nonaqueous electrolyte battery Properties or safety tend to be better.

  In addition, calcium silicate hydrate has water molecules in the crystal. The weight ratio of water molecules contained in the crystal is, for example, a thermal analysis method, specifically TG-DTA (simultaneous measurement of differential heat and thermogravimetry), and the water content is about 100 ° C to 300 ° C. It can be measured from the weight loss of water molecules as well as the endothermic peak at the time of inclusion. However, as long as the interlayer distance is not less than 0.40 nm and not more than 2.0 nm, the function as an adsorbent is not affected at all, so the content of water molecules present in the crystal of calcium silicate is not questioned. Examples of the dehydration method include dehydration by a solvent or dehydration by heat treatment. Further, the adsorption site of calcium silicate hydrate vacated by dehydration may be substituted with organic molecules or metal ions.

  In calcium silicate hydrate, a part of the Ca or Si element may be substituted with another element. The substitution element is not particularly limited. For example, in the tobermorite system, a part of Si element can be substituted with Al element, and Na, K element, etc. can be simultaneously introduced for charge compensation. In this case, it is preferable to use a powder X-ray diffraction pattern in which a (220) plane diffraction peak appears at 28 to 30 ° (2θ).

  The amount of substitution with other elements is preferably 40 mol% or less based on the total amount of Si and Al elements before substitution in order to maintain the crystal structure.

  The average secondary particle diameter (D50) of calcium silicate hydrate is preferably 0.05 μm to 4.0 μm, more preferably 0.1 μm to 3.5 μm, and 0.2 μm. More preferably, it is -3.5 micrometers. When the average secondary particle diameter is adjusted within the above range, the energy density of the nonaqueous electrolyte battery tends to increase. In addition, although it does not restrict | limit especially about a primary particle diameter, 10 nm-2.0 micrometers are preferable.

  The method for controlling the average secondary particle diameter (D50) of calcium silicate hydrate within the above range is not particularly limited, but conventionally known methods such as an axial flow mill method, an annular mill method, a roll mill Method, ball mill method, jet mill method, container rotary compression shear type mill method, method of pulverizing in a porcelain mortar, and the like.

The calcium silicate hydrate is not particularly limited, but may be post-treated by a method such as acid or alkali treatment.
The calcium silicate hydrate is not particularly limited, but may contain other components. The content of other components may be in the range of 0 to 50%. The other components are not particularly limited as long as the chemical structure or crystal structure of calcium silicate hydrate is maintained. For example, a desiccant such as silica gel may be included for humidity control.

The calcium silicate hydrate preferably has a BET specific surface area (BET2 described above) of 10 m ² / g or more. When the BET specific surface area is 10 m ² / g or more, the life characteristics or safety of the nonaqueous electrolyte battery can be further improved. The BET specific surface area is more preferably 10 m ² / g or more and 200 m ² / g or less. When the BET specific surface area exceeds 200 m ² / g, gas is generated and the battery tends to swell.

  The method for producing calcium silicate hydrate is not particularly limited and may be a conventionally known method. For example, after dispersing a siliceous raw material and a calcareous raw material in water, curing is performed under high temperature and high pressure conditions. Hydrothermal synthesis technology.

The siliceous raw materials, the content of SiO ₂ therein refers to 50 mass% or more ingredients. For example, crystalline quartzite, quartz sand, rocks having a high quartz content, or natural clay minerals such as diatomaceous earth, silica fume, fly ash, kaolin clay, and montmorillonite clay, or a fired product thereof. An aqueous silicic acid solution such as water glass can also be used as the siliceous material.

  The calcareous raw material is a raw material containing 50 mass% or more of CaO in terms of oxide, and refers to quick lime, slaked lime, and the like. Furthermore, high purity nitrates, sulfates, acetates, chlorides and the like containing calcium can also be used as calcareous raw materials. In addition to these, cements mainly composed of calcium components, that is, ordinary Portland cement, early-strength Portland cement, belite cement, various alumina cements, and the like can also be used as the calcareous raw material.

  When synthesizing crystalline layered calcium silicate hydrates such as tobermorite and gyrolite, curing under saturated steam at 150 ° C to 250 ° C, that is, curing using an autoclave as hydrothermal synthesis conditions. Available. The synthesis temperature for synthesizing the low crystalline calcium silicate hydrate (CSH) is preferably 150 ° C. or less, more preferably 100 ° C. or less, and still more preferably around room temperature.

  In general, it has been reported that CSH is a main component of a hardened cement obtained by hydrating Portland cement or the like. That is, a hydrate obtained by hydrating cement as CSH can be used as calcium silicate hydrate. In this case, the fully hydrated cured product can be pulverized by the method described above, and the pulverized product can be used as it is.

Next, the Ca / Si element ratio (hereinafter simply referred to as “C / S ratio”) of the siliceous raw material (SiO ₂ ) of calcium silicate hydrate and the calcareous raw material (CaO) will be described.
The C / S ratio of calcium silicate hydrate is preferably 0.3 or more and 2.0 or less. When the C / S ratio is 0.3 or more, the life characteristics or safety of the nonaqueous electrolyte battery tends to be further improved. Moreover, since it becomes difficult to form a layered structure when the C / S ratio exceeds 2.0, the adsorption ability that excludes the adverse effects of eluted metal ions tends to decrease. The C / S ratio is more preferably 0.6 or more and 2.0 or less.
The C / S ratio of calcium silicate hydrate can be measured by performing general elemental analysis, for example, ICP emission spectroscopic analysis after decomposition with an acid such as nitric acid.

  The calcium silicate hydrate described above may be used alone or in combination of two or more.

  In addition, in nonaqueous electrolyte batteries, calcium silicate hydrate is present at any position between the positive electrode and the negative electrode including the positive electrode, the negative electrode, and the separator, thereby reducing the adverse effects of the precipitated metal ions more effectively. it can. Therefore, the calcium silicate hydrate is preferably contained in the positive electrode, the negative electrode, and the separator, and is more preferably contained in the separator because of excellent versatility in the manufacturing process of the nonaqueous electrolyte battery.

[Zirconium phosphate]
Zirconium phosphate includes crystalline, amorphous, layered structures and network structures. Among these, Zr ₂ (HPO ₄ ) ₂ .nH ₂ O, which is a layered zirconium phosphate having a layered structure, is preferable among them because of its excellent metal adsorption ability and HF removal ability.

  Zirconium phosphate may substitute a part of Zr element, a part of P element, a part and / or whole of H element with another element. The substitution element is not particularly limited as long as the interlayer distance is not less than 0.40 nm and not more than 2.0 nm and exchangeable cations are held between the layers. For example, some Zr elements are substituted with Hf elements. be able to. By substituting some of the Zr elements with Hf elements, the metal adsorption capacity can be further increased. Further, a part and / or all of the H element can be replaced with an alkali metal such as Li ion, a monovalent cation such as ammonium ion and oxonium ion. By replacing the H element with Li ions, the life characteristics or safety of the nonaqueous electrolyte battery can be further improved.

  Zirconium phosphate has water molecules in the crystal. The weight ratio of water molecules contained in the crystal is, for example, a thermal analysis method, specifically TG-DTA (simultaneous measurement of differential heat and thermogravimetry), and the water content is about 100 ° C to 300 ° C. It can be measured from the weight loss of water molecules as well as the endothermic peak at the time of inclusion. However, as long as the interlayer distance is not less than 0.40 nm and not more than 2.0 nm, the function as an adsorbent is not affected at all, so the content of water molecules present in the crystal of zirconium phosphate is not questioned. Examples of the dehydration method include dehydration by a solvent or dehydration by heat treatment. Moreover, the adsorption site of zirconium phosphate vacated by dehydration may be substituted with organic molecules or metal ions.

  The production method of zirconium phosphate is not particularly limited and may be a conventionally known method. For example, a wet method in which raw materials are mixed in water and then heated under normal pressure to produce the product, in a state containing water or water And a hydrothermal method in which the raw materials are mixed and then pressurized and humidified.

  Specifically, the wet method is produced by mixing an aqueous solution containing a zirconium compound and an aqueous solution containing phosphoric acid and / or a salt thereof to form a precipitate, followed by aging.

In the production process, an oxalic acid compound may be added as desired. By adding the oxalic acid compound, it can be produced more quickly and efficiently.
The aging may be performed at room temperature, but is preferably performed at a wet atmospheric pressure of 90 ° C. or higher in order to accelerate the aging, and is performed under hydrothermal conditions that are conditions exceeding 100 ° C. in a pressure atmosphere higher than normal pressure. Also good. When producing layered zirconium phosphate under hydrothermal conditions, it is preferable to carry out at 130 ° C. or less from the viewpoint of production cost.

  The time for producing zirconium phosphate is not particularly limited as long as the layered structure is obtained. For example, phosphoric acid and / or a salt thereof and a zirconium compound are mixed to cause precipitation, and then ripened to obtain zirconium phosphate. The aging time varies depending on the temperature. In the case of 90 ° C., 4 hours or more is preferable. The aging time is preferably within 24 hours from the viewpoint of productivity.

  The produced zirconium phosphate is further filtered, washed well with water, dried and pulverized to obtain fine-grained zirconium phosphate.

  Zirconium compounds that can be used as a raw material for the synthesis of zirconium phosphate include zirconium nitrate, zirconium acetate, zirconium sulfate, zirconium carbonate, basic zirconium sulfate, zirconium oxysulfate, and zirconium oxychloride. Zirconium nitrate, zirconium acetate, Zirconium sulfate and zirconium carbonate are preferable, and zirconium oxychloride is more preferable in consideration of reactivity and economy.

  Examples of phosphoric acid or phosphate that can be used as a raw material for synthesizing layered zirconium phosphate include phosphoric acid, sodium phosphate, potassium phosphate, and ammonium phosphate. Phosphoric acid is preferable, and 75% to 75% by mass concentration. It is more preferable that the concentration is about 85% phosphoric acid.

  Examples of the oxalic acid compound that can be used as a raw material for synthesizing zirconium phosphate include oxalic acid dihydrate, ammonium oxalate, and ammonium hydrogen oxalate, and oxalic acid dihydrate is more preferable.

The blending ratio of various synthetic raw materials for zirconium phosphate is described below.
The mixing ratio of phosphoric acid or phosphate is preferably a molar ratio of charging to the zirconium compound, preferably 2 to 3, and more preferably 2.1 to 2.6. By using this ratio, layered zirconium phosphate is produced with high yield.

  The mixing ratio of oxalic acid is a molar ratio with respect to the zirconium compound, preferably 2.5 to 3.5, and more preferably 2.8 to 3.0. By making this ratio, the production of zirconium phosphate becomes easy.

  The solid content concentration in the reaction slurry when producing zirconium phosphate is preferably 3% by mass or more, and more preferably 7% to 15% in consideration of production costs.

The average secondary particle diameter (D50) of zirconium phosphate is preferably 0.05 μm to 4.0 μm, more preferably 0.1 μm to 3.5 μm, and 0.2 μm to 3. More preferably, it is 0 μm. When the average secondary particle diameter (D50) is adjusted within the above range, the energy density of the nonaqueous electrolyte battery tends to increase.
The method for controlling the average secondary particle diameter of zirconium phosphate within the above range is not particularly limited, but the above-described method for controlling the average secondary particle diameter of calcium silicate hydrate can be similarly applied.

  Moreover, although zirconium phosphate is not specifically limited, it may be post-treated by a method such as acid or alkali treatment.

  Further, zirconium phosphate is not particularly limited, but may contain other components. The content of other components may be in the range of 0 to 50%. The other components are not particularly limited as long as the chemical structure or crystal structure of the layered zirconium phosphate is maintained. For example, a desiccant such as silica gel may be included for humidity control.

It is preferable that the BET specific surface area (BET2 explained above) of zirconium phosphate is 3 m ² / g or more. When the BET specific surface area is 3 m ² / g or more, the life characteristics or safety of the nonaqueous electrolyte battery can be further improved. The BET specific surface area is more preferably 10 m ² / g or more and 200 m ² / g or less. When the BET specific surface area exceeds 200 m ² / g, gas is generated and the battery tends to swell.

[Second inorganic particles]
It is preferable that the layer containing the first inorganic particles, which are inorganic particles for a nonaqueous electrolyte battery, further contains second inorganic particles. The inorganic particles for a non-aqueous electrolyte battery can adsorb metal in the battery, extend the life of the non-aqueous electrolyte battery, and improve safety. However, when the particles are agglomerated, the contact area with the electrolytic solution decreases, making it difficult to exhibit good metal adsorption characteristics. In order to prevent this, it is preferable to mix the second inorganic particles with non-aqueous electrolyte inorganic particles. By mixing the second inorganic particles with the inorganic particles for non-aqueous electrolyte, it is possible to prevent aggregation of inorganic particles for non-aqueous electrolyte battery, maximize adsorption characteristics, and develop good metal adsorption characteristics Become.
The second inorganic particles are preferably non-metallic, that is, a semiconductor or an insulator. In particular, the electrical resistivity is preferably 10 ³ Ω · m or more. A semiconductor or insulator having an electrical resistivity of 10 ³ Ω · m or more is preferable because it does not impair charge / discharge characteristics or safety in the battery.

  From the viewpoint of improving the dispersibility of the first inorganic particles in the mixture of the first inorganic particles and the second inorganic particles containing the layered compound described above, the second inorganic particles obtained by SEM observation Is larger than the average particle size of the first inorganic particles obtained by SEM observation.

In this specification, the average particle diameter of the inorganic particles is the sum of the lengths of the shortest line segments traversing through the center of the individual particle image in the scanning electron microscope (SEM) observation of n inorganic particles. The average thickness obtained by dividing by. The average particle diameter of the inorganic particles is, for example, 20 in SEM observation of a dry powder of inorganic particles or SEM observation of a cross section of a coating layer obtained by applying a dispersion liquid containing inorganic particles to a separator and drying. It is calculated by measuring the thickness of the inorganic particles and dividing the total thickness by 20.
In the present specification, “average particle size of inorganic particles” obtained by SEM observation is distinguished from “average secondary particle size (D50) of inorganic particles” obtained by measuring the particle size distribution of the inorganic particle-containing dispersion. Is.

  From the viewpoint of dispersibility of the first inorganic particles, the shape of the second inorganic particles is preferably a plate shape. From the same viewpoint, for the mixture containing the first inorganic particles and the second inorganic particles, the average particle diameter of the first inorganic particles corresponding to the layered compound is 0.01 μm or more and 2 μm or less, and the second The average particle size of the inorganic particles is preferably 0.1 μm or more and 3 μm or less, the average particle size of the first inorganic particles is 0.02 μm or more and 1 μm or less, and the average particle size of the second inorganic particles Is more preferably 0.5 μm or more and 2 μm or less.

  Moreover, it is preferable that it is 0.1 micrometer-5.0 micrometers about the average secondary particle diameter (D50) of a 2nd inorganic particle. The lower limit is more preferably 0.2 μm or more, and further preferably 0.3 μm or more. Further, the upper limit thereof is more preferably 4.5 μm or less, and further preferably 4.0 μm or less. When the average secondary particle diameter (D50) is adjusted within the above range, the energy density of the nonaqueous electrolyte battery tends to increase. In addition, although it does not restrict | limit in particular about a primary particle diameter, 10 nm-3.0 micrometers are preferable.

  The method for controlling the average secondary particle diameter (D50) of the second inorganic particles within the range of 0.1 μm to 5.0 μm is not particularly limited, but conventionally known methods such as an axial flow mill method, Examples thereof include an annular mill method, a roll mill method, a ball mill method, a jet mill method, a container rotary compression shearing mill method, and a method of pulverizing with a porcelain mortar.

  The shape of the second inorganic particles may be a plate shape, a scale shape, a needle shape, a columnar shape, a spherical shape, a polyhedral shape, a lump shape, or the like. From the viewpoint of dispersibility of the first inorganic particles that are inorganic particles for nonaqueous electrolyte batteries, the second inorganic particles are preferably plate-shaped or needle-shaped, but the aspect ratio is not a problem.

The BET specific surface area (BET2 described above) of the second inorganic particles is preferably 0.1 m ² / g or more. When the BET specific surface area is 0.1 m ² / g or more, the dispersibility of the first inorganic particles can be further improved. The BET specific surface area is more preferably 1 m ² / g or more and 20 m ² / g or less. When the BET specific surface area exceeds 20 m ² / g, gas is generated and the battery tends to swell.

  The 2nd inorganic particle demonstrated above may be used individually by 1 type, and may use 2 or more types together.

The second inorganic particles are preferably layered double hydroxides (Mg—Al type, Mg—Fe type, Ni—Fe type, Li—Al type), layered double hydroxide-alumina silica gel composite, boehmite, Anion adsorbents such as alumina, zinc oxide, lead oxide, iron oxide, iron oxyhydroxide, hematite, bismuth oxide, tin oxide, titanium oxide, zirconium oxide, cation adsorbents such as hydroxyapatite, zeolite, calcium sulfate, Carbonate and sulfate such as magnesium sulfate, aluminum sulfate, gypsum, barium sulfate, alumina trihydrate (ATH), fumed silica, precipitated silica, zirconia, yttria and other oxide ceramics, silicon nitride, titanium nitride, Nitride ceramics such as boron nitride, magnesium hydroxide, silicon carbide , Talc, dickite, nacrite, halloysite, pyrophyllite, montmorillonite, sericite, amesite, bentonite and other layered silicates, asbestos, diatomaceous earth, glass fiber, synthetic layered silicates, eg mica or fluoromica Silicates such as hectorite, saponite, or vermiculite, nanoclays, natural or synthetic layered silicates containing modifiers that improve intercalation and exfoliation, zinc borate, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, oxidation barium, lanthanum oxide, cerium oxide, strontium oxide, vanadium _oxide, SiO 2 -MgO (magnesium silicate), magnesium _hydroxide, SiO 2 -CaO (calcium silicate), Hyde Hydrotalcite, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, lanthanum carbonate, cerium carbonate, or inorganic particles are selected from the group consisting of basic copper acetate and basic lead sulfate.

  In particular, the second inorganic particles are preferably an anion adsorbent and / or basic inorganic particles. When the second inorganic particles are an anion adsorbent, the metal adsorption ability of the non-aqueous electrolyte battery inorganic particles is further increased. Moreover, HF can be adsorbed more efficiently because the second inorganic particles are basic inorganic particles.

Examples of the anion adsorbent include, but are not limited to, layered double hydroxides (Mg—Al type, Mg—Fe type, Ni—Fe type, Li—Al type), layered double hydroxide-alumina silica gel composite Boehmite, alumina, zinc oxide, lead oxide, iron oxide, iron oxyhydroxide, hematite, bismuth oxide, tin oxide, titanium oxide, zirconium oxide and the like. From the viewpoint of relatively low water content and preventing battery swelling, boehmite, alumina, zinc oxide, lead oxide, iron oxide, iron oxyhydroxide, hematite, lanthanum oxide, bismuth oxide, tin oxide Basic inorganic particles such as titanium oxide, cerium oxide, and zirconium oxide include sodium oxide, potassium oxide, magnesium oxide, calcium oxide, barium oxide, lanthanum oxide, cerium oxide, strontium oxide, vanadium oxide, SiO ₂ -MgO ( magnesium silicate), magnesium _hydroxide, SiO 2 -CaO (calcium silicate), hydrotalcite, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, lanthanum carbonate, cerium carbonate, basic copper acetate and a base Lead sulfate is preferred. The anion adsorbent and / or basic inorganic particles may be used alone or in combination of two or more.
Further, the first inorganic particles and the second inorganic particles are obtained by measuring X-ray or electron diffraction or TEM (transmission electron microscope) on two or more kinds of inorganic particles having different average particle diameters. The first inorganic particles having a small average particle diameter and having a layered structure can be clearly distinguished from the second inorganic particles having a large average particle diameter and not having a layered structure.

[Battery materials]
The battery constituent materials forming the nonaqueous electrolyte battery are a positive electrode, a negative electrode, an electrode terminal, a separator, a nonaqueous electrolyte, a nonaqueous electrolyte, a packaging material, an exterior body, and the like. Battery constituent material including inorganic particles for non-aqueous electrolyte battery described above and battery constituent material including mixture of inorganic particles for non-aqueous electrolyte battery (first inorganic particles) and second inorganic particles described above Is also an embodiment of the present invention.

[Separator]
Any separator may be used as long as it has a high ion permeability and has a function of electrically isolating the positive electrode and the negative electrode. The conventionally well-known separator used for a nonaqueous electrolyte battery can be used, and it does not restrict | limit in particular.

  Specifically, it is stable to non-aqueous electrolytes in batteries, such as polyolefin (for example, polyethylene (PE), polypropylene (PP), etc.), polyester, polyimide, polyamide, polyurethane, and electrochemical. A microporous film or a nonwoven fabric made of a highly stable material can be used as the separator. In addition, it is preferable that a separator has the property (namely, shutdown function) which the hole obstruct | occludes in 80 degreeC or more (more preferably 100 degreeC or more) and 180 degrees C or less (more preferably 150 degreeC or less). Therefore, the separator has a melting temperature of 80 ° C. or higher (more preferably 100 ° C. or higher), 180 ° C., which is measured using a differential scanning calorimeter (DSC) according to JIS K 7121. It is more preferable to use a microporous film or a nonwoven fabric containing the following polyolefin (more preferably 150 ° C. or lower). In this case, the microporous film or nonwoven fabric used as the separator may be formed of, for example, only PE or PP, and may further include two or more kinds of materials. The separator may also be a laminate of a PE microporous membrane and a PP microporous membrane (for example, a PP / PE / PP three-layer laminate).

  As the above-mentioned microporous membrane, for example, an ion-permeable porous membrane having many holes formed by a conventionally known solvent extraction method, dry type or wet drawing method (separator for non-aqueous electrolyte battery) Can be used.

  A separator for a nonaqueous electrolyte battery containing the adsorbent described above (that is, the inorganic particles for nonaqueous electrolyte battery and the inorganic particle mixture for nonaqueous electrolyte battery described above) is also an embodiment of the present invention.

  When inorganic particles are included in the separator, not only can the inorganic particles be included in the microporous membrane or nonwoven fabric to form a single-layer separator, but also the microporous membrane or nonwoven fabric can be used as a basis. A separator having a multilayer structure can be formed by using a porous layer containing inorganic particles on one side or both sides thereof as a material.

  In the separator having the multilayer structure described above, the microporous film or nonwoven fabric serving as the base material becomes a layer having the original function of transmitting ions while preventing a short circuit between the positive electrode and the negative electrode, and the inorganic particles The contained porous layer plays a role of adsorbing metal ions eluted from the positive electrode active material into the non-aqueous electrolyte. From such a viewpoint, a separator in which inorganic particles for a nonaqueous electrolyte battery or a mixture of inorganic particles for a nonaqueous electrolyte battery is formed on at least one surface of a substrate is preferable.

  Further, in the separator having the multilayer structure, in order to ensure a shutdown function, the base material is preferably a microporous film or a non-woven fabric mainly composed of polyolefin having the melting temperature described above. A microporous membrane mainly composed of a polyolefin having temperature is more preferable. That is, the separator having a multilayer structure particularly preferably has a porous layer containing inorganic particles and a porous layer mainly composed of polyolefin having the above melting temperature.

  In the separator having the multilayer structure described above, the non-porous film or nonwoven fabric serving as the base material and the porous layer containing inorganic particles may be integrated, and each is an independent film, The separators may be formed by being overlapped with each other.

  In a separator having a multilayer structure having a porous layer containing inorganic particles and a porous layer mainly composed of polyolefin having the above melting temperature, the porous layer mainly composed of polyolefin has a total volume of its constituent components ( The polyolefin content in the total volume excluding the void portion is preferably 50% by volume or more, more preferably 70% by volume or more, and particularly preferably 100% by volume or less.

  For a separator having a multilayer structure having a porous layer containing inorganic particles and a porous layer mainly composed of polyolefin having the above melting temperature, a porous layer mainly composed of polyolefin (particularly a microporous membrane) Is susceptible to thermal shrinkage due to the high temperature inside the battery. However, in the separator having the multilayer structure described above, the porous layer containing inorganic particles that hardly undergo heat shrinkage acts as a heat-resistant layer, and the heat shrinkage of the entire separator is suppressed. An excellent nonaqueous electrolyte battery can be achieved.

  When using the separator having the multilayer structure described above, the layer containing inorganic particles is used to bind inorganic particles together, or a layer containing inorganic particles and a substrate (the above-mentioned nonwoven fabric or microporous membrane) and In order to bind the binder, it is preferable to contain a binder.

  Although there is no limitation in particular as said binder, For example, when using a separator, what is insoluble or hardly soluble with respect to electrolyte solution, and an electrochemically stable thing is preferable. The binder is not particularly limited, but examples thereof include polyolefins such as polyethylene and polypropylene; fluorine-containing resins such as vinylidene fluoride and polytetrafluoroethylene; vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer. Fluorine-containing rubber such as ethylene-tetrafluoroethylene copolymer; styrene-butadiene copolymer and its hydride, acrylonitrile-butadiene copolymer and its hydride, acrylonitrile-butadiene-styrene copolymer and its hydride, Methacrylic acid ester-acrylic acid ester copolymer, styrene-acrylic acid ester copolymer, acrylonitrile-acrylic acid ester copolymer, ethylene propylene rubber, polyvinyl alcohol, polyvinyl acetate, etc. Cellulose derivatives such as ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose; melting point and / or glass transition temperature of polyphenylene ether, polysulfone, polyether sulfone, polyphenyl sulfone, polyphenylene sulfide, polyetherimide, polyamideimide, polyester, etc. Examples thereof include resins having a temperature of 180 ° C. or higher.

  Among these, a resin latex binder is preferable. In the present specification, “resin made of resin” refers to a resin dispersed in a medium. The separator having a layer containing an adsorbent and a resinous latex binder is unlikely to have low ion permeability and high output characteristics tend to be obtained. In addition, even when the temperature rise at the time of abnormal heat generation is fast, smooth shutdown performance is exhibited, heat resistant shrinkage is high, and high safety tends to be obtained.

  The resin latex binder is not particularly limited, and can be obtained, for example, by emulsion polymerization of an aliphatic conjugated diene monomer or an unsaturated carboxylic acid monomer and other monomers copolymerizable therewith. Things. By using such a resinous latex binder, the electrochemical stability and the binding property tend to be further improved. In addition, it does not specifically limit as an emulsion polymerization method, A conventionally well-known method can be used. Moreover, it does not specifically limit also about the addition method of a monomer and another component, Any of the batch addition method, the division | segmentation addition method, or the continuous addition method is employable. Any one-stage polymerization, two-stage polymerization, or multi-stage polymerization can be employed.

  The aliphatic conjugated diene monomer is not particularly limited. For example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1 , 3-butadiene, substituted linear conjugated pentadienes, substituted and side chain conjugated hexadienes, and the like. Among these, 1,3-butadiene is preferable. The aliphatic conjugated diene monomer may be used alone or in combination of two or more.

  The unsaturated carboxylic acid monomer is not particularly limited, and examples thereof include mono- or dicarboxylic acids (anhydrides) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. Among these, acrylic acid and / or methacrylic acid are preferable. An unsaturated carboxylic acid monomer may be used individually by 1 type, or may use 2 or more types together.

  Examples of other monomers copolymerizable with the aliphatic conjugated diene monomer or unsaturated carboxylic acid monomer include, but are not limited to, for example, aromatic vinyl monomers, vinyl cyanide monomers , Unsaturated carboxylic acid alkyl ester monomers, hydroxyalkyl group-containing unsaturated monomers, unsaturated carboxylic acid amide monomers, and the like. Among these, unsaturated carboxylic acid alkyl ester monomers are preferable. These may be used alone or in combination of two or more.

  Examples of unsaturated carboxylic acid alkyl ester monomers include, but are not limited to, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl Examples include maleate, dimethyl itaconate, monomethyl fumarate, monoethyl fumarate, 2-ethylhexyl acrylate, and the like. Among these, methyl methacrylate is preferable. These may be used alone or in combination of two or more.

  In addition to the monomers described above, monomer components other than those described above can be further used to improve various qualities and physical properties.

  The average particle size of the resin latex binder is preferably 50 nm to 500 nm, more preferably 60 nm to 460 nm, and even more preferably 70 nm to 420 nm. When the average particle size is 50 nm or more, the ion permeability of the separator having a layer containing an adsorbent and a resinous latex binder is unlikely to decrease, and high output characteristics tend to be easily obtained. In addition, even when the temperature rise during abnormal heat generation is fast, the separator tends to exhibit a smooth shutdown performance, has high heat shrinkage resistance, and is excellent in safety. Further, when the average particle diameter is 500 nm or less, good binding properties are exhibited, and when the separator is formed as a multilayer porous film, the heat shrinkability is good and the safety tends to be excellent.

  The average particle size of the resin latex binder can be controlled by adjusting the polymerization time, polymerization temperature, raw material composition ratio, raw material charging order, pH, and the like.

In the case where the separator contains inorganic particles, the content of the inorganic particles in the separator is, for example, 0.1 g / m ² or more in terms of the amount per area of the separator from the viewpoint of ensuring the effect of its use. Is preferable, and it is more preferable that it is 0.5 g / m ² or more. However, when there is too much content of the inorganic particle in a separator, a separator will become thick and it will become a factor of the fall of the energy density of a battery, or an internal resistance rise. Therefore, the content of the inorganic particles in the separator is, for example, 15 g / m ² or less, more preferably 10 g / m ² or less in terms of the amount per area of the separator.

  Further, when the separator has a porous layer containing inorganic particles, the content of the inorganic particles in the porous layer in the total volume of the constituent components of the porous layer (total volume excluding the void portion) is From the viewpoint of ensuring a good effect by use, it is preferably 1% by volume or more, and more preferably 5% by volume or more and 100% by volume or less.

  Further, the separator may contain inorganic fine particles other than the first inorganic particles and the second inorganic particles (hereinafter referred to as “other inorganic fine particles”) or resin fine particles. When the separator contains these fine particles, for example, the shape stability of the entire separator at a high temperature can be further improved.

  Other inorganic fine particles are not particularly limited, but for example, those having a melting point of 200 ° C. or higher, high electrical insulating properties, and electrochemically stable within the use range of the nonaqueous electrolyte battery are preferable. Such inorganic particles are not particularly limited. For example, oxide ceramics such as alumina, silica, titania, zirconia, magnesia, ceria, yttria, zinc oxide, iron oxide; silicon nitride, titanium nitride, boron nitride, etc. Nitride ceramics: silicon carbide, calcium carbonate, magnesium sulfate, aluminum sulfate, aluminum hydroxide, aluminum hydroxide oxide, talc, dickite, nacrite, halloysite, pyrophyllite, montmorillonite, sericite, amesite, bentonite, asbestos And ceramics such as zeolite, anhydrous calcium silicate, magnesium silicate, diatomaceous earth, and silica sand; and glass fiber. An inorganic particle may be used individually by 1 type, and may use 2 or more types together.

  Among these, aluminum oxide compounds such as alumina and aluminum hydroxide oxide; or aluminum silicate compounds having no ion exchange ability such as dickite, nacrite, halloysite, and pyrophyllite are preferable. By using such inorganic particles, the electrochemical stability and the heat shrinkage inhibiting property of the multilayer porous film tend to be further improved.

  In addition, the resin fine particles are composed of an electrochemically stable resin that has heat resistance and electrical insulation, is stable with respect to the non-aqueous electrolyte in the battery, and is hardly oxidized / reduced in the battery operating voltage range. The ones made are preferred. Examples of the resin for forming such resin fine particles include styrene resin (polystyrene, etc.), styrene butadiene rubber, acrylic resin (polymethyl methacrylate, etc.), polyalkylene oxide (polyethylene oxide, etc.), fluororesin (polyvinylidene fluoride, etc.) And a cross-linked product of at least one resin selected from the group consisting of these derivatives; urea resin; polyurethane; and the like. As the resin fine particles, the resins exemplified above may be used alone or in combination of two or more. Moreover, the resin fine particles may contain a known additive that can be added to the resin, for example, an antioxidant, if necessary.

  The form of other inorganic fine particles or resin fine particles may be any form such as a plate shape, a scale shape, a needle shape, a columnar shape, a spherical shape, a polyhedral shape, and a lump shape. The inorganic particles having the above form may be used alone or in combination of two or more. From the viewpoint of improving permeability, a polyhedral shape having a plurality of surfaces is preferable.

  As the particle diameter of other inorganic fine particles or resin fine particles, the average secondary particle diameter (D50) is preferably 0.1 μm to 4.0 μm, more preferably 0.2 μm to 3.5 μm. More preferably, it is more preferably 0.4 μm to 3.0 μm. By adjusting the average secondary particle diameter (D50) within such a range, thermal shrinkage at high temperatures tends to be further suppressed.

  When other inorganic fine particles or resin fine particles are contained, these fine particles are, for example, (i) a porous layer containing an adsorbent, or (ii) a porous layer containing an adsorbent and a nonwoven fabric used as a substrate. Alternatively, it may be contained in a porous layer different from the microporous membrane (a porous layer mainly containing inorganic fine particles or resin fine particles other than the first inorganic particles and the second inorganic particles).

  In addition, when other inorganic fine particles or resin fine particles are contained in the porous layer containing (i) the adsorbent, the content of the other inorganic fine particles or resin fine particles is described above. It is preferably adjusted so that it is within the preferred range.

  Further, other inorganic fine particles or resin fine particles (ii) a porous layer containing an adsorbent and a porous layer different from the nonwoven fabric or microporous film as a substrate (mainly other inorganic fine particles or resin fine particles) The porous layer containing these fine particles is, for example, opposite to the surface in contact with the one side of the nonwoven fabric or microporous membrane that is the base material (mainly adsorbent-containing porous layer). Of the porous layer containing the adsorbent disposed on the surface of the substrate, or disposed between the porous layer containing the adsorbent and the substrate. It can arrange | position to the surface on the opposite side to the surface which touches.

  In addition, the porous layer mainly containing other inorganic fine particles or resin fine particles may be integrated with a nonwoven fabric or woven fabric serving as a base material or a porous layer containing an adsorbent, and exists as an independent film. The separator may be formed by overlapping with another layer (independent film) in the battery.

  Further, other inorganic fine particles or resin fine particles (ii) a porous layer containing an adsorbent and a porous layer different from the nonwoven fabric or microporous film as a substrate (mainly other inorganic fine particles or resin fine particles) In the porous layer containing these fine particles, the content of these fine particles is 5 volumes in the total volume (total volume excluding the voids) of the constituent components of the layer. % Or more, preferably 10% by volume or more, and more preferably 50% by volume or more.

  In addition, other inorganic fine particles and resin fine particles are made of (ii) a porous layer containing an adsorbent and a porous layer different from a nonwoven fabric or microporous film as a base (mainly other inorganic fine particles or resin fine particles. In the case where the porous layer is contained, it is preferable that the porous layer contains a binder. Therefore, the content of these fine particles in the porous layer mainly containing other inorganic fine particles and resin fine particles is 99.5% by volume in the total volume (total volume excluding voids) of the constituent components of the layer. The following is preferable. As the binder in this case, the same binders as those exemplified above as those that can be used for the porous layer containing the adsorbent can be used.

  Further, when the nonaqueous electrolyte battery contains the adsorbent in a place other than the separator, the separator uses the nonwoven fabric or the microporous membrane as a base material, and other inorganic fine particles or A separator having a porous layer mainly containing resin fine particles may be used.

The porosity of the separator used in the non-aqueous electrolyte battery is preferably 30% or more in the dry state of the separator in order to ensure the amount of non-aqueous electrolyte retained and improve the ion permeability. More preferably, it is 40% or more. On the other hand, from the viewpoint of ensuring the strength of the separator and preventing internal short circuit, the porosity of the separator is preferably 80% or less, and more preferably 70% or less in the dry state of the separator. The porosity P (%) of the separator can be calculated by obtaining the sum for each component i using the following formula from the thickness of the separator, the mass per area, and the density of the constituent components.
P = {1- (m / t) / (Σa _i · ρ _i )} × 100
{Wherein, a _i is the ratio of component i when the total mass is 1, ρ _i is the density (g / cm ³ ) of component i, and m is the unit area of the separator Mass (g / cm ² ), and t is the thickness (cm) of the separator. }

  The thickness of the separator is preferably 2 μm or more and 200 μm or less, more preferably 5 μm or more and 100 μm or less, and even more preferably 7 μm or more and 30 μm or less in both the single layer structure and the multilayer structure. When the thickness of the separator is 2 μm or more, the mechanical strength of the separator tends to be further improved. Moreover, since the occupied volume of the separator in the battery is reduced when the thickness of the separator is 200 μm or less, the nonaqueous electrolyte battery tends to have a higher capacity and the ion permeability tends to be further improved.

  The air permeability of the separator is preferably 10 seconds / 100 cc to 500 seconds / 100 cc, more preferably 20 seconds / 100 cc to 450 seconds / 100 cc, and even more preferably 30 seconds / 100 cc to 450 seconds / 100cc or less. When the air permeability is 10 seconds / 100 cc or more, self-discharge tends to be less when the separator is used in a non-aqueous electrolyte battery. Further, when the air permeability is 500 seconds / 100 cc or less, better charge / discharge characteristics tend to be obtained.

  Moreover, when the separator has a porous layer containing an adsorbent and a nonwoven fabric or a microporous film as a base material, the thickness of the porous layer containing the adsorbent is preferably 1 μm to 10 μm.

  Furthermore, when the separator has a porous layer containing an adsorbent and a nonwoven fabric or microporous film as a base material, or in addition to these layers, the porous material mainly contains other inorganic fine particles or resin fine particles. When it has a layer, it is preferable that the thickness of the nonwoven fabric or porous film used as a base material is 5 μm to 40 μm.

  When the separator has a porous layer mainly containing other inorganic fine particles or resin fine particles, the thickness of the porous layer is preferably 1 μm to 10 μm.

  The porous layer containing the adsorbent is expected to be formed from a composition (for example, paste, slurry, etc.) prepared by dispersing or dissolving the adsorbent, binder, etc. in water or an organic solvent. It can be formed through a step of applying to a location and drying, or the composition can be applied to a substrate such as a resin film, dried and then peeled off to form an independent film.

  In addition, a porous layer mainly containing other inorganic fine particles or resin fine particles is also applied with a composition (for example, paste, slurry, etc.) prepared by dispersing or dissolving these fine particles, binder, etc. in water or an organic solvent. It is applied to a place where the porous layer is to be formed and then dried, or the composition is applied to a substrate such as a resin film, dried and then peeled to form an independent film. be able to.

[Positive electrode]
The positive electrode preferably includes a positive electrode active material, a conductive material, a binder, and a current collector.

As the positive electrode active material that can be included in the positive electrode, a known material that can electrochemically occlude and release lithium ions can be used. Among these, as the positive electrode active material, a material containing lithium is preferable. As the positive electrode active material, for example,
Following formula (1):
Li _x Mn _{2- y My} O _z (1)
{Wherein M represents at least one element selected from the group consisting of transition metal elements, 0 <x ≦ 1.3, 0.2 <y <0.8, and 3.5 <z <4. .5. }
An oxide represented by:
Following formula (2):
_{Li x M y O z (2} )
{Wherein M represents at least one element selected from the group consisting of transition metal elements, 0 <x ≦ 1.3, 0.8 <y <1.2, and 1.8 <z <2. .2. }
A layered oxide represented by:
Following formula (3):
_{LiMn 2-x Ma x O 4} (3)
{In the formula, Ma represents at least one element selected from the group consisting of transition metal elements, and 0.2 ≦ x ≦ 0.7. }
A spinel oxide represented by:
Following formula (4):
Li ₂ McO ₃ (4)
{In the formula, Mc represents at least one element selected from the group consisting of transition metal elements. } And the following formula (5):
LiMdO ₂ (5)
{Wherein Md represents at least one element selected from the group consisting of transition metal elements. } Is a composite oxide with an oxide represented by the following formula (6):
_{zLi 2 McO 3 - (1-} z) LiMdO 2 (6)
{In the formula, Mc and Md are synonymous with Mc and Md in the above formulas (4) and (5), respectively, and 0.1 ≦ z ≦ 0.9. }
Li-excess layered oxide positive electrode active material represented by:
Following formula (7):
LiMb _1-y Fe _y PO ₄ (7)
{In the formula, Mb represents at least one element selected from the group consisting of Mn and Co, and 0 ≦ y ≦ 1.0. }
An olivine-type positive electrode active material represented by: and the following formula (8):
Li ₂ MePO ₄ F (8)
{In the formula, Me represents at least one element selected from the group consisting of transition metal elements. } The compound represented by this is mentioned. These positive electrode active materials may be used alone or in combination of two or more.

  Among the positive electrode active materials described above, those that can be operated at a higher potential to increase the energy density of the battery are preferable. Furthermore, the non-aqueous electrolyte battery can effectively trap metal ions that are eluted from the positive electrode active material and deposited on the negative electrode, thereby degrading battery characteristics and causing short circuits, thereby reducing battery performance. Since it can suppress, it is preferable to use at least 1 sort (s) selected from the group which consists of the spinel type lithium manganese oxide represented by the said Formula (3), and the layered compound represented by the said Formula (2).

  In order to form the positive electrode, a conductive material, a binder, and a current collector known in this technical field may be used.

  Although it does not specifically limit when making adsorbent contain in a positive electrode, a conventionally well-known method can be used. For example, a method of containing an adsorbent in the positive electrode mixture layer or a method of forming a porous layer containing the adsorbent on the surface of the positive electrode mixture layer can be mentioned. In the case of the latter method, the porous layer containing the adsorbent can be formed by the same method as the porous layer containing the adsorbent described for the separator having the multilayer structure, and the configuration thereof is also described above. It can be set as the same structure as the porous layer containing the adsorption agent concerning the separator of a multilayer structure.

  In the case where the positive electrode has an adsorbent, the content of the adsorbent in the positive electrode is, for example, from the viewpoint of ensuring a good effect due to its use, for example, the total volume of the components of the positive electrode excluding the current collector Product) is preferably 0.5% by volume or more, more preferably 1% by volume or more. However, if the content of the adsorbent in the positive electrode is too large, it tends to cause a decrease in battery energy density or an increase in internal resistance. Therefore, the content of the adsorbent in the positive electrode is preferably 10% by volume or less, for example, 6% by volume or less in the total volume of the components of the positive electrode excluding the current collector (total volume excluding the void portion). It is more preferable that

  Moreover, in the positive mix layer concerning a positive electrode, when a positive mix layer does not contain an adsorbent, content of a positive electrode active material is adjusted to 87 mass%-97 mass%, and content of a conductive support agent Is preferably adjusted to 1.5 mass% to 6.5 mass%, and / or the binder content is preferably adjusted to 1.5 mass% to 6.5 mass%.

  On the other hand, when the positive electrode mixture layer contains an adsorbent, when the total amount of components other than the adsorbent in the positive electrode mixture layer is 100% by mass, the content of the positive electrode active material is 79.4% by mass to It is adjusted to 96.4% by mass, the content of the conductive auxiliary agent is adjusted to 1.4% by mass to 6.5% by mass, and / or the content of the binder is 1.4% by mass to 6.5% by mass. It is preferable to adjust to.

[Negative electrode]
The negative electrode preferably includes a negative electrode active material, a binder, and a current collector.

  As the negative electrode active material that can be contained in the negative electrode, a known material that can electrochemically occlude and release lithium ions can be used. Such a negative electrode active material is not particularly limited, and for example, carbon materials such as graphite powder, mesophase carbon fiber, and mesophase microspheres; and metals, alloys, oxides, and nitrides are preferable. These may be used alone or in combination of two or more.

  As the binder that can be included in the negative electrode, a known material that can bind at least two of the negative electrode active material, the conductive material that can be included in the negative electrode, and the current collector that can be included in the negative electrode can be used. Such a binder is not particularly limited, and for example, carboxymethyl cellulose, styrene-butadiene crosslinked rubber latex, acrylic latex, and polyvinylidene fluoride are preferable. These may be used alone or in combination of two or more.

  Although it does not specifically limit as a collector which can be contained in a negative electrode, For example, metal foil, such as copper, nickel, and stainless steel; Expand metal; Punch metal; Foam metal; Carbon cloth; These may be used alone or in combination of two or more.

  Although it does not specifically limit when making adsorbent contain in a negative electrode, a conventionally well-known method can be used. For example, a method of containing an adsorbent in the negative electrode mixture layer or a method of forming a porous layer containing the adsorbent on the surface of the negative electrode (the surface of the negative electrode mixture layer or the negative electrode agent layer) can be mentioned. In the case of the latter method, the porous layer containing the adsorbent can be formed by the same method as the porous layer containing the adsorbent described for the separator having the multilayer structure, and the configuration thereof is also described above. It can be set as the same structure as the porous layer containing the adsorption agent concerning the separator of a multilayer structure.

  In the case where the negative electrode has an adsorbent, the content of the adsorbent in the negative electrode is, for example, from the viewpoint of ensuring the effect of its use, for example, the total volume of the constituent components of the negative electrode excluding the current collector (the whole excluding the void portion) Product) is preferably 1.5% by volume or more, more preferably 2% by volume or more. However, if the amount of adsorbent in the negative electrode is too large, it tends to cause a decrease in battery energy density or an increase in internal resistance. Therefore, the content of the adsorbent in the negative electrode is preferably 25% by volume or less, and preferably 15% by volume or less, in the total volume of the components of the negative electrode excluding the current collector (total volume excluding the pores). It is more preferable.

  Moreover, in the negative mix layer concerning a negative electrode, when a negative mix layer does not contain adsorption agent, content of a negative electrode active material is adjusted to 88 mass%-99 mass%, and / or inclusion of a binder. The amount is preferably adjusted to 1% by mass to 12% by mass, and when a conductive auxiliary is used, the content of the conductive auxiliary is preferably adjusted to 0.5% by mass to 6% by mass.

  On the other hand, when the negative electrode mixture layer contains an adsorbent, when the total amount of components other than the adsorbent in the negative electrode mixture layer is 100% by mass, the content of the negative electrode active material is 68% by mass to 98% by mass. % And / or the binder content is preferably adjusted to 0.8% to 11.8% by mass. When a conductive additive is used, the conductive auxiliary agent content is preferably set to 0.00%. It is preferable to adjust to 9 mass%-5.9 mass%.

[Nonaqueous electrolyte]
As the non-aqueous electrolyte, for example, a solution (non-aqueous electrolyte) in which a lithium salt is dissolved in an organic solvent is used. The lithium salt is not particularly limited, and a conventionally known lithium salt can be used. Such a lithium salt is not particularly limited. For example, LiPF ₆ (lithium hexafluorophosphate), LiClO ₄ , LiBF ₄ , LiAsF ₆ , Li ₂ SiF ₆ , LiOSO ₂ C _k F _{2k + 1} [wherein k is an integer of 1 to 8], LiN (SO ₂ C _k F _{2k + 1} ) ₂ [wherein k is an integer of 1 to 8], LiPF _n (C _k F _{2k + 1} ) _6-n [wherein , N is an integer of 1 to 5 and k is an integer of 1 to 8], LiPF ₄ (C ₂ O ₄ ), and LiPF ₂ (C ₂ O ₄ ) ₂ . Among these, LiPF ₆ is preferable. By using LiPF ₆ , the battery characteristics and safety tend to be superior even at high temperatures. These lithium salts may be used individually by 1 type, or may use 2 or more types together.

  It does not specifically limit as a non-aqueous solvent used for a non-aqueous electrolyte, A conventionally well-known thing can be used. Such a non-aqueous solvent is not particularly limited, but for example, an aprotic polar solvent is preferable.

  The aprotic polar solvent is not particularly limited. For example, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate. Cyclic carbonates such as trifluoromethylethylene carbonate, fluoroethylene carbonate and 4,5-difluoroethylene carbonate; lactones such as γ-ptyrolactone and γ-valerolactone; cyclic sulfones such as sulfolane; cyclic ethers such as tetrahydrofuran and dioxane; Dimethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, dipropyl carbonate, methyl butyl carbonate Chain carbonates such as boronate, dibutyl carbonate, ethylpropyl carbonate and methyl trifluoroethyl carbonate; nitriles such as acetonitrile; chain ethers such as dimethyl ether; chain carboxylic acid esters such as methyl propionate; and chains such as dimethoxyethane An ether carbonate compound is mentioned. One of these may be used alone, or two or more may be used in combination.

  The concentration of the lithium salt in the non-aqueous electrolyte is preferably 0.5 mol / L to 6.0 mol / L. In the case of a non-aqueous electrolyte of a concentrated electrolytic salt of 3.0 to 6.0 mol / l, it is preferable that the elution of metal ions can be effectively prevented when the concentration of the lithium salt is within the above range. From the viewpoint of reducing the viscosity of the non-aqueous electrolyte, the concentration of the lithium salt in the non-aqueous electrolyte is preferably 0.9 mol / L to 1.25 mol / L. The concentration of the lithium salt in the non-aqueous electrolyte can be selected according to the purpose.

  The nonaqueous electrolyte may be a liquid electrolyte or a solid electrolyte.

  When the adsorbent is contained in the non-aqueous electrolyte, the content of the adsorbent in the non-aqueous electrolyte is preferably 5 mg or more per 1 mL of the non-aqueous electrolyte from the viewpoint of ensuring a good effect due to its use. More preferably.

[Non-aqueous electrolyte battery paint and resin solid]
A paint or resin solid used for a nonaqueous electrolyte battery and containing the adsorbent described above is also an aspect of the present invention.

  In addition to adsorbents of substances that affect battery life characteristics or safety, paints are liquid paints that contain additional components such as resins, dispersants, water, and organic solvents, or adsorbents and film formation of resins, etc. It may be a powder paint containing the components. As the resin contained in the paint, the various resins described above for forming the constituent elements of the nonaqueous electrolyte battery may be used. The paint can be formed by a known method such as mixing, stirring, and dispersion.

  The resin solid material includes at least one resin in addition to an adsorbent of a substance that affects the life characteristics or safety of the battery. As the resin contained in the resin solid material, various resins described above may be used in order to form the constituent elements of the nonaqueous electrolyte battery. The resin solid can be formed by a known method such as kneading, mixing, extrusion, or molding.

[Additional configuration, form and use of nonaqueous electrolyte battery]
The non-aqueous electrolyte battery has an adsorption layer containing inorganic particles for non-aqueous electrolyte batteries, or inorganic particles for non-aqueous electrolyte batteries (first inorganic particles) and second inorganic particles inside or on the entire surface of the battery constituent material. It is preferable to provide an adsorption layer containing a mixture of

  From the relationship between the arrangement of the adsorption layer and the metal or HF adsorption capacity, the nonaqueous electrolyte battery preferably includes a positive electrode, a negative electrode, and a separator as battery constituent materials. From the same viewpoint, the adsorption layer is formed on at least one of the inside of the separator, the opposing surface of the positive electrode and the separator, and the opposing surface of the negative electrode and the separator, and the formed adsorption layer is the entire inside of the separator or It is preferable to be formed on a part thereof, the entire surface of each facing surface, or a part thereof.

  In the nonaqueous electrolyte battery, the positive electrode and the negative electrode can be used in the form of a laminated body laminated via a separator, or in the form of an electrode winding body obtained by further winding the laminated body.

  Examples of the form of the nonaqueous electrolyte battery include a cylindrical shape using a steel can, an aluminum can, or the like as an outer can (for example, a rectangular tube shape, a cylindrical shape, etc.). In addition, a non-aqueous electrolyte battery can be formed by using a laminated film on which a metal is deposited as an exterior body.

  When the non-aqueous electrolyte battery is a lithium ion secondary battery, a positive electrode, a laminated body in which the adsorption layer containing the inorganic particles for non-aqueous electrolyte described above, a separator, and a negative electrode are laminated in this order or The wound body and the non-aqueous electrolyte are preferably contained in a lithium ion secondary battery. By arranging a plurality of components of the lithium ion secondary battery in such an order, the movement of lithium ions within the battery is ensured, and the adsorption of substances that affect the life characteristics or safety of the battery is remarkable. Become. The adsorption layer containing inorganic particles may be formed using the non-aqueous electrolyte battery paint and resin solid described above, or may be formed as a part of the multilayer separator described above. it can.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. Unless otherwise specified, various measurements and evaluations were performed under conditions of room temperature 23 ° C., 1 atm, and relative humidity 50%.

[Example 1]
<Preparation of zirconium phosphate>
After dissolving hafnium 2% -containing zirconium oxychloride octahydrate in water, oxalic acid dihydrate was dissolved. Here, the molar ratio of hafnium 2% -containing zirconium oxychloride octahydrate and oxalic acid dihydrate was 1: 2.9, and the weight ratio of water to these was 4.5. While this solution was stirred, phosphoric acid was added, and the mixture was stirred and refluxed for 8 hours. Here, phosphoric acid was added so that the molar ratio of hafnium-containing zirconium oxychloride octahydrate to phosphoric acid was 1: 2.1. After cooling, the resulting precipitate was washed with water, immersed in a 0.1N LiOH aqueous solution for 8 hours, and dried to obtain zirconium phosphate A. The obtained zirconium phosphate A was pulverized with a ball mill to have a BET specific surface area of 10 m ² / g. This BET specific surface area is BET2 described above, and was measured by the BET method (multipoint method, 5 points in the range of relative pressure of about 0.1 to 0.2) from the adsorption isotherm by nitrogen.

<X-ray diffraction measurement>
For the obtained zirconium phosphate A, using an X-ray diffractometer (D2 PHASER manufactured by Bruker), using Cu-Kα rays, acceleration voltage 30 kV, tube current 10 mA, diverging slit 1 mm, solar slit 4 °, air Powder X-ray diffraction measurement was performed under the conditions of a scatter screen of 1 mm, a Kβ filter of 0.5 mm, a counting time of 0.15 seconds, a 0.02 ° step, and a measurement range of 5 ° to 40 °. Standard silicon powder was used for correction of the X-ray diffractometer. From the obtained diffraction pattern, a diffraction peak derived from the (002) plane was observed in the vicinity of 13 ° (2θ), and it was confirmed that the structure was a layered zirconium phosphate. Further, the average spacing between the (002) planes was 0.7 nm.

<Surface modification>
100 parts by mass of the produced zirconium phosphate A and 2 parts by mass of octadecylphosphonic acid (ODPA, manufactured by Dojindo Laboratories) were mixed with THF and stirred for 12 hours. Thereafter, THF was volatilized and removed from the mixture. Furthermore, the dried product was vacuum-dried at 120 ° C. for 1 hour to obtain inorganic particles.

In addition, BET1 and BET2 of the inorganic particles were calculated from the adsorption isotherm by water vapor and nitrogen by the BET method (multipoint method, 5 points in the range of relative pressure of about 0.1 to 0.2). BET1 was calculated as 8.2 m ² / g, and BET2 was calculated as 10.2 m ² / g. Therefore, the value of BET1 / BET2 was calculated as 0.8.

<Preparation of separator>
Using a tumbler blender, 47.5 parts by mass of Mv 700,000 homopolymer polyethylene, 47.5 parts by mass of Mv 250,000 homopolymer polyethylene, and 5 parts by mass of Mv 400,000 homopolymer polypropylene were dried using a tumbler blender. Blended to obtain a polyolefin resin mixture. 1% by mass of pentaerythrityl-tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as an antioxidant is added to 99% by mass of the obtained polyolefin resin mixture. Then, a polyolefin resin composition was obtained by dry blending again using a tumbler blender.

The obtained polyolefin resin composition was substituted with nitrogen and then fed to a twin-screw extruder by a feeder under a nitrogen atmosphere. Further, liquid paraffin (kinematic viscosity at 37.78 ° C .: 7.59 × 10 ⁻⁵ m ² / s) was injected into the extruder cylinder by a plunger pump. The feeder and the pump were adjusted so that the liquid paraffin content ratio in the total mixture to be extruded was 66 mass% (resin composition concentration was 34%). The melt kneading conditions were a set temperature of 200 ° C., a screw rotation speed of 100 rpm, and a discharge rate of 12 kg / h.

  Subsequently, the melt-kneaded product was extruded and cast on a cooling roll controlled at a surface temperature of 25 ° C. through a T-die, to obtain a gel sheet having a thickness of 1600 μm. Next, the obtained gel sheet was guided to a simultaneous biaxial tenter stretching machine, and biaxial stretching was performed. The set stretching conditions were an MD magnification of 7.0 times, a TD magnification of 6.1 times, and a preset temperature of 123 ° C. Next, the biaxially stretched gel sheet was introduced into a methyl ethyl ketone bath and sufficiently immersed in methyl ethyl ketone to extract and remove liquid paraffin, and then methyl ethyl ketone was removed by drying. Finally, the dried gel sheet was guided to a TD tenter, and stretched and thermally relaxed to obtain a polyolefin microporous membrane. The stretching temperature was 125 ° C., the thermal relaxation temperature was 133 ° C., the TD maximum magnification was 1.65 times, and the relaxation rate was 0.9. The resulting polyolefin microporous membrane had a thickness of 12 μm and a porosity of 40%.

  Further, in 100 parts by mass of ion-exchanged water, 29 parts by mass of inorganic particles obtained by surface modification of zirconium phosphate A, 0.29 parts by mass of an ammonium polycarboxylate aqueous solution (SN Dispersant 5468 manufactured by San Nopco), Were mixed. After mixing, a bead mill treatment was performed to adjust the average particle size (D50) to 1.5 μm to obtain a dispersion. Further, 2.2 parts by mass of an acrylic latex suspension (solid concentration: 40%, average particle size: 150 nm) as a binder is mixed with 100 parts by mass of the obtained dispersion, thereby forming a uniform porous layer forming composition. A product was prepared. The average particle size of the inorganic particles in the above dispersion is a particle whose particle size distribution is 50% by measuring the particle size distribution using a laser particle size distribution measuring device (Microtrack MT3300EX manufactured by Nikkiso Co., Ltd.). The diameter was the average secondary particle diameter (μm). Moreover, the average particle diameter of the resin latex binder was determined as the average particle diameter by measuring the volume average particle diameter (nm) using a particle size measuring apparatus (LEC & TRATCHUPA 150 manufactured by LEED & NORTHRUP) using a light scattering method.

  Next, the composition for forming a porous layer is applied to the surface of the polyolefin microporous film using a micro gravure coater, dried at 60 ° C. to remove water, and 5 μm thick on the polyolefin microporous film. A porous layer containing surface-modified zirconium phosphate A-containing inorganic particles was disposed to obtain a multilayer separator including surface-modified zirconium phosphate A-containing inorganic particles. In addition, the volume ratio of the zirconium phosphate in the porous layer containing the surface-modified zirconium phosphate A-containing inorganic particles of this separator was 97% by volume.

<Preparation of positive electrode>
93.9: 3.3: Solid content ratio of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ as a positive electrode active material, acetylene black powder as a conductive additive, and a polyvinylidene fluoride solution as a binder. Mixed at a mass ratio of 2.8. To the obtained mixture, N-methyl-2-pyrrolidone as a dispersion solvent was added so as to have a solid content of 35% by mass and further mixed to prepare a slurry solution. This slurry solution was applied to both surfaces of an aluminum foil having a thickness of 10 μm. At this time, a part of the aluminum foil was exposed. Then, the solvent was removed by drying and rolled with a roll press. The rolled sample is cut so that the size of the coated part is 30 mm × 50 mm and includes the exposed part of the aluminum foil, and an aluminum lead piece for taking out the current is welded to the exposed part of the aluminum foil. Thus, a positive electrode was obtained.

<Production of negative electrode>
Graphite powder as a negative electrode active material and styrene butadiene rubber and carboxymethyl cellulose aqueous solution as a binder were mixed at a solid content mass ratio of 97.5: 1.5: 1.0. The obtained mixture was added to water as a dispersion solvent so that the solid content concentration was 45% by mass to prepare a slurry-like solution. This slurry solution was applied to one and both sides of a 10 μm thick copper foil. At this time, a part of the copper foil was exposed. Then, the solvent was removed by drying and rolled with a roll press. The sample after rolling is cut so that the size of the coated part is 32 mm × 52 mm and includes the exposed part of the copper foil, and a nickel lead piece for taking out the current is welded to the exposed part of the copper foil. Thus, a negative electrode was obtained.

<Preparation of nonaqueous electrolyte>
In an argon gas atmosphere, LiPF ₆ was dissolved in a mixed solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 1: 2 so as to be 1 mol / L, and a non-aqueous electrolyte ( A non-aqueous electrolyte solution was obtained.

<Production of nonaqueous electrolyte battery>
The positive electrode and the negative electrode were overlapped with the separator interposed therebetween to obtain a laminated electrode body. In addition, the separator was arrange | positioned so that the porous layer containing layered calcium silicate hydrate might oppose a positive electrode. This laminated electrode body was inserted into an aluminum laminate outer package of 80 × 60 mm. Next, the nonaqueous electrolyte (nonaqueous electrolyte) is injected into the exterior body, and then the opening of the exterior body is sealed, and the nonaqueous electrolyte battery (lithium ion secondary battery) having the laminated electrode body inside ) Was produced. The rated capacity of the obtained nonaqueous electrolyte battery was 90 mAh.

<Measurement of metal adsorption capacity>
(1) Measurement of Mn adsorption capacity Under an argon gas atmosphere, manganese trifluoromethanesulfonate [Mn (CF ₃ SO ₃ ) ₂ ] was added to the non-aqueous electrolyte used in the non-aqueous electrolyte battery, and the Mn concentration was 5 ppm. It dissolved so that it might become. Under an argon gas atmosphere, 100 parts by mass of this non-aqueous electrolyte in which Mn was dissolved and 0.035 parts by mass of surface-modified zirconium phosphate A were placed in a polypropylene sealed container, and a variable mix rotor VMR-5R (manufactured by ASONE Co., Ltd.). ) And agitation with shaking at 100 rpm for 6 hours in an atmosphere of 23 ° C. Then, it filtered with the membrane filter made from PTFE with the hole diameter of 0.2 micrometer. The Mn concentration (Mx) (unit: ppm) in this filtrate was measured, and the adsorption rate (Ax) (unit:%) was calculated from the following equation.
Ax = [(5-Mx) / 5] × 100

(2) Measurement of Fe adsorption ability The same as the measurement of Mn adsorption ability described above, except that iron (II) trifluoromethanesulfonate [Fe (CF ₃ SO ₃ ) ₂ ] was used instead of manganese trifluoromethanesulfonate. Thus, the Fe adsorption rate was calculated.

  In addition, the measurement of the density | concentration of Mn was measured by ICP emission-spectral-analysis (ICP emission-spectral-analysis apparatus: Optima8300 (made by Perkin Elmer)). In addition, acid decomposition (microwave method) was performed for the pretreatment of the measurement sample.

<Evaluation of HF adsorption capacity>
In an argon gas atmosphere, distilled water was added to the non-aqueous electrolyte used in the non-aqueous electrolyte battery, and then stored at 23 ° C. for 2 weeks to prepare a non-aqueous electrolyte containing 800 ppm of HF. 100 parts by mass of this non-aqueous electrolyte and 8 parts by mass of surface-modified zirconium phosphate A were placed in a polypropylene sealed container, and stirred at 23 ° C. for 5 minutes with shaking. Then, it filtered with the membrane filter made from PTFE with the hole diameter of 0.2 micrometer. Fluoride ion concentration in this filtrate is quantified by ion chromatography analysis, HF concentration is calculated, HF concentration is less than 10 ppm, HF adsorption ability: “Yes”, HF adsorption ability is 10 ppm or more Noh: “No”.

<Evaluation of life characteristics>
-Initial charging / discharging The obtained non-aqueous electrolyte secondary battery (hereinafter, also simply referred to as "battery") is accommodated in a thermostatic bath (manufactured by Futaba Kagaku, PLM-73S, manufactured by Futaba Kagaku) and charged. It connected to the discharge device (ASKA Electronics Co., Ltd. charge / discharge device ACD-01). Next, the battery was charged at a constant current of 0.05 C, reached 4.35 V, charged for 2 hours at a constant voltage of 4.35 V, and discharged to 3.0 V at a constant current of 0.2 C. 1C is a current value at which the battery is discharged in one hour.

-Cycle test The battery after the initial charge is accommodated in a thermostatic chamber (manufactured by Futaba Kagaku Co., Ltd., thermostatic chamber PLM-73S) set to 50 ° C, and a charge / discharge device (manufactured by Asuka Electronics Co., Ltd., charge / discharge device ACD-). 01). Next, the battery was charged to 4.35V with a constant current of 1C, reached 4.35V, charged for 1 hour with a constant voltage of 4.35V, and discharged to 3.0V with a constant current of 1C. This series of charging / discharging was made into 1 cycle, and also 99 cycles charging / discharging was performed. At this time, the discharge capacity retention rate and the presence or absence of a slight short circuit were evaluated. In addition, about the presence or absence of a fine short-circuit, when the charge capacity becomes more than twice the rated capacity between the first cycle and the 100th cycle, the presence or absence of fine short-circuit: “Yes” is less than twice The case where there existed was evaluated as the presence or absence of a fine short circuit: "None". In addition, the amount of gas generated in the battery was measured using the Archimedes method before and after the cycle test. Based on the battery described in Comparative Example 1 below, the case where the gas generation amount was smaller than that of the battery of Comparative Example 1 was evaluated as “◯”, and the case where the amount of gas generation was more than equivalent was evaluated as “X”.

[Examples 2 to 8]
Except for changing the surface modifier, the surface modification of zirconium phosphate A was performed in the same manner as in Example 1 to obtain inorganic particles. Further, measurement and evaluation were performed in the same manner as in Example 1.

[Example 9]
In the same manner as in Example 1, ion-exchanged water, surface-modified zirconium phosphate A described in Example 1, and an aqueous solution of ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco) were mixed. Thereafter, in Example 9, the average particle size (D50) was adjusted to 1.0 μm by bead mill treatment to obtain a dispersion. Other than that, it measured and evaluated similarly to Example 1. FIG.

[Example 10]
Without surface modification, zirconium phosphate A was baked in a muffle furnace at 600 ° C. for 3 hours, and measurement and evaluation were performed in the same manner as in Example 1.

[Example 11]
Measurement and evaluation were performed in the same manner as in Example 1 without performing surface modification.

[Example 12]
In the same manner as in Example 1, ion-exchanged water, zirconium phosphate A described in Example 1 that was not subjected to surface modification, and an aqueous ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco) were mixed. In Example 12, the average particle diameter (D50) of zirconium phosphate A that was not subjected to surface modification was adjusted to 0.3 μm by bead mill treatment to obtain a dispersion. Other than that, it measured and evaluated similarly to Example 1. FIG.

[Comparative Example 1]
A separator having a multilayer structure containing aluminum silicate was obtained in the same manner as in Example 1 except that aluminum silicate (Al ₂ O ₃ .2SiO ₂ ) was used as the inorganic particles. In addition, the volume ratio of the aluminum silicate in the porous layer containing this aluminum silicate of this separator was 97 volume%. Further, in the same manner as in Example 1, measurement of metal adsorption capacity, evaluation of HF adsorption capacity and evaluation of life characteristics were performed.

  The results are shown in Table 1.

  The zirconium phosphate A-containing inorganic particles described in Examples 1 to 12 showed good adsorption characteristics such that the metal adsorption capacity was Mn adsorption rate: 23 to 34%. Moreover, these inorganic particles were determined to have “HF” adsorbing ability for HF. The battery provided with the separator containing the inorganic particles also had good life characteristics, and the short-circuit was determined to be “none”, indicating a high discharge capacity retention rate. Further, in the battery using the surface-modified zirconium phosphate A described in Examples 1 to 9, the amount of gas generated inside the battery, which is difficult to be compatible with the discharge capacity maintenance rate, was also determined as “◯”. In Example 10 as well, the amount of gas generated inside the battery was determined to be “◯”. On the other hand, the aluminum silicate described in Comparative Example 1 has a metal adsorption capacity of Mn adsorption rate: 0%, an HF adsorption capacity of “no”, and a life characteristic of a battery equipped with a separator containing these inorganic particles. The discharge capacity retention rate was 5%, and the gas generation amount was determined to be “x”.

  The nonaqueous electrolyte secondary battery according to this embodiment can be used for various consumer equipment power supplies, automobile power supplies, and the like.

Claims (12)

  In the crystal structure, a metal element having an electronegativity smaller than that of manganese is included, and a layered compound having an interlayer distance of 0.40 nm to 2.0 nm and having an exchangeable cation other than a hydrogen ion between the layers is included. Inorganic particles for non-aqueous electrolyte batteries.   The inorganic for non-aqueous electrolyte battery according to claim 1, wherein the exchangeable cation is selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, organic cations, and any mixture thereof. particle. The inorganic particles are 0.035 parts by mass in an atmosphere of 23 ° C. with respect to 100 parts by mass of a mixed solution of 5 ppm of Mn ²⁺ ions, 1 mol / L LiPF ₆ and cyclic and / or chain carbonate. The inorganic particles for nonaqueous electrolyte batteries according to claim 1 or 2, wherein the adsorption rate of the Mn ²⁺ ions when immersed for a period of time is 5% or more. The inorganic particles were immersed in 100 parts by mass of a mixture of 800 ppm of HF, 1 mol / L LiPF ₆ and cyclic and / or chain carbonate in an amount of 8 parts by mass in an atmosphere of 23 ° C. for 5 minutes. The inorganic particle for nonaqueous electrolyte batteries according to any one of claims 1 to 3, wherein the HF concentration at the time decreases by 10% or more. Following formula:
Hydrophilic parameter A = BET1 / BET2
{In the formula, BET1 means the specific surface area of the inorganic particles calculated using the BET method from the adsorption isotherm measured by adsorbing water vapor to the inorganic particles, and BET2 is nitrogen in the inorganic particles. It means the specific surface area of the inorganic particles calculated using the BET method from the adsorption isotherm measured by adsorbing. }
The inorganic particle for nonaqueous electrolyte batteries according to any one of claims 1 to 4, wherein the hydrophilic parameter A of the inorganic particle defined by (1) is greater than 0.65 and not more than 2.0.   The inorganic particles for nonaqueous electrolyte batteries according to any one of claims 1 to 5, wherein the inorganic particles are surface-modified. The BET specific surface area of the inorganic particles calculated by using a BET method from an adsorption isotherm measured by adsorbing nitrogen to the inorganic particles is 3 m ² / g or more and 200 m ² / g or less. The inorganic particle for nonaqueous electrolyte batteries according to any one of 6. The BET specific surface area of the inorganic particles calculated by using a BET method from an adsorption isotherm measured by adsorbing nitrogen to the inorganic particles is 3 m ² / g or more and 30 m ² / g or less. The inorganic particle for nonaqueous electrolyte batteries according to any one of 7.   The inorganic particle for nonaqueous electrolyte batteries according to any one of claims 1 to 8, wherein the inorganic particle is zirconium phosphate.   Battery constituent material containing the inorganic particle for nonaqueous electrolyte batteries as described in any one of Claims 1-9.   A nonaqueous electrolyte battery comprising an adsorption layer composed of the inorganic particles for a nonaqueous electrolyte battery according to claim 1.   The non-aqueous electrolyte battery includes a positive electrode, a negative electrode, and a separator as battery constituent materials, and the adsorption layer includes at least one of the inside of the separator, the facing surface of the positive electrode and the separator, and the facing surface of the negative electrode and the separator. The non-aqueous electrolyte according to claim 11, wherein the adsorbing layer is formed on the whole or a part of the inside of the separator, or on the whole or a part of each facing surface. battery.