JP2018170276A - Nonaqueous electrolyte solution primary battery and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte solution primary battery which enables the improvement in high-temperature storage characteristic to increase the reliability; and a method for manufacturing the nonaqueous electrolyte solution primary battery.SOLUTION: A nonaqueous electrolyte solution primary battery of the present invention comprises: a negative electrode including metallic lithium or a lithium alloy; and a nonaqueous electrolyte solution containing at least one lithium salt A selected from LiClO, LiCFSO, LiCFSO, LiN(FSO)and LiN(CFSO), at least one lithium salt B selected from LiPF, LiBF, LiAsFand LiSbF, and LiB(CO). In the nonaqueous electrolyte solution, the content of the lithium salt B is more than 20 mol% to a total of 100 mol% of the lithium salt A and the lithium salt B. In the nonaqueous electrolyte solution, the content of the lithium salt A is 0.3-1.2 mol/l. In the nonaqueous electrolyte solution, the content of LiB(CO)is 0.1-2 mass%.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a non-aqueous electrolyte primary battery having a negative electrode containing metallic lithium or a lithium alloy and excellent in reliability, and a method for producing the same.

  Currently, non-aqueous electrolyte batteries such as lithium primary batteries and lithium ion secondary batteries that have non-aqueous electrolytes are exposed to high temperatures, such as power sources for portable devices and pressure sensors inside tires, and Although it is applied in various fields such as a use subject to large vibrations, attempts have been made to improve various characteristics in response to the spread of the use.

In a non-aqueous electrolyte battery using a lithium alloy such as metallic lithium or a lithium-aluminum alloy as a negative electrode active material, particularly a coin-type lithium primary battery, LiClO ₄ having high ionic conductivity and excellent discharge characteristics can be realized. In general, non-aqueous electrolytes using LiN (CF ₃ SO ₂ ) ₂ or the like as electrolytes are used. In addition, in cylindrical lithium primary batteries, non-aqueous electrolytes using LiCF ₃ SO ₃ or the like as electrolytes are generally used. It is used.

  However, when the battery is stored at a high temperature, the reaction between the electrolyte and the electrode occurs, and problems such as battery swelling occur. Therefore, in applications where the battery is used in a high temperature environment, the electrolyte and the electrode Measures to suppress the reaction with are required.

  On the other hand, sulfur-based compounds such as propane sultone are used as additives capable of suppressing reaction with the electrolyte and suppressing battery swelling during high-temperature storage by forming a film on the surface of the positive or negative electrode. Is known (Patent Document 1).

  However, when the sulfur-based compound is included in the electrolytic solution in an addition amount of a certain amount or more so as to produce a sufficient effect for suppressing battery swelling, the coating formed on the electrode surface inhibits the discharge reaction, Since the internal resistance of the battery is increased, a problem that the discharge characteristics are deteriorated after high-temperature storage is likely to occur.

On the other hand, Patent Document 2 uses a nonaqueous electrolytic solution containing lithium bisoxalate borate [LiB (C ₂ O ₄ ) ₂ ] and LiBF ₄ in a molar ratio of 2: 8 to 5: 5. Therefore, it is possible to prevent a rise in internal resistance caused by moisture liberated from the positive electrode active material from the cathode active material at a high temperature and a rise in internal pressure due to the decomposition of the electrolyte, and it is possible to constitute a battery with excellent characteristics at low and high temperatures. It is disclosed.

JP 2004-47413 A JP 2006-269173 A

  However, there are applications that require further high-temperature resistance of the battery, such as medical applications that require heat sterilization and space applications where high-temperature environments are assumed. Development of technology for further improving the heat resistance of the electrolyte battery is required.

  The present invention has been made in view of the above circumstances, and in a non-aqueous electrolyte primary battery including a negative electrode having metallic lithium or a lithium alloy, improving storage at high temperature and increasing reliability; It aims at providing the manufacturing method of the said nonaqueous electrolyte primary battery.

The non-aqueous electrolyte primary battery of the present invention that can achieve the above object includes a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte, and the negative electrode includes metallic lithium or a lithium alloy, and the non-aqueous electrolyte includes: At least one lithium salt A selected from LiClO ₄ , LiCF ₃ SO ₃ , LiC ₂ F ₅ SO ₃ , LiN (FSO ₂ ) ₂ and LiN (CF ₃ SO ₂ ) ₂ , LiPF ₆ , LiBF ₄ , LiAsF ₆ and at least one lithium salt B selected from LiSbF ₆ and LiB (C ₂ O ₄ ) _2, and the lithium salt A and the lithium salt B in the non-aqueous electrolyte When the total is 100 mol%, the proportion of the lithium salt B is more than 20 mol%, and the content of the lithium salt A in the non-aqueous electrolyte is 0.3 to 1.2. mol / l, and the content of LiB (C ₂ O ₄ ) ₂ in the non-aqueous electrolyte is 0.1 to ₂ % by mass.

The production method of the present invention is a method for producing a non-aqueous electrolyte primary battery including a negative electrode, a positive electrode, a separator, and a non-aqueous electrolyte, and the non-aqueous electrolyte includes LiClO ₄ , LiCF ₃ SO ₃ , and _{LiC 2 F 5 SO 3, LiN} (FSO 2) 2 and _LiN (CF 3 _{SO 2)} at least one lithium salt a is selected from _2, is selected from LiPF _6, LiBF 4, LiAsF ₆ and LiSbF ₆ The lithium in which at least one lithium salt B and LiB (C ₂ O ₄ ) ₂ are contained, and the total of the lithium salt A and the lithium salt B in the non-aqueous electrolyte is 100 mol%. The ratio of the salt B is set to more than 20 mol%, the content of the lithium salt A in the non-aqueous electrolyte is 0.3 to 1.2 mol / l, and the non-aqueous electrolyte includes The content of LiB (C ₂ O ₄ ) ₂ is 0.1 to ₂ % by mass.

  ADVANTAGE OF THE INVENTION According to this invention, the swelling of the battery at the time of high temperature storage and the raise of internal resistance can be suppressed, and the nonaqueous electrolyte primary battery excellent in reliability and its manufacturing method can be provided.

It is sectional drawing which represents typically an example of the nonaqueous electrolyte primary battery of this invention. It is a graph showing the change of the swelling with respect to the storage time of the nonaqueous electrolyte primary battery of Examples 1-4 and Comparative Examples 1-3. It is a graph showing the change of CCV with respect to the storage time of the nonaqueous electrolyte primary battery of Examples 1-4 and Comparative Examples 1-3. 5 is a graph showing changes in swelling with respect to storage time of the nonaqueous electrolyte primary batteries of Examples 3 to 8 and Comparative Example 1. FIG. It is a graph showing the change of CCV with respect to the storage time of the nonaqueous electrolyte primary battery of Examples 3-8 and Comparative Example 1. It is a graph showing the change of CCV with respect to the storage time in the hot and humid environment of the nonaqueous electrolyte primary battery of Examples 3-8 and Comparative Example 1.

The non-aqueous electrolyte primary battery of the present invention uses a non-aqueous electrolyte obtained by dissolving a lithium salt in, for example, an organic solvent. The non-aqueous electrolyte is at least one lithium salt A selected from LiClO ₄ , LiCF ₃ SO ₃ , LiC ₂ F ₅ SO ₃ , LiN (FSO ₂ ) ₂ and LiN (CF ₃ SO ₂ ) _2. And at least one lithium salt B selected from LiPF ₆ , LiBF ₄ , LiAsF ₆ and LiSbF ₆ , and LiB (C ₂ O ₄ ) ₂ .

  The lithium salt A functions as an electrolyte salt for ensuring lithium ion conductivity in the nonaqueous electrolytic solution. Moreover, since the lithium salt A is excellent in heat resistance among the electrolyte salts that can be used for the non-aqueous electrolyte, the use of the non-aqueous electrolyte containing the lithium salt A allows, for example, a non-aqueous electrolyte primary battery. High temperature storage characteristics (reliability of batteries during high temperature storage and after high temperature storage) can be improved.

On the other hand, the lithium salt B is usually used as an electrolyte salt for ensuring lithium ion conductivity in the non-aqueous electrolyte, but acts in this way in the non-aqueous electrolyte primary battery of the present invention. In addition to LiB (C ₂ O ₄ ) ₂ , a protective coating that suppresses the reaction between the non-aqueous electrolyte and the negative electrode is formed on the negative electrode surface by contacting the lithium metal or lithium alloy of the negative electrode. Since this protective film works effectively even in a high-temperature environment of, for example, 110 ° C. or higher, even when the battery is placed in a high-temperature environment, the reaction between the non-aqueous electrolyte and the negative electrode surface is sufficiently suppressed. It is possible to satisfactorily suppress the increase in internal resistance due to the generation of gas accompanying decomposition of the water electrolyte component and the generation of by-products not involved in discharge.

As described above, in the non-aqueous electrolyte primary battery of the present invention, the above-described action by the lithium salt A and the above-described action by the lithium salt B and LiB (C ₂ O ₄ ) ₂ are made to function synergistically. Suppression of battery swelling and increase in internal resistance during storage can be suppressed to ensure high reliability.

  When a lithium alloy is used as the negative electrode active material, it is common to form an alloy element by reacting an alloy element (for example, aluminum) for forming the lithium alloy with lithium in the battery. In this case, when an alloying element generally used in the form of particles or a film is alloyed with lithium, the active material is detached from the negative electrode due to the influence of vibration or the like, causing a problem such as a short circuit. Is likely to occur.

However, in the non-aqueous electrolyte primary battery of the present invention, the protective film formed on the negative electrode surface by using a non-aqueous electrolyte containing lithium salt B and LiB (C ₂ O ₄ ) ₂ in specific amounts, respectively. However, in order to suppress the electrochemical reaction between lithium and the alloy element and to suppress the production of a large amount of fine powder accompanying the formation of the lithium alloy, a short circuit that can occur due to the lithium alloy fine powder being detached from the negative electrode, etc. It is estimated that this problem can be prevented.

  Therefore, even when a separator having a relatively large gap size and a fine powder of the active material that has fallen off the electrode easily passes through the gap, such as a nonwoven fabric separator, a short circuit due to the pulverization of the negative electrode active material. It is considered that a non-aqueous electrolyte primary battery excellent in vibration resistance can be formed.

  Examples of organic solvents that can be used in the non-aqueous electrolyte for non-aqueous electrolyte primary batteries include cyclic carbonates such as ethylene carbonate, propylene carbonate (PC), butylene carbonate, and vinylene carbonate; dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and the like 1,2-dimethoxyethane (DME), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetraglyme (tetraethylene glycol dimethyl ether), methoxyethoxyethane, 1,2-diethoxyethane, Ethers such as tetrahydrofuran; cyclic esters such as γ-butyrolactone; nitriles, etc., and only one of these may be used, It may be used in combination with more species. In particular, it is preferable to use the carbonate and ether in combination.

  When carbonate and ether are used in combination as the nonaqueous electrolyte solvent, the amount ratio (mixing ratio) of carbonate and ether in the total solvent is a volume ratio of carbonate: ether = 30: 70 to 70:30. It is preferable that

  It is also preferable to use nitrile as the non-aqueous electrolyte solvent. Since nitrile has a low viscosity and a high dielectric constant, the load characteristics of the non-aqueous electrolyte primary battery can be further improved by using it as a non-aqueous electrolyte solvent.

  Specific examples of nitriles include mononitriles such as acetonitrile, propionitrile, butyronitrile, valeronitrile, benzonitrile, acrylonitrile; malononitrile, succinonitrile, glutaronitrile, adiponitrile, 1,4-dicyanoheptane, 1,5- Dicyanopentane, 1,6-dicyanohexane, 1,7-dicyanoheptane, 2,6-dicyanoheptane, 1,8-dicyanooctane, 2,7-dicyanooctane, 1,9-dicyanononane, 2,8-dicyanononane, And dinitriles such as 1,10-dicyanodecane, 1,6-dicyanodecane and 2,4-dimethylglutaronitrile; cyclic nitriles such as benzonitrile; alkoxy-substituted nitriles such as methoxyacetonitrile; Among these, acetonitrile is particularly preferable.

  When nitrile is used as the non-aqueous electrolyte solvent, the nitrile content in the total amount of the non-aqueous electrolyte solvent is 5% by volume or more from the viewpoint of better securing the above-described effect due to the use of the nitrile. Preferably, it is 8 volume% or more. However, since nitrile is highly reactive with lithium in the negative electrode, it is preferable to limit the amount of nitrile used to some extent to suppress excessive reaction between them. Therefore, the nitrile content in the total amount of the nonaqueous electrolyte solvent is preferably 20% by volume or less, and more preferably 17% by volume or less.

  The content of the lithium salt A in the nonaqueous electrolytic solution is 0.3 mol / l or more, preferably 0.4 mol / l or more, from the viewpoint of ensuring good lithium ion conductivity, l or less, preferably 1.0 mol / l or less.

  Moreover, the ratio of the lithium salt B when the total of the lithium salt A and the lithium salt B in the nonaqueous electrolytic solution is 100 mol% is 20 mol% or more from the viewpoint of ensuring the above-described effect by the lithium salt B satisfactorily. More, it is preferably 25 mol% or more, and more preferably 30 mol% or more. However, if the proportion of the lithium salt B in the total of the lithium salt A and the lithium salt B in the non-aqueous electrolyte is too large, the protective film formed on the negative electrode surface becomes too thick, and the internal resistance of the battery is rather reduced. There is a risk that the battery characteristics will be reduced. Therefore, from the viewpoint of improving battery characteristics, the ratio of the lithium salt B when the total of the lithium salt A and the lithium salt B in the non-aqueous electrolyte is 100 mol% is preferably 70 mol% or less, More preferably, it is 50 mol% or less.

  The non-aqueous electrolyte may contain a lithium salt other than the lithium salt A and the lithium salt B (such as a lithium salt usually used in non-aqueous electrolytes for non-aqueous electrolyte batteries). In this case, it is preferable that the total amount of the lithium salt in the non-aqueous electrolyte is 1.5 mol / l or less.

Furthermore, the content of LiB (C ₂ O ₄ ) ₂ in the nonaqueous electrolytic solution is 0.1% by mass or more from the viewpoint of favorably securing the above-described effect due to LiB (C ₂ O ₄ ) ₂ . It is preferably 0.3% by mass or more, and more preferably 0.5% by mass or more. However, if the amount of LiB (C ₂ O ₄ ) _{2 in} the nonaqueous electrolytic solution is too large, the internal resistance of the battery may increase and the battery characteristics may be deteriorated. Therefore, from the viewpoint of improving battery characteristics, the content of LiB (C ₂ O ₄ ) ₂ in the nonaqueous electrolytic solution is 2% by mass or less, and preferably 1.5% by mass or less.

Moreover, it is preferable to contain a sultone compound in a non-aqueous electrolyte. It is considered that the sultone compound can form a film on the positive electrode surface to suppress decomposition of the non-aqueous electrolyte and gas generation at the positive electrode, and coexist with lithium salt B and LiB (C ₂ O ₄ ) _2. As a result, battery swelling during high-temperature storage can be further suppressed, and the reliability of the nonaqueous electrolyte primary battery can be further improved.

  The sultone compound is classified into a compound having no unsaturated bond in the ring and a compound having an unsaturated bond in the ring. A ring compound is preferably used, and one having a 5-membered ring structure is more preferably used.

  Examples of the compound having no unsaturated bond in the ring include 1,3-propane sultone and 1,4-butane sultone, and 1,3-propane sultone is preferably used.

  Examples of the compound having an unsaturated bond in the ring include those having a 5-membered ring structure represented by the following general formula (1).

In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, fluorine, or a carbon number of 1 to 12, and a part or all of the hydrogens are substituted with fluorine. It may be a hydrocarbon group.

Among the compounds represented by the general formula (1), R ¹ , R ² , R ³ and R ⁴ each have hydrogen, fluorine, or 1 to 3 carbon atoms, and part or all of the hydrogen is fluorine. Is preferably a hydrocarbon group which may be substituted with 1,3-propene sultone (PRS).

  From the viewpoint of ensuring the above-described effect of the sultone compound satisfactorily, the content of the sultone compound in the non-aqueous electrolyte is preferably 0.5% by mass or more, and more preferably 1% by mass or more. However, if the amount of the sultone compound in the non-aqueous electrolyte is too large, the internal resistance of the battery may increase and the discharge characteristics may deteriorate. Therefore, from the viewpoint of suppressing a decrease in discharge characteristics, the content of the sultone compound in the nonaqueous electrolytic solution is preferably 3% by mass or less, and more preferably 2.5% by mass or less.

Furthermore, additives other than LiB (C ₂ O ₄ ) ₂ and sultone compounds can be added to the non-aqueous electrolyte as necessary. Examples of such additives include phosphoric acid compounds such as tris (trimethylsilyl) phosphate; boric acid compounds such as tris (trimethylsilyl) borate; acid anhydrides such as maleic anhydride and phthalic anhydride; and the like.

In particular, it is preferable to contain a phosphoric acid compound or boric acid compound having a group represented by the following general formula (2) in the molecule as an additive for the non-aqueous electrolyte.

In the general formula (2), X is Si, Ge or Sn, and R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or Represents an aryl group having 6 to 10 carbon atoms, and part or all of the hydrogen atoms may be substituted with fluorine.

  By incorporating the phosphoric acid compound or boric acid compound having the group represented by the general formula (2) in the molecule into the non-aqueous electrolyte, it is possible to further suppress the deterioration of the battery characteristics in a high temperature environment. .

  In addition, when a battery using a non-aqueous electrolyte containing a lithium salt B that easily generates hydrofluoric acid by reaction with moisture is left in a high temperature and high humidity environment for a long time, due to loose sealing or By allowing moisture to permeate through the resin constituting the gasket, moisture enters the battery and reacts with the non-aqueous electrolyte, which easily deteriorates the characteristics of the battery. However, by incorporating the phosphoric acid compound or boric acid compound into the non-aqueous electrolyte, it is possible to suppress the above characteristic deterioration, and to constitute a battery having excellent storage characteristics in a high temperature and high humidity environment. it can.

  In the general formula (2), X is Si, Ge, or Sn. As the phosphoric acid compound, a phosphoric acid silyl ester in which X is Si is preferably used, and as the boric acid compound, X is Si. The boric acid silyl ester is preferably used.

In the general formula (2), R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. However, a methyl group or an ethyl group is more preferable. In addition, R ⁵ , R ⁶ and R ⁷ may be partially or wholly substituted with fluorine. The group represented by the general formula (2) is particularly preferably a trimethylsilyl group.

  In the phosphoric acid compound, only one of the hydrogen atoms of phosphoric acid may be substituted with the group represented by the general formula (2), and two of the hydrogen atoms of phosphoric acid may be The group represented by the general formula (2) may be substituted, and all three hydrogen atoms of phosphoric acid may be substituted with the group represented by the general formula (2). It is more preferable that all three hydrogen atoms of phosphoric acid are substituted with a group represented by the general formula (2).

  Examples of the phosphoric acid compound include mono (trimethylsilyl) phosphate, di (trimethylsilyl) phosphate, tris (trimethylsilyl) phosphate, dimethyltrimethylsilyl phosphate, methylbis (trimethylsilyl) phosphate, diethyltrimethylsilyl phosphate, Diphenyl phosphate (trimethylsilyl), Tris phosphate (triethylsilyl), Tris phosphate (vinyldimethylsilyl), Tris phosphate (triisopropylsilyl), Tris phosphate (dimethylethylsilyl), Tris phosphate (methyldiethylsilyl) , Tris (butyldimethylsilyl) phosphate, tris (vinyldimethylsilyl) phosphate, tris (triphenylsilyl) phosphate, mono (trimethylsilyl) phosphate, di (trimethylsilyl) phosphate, Tris (trimethylsilyl) phosphate dimethyl trimethylsilyl, methyl bis phosphate (trimethylsilyl) are preferred, phosphoric acid tris (trimethylsilyl) are particularly preferred.

  In the boric acid compound, only one of the hydrogen atoms possessed by boric acid may be substituted with the group represented by the general formula (2). Two of them may be substituted with a group represented by the general formula (2), and all three hydrogen atoms of boric acid may be substituted with a group represented by the general formula (2). However, it is more preferable that all three hydrogen atoms of boric acid are substituted with the group represented by the general formula (2).

  Examples of such boric acid compounds include mono (trimethylsilyl) borate, di (trimethylsilyl) borate, tris (trimethylsilyl) borate, dimethyltrimethylsilylborate, methylbis (trimethylsilyl) borate, diethyltrimethylsilylborate, Diphenyl borate (trimethylsilyl), tris (triethylsilyl) borate, tris (vinyldimethylsilyl) borate, tris (triisopropylsilyl) borate, tris (dimethylethylsilyl) borate, tris (methyldiethylsilyl) borate, Examples include tris (butyldimethylsilyl) borate, tris (vinyldimethylsilyl) borate, tris (triphenylsilyl) borate, mono (trimethylsilyl) borate, di (trimethylsilyl) borate, boron Tris (trimethylsilyl) borate dimethyl trimethylsilyl, methyl bis borate (trimethylsilyl) are preferred, boric acid tris (trimethylsilyl) are particularly preferred.

  The content of the phosphoric acid compound or boric acid compound having the group represented by the general formula (2) in the molecule in the nonaqueous electrolytic solution (the total amount when both are contained) depends on the use thereof. From the viewpoint of ensuring a better effect, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, particularly preferably 0.5% by mass or more. Most preferably, it is at least mass%. On the other hand, if the content is too large, the thickness of the film formed on the surface of the negative electrode due to the compound increases, which may increase resistance and reduce load characteristics. The content of the phosphoric acid compound or boric acid compound having the group represented by the general formula (2) in the liquid or boric acid compound in the liquid (the total amount when containing both) is 5% by mass or less. Is preferably 4% by mass or less, more preferably 3% by mass or less, and most preferably 2.5% by mass or less.

  In addition, it is preferable to adjust the content of the phosphoric acid compound or boric acid compound having the group represented by the general formula (2) in the molecule according to the content of the lithium salt B. The content of the boric acid compound in the non-aqueous electrolyte (the total amount when both are contained) is preferably 0.1 or more in terms of molar ratio to the content of the lithium salt B. .2 or more is preferable, and in order to prevent a decrease in load characteristics, the molar ratio is preferably 0.5 or less, and more preferably 0.4 or less.

  Further, as the non-aqueous electrolyte, a gelled gel (gel electrolyte) can be used by adding a known gelling agent.

  The negative electrode according to the nonaqueous electrolyte primary battery contains metallic lithium or a lithium alloy. As the negative electrode containing metallic lithium, a metallic lithium foil can be used as it is, or a metallic lithium foil having a structure in which the metallic lithium foil is pressure-bonded to one side or both sides of the current collector can also be used.

  Moreover, as a negative electrode containing a lithium alloy, a lithium alloy foil can be used as it is, or a lithium alloy foil having a structure in which a lithium alloy foil is pressure-bonded to one side or both sides of a current collector can be used.

  Furthermore, in the case of a negative electrode containing a lithium alloy, lamination was performed by, for example, pressing a layer containing an alloy element for forming a lithium alloy on the surface of a lithium layer (a layer containing lithium) composed of a metal lithium foil or the like. By using a laminate and bringing the laminate into contact with a non-aqueous electrolyte in the battery, a lithium alloy can be formed on the surface of the lithium layer to form a negative electrode. In the case of such a negative electrode, a laminate having a layer containing an alloy element only on one side of the lithium layer may be used, or a laminate having a layer containing an alloy element on both sides of the lithium layer may be used. The said laminated body can be formed by crimping | bonding the metal lithium foil and the foil comprised with the alloy element, for example.

  The current collector can also be used when a negative electrode is formed by forming a lithium alloy in the battery. For example, the negative electrode current collector has a lithium layer on one side of the negative electrode current collector and has a lithium layer. A laminate having a layer containing an alloy element on the surface opposite to the surface of the negative electrode may have a lithium layer on both surfaces of the negative electrode current collector, and the surface of each lithium layer opposite to the negative electrode current collector Alternatively, a laminate having a layer containing an alloy element may be used. The negative electrode current collector and the lithium layer (metal lithium foil) may be laminated by pressure bonding or the like.

  Examples of the alloy element for forming the lithium alloy include aluminum, lead, bismuth, indium, and gallium. Aluminum is preferable.

  For the layer containing the alloy element according to the laminate for forming a negative electrode, for example, a foil composed of these alloy elements can be used. The thickness of the layer containing the alloy element is preferably 1 μm or more, more preferably 3 μm or more, preferably 20 μm or less, and more preferably 12 μm or less.

  For example, a metal lithium foil or the like can be used for the lithium layer according to the laminate for forming the negative electrode. The thickness of the lithium layer is preferably 0.1 to 1.5 mm. Moreover, it is preferable that the thickness of the lithium layer (metal lithium foil used for the formation) when it is set as the negative electrode containing metallic lithium is also 0.1 to 1.5 mm.

  Examples of the negative electrode current collector include those made of copper, nickel, iron, and stainless steel, and the forms thereof include plain weave metal mesh, expanded metal, lath net, punching metal, metal foam, foil (plate), etc. Can be illustrated. The thickness of the current collector is preferably 5 to 100 μm, for example. It is also desirable to apply a paste-like conductive material such as carbon paste or silver paste to the surface of such a current collector.

  For the positive electrode related to the non-aqueous electrolyte primary battery, for example, a molded body obtained by forming a mixture containing a positive electrode active material, a conductive additive, a binder, etc. (positive electrode mixture) into a pellet form, or the positive electrode mixture A layer having a layer (positive electrode mixture layer) to be formed on one side or both sides of the current collector can be used.

Examples of the positive electrode active material include manganese dioxide and lithium-containing manganese oxides (for example, LiMn ₃ O ₆ and the same crystal structure as manganese dioxide (such as β-type, γ-type, or a structure in which β-type and γ-type are mixed)). A composite oxide having a Li content of 3.5% by mass or less, preferably 2% by mass or less, more preferably 1.5% by mass or less, and particularly preferably 1% by mass or less], Li _a Ti _{5 / 3} O ₄ (4/3 ≦ a <7/3) and other lithium-containing composite oxides; vanadium oxides; niobium oxides; titanium oxides; sulfides such as iron disulfide; It is done.

  Moreover, as a conductive support agent which concerns on a positive electrode mixture, for example, scaly graphite, acetylene black, ketjen black, carbon black etc. are mentioned, only 1 type may be used among these, and 2 or more types may be used. You may use together.

  Furthermore, examples of the binder related to the positive electrode mixture include fluororesins such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and a polymer of propylene hexafluoride. May be used alone, or two or more of them may be used in combination.

  In the case of a molded body of a positive electrode mixture, for example, the positive electrode can be manufactured by pressure-molding a positive electrode mixture prepared by mixing a positive electrode active material, a conductive additive and a binder into a predetermined shape. it can.

  In the case of a positive electrode having a positive electrode mixture layer and a current collector, for example, a positive electrode active material, a conductive aid, a binder, and the like are mixed with water or an organic solvent such as N-methyl-2-pyrrolidone (NMP). To prepare a positive electrode mixture-containing composition (slurry, paste, etc.) (the binder may be dissolved in a solvent), which is coated on a current collector and dried, and if necessary, a calendering treatment It can manufacture through the process of performing press processing, such as.

  However, a positive electrode is not limited to what was manufactured by said each method, The thing manufactured by the other method may be used.

  As a composition in the positive electrode mixture relating to the positive electrode, the amount of the positive electrode active material is preferably 80 to 90% by mass, the content of the conductive auxiliary agent is preferably 1.5 to 10% by mass, and the binder The content of is preferably 0.3 to 10% by mass.

  In the case of a molded body of a positive electrode mixture, the thickness is preferably 0.15 to 4 mm. On the other hand, in the case of a positive electrode having a positive electrode mixture layer and a current collector, the thickness of the positive electrode mixture layer (thickness per one side of the current collector) is preferably 30 to 300 μm.

  In the case where a current collector is used for the positive electrode, examples of the current collector include those made of stainless steel such as SUS316, SUS430, and SUS444. Examples of the current collector include plain weave wire mesh, expanded metal, lath. Examples thereof include a net, punching metal, metal foam, and foil (plate). The thickness of the current collector is preferably, for example, 0.05 to 0.2 mm. It is also desirable to apply a paste-like conductive material such as carbon paste or silver paste to the surface of such a current collector.

  In a non-aqueous electrolyte primary battery, when using a negative electrode having a current collector (or a laminate for a negative electrode) and a positive electrode having a current collector, a laminated body (laminated electrode body) laminated via a separator, A wound body (wound electrode body) obtained by winding the laminated body in a spiral shape, and a flat wound body (flat wound electrode body) obtained by forming the wound body so as to have a flat cross section. ) Can be used. In addition, when using a positive electrode formed of a positive electrode mixture and a negative electrode (or a laminate for a negative electrode) that does not have a current collector, a flat battery case with a separator interposed therebetween Can be housed and used.

  Non-woven fabric and microporous film (microporous film) are used for the separator. Polyolefin such as polyethylene (PE), polypropylene (PP), and ethylene-propylene copolymer can be used as the material. When heat resistance is required in relation to the use of Fluorine resin such as tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), polyphenylene sulfide (PPS), polyether ether ketone (PEEK), poly Butylene terephthalate (PBT), polymethylpentene, polyamide, polyimide, aramid, cellulose and the like can also be used. As the material for the nonwoven fabric or the microporous film, only one of the above-described examples may be used, or two or more may be used. In addition, the nonwoven fabric or microporous membrane used as the separator has a single layer structure composed of the above-mentioned materials, for example, a laminated structure in which a plurality of nonwoven fabrics or microporous membranes composed of different materials are laminated. Can also be used.

  The thickness of the separator may be, for example, 500 μm or less, preferably 450 μm or less, and more preferably 300 μm or less, from the viewpoint of suppressing a decrease in the energy density of the battery. However, if the separator is too thin, there is a possibility that the function of preventing a short circuit may be deteriorated. Therefore, when using a nonwoven fabric, the thickness may be, for example, 30 μm or more, preferably 100 μm or more, and 150 μm. More preferably. Moreover, when using a microporous film, it is preferable that it is 10 micrometers or more, and it is more preferable that it is 15 micrometers or more.

  The form of the non-aqueous electrolyte primary battery is not particularly limited, and various forms such as a flat form (including coin form and button form), a laminate form, and a tubular form (cylindrical form, square form (square tubular form)) are available. It is possible. Moreover, as an exterior body (battery case) that accommodates the negative electrode, the positive electrode, the separator, and the non-aqueous electrolyte, a metal can (exterior can) having an opening and a lid (sealing can) may be used in combination. A laminate film can be used.

  Specifically, a flat or cylindrical battery can be produced by caulking and sealing the outer can and the sealing can via a gasket, or by welding and sealing the outer can and the sealing can. In addition, a laminated battery can be manufactured by stacking two metal laminate films or bending one metal laminate film and pasting and sealing the periphery.

  In addition, when using an exterior body with a caulking seal, PP, nylon, etc. can be used as the gasket material interposed between the exterior can and the seal can. When high heat resistance is required, the melting point or heat of fluorine resin such as PFA, polyphenylene ether (PEE), polysulfone (PSF), polyarylate (PAR), polyethersulfone (PES), PPS, PEEK, etc. A heat resistant resin having a decomposition temperature of 200 ° C. or higher can also be used. Further, when the battery is applied to an application requiring heat resistance, a glass hermetic seal can be used for the sealing.

  Since the non-aqueous electrolyte primary battery of the present invention is excellent in reliability in a high temperature environment, taking advantage of these characteristics, particularly in automotive applications such as a power supply for a pressure sensor inside a tire, particularly at high temperatures. In addition to being suitably used for applications that are easily exposed, the present invention can also be applied to the same applications as those for which conventionally known nonaqueous electrolyte primary batteries are employed.

  Hereinafter, the present invention will be described in detail based on examples. However, the following examples do not limit the present invention.

Example 1
<Preparation of positive electrode>
A positive electrode mixture prepared by mixing manganese dioxide, which is a positive electrode active material, carbon black, which is a conductive auxiliary agent, and PTFE, which is a binder, in a mass ratio of 93: 3: 4, is formed, and has a diameter of 16 mm. A positive electrode (positive electrode mixture molded body) having a thickness of 1.8 mm was obtained.

<Preparation of laminate for negative electrode>
An aluminum foil having a thickness of 0.01 μm was pressure-bonded to one surface of a lithium foil having a thickness of 0.6 mm, and this was punched into a circle having a diameter of 16 mm to obtain a laminate for negative electrode.

<Preparation of non-aqueous electrolyte>
LiClO ₄ (lithium salt A) and LiPF ₆ (lithium salt B) were mixed in a mixed solvent in which PC and DME were mixed at a mass ratio of 41.8: 51.2, 0.49 mol / l, 0.21 mol, respectively. LiB (C ₂ O ₄ ) ₂ [LiBOB] in an amount of 1% by mass (0.05 mol / l) and 1,3-propane sultone (PS) in an amount of 2% by mass. And a non-aqueous electrolyte was prepared. The ratio of LiPF _{6 in} the total of LiClO ₄ and LiPF ₆ in this nonaqueous electrolytic solution was 30.0 mol%.

<Battery assembly>
Using the positive electrode, the negative electrode laminate, and the non-aqueous electrolyte, and using a non-woven fabric made of PPS (thickness: 170 μm) for the separator, the structure shown in FIG. 1 has a diameter of 20 mm and a height of 3.2 mm. A water electrolyte primary battery was assembled.

  FIG. 1 is a longitudinal sectional view schematically showing a non-aqueous electrolyte primary battery of Example 1. In the non-aqueous electrolyte primary battery 1 of Example 1, the positive electrode 2 is an outer can made of stainless steel. 5 is accommodated inside, and the negative electrode 3 is disposed thereon via a separator 4. The negative electrode 3 is pressure-bonded to the inner surface of the sealing can 6 on the surface on the lithium layer (lithium foil) side. Although not shown in FIG. 1, a lithium-aluminum alloy is formed on the surface of the negative electrode 3 on the separator 4 side. Further, a non-aqueous electrolyte (not shown) is injected into the battery 1.

  In the nonaqueous electrolyte primary battery 1, the outer can 5 also serves as a positive electrode terminal, and the sealing can 6 also serves as a negative electrode terminal. The sealing can 6 is fitted to the opening of the outer can 5 via an insulating gasket 7 made of PPS, and the opening end of the outer can 5 is tightened inward, whereby the insulating gasket 7 is By contacting the sealing can 6, the opening of the outer can 5 is sealed and the inside of the battery has a sealed structure. That is, the nonaqueous electrolyte primary battery 1 is formed of an outer can 5, a sealing can 6, and an insulating gasket 7 interposed therebetween, and the positive electrode 2, the separator 4, and the negative electrode 3 are enclosed in a sealed battery case. And a non-aqueous electrolyte solution are accommodated.

(Example 2)
A non-aqueous electrolyte was prepared in the same manner as in Example 1 except that the concentration of LiPF ₆ was changed to 0.35 mol / l, and non-aqueous electrolysis was performed in the same manner as in Example 1 except that this non-aqueous electrolyte was used. A liquid primary battery was produced. The ratio of LiPF _{6 in} the total of LiClO ₄ and LiPF ₆ in this nonaqueous electrolytic solution was 41.7 mol%.

(Example 3)
A nonaqueous electrolytic solution was prepared in the same manner as in Example 1 except that the lithium salt B was changed from LiPF ₆ to LiBF ₄ and the concentration was changed to 0.34 mol / l. Except that this nonaqueous electrolytic solution was used. A non-aqueous electrolyte primary battery was produced in the same manner as in Example 1. The ratio of LiBF _{4 in} the total of LiClO ₄ and LiBF ₄ in this nonaqueous electrolytic solution was 41.0 mol%.

Example 4
A nonaqueous electrolytic solution was prepared in the same manner as in Example 3 except that the concentration of LiBF ₄ was changed to 0.56 mol / l, and nonaqueous electrolysis was performed in the same manner as in Example 1 except that this nonaqueous electrolytic solution was used. A liquid primary battery was produced. The ratio of LiBF _{4 in} the total of LiClO ₄ and LiBF ₄ in this nonaqueous electrolytic solution was 53.3 mol%.

(Comparative Example 1)
A non-aqueous electrolyte was prepared in the same manner as in Example 1 except that LiPF ₆ was not added, and a non-aqueous electrolyte primary battery was prepared in the same manner as in Example 1 except that this non-aqueous electrolyte was used. .

(Comparative Example 2)
A non-aqueous electrolyte was prepared in the same manner as in Example 1 except that the concentration of LiPF ₆ was changed to 0.07 mol / l, and non-aqueous electrolysis was performed in the same manner as in Example 1 except that this non-aqueous electrolyte was used. A liquid primary battery was produced. The ratio of LiPF _{6 in} the total of LiClO ₄ and LiPF ₆ in this non-aqueous electrolyte was 12.5 mol%.

(Comparative Example 3)
A nonaqueous electrolytic solution was prepared in the same manner as in Example 3 except that the concentration of LiBF ₄ was changed to 0.11 mol / l, and nonaqueous electrolysis was performed in the same manner as in Example 1 except that this nonaqueous electrolytic solution was used. A liquid primary battery was produced. The ratio of LiBF _{4 in} the total of LiClO ₄ and LiBF ₄ in this nonaqueous electrolytic solution was 18.3 mol%.

(Comparative Example 4)
A nonaqueous electrolytic solution was prepared in the same manner as in Example 2 except that the LiBOB content was 3% by mass (0.15 mol / l), and the same as in Example 2 except that this nonaqueous electrolytic solution was used. Thus, a non-aqueous electrolyte primary battery was produced.

<Reliability evaluation under high temperature environment>
The non-aqueous electrolyte primary batteries of Examples 1 to 4 and Comparative Examples 1 to 3 were each divided into two, and a resistance of 15 kΩ was connected to one side, and discharging was performed until the depth of discharge with respect to the positive electrode capacity was 60%. . The batteries of Examples and Comparative Examples (DOD: 0% batteries) that were not discharged, and the batteries of Examples and Comparative Examples (DOD: 60% batteries) with a discharge depth of 60%, It was put in a thermostat adjusted to 140 ° C., and the height of each battery was measured every time shown in Table 2, and the amount of change (battery swelling) from the height (3.2 mm) immediately after the battery was manufactured was obtained. . However, when the measured battery swelling amount exceeded 1 mm, the measurement was not performed during the subsequent storage time.

<Evaluation of battery characteristics after high temperature storage>
Regarding the non-aqueous electrolyte primary batteries of Examples 1 to 4 and Comparative Examples 1 to 3, evaluation of battery characteristics after high-temperature storage in the case of DOD: 0% and DOD: 60% under the following conditions Went. Moreover, about the nonaqueous electrolyte primary battery of the comparative example 4, the battery characteristic after the high temperature storage in the case of DOD: 0% was evaluated.

  Each battery was put in a thermostat adjusted to 140 ° C., taken out every time shown in Tables 3 and 4, and allowed to discharge after being allowed to cool and connected with a 100Ω resistor in an environment of 20 ° C. The closed circuit voltage (CCV) of the battery after 3 seconds was measured. However, when the measured CCV became a value close to 0V, the measurement in the subsequent storage time was not performed.

  Tables 1 to 4 show the structures of the non-aqueous electrolytes according to the non-aqueous electrolyte primary batteries of Examples 1 to 4 and Comparative Examples 1 to 4, and Tables 2 to 4 show the evaluation results. As for the evaluation results of the battery with DOD: 60%, FIG. 2 and FIG. 3 show the change of the battery swelling and the change of the CCV with respect to the storage time of the battery, respectively. The “ratio of lithium salt B” in Table 1 means the ratio of lithium salt B in the total of lithium salt A and lithium salt B (the same applies to Table 5 described later). In Tables 2 and 4, “-” means that measurement was not performed for the above reason (the same applies to Tables 6 and 8 described later).

As shown in Tables 1 to 4 and FIGS. 2 and 3, Examples 1 to 4 using non-aqueous electrolytes using lithium salt A, lithium salt B, and LiB (C ₂ O ₄ ) ₂ in appropriate amounts. The non-aqueous electrolyte primary battery of the present invention is high in that the swelling of the battery and the increase in internal resistance are suppressed over a long period of time in a high-temperature environment of 140 ° C., regardless of whether the depth of discharge is 0% or 60%. It had reliability.

  On the other hand, the batteries of Comparative Examples 2 and 3 using the non-aqueous electrolyte in which the ratio of the lithium salt B in the total of the lithium salt A and the lithium salt B is 20 mol% or less use the lithium salt B. Compared with the battery of Comparative Example 1 using a non-aqueous electrolyte, the battery characteristics after high-temperature storage were improved, but the effect of suppressing the swelling of the battery was lower than that of the battery of the above Example, and the discharge When the depth was 60%, the increase in internal resistance could not be sufficiently suppressed.

  Further, as is clear from the results of the batteries of Examples 1 and 2 and the results of the batteries of Examples 3 and 4 shown in FIG. 3, at least in the state where the depth of discharge is 60%, the lithium salt B Since the internal resistance increases and the CCV decreases when the ratio of the lithium salt B increases, the ratio of the lithium salt B in the total of the lithium salt A and the lithium salt B is preferably 70 mol% or less.

Further, from the results of the batteries of Example 2 and Comparative Example 4 shown in Table 3, when the content of LiB (C ₂ O ₄ ) ₂ is more than 2% by mass, the internal resistance is increased and the load characteristics are increased. It turns out that it falls.

(Example 5)
LiClO ₄ (lithium salt A) and LiBF ₄ (lithium salt B) were mixed in a mixed solvent in which PC and DME were mixed at a mass ratio of 41.8: 51.2, 0.49 mol / l and 0.21 mol, respectively. 1% (0.05 mol / l) of LiBOB in an amount of 1% by mass (0.05 mol / l), 2% by mass of PS and 1.5% by mass (0.05 mol / l) of Tris (trimethylsilyl) phosphate (TMSP) was added to prepare a non-aqueous electrolyte. A nonaqueous electrolyte primary battery was produced in the same manner as in Example 1 except that this nonaqueous electrolyte was used. The ratio of LiBF _{4 in} the total of LiClO ₄ and LiBF ₄ in this nonaqueous electrolytic solution was 41.0 mol%. Further, the TMSP content relative to the LiBF ₄ content was 0.15 in molar ratio.

(Example 6)
A nonaqueous electrolytic solution was prepared in the same manner as in Example 5 except that the concentration of LiBF ₄ was changed to 0.56 mol / l, and nonaqueous electrolysis was performed in the same manner as in Example 5 except that this nonaqueous electrolytic solution was used. A liquid primary battery was produced. The ratio of LiBF _{4 in} the total of LiClO ₄ and LiBF ₄ in this nonaqueous electrolytic solution was 53.3 mol%. Further, the TMSP content relative to the LiBF ₄ content was 0.09 in molar ratio.

(Example 7)
A non-aqueous electrolyte was prepared in the same manner as in Example 5 except that the amount of TMSP added was changed to 3% by mass (0.1 mol / l), and the same as in Example 5 except that this non-aqueous electrolyte was used. Thus, a non-aqueous electrolyte primary battery was produced. The ratio of LiBF _{4 in} the total of LiClO ₄ and LiBF ₄ in this nonaqueous electrolytic solution was 41.0 mol%. The TMSP content relative to the LiBF ₄ content was 0.29 in terms of molar ratio.

(Example 8)
A non-aqueous electrolyte was prepared in the same manner as in Example 6 except that the amount of TMSP added was changed to 3% by mass (0.1 mol / l), and the same as in Example 6 except that this non-aqueous electrolyte was used. Thus, a non-aqueous electrolyte primary battery was produced. The ratio of LiBF _{4 in} the total of LiClO ₄ and LiBF ₄ in this nonaqueous electrolytic solution was 53.3 mol%. Further, the TMSP content relative to the LiBF ₄ content was 0.18 in molar ratio.

  For the non-aqueous electrolyte primary batteries of Examples 5 to 8, “reliability evaluation under high temperature environment” and “battery characteristic evaluation after high temperature storage” were performed in the same manner as described above.

  Table 5 shows the configurations of the nonaqueous electrolyte solutions according to the nonaqueous electrolyte primary batteries of Examples 5 to 8, and Tables 6 to 8 show the evaluation results. In Tables 5 to 8, the configurations of the nonaqueous electrolyte solutions and the evaluation results according to the nonaqueous electrolyte primary batteries of Examples 3 and 4 and Comparative Example 1 are shown. As for the evaluation results of the battery with DOD: 60%, FIG. 4 and FIG. 5 show the change of the battery swelling and the change of the CCV with respect to the storage time of the battery, respectively.

  As shown in Tables 5 to 8 and FIGS. 4 and 5, the batteries of Examples 5 to 8 to which TMSP was added can suppress the swelling of the battery for a long time as in the batteries of Examples 3 and 4. It was. Moreover, by adding TMSP, it was possible to further suppress the decrease in CCV due to the increase in internal resistance.

<Battery characteristics evaluation after storage in high temperature and humidity environment>
For the nonaqueous electrolyte primary batteries (DOD: 0%) of Examples 3 to 8 and Comparative Example 1, the battery characteristics after storage in a high temperature and high humidity environment were evaluated under the following conditions.

  Each battery was put in a thermostat adjusted to 90% relative humidity at 80 ° C., taken out every time shown in Table 9, and allowed to discharge after being allowed to cool and connected with a resistance of 100Ω in an environment of 20 ° C. The closed circuit voltage (CCV) of the battery after 0.3 seconds was measured. These evaluation results are shown in Table 9 and FIG.

As shown in Table 9 and Figure 6, the battery of LiBF 4 Examples 3 and 4 were added _(lithium salt B), by which is stored at high temperature and high humidity environment, moisture and LiBF ₄ which has entered the battery As a result, the internal resistance increased and the CCV decreased as compared with the battery of Comparative Example 1. On the other hand, in the batteries of Examples 5 to 8 to which TMSP was added, the above problems were prevented, and excellent battery characteristics could be maintained for a long time even in storage in a high temperature and high humidity environment. In particular, in the batteries of Example 5, Example 7 and Example 8 in which the TMSP content is 0.1 or more in terms of molar ratio with respect to the LiBF ₄ content, it is possible to achieve better storage properties. did it.

DESCRIPTION OF SYMBOLS 1 Nonaqueous electrolyte primary battery 2 Positive electrode 3 Negative electrode 4 Separator 5 Exterior can 6 Sealing can 7 Insulation gasket

Claims (10)

A non-aqueous electrolyte primary battery having a positive electrode, a negative electrode, a separator and a non-aqueous electrolyte,
The negative electrode includes metallic lithium or a lithium alloy,
The non-aqueous electrolyte includes at least one lithium salt A selected from LiClO ₄ , LiCF ₃ SO ₃ , LiC ₂ F ₅ SO ₃ , LiN (FSO ₂ ) ₂ and LiN (CF ₃ SO ₂ ) ₂ ; Containing at least one lithium salt B selected from LiPF ₆ , LiBF ₄ , LiAsF ₆ and LiSbF ₆ , and LiB (C ₂ O ₄ ) ₂ ;
When the total of the lithium salt A and the lithium salt B in the non-aqueous electrolyte is 100 mol%, the ratio of the lithium salt B is more than 20 mol%,
The content of the lithium salt A in the non-aqueous electrolyte is 0.3 to 1.2 mol / l,
Non-aqueous electrolyte primary battery, wherein the content of _{LiB (C 2} O _{4) 2} in the non-aqueous electrolyte is 0.1 to 2 wt%.   2. The non-aqueous electrolyte primary battery according to claim 1, wherein a ratio of the lithium salt B is 70 mol% or less when a total of the lithium salt A and the lithium salt B in the non-aqueous electrolyte is 100 mol%. .   The non-aqueous electrolyte primary battery according to claim 1, wherein the non-aqueous electrolyte further contains a sultone compound.   The non-aqueous electrolyte primary battery according to claim 3, wherein a content of the sultone compound in the non-aqueous electrolyte is 0.5 to 3% by mass. The nonaqueous electrolytic solution according to any one of claims 1 to 4, wherein the nonaqueous electrolytic solution further contains a phosphoric acid compound or a boric acid compound having a group represented by the following general formula (2) in the molecule. Liquid primary battery.

[In the general formula (2), X is Si, Ge or Sn, and R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Alternatively, it represents an aryl group having 6 to 10 carbon atoms, and part or all of the hydrogen atoms may be substituted with fluorine. ]   The nonaqueous electrolyte primary battery according to claim 5, wherein a content of the phosphoric acid compound or the boric acid compound is 0.1 to 5% by mass.   7. The nonaqueous electrolyte primary battery according to claim 5, wherein a content of the phosphoric acid compound or the boric acid compound is 0.1 or more in terms of a molar ratio with respect to a content of the lithium salt B. 8. A battery container comprising an outer can, a sealed can and a gasket interposed therebetween,
The nonaqueous electrolyte primary battery according to any one of claims 1 to 7, wherein the gasket is made of a heat-resistant resin having a melting point or a thermal decomposition temperature of 200 ° C or higher. A method for producing a non-aqueous electrolyte primary battery including a negative electrode, a positive electrode, a separator and a non-aqueous electrolyte,
The non-aqueous electrolyte includes at least one lithium salt A selected from LiClO ₄ , LiCF ₃ SO ₃ , LiC ₂ F ₅ SO ₃ , LiN (FSO ₂ ) ₂ and LiN (CF ₃ SO ₂ ) ₂ ; Containing at least one lithium salt B selected from LiPF ₆ , LiBF ₄ , LiAsF ₆ and LiSbF ₆ , and LiB (C ₂ O ₄ ) ₂ ;
The ratio of the lithium salt B when the total of the lithium salt A and the lithium salt B in the nonaqueous electrolytic solution is 100 mol% is more than 20 mol%,
The content of the lithium salt A in the non-aqueous electrolyte is 0.3 to 1.2 mol / l,
The method for producing a non-aqueous electrolyte primary battery, wherein the content of LiB (C ₂ O ₄ ) ₂ in the non-aqueous electrolyte is 0.1 to ₂ % by mass. The method for producing a nonaqueous electrolyte primary battery according to claim 9, further comprising a phosphoric acid compound or a boric acid compound having a group represented by the following general formula (2) in the molecule.

[In the general formula (2), X is Si, Ge or Sn, and R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Alternatively, it represents an aryl group having 6 to 10 carbon atoms, and part or all of the hydrogen atoms may be substituted with fluorine. ]

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