JP7020976B2 - Non-aqueous electrolyte primary battery and its manufacturing method - Google Patents

Description

The present invention relates to a non-aqueous electrolytic solution primary battery having a negative electrode containing metallic lithium or a lithium alloy and having excellent 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 and are exposed to high temperatures, such as the power supply for portable devices and the power supply for pressure sensors inside tires. It is applied in various fields such as applications that receive large vibrations, but with the expansion of its applications, attempts are being made to improve various characteristics.

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 _- shaped lithium primary cell, has high ionic conductivity and can realize excellent discharge characteristics. , LiN (CF ₃ SO ₂ ) ₂ or the like as an electrolyte is generally used, and in a cylindrical lithium primary battery, a non-aqueous electrolyte solution having LiCF ₃ SO ₃ or the like as an electrolyte is generally used. It is used.

However, when the battery is stored at a high temperature, a reaction occurs between the electrolytic solution and the electrode, which causes problems such as swelling of the battery. Therefore, in applications where the battery is used in a high temperature environment, the electrolytic solution and the electrode are used. There is a need for measures to suppress the reaction with.

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

However, when the sulfur-based compound is contained in the electrolytic solution in an amount of a certain amount or more so as to sufficiently suppress the swelling of the battery, the film formed on the electrode surface inhibits the discharge reaction. Since the internal resistance of the battery is increased, the problem that the discharge characteristics are deteriorated after high temperature storage is likely to occur.

On the other hand, Patent Document 2 uses a non-aqueous electrolyte solution containing lithium bisoxalate volate [LiB (C ₂ O ₄ ) ₂ ] and LiBF ₄ in a molar ratio in the range of 2: 8 to 5: 5. As a result, it is possible to prevent an increase in internal resistance caused by moisture liberated from the positive electrode active material in the positive electrode active material at high temperature and an increase in internal pressure due to decomposition of the electrolytic solution, and to construct a battery having excellent characteristics at both low and high temperatures. It has been disclosed.

Japanese Unexamined Patent Publication No. 2004-47413 Japanese Unexamined Patent Publication No. 2006-269173

However, there are also applications that require higher temperature resistance of batteries, such as medical applications that require heat sterility and space applications that are expected to be in a high temperature environment, so that they can withstand a long time in a high temperature environment. There is a need for technological development to further improve the heat resistance of electrolyte batteries.

The present invention has been made in view of the above circumstances, and in a non-aqueous electrolytic solution primary battery provided with a negative electrode having a metallic lithium or a lithium alloy, the storage property at a high temperature is improved and the reliability is enhanced. It is an object of the present invention to provide a method for manufacturing the non-aqueous electrolytic solution primary battery.

The non-aqueous electrolytic solution primary battery of the present invention that has achieved the above object includes a positive electrode, a negative electrode, a separator and a non-aqueous electrolytic solution, the negative electrode contains metallic lithium or a lithium alloy, and the non-aqueous electrolytic solution is a non-aqueous electrolytic solution. 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 LiPF ₆ , LiBF ₄ , LiAsF. ₆ and at least one lithium salt B selected from LiSbF ₆ and LiB (C ₂ O ₄ ) ₂ are contained, and the lithium salt A and the lithium salt B in the non-aqueous electrolytic solution are contained. When the total 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 electrolytic solution is 0.3 to 1.2 mol / l, and the non-aqueous electrolysis It is characterized in that the content of LiB (C ₂ O ₄ ) ₂ in the liquid is 0.1 to 2% by mass.

Further, the manufacturing method of the present invention is a method for manufacturing a non-aqueous electrolytic solution primary battery including a negative electrode, a positive electrode, a separator and a non-aqueous electrolytic solution, wherein LiClO ₄ , LiCF ₃ SO ₃ and LiClO 4 and LiCF 3 SO 3 are added to the non-aqueous electrolytic solution. Selected from at least one lithium salt A selected from LiC ₂ F ₅ SO ₃ , LiN (FSO ₂ ) ₂ and LiN (CF ₃ SO ₂ ) ₂ , and selected from LiPF ₆ , LiBF ₄ , LiAsF ₆ and LiSbF ₆ . The lithium when at least one kind of 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 electrolytic solution is 100 mol%. The ratio of the salt B was increased to more than 20 mol%, the content of the lithium salt A in the non-aqueous electrolytic solution was set to 0.3 to 1.2 mol / l, and LiB (C ₂ O ₄ ) ₂ in the non-aqueous electrolytic solution was used. It is characterized in that the content of is 0.1 to 2% by mass.

According to the present invention, it is possible to provide a highly reliable non-aqueous electrolyte primary battery capable of suppressing swelling of the battery and an increase in internal resistance during high-temperature storage, and a method for producing the same.

It is sectional drawing which shows typically the example of the non-aqueous electrolytic solution primary battery of this invention. 3 is a graph showing changes in swelling with respect to the storage time of the non-aqueous electrolyte primary batteries of Examples 1 to 4 and Comparative Examples 1 to 3. 3 is a graph showing changes in CCV with respect to the storage time of the non-aqueous electrolyte primary batteries of Examples 1 to 4 and Comparative Examples 1 to 3. 3 is a graph showing changes in swelling with respect to the storage time of the non-aqueous electrolyte primary batteries of Examples 3 to 8 and Comparative Example 1. It is a graph which shows the change of CCV with respect to the storage time of the non-aqueous electrolyte primary battery of Examples 3-8 and the comparative example 1. FIG. 3 is a graph showing changes in CCV with respect to the storage time of the non-aqueous electrolyte primary batteries of Examples 3 to 8 and Comparative Example 1 in a high temperature and high humidity environment.

The non-aqueous electrolytic solution primary battery of the present invention uses a non-aqueous electrolytic solution obtained by dissolving a lithium salt in, for example, an organic solvent. The non-aqueous electrolyte solution 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 . It contains at least one lithium salt B selected from LiPF ₆ , LiBF ₄ , LiAsF ₆ and LiSbF ₆ and LiB ( _C2 O ₄ ) ₂ .

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

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 solution, but in the non-aqueous electrolyte solution primary battery of the present invention, it acts in this way. In addition, by contacting LiB (C ₂ O ₄ ) ₂ together with the metallic lithium or lithium alloy of the negative electrode, a protective film that suppresses the reaction between the non-aqueous electrolyte solution and the negative electrode is formed on the surface of the negative electrode. Since this protective film works effectively even in a high temperature environment of, for example, 110 ° C. or higher, it sufficiently suppresses the reaction between the non-aqueous electrolyte solution and the surface of the negative electrode even when the battery is placed in a high temperature environment. It is possible to satisfactorily suppress the increase in internal resistance due to the generation of gas due to the decomposition of the water electrolyte component and the generation of by-products that are not involved in the discharge.

As described above, in the non-aqueous electrolytic solution primary battery of the present invention, the above-mentioned action by the lithium salt A and the above-mentioned action by the lithium salts B and LiB (C ₂ O ₄ ) ₂ are made to function synergistically at a high temperature. It suppresses the swelling of the battery during storage and the increase in internal resistance, making it possible to ensure high reliability.

When a lithium alloy is used as the negative electrode active material, it is common to react an alloying element (for example, aluminum) for forming the lithium alloy with lithium in the battery to form the lithium alloy. In this case, when the alloying element generally used in the shape of a particle or a film is alloyed with lithium, it expands in volume and becomes fine powder, so that the active material is desorbed from the negative electrode due to the influence of vibration and the like, resulting in a short circuit. Is likely to occur.

However, in the non-aqueous electrolytic solution primary cell of the present invention, a protective film formed on the surface of the negative electrode by using a non-aqueous electrolytic solution 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 alloying element and suppress the formation of a large amount of fine powder due to the formation of the lithium alloy, a short circuit that may occur due to the desorption of the fine powder of the lithium alloy from the negative electrode, etc. It is presumed that the problem of can be prevented.

Therefore, even when a separator such as a non-woven separator, which has a relatively large void size and allows fine powder of the active material that has fallen off from the electrode to easily pass through the void, is used, a short circuit occurs due to the pulverization of the negative electrode active material. It is considered that a non-aqueous electrolyte primary battery having excellent vibration resistance can be constructed.

Non-aqueous electrolyte solution Examples of the organic solvent that can be used in the non-aqueous electrolyte solution for the primary battery 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. Chain carbonate; 1,2-dimethoxyethane (DME), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetraglyme (tetraethylene glycol dimethyl ether), methoxyethoxyethane, 1,2-diethoxyethane, Examples thereof include ethers such as tetrahydrofuran; cyclic esters such as γ-butyrolactone; nitriles; and the like, and only one of these may be used, or two or more thereof may be used in combination. In particular, it is preferable to use the above-mentioned carbonate and ether in combination.

When a carbonate and an ether are used in combination as a non-aqueous electrolyte solvent, the amount ratio (mixing ratio) of the carbonate and the ether in the total solvent is a volume ratio, and the carbonate: ether = 30: 70 to 70:30. Is preferable.

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

Specific examples of nitriles include mononitriles such as acetonitrile, propionitrile, butyronitrile, valeronitrile, benzonitrile, and 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, Dinitriles such as 1,10-dicyanodecane, 1,6-dicyanodecane, and 2,4-dimethylglutaronitrile; cyclic nitriles such as benzonitrile; alkoxy-substituted nitriles such as methoxynitrile; and the like. Of these, acetonitrile is particularly preferred.

When nitrile is used as the non-aqueous electrolyte solvent, the content of nitrile in the total amount of the non-aqueous electrolyte solvent may be 5% by volume or more from the viewpoint of better ensuring the above-mentioned effect by using the nitrile. It is preferably 8% by volume or more, and more preferably 8% by volume or more. However, since nitrile has high reactivity with lithium in the negative electrode, it is preferable to limit the amount of nitrile used to some extent to suppress an excessive reaction between them. Therefore, the content of nitrile in the total amount of the non-aqueous electrolytic solution solvent is preferably 20% by volume or less, and more preferably 17% by volume or less.

The content of lithium salt A in the non-aqueous electrolytic solution is 0.3 mol / l or more, preferably 0.4 mol / l or more, preferably 1.2 mol / l, from the viewpoint of ensuring good lithium ion conductivity. It is l or less, preferably 1.0 mol / l or less.

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

Further, the non-aqueous electrolytic solution may contain a lithium salt other than the lithium salt A and the lithium salt B (such as the lithium salt normally used for the non-aqueous electrolytic solution for the non-aqueous electrolytic solution battery). In this case, the total amount of lithium salts in the non-aqueous electrolytic solution is preferably 1.5 mol / l or less.

Further, the content of LiB (C ₂ O ₄ ) ₂ in the non-aqueous electrolytic solution is 0.1% by mass or more from the viewpoint of ensuring the above-mentioned effect of LiB (C ₂ O ₄ ) ₂ satisfactorily. 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 non-aqueous electrolytic solution is too large, the internal resistance of the battery may increase and the battery characteristics may deteriorate. Therefore, from the viewpoint of improving the battery characteristics, the content of LiB (C ₂ O ₄ ) ₂ in the non-aqueous electrolytic solution is preferably 2% by mass or less, preferably 1.5% by mass or less.

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

Sulton compounds are classified into compounds having no unsaturated bond in the ring and compounds having an unsaturated bond in the ring, and each is a 5-membered ring to 7-membered compound in terms of solubility in an electrolytic solution and the like. Ring compounds are preferably used, and those having a 5-membered ring structure are more preferably used.

Examples of the compound having no unsaturated bond in the ring include 1,3-propanesulton, 1,4-butanesulton and the like, and 1,3-propanesulton 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 independently hydrogen, fluorine, or have 1 to 12 carbon atoms, and some or all of the hydrogen is replaced with fluorine. It is a hydrocarbon group that may be used.

Among the compounds represented by the general formula (1), R ¹ , R ² , R ³ and R ⁴ have hydrogen, fluorine, or carbon atoms of 1 to 3, respectively, and some or all of hydrogen is fluorine. Those which are hydrocarbon groups which may be substituted with are preferable, and 1,3-propensultone (PRS) are more preferable.

From the viewpoint of ensuring the above-mentioned effect of the sultone compound satisfactorily, the content of the sultone compound in the non-aqueous electrolytic solution 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 electrolytic solution is too large, the internal resistance of the battery may increase and the discharge characteristics may deteriorate. Therefore, from the viewpoint of suppressing deterioration of the discharge characteristics, the content of the sultone compound in the non-aqueous electrolytic solution is preferably 3% by mass or less, and more preferably 2.5% by mass or less.

Further, an additive other than LiB (C ₂ O ₄ ) ₂ or a sultone compound can be added to the non-aqueous electrolytic solution, if necessary. Examples of such an additive include a phosphoric acid compound such as tris (trimethylsilyl) phosphate; a boric acid compound such as tris borate (trimethylsilyl); an acid anhydride such as maleic anhydride and phthalic anhydride; and the like.

In particular, as an additive for the non-aqueous electrolytic solution, it is preferable to contain 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 independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. It represents an aryl group having 6 to 10 carbon atoms, and a part or all of its hydrogen atom may be substituted with fluorine.

By incorporating a phosphoric acid compound or a boric acid compound having a group represented by the general formula (2) in the molecule in the non-aqueous electrolytic solution, deterioration of battery characteristics in a high temperature environment can be further suppressed. ..

Further, when a battery using a non-aqueous electrolytic solution containing lithium salt B, which easily generates hydrofluoric acid by reaction with water, is left in a high temperature and high humidity environment for a long time, the sealing may be loosened or the battery may be left. When water permeates the inside of the resin constituting the gasket, the water permeates into the battery and reacts with the non-aqueous electrolytic solution, which tends to deteriorate the characteristics of the battery. However, by incorporating the phosphoric acid compound or the boric acid compound in the non-aqueous electrolytic solution, the deterioration of the above-mentioned characteristics can be suppressed, and a battery having excellent storage characteristics in a high temperature and high humidity environment can be configured. can.

In the general formula (2), X is Si, Ge or Sn, but 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.

Further, in the above general formula (2), R ⁵ , R ⁶ and R ⁷ are 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, respectively. However, a methyl group or an ethyl group is more preferable. Further, in R ⁵ , R ⁶ and R ⁷ , a part or all of the hydrogen atom thereof may be substituted with fluorine. The trimethylsilyl group is particularly preferable as the group represented by the general formula (2).

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

Examples of such phosphoric acid compounds include mono (trimethylsilyl) phosphate, di (trimethylsilyl) phosphate, tris (trimethylsilyl) phosphate, dimethyltrimethylsilyl phosphate, methylbis phosphate (trimethylsilyl), and 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, etc., mono (trimethylsilyl) phosphate, di (trimethylsilyl) phosphate, phosphoric acid Tris (trimethylsilyl), dimethyltrimethylsilyl phosphate, methylbis phosphate (trimethylsilyl) are preferred, and Tris phosphate (trimethylsilyl) is particularly preferred.

Further, in the boric acid compound, only one of the hydrogen atoms of boric acid may be substituted with the group represented by the general formula (2), and among the hydrogen atoms of boric acid. Two may be substituted with the group represented by the general formula (2), and all three hydrogen atoms of boric acid may be substituted with the 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 monoboric acid (trimethylsilyl), di (trimethylsilyl) borate, tris borate (trimethylsilyl), dimethyltrimethylsilyl borate, methylbis borate (trimethylsilyl), diethyltrimethylsilyl borate, and the like. Diphenyl borate (trimethylsilyl), Tris borate (triethylsilyl), Tris borate (vinyldimethylsilyl) Trisborate (triisopropylsilyl), Tris borate (dimethylethylsilyl), Tris borate (methyldiethylsilyl), Tris borate (butyldimethylsilyl), trisborate (vinyldimethylsilyl), trisborate (triphenylsilyl) and the like can be mentioned, such as monoborate (trimethylsilyl), di (trimethylsilyl) borate, trisborate. (Trimethylsilyl), dimethyltrimethylsilyl borate, methylbis borate (trimethylsilyl) are preferred, and tris borate (trimethylsilyl) is 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 non-aqueous electrolytic solution (in the case of containing both, the total amount thereof) is the above-mentioned by its use. From the viewpoint of ensuring the effect of 1), it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more. Most preferably, it is by mass or more. 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 the resistance and deteriorate the load characteristics. Therefore, non-aqueous electrolysis The content of the phosphoric acid compound or boric acid compound having the group represented by the general formula (2) in the liquid (the total amount when both are contained) shall be 5% by mass or less. Is more preferable, 4% by mass or less is more preferable, 3% by mass or less is more preferable, and 2.5% by mass or less is most preferable.

The content of the phosphoric acid compound or boric acid compound having a group represented by the general formula (2) in the molecule is preferably adjusted according to the content of the lithium salt B, and the phosphoric acid compound or The content of the boric acid compound in the non-aqueous electrolytic solution (the total amount when both are contained) is preferably 0.1 or more in terms of molar ratio with respect to the content of the lithium salt B, and is 0. It is more preferably .2 or more, and in order to prevent deterioration of the load characteristics, the molar ratio is preferably 0.5 or less, and more preferably 0.4 or less.

Further, as the non-aqueous electrolyte solution, a gel-like solution (gel-like electrolyte) to which a known gelling agent is added can also be used.

The negative electrode of the non-aqueous electrolytic solution primary battery contains metallic lithium or a lithium alloy. As the negative electrode containing metallic lithium, the metallic lithium foil can be used as it is, or a structure in which the metallic lithium foil is crimped on one side or both sides of the current collector can be used.

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

Further, in the case of a negative electrode containing a lithium alloy, a layer containing an alloying element for forming a lithium alloy is laminated by pressure bonding on the surface of a lithium layer (a layer containing lithium) composed of a metallic lithium foil or the like. By using a laminated body and bringing the laminated body into contact with a non-aqueous electrolytic solution 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 on only 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 laminate can be formed, for example, by pressure-bonding a metallic lithium foil and a foil composed of an alloying element.

A current collector can also be used when a lithium alloy is formed in a battery to form a negative electrode. For example, a negative electrode current collector having a lithium layer on one side of the negative electrode current collector and having a lithium layer is used. A laminate having a layer containing an alloying element on the surface opposite to the above may be used, the surface opposite to the negative electrode current collector of each lithium layer having lithium layers on both sides of the negative electrode current collector. A laminate having a layer containing an alloying 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 alloying element for forming the lithium alloy include aluminum, lead, bismuth, indium, gallium, and the like, but aluminum is preferable.

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

For example, a metallic lithium foil or the like can be used for the lithium layer related to the laminated body used as the negative electrode. The thickness of the lithium layer is preferably 0.1 to 1.5 mm. Further, the thickness of the lithium layer (metal lithium foil used for forming the negative electrode) in the case of using a negative electrode containing metallic lithium is also preferably 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 woven wire mesh, expanded metal, lath mesh, punching metal, metal foam, and foil (plate). Can be exemplified. The thickness of the current collector is preferably, for example, 5 to 100 μm. 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.

The positive electrode of the non-aqueous electrolyte primary battery can be, for example, from a molded body obtained by molding a mixture containing a positive electrode active material, a conductive auxiliary agent, a binder, etc. (positive electrode mixture) into pellets, or from the positive electrode mixture. A layer having a layer (positive electrode mixture layer) on one side or both sides of the current collector can be used.

As the positive electrode active material, manganese dioxide and lithium-containing manganese oxide [for example, LiMn ₃ O6 and the _same crystal structure as manganese dioxide (β-type, γ-type, or a structure in which β-type and γ-type are mixed, etc.) are present. 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 . Lithium-containing composite oxides such as / ₃ O4 ( _4/3 ≤ a <7/3); vanadium oxides; niobium oxides; titanium oxides; sulfides such as iron disulfide; graphite fluoride; etc. Be done.

Examples of the conductive auxiliary agent related to the positive electrode mixture include scaly graphite, acetylene black, ketjen black, carbon black, and the like, and only one of these may be used, and two or more thereof may be used. It may be used together.

Further, 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, and one of them. Only may be used, or two or more kinds may be used in combination.

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

Further, 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 auxiliary agent, a binder and the like are mixed with water or an organic solvent such as N-methyl-2-pyrrolidone (NMP). A positive electrode mixture-containing composition (slurry, paste, etc.) is prepared (the binder may be dissolved in a solvent), this is applied onto a current collector, dried, and if necessary, calendered. It can be manufactured through a process of pressing such as.

However, the positive electrode is not limited to the one manufactured by each of the above methods, and may be manufactured by another method.

The composition of the positive electrode mixture relating to the positive electrode is preferably such that the amount of the positive electrode active material is 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 product of a positive electrode mixture, the thickness thereof 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.

When 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, and the form thereof includes a plain woven wire mesh, an expanded metal, and a lath. Examples include mesh, 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 a negative electrode having a current collector (or a laminated body for the negative electrode) and a positive electrode having a current collector are used, a laminated body (laminated electrode body) laminated via a separator or , A wound body (wound electrode body) in which this laminated body is wound in a spiral shape, and a flat wound body (flat wound electrode body) obtained by molding this wound body so that the cross section is flat. ) Can be used. Further, when using a positive electrode made of a molded body of a positive electrode mixture and a negative electrode (or a laminated body for a negative electrode) having no current collector, the inside of a flat battery case has a separator interposed therebetween. Can be housed in and used.

A non-woven fabric or a microporous film (microporous film) is used for the separator, and as the material thereof, polyimides such as polyethylene (PE), polypropylene (PP), and ethylene-propylene copolymer can be used, and batteries. When heat resistance is required in relation to the above application, fluororesin such as tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), polyphenylene sulfide (PPS), polyetheretherketone (PEEK), poly Butylene terephthalate (PBT), polymethylpentene, polyamide, polyimide, aramid, cellulose and the like can also be used. As the material of the nonwoven fabric or the microporous membrane, only one of the above-exemplified materials may be used, or two or more of them may be used. Further, the nonwoven fabric and the microporous film serving as the separator are those having a single-layer structure made of the above-exemplified materials, and for example, those having a laminated structure in which a plurality of nonwoven fabrics and microporous films made of different materials are laminated. Can also be used.

From the viewpoint of suppressing a decrease in the energy density of the battery, 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. However, if the separator is too thin, the function of preventing a short circuit may be deteriorated. Therefore, when using a non-woven fabric, the thickness may be, for example, 30 μm or more, preferably 100 μm or more, preferably 150 μm. The above is more preferable. When a microporous membrane is used, it is preferably 10 μm or more, and more preferably 15 μm or more.

The form of the non-aqueous electrolyte primary battery is not particularly limited, and may be various forms such as flat type (including coin type and button type), laminated type, and tubular type [cylindrical type, square type (square tubular type)]. It is possible. Further, as an exterior body (battery case) for accommodating a negative electrode, a positive electrode, a separator and a non-aqueous electrolytic solution, a metal can (exterior can) having an opening and a lid (sealing can) may be used in combination, or metal. A laminated film can be used.

Specifically, a flat or tubular battery can be manufactured by caulking the outer can and the sealing can via a gasket, or by welding the outer can and the sealing can to seal the can. It is possible to produce a laminated battery by stacking two metal laminate films or folding one metal laminate film and laminating the surroundings to seal the seal.

When using an exterior body that is caulked, PP, nylon, etc. can be used as the material of the gasket that is interposed between the exterior can and the sealing can, and it is particularly advanced in relation to the application of the battery. When heat resistance is required, fluororesin such as PFA, polyphenylene ether (PEE), polysulfone (PSF), polyallylate (PAR), polyethersulfone (PES), PPS, PEEK and the like melting point or heat. 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 has excellent reliability in a high temperature environment, it makes use of these characteristics to make it particularly high temperature, such as an automobile application such as a power supply application for a pressure sensor inside a tire. In addition to being suitable for applications that are easily exposed, it can also be applied to the same applications as various applications in which a conventionally known non-aqueous electrolyte primary battery is adopted.

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

(Example 1)
<Manufacturing 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, at a mass ratio of 93: 3: 4 is formed to form a positive electrode mixture having a diameter of 16 mm. A positive electrode (positive electrode mixture molded body) having a thickness of 1.8 mm was obtained.

<Manufacturing of laminate for negative electrode>
An aluminum foil having a thickness of 0.01 μm was crimped onto one side of a lithium foil having a thickness of 0.6 mm and punched into a circle having a diameter of 16 mm to obtain a laminate for a negative electrode.

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

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

FIG. 1 is a vertical sectional view schematically showing the non-aqueous electrolytic solution primary battery of Example 1. In the non-aqueous electrolytic solution primary battery 1 of Example 1, the positive electrode 2 is an outer can made of stainless steel. It is housed inside the 5, and the negative electrode 3 is arranged on the negative electrode 3 via the separator 4. Further, 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 electrolytic solution (not shown) is injected into the battery 1.

In the non-aqueous electrolytic solution 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 into 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 formed. By abutting on the sealing can 6, the opening of the outer can 5 is sealed and the inside of the battery is sealed. That is, the non-aqueous electrolytic solution primary battery 1 is formed of an outer can 5, a sealing can 6, and an insulating gasket 7 interposed between them, and a positive electrode 2, a separator 4, and a negative electrode 3 are housed in a sealed battery case. A non-aqueous electrolytic solution and a non-aqueous electrolytic solution are housed.

(Example 2)
A non-aqueous electrolytic solution 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 electrolytic solution was prepared in the same manner as in Example 1 except that this non-aqueous electrolytic solution was used. A liquid primary battery was manufactured. The ratio of LiPF ₆ in the total of LiClO ₄ and LiPF ₆ in this non-aqueous electrolytic solution was 41.7 mol%.

(Example 3)
A non-aqueous 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 0.34 mol / l, except that this non-aqueous electrolytic solution was used. A non-aqueous electrolytic solution 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 non-aqueous electrolytic solution was 41.0 mol%.

(Example 4)
A non-aqueous 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 non-aqueous electrolytic solution was prepared in the same manner as in Example 1 except that this non-aqueous electrolytic solution was used. A liquid primary battery was manufactured. The ratio of LiBF ₄ in the total of LiClO ₄ and LiBF ₄ in this non-aqueous electrolytic solution was 53.3 mol%.

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

(Comparative Example 2)
A non-aqueous electrolytic solution 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 electrolytic solution was prepared in the same manner as in Example 1 except that this non-aqueous electrolytic solution was used. A liquid primary battery was manufactured. The ratio of LiPF ₆ in the total of LiClO ₄ and LiPF ₆ in this non-aqueous electrolytic solution was 12.5 mol%.

(Comparative Example 3)
A non-aqueous 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 non-aqueous electrolytic solution was prepared in the same manner as in Example 1 except that this non-aqueous electrolytic solution was used. A liquid primary battery was manufactured. The ratio of LiBF ₄ in the total of LiClO ₄ and LiBF ₄ in this non-aqueous electrolytic solution was 18.3 mol%.

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

<Reliability evaluation in high temperature environment>
The non-aqueous electrolytic solution primary batteries of Examples 1 to 4 and Comparative Examples 1 to 3 were each divided into two, a 15 kΩ resistor was connected to one of them, and discharge was performed until the discharge depth with respect to the positive electrode capacity became 60%. .. The other non-discharging example and comparative battery (DOD: 0% battery) and the example and comparative battery (DOD: 60% battery) having a discharge depth of 60% were used. The battery was placed in a constant temperature bath 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 amount) from the height (3.2 mm) immediately after the battery was manufactured was determined. .. However, when the measured battery swelling amount exceeded 1 mm, the measurement was not performed in the storage time after that.

<Evaluation of battery characteristics after high temperature storage>
Evaluation of battery characteristics of the non-aqueous electrolyte primary batteries of Examples 1 to 4 and Comparative Examples 1 to 3 after high-temperature storage under the following conditions under the conditions of DOD: 0% and DOD: 60%. Was done. Further, for the non-aqueous electrolytic solution primary battery of Comparative Example 4, the battery characteristics after high temperature storage in the case of DOD: 0% were evaluated.

Each battery is placed in a constant temperature bath adjusted to 140 ° C., taken out at intervals shown in Tables 3 and 4, and after allowing to cool, a 100Ω resistor is connected and discharged 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 was not performed in the storage time after that.

Table 1 shows the configurations of the non-aqueous electrolytic solutions according to the non-aqueous electrolytic solution primary batteries of Examples 1 to 4 and Comparative Examples 1 to 4, and Tables 2 to 4 show the above-mentioned evaluation results. Regarding the evaluation results of the battery with DOD: 60%, the changes in the swelling of the battery and the changes in the CCV with respect to the storage time of the battery are shown in FIGS. 2 and 3, respectively. The "ratio of lithium salt B" in Table 1 means the ratio of the lithium salt B in the total of the lithium salt A and the lithium salt B (the same applies to Table 5 below). Further, "-" in Tables 2 and 4 means that the 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, FIGS. 2 and 3, Examples 1 to 4 using a non-aqueous electrolytic solution using lithium salt A, lithium salt B and LiB (C ₂ O ₄ ) ₂ in appropriate amounts. The non-aqueous electrolyte primary battery is high in that the swelling of the battery and the increase in internal resistance are suppressed for a long time in a high temperature environment of 140 ° C. in both the state of the discharge depth of 0% and 60%. It was reliable.

On the other hand, the batteries of Comparative Examples 2 and 3 using the non-aqueous electrolyte solution 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. Although the battery characteristics after high-temperature storage were improved as compared with the battery of Comparative Example 1 using the non-aqueous electrolyte solution, the effect of suppressing the swelling of the battery was lower than that of the battery of the above-mentioned example, and the battery was discharged. At a depth of 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 shown in FIG. 3 and the results of the batteries of Examples 3 and 4, at least in a state where the discharge depth is 60%, the lithium salt B is used. As the proportion of the above increases, the internal resistance increases and the CCV decreases. Therefore, the proportion 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 becomes high and the load characteristics become high. It turns out that it decreases.

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

(Example 6)
A non-aqueous 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 non-aqueous electrolytic solution was prepared in the same manner as in Example 5 except that this non-aqueous electrolytic solution was used. A liquid primary battery was manufactured. The ratio of LiBF ₄ in the total of LiClO ₄ and LiBF ₄ in this non-aqueous electrolytic solution was 53.3 mol%. The content of TMSP with respect to the content of LiBF ₄ was 0.09 in terms of molar ratio.

(Example 7)
A non-aqueous electrolytic solution 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 electrolytic solution was used. A non-aqueous electrolyte primary battery was produced. The ratio of LiBF ₄ in the total of LiClO ₄ and LiBF ₄ in this non-aqueous electrolytic solution was 41.0 mol%. The content of TMSP with respect to the content of LiBF ₄ was 0.29 in terms of molar ratio.

(Example 8)
A non-aqueous electrolytic solution 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 electrolytic solution was used. A non-aqueous electrolyte primary battery was produced. The ratio of LiBF ₄ in the total of LiClO ₄ and LiBF ₄ in this non-aqueous electrolytic solution was 53.3 mol%. The content of TMSP with respect to the content of LiBF ₄ was 0.18 in terms of molar ratio.

For the non-aqueous electrolytic solution primary batteries of Examples 5 to 8, "reliability evaluation in a high temperature environment" and "battery characteristic evaluation after high temperature storage" were carried out in the same manner as described above, respectively.

The configurations of the non-aqueous electrolytic solution according to the non-aqueous electrolytic solution primary battery of Examples 5 to 8 are shown in Table 5, and the evaluation results of each of the above are shown in Tables 6 to 8. In Tables 5 to 8, the configurations of the non-aqueous electrolytic solution according to the non-aqueous electrolytic solution primary batteries of Examples 3, 4 and Comparative Example 1 and the evaluation results are also shown. Regarding the evaluation results of the battery with DOD: 60%, changes in battery swelling and changes in CCV with respect to the battery storage time are shown in FIGS. 4 and 5, respectively.

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

<Evaluation of battery characteristics after storage in a hot and humid environment>
The non-aqueous electrolyte primary batteries (DOD: 0%) of Examples 3 to 8 and Comparative Example 1 were evaluated for battery characteristics after storage in a high temperature and high humidity environment under the following conditions.

Each battery is placed in a constant temperature bath adjusted to a relative humidity of 90% at 80 ° C, taken out every time shown in Table 9, allowed to cool, and then discharged by connecting a 100Ω resistor in an environment of 20 ° C. The closed circuit voltage (CCV) of the battery after 0.3 seconds was measured. The results of these evaluations are shown in Table 9 and FIG.

As shown in Table 9 and FIG. 6, the batteries of Examples 3 and 4 to which LiBF ₄ (lithium salt B) was added were stored in a high temperature and high humidity environment, and thus the moisture and LiBF ₄ that entered the battery were contained. As a result, the internal resistance increased and the CCV decreased as compared with the battery of Comparative Example 1. On the other hand, the batteries of Examples 5 to 8 to which TMSP was added were able to prevent the above-mentioned problems and maintain excellent battery characteristics for a long time even when stored in a high temperature and high humidity environment. In particular, in the batteries of Examples 5, 7, and 8 in which the content of TMSP is 0.1 or more in terms of molar ratio with respect to the content of LiBF ₄ , better storage stability can be realized. did it.

1 Non-aqueous electrolyte primary battery 2 Positive electrode 3 Negative electrode 4 Separator 5 Exterior can 6 Sealed can 7 Insulation gasket

Claims (10)

A non-aqueous electrolytic solution primary battery having a positive electrode, a negative electrode, a separator and a non-aqueous electrolytic solution.
The negative electrode contains metallic lithium or a lithium alloy and contains.
The non-aqueous electrolyte solution contains 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 . It contains at least one lithium salt B selected from LiPF ₆ , LiBF ₄ , LiAsF ₆ and LiSbF ₆ and LiB ( _C2 O ₄ ) ₂ .
When the total of the lithium salt A and the lithium salt B in the non-aqueous electrolytic solution 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 electrolytic solution is 0.3 to 1.2 mol / l, and the content is 0.3 to 1.2 mol / l.
A non-aqueous electrolytic solution primary battery characterized in that the content of LiB (C ₂ O ₄ ) ₂ in the non-aqueous electrolytic solution is 0.1 to 2% by mass. The non-aqueous electrolytic solution primary battery according to claim 1, wherein the ratio of the lithium salt B is 70 mol% or less when the total of the lithium salt A and the lithium salt B in the non-aqueous electrolytic solution is 100 mol%. .. The non-aqueous electrolytic solution primary battery according to claim 1 or 2, wherein the non-aqueous electrolytic solution further contains a sultone compound. The non-aqueous electrolytic solution primary battery according to claim 3, wherein the content of the sultone compound in the non-aqueous electrolytic solution is 0.5 to 3% by mass. The non-aqueous electrolysis according to any one of claims 1 to 4, wherein the non-aqueous 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 independently an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms, respectively. Alternatively, it represents an aryl group having 6 to 10 carbon atoms, and a part or all of its hydrogen atom may be substituted with fluorine. ] The non-aqueous electrolytic solution primary battery according to claim 5, wherein the content of the phosphoric acid compound or the boric acid compound is 0.1 to 5% by mass. The non-aqueous electrolytic solution primary battery according to claim 5 or 6, wherein the content of the phosphoric acid compound or the boric acid compound is 0.1 or more in terms of molar ratio with respect to the content of the lithium salt B. It is equipped with a battery container consisting of an outer can, a sealing can and a gasket intervening between them.
The non-aqueous 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 manufacturing a non-aqueous electrolytic solution primary battery including a negative electrode, a positive electrode, a separator and a non-aqueous electrolytic solution.
Metallic lithium or lithium alloy is used for the negative electrode.
The non-aqueous electrolyte solution contains 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 . At least one lithium salt B selected from LiPF ₆ , LiBF ₄ , LiAsF ₆ and LiSbF ₆ and LiB ( _C2 O ₄ ) ₂ are contained.
When the total of the lithium salt A and the lithium salt B in the non-aqueous electrolytic solution is 100 mol%, the ratio of the lithium salt B is increased to more than 20 mol%.
The content of the lithium salt A in the non-aqueous electrolytic solution is set to 0.3 to 1.2 mol / l.
A method for producing a non-aqueous electrolytic solution primary battery, wherein the content of LiB (C ₂ O ₄ ) ₂ in the non-aqueous electrolytic solution is 0.1 to 2% by mass. The method for producing a non-aqueous electrolytic solution primary battery according to claim 9, wherein the non-aqueous 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.

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

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