JP7346799B2 - Lithium boron phosphate compound, additive for lithium secondary batteries, non-aqueous electrolyte for lithium secondary batteries, lithium secondary battery precursor, method for producing lithium secondary batteries, and lithium secondary batteries - Google Patents

Description

The present disclosure relates to a novel lithium boron phosphate compound, an additive for lithium secondary batteries, a nonaqueous electrolyte for lithium secondary batteries, a lithium secondary battery precursor, a method for producing a lithium secondary battery, and a lithium secondary battery. Regarding.

In order to improve the performance of batteries using non-aqueous electrolytes (for example, lithium secondary batteries), various additives have been incorporated into non-aqueous electrolytes.
BACKGROUND ART Nonaqueous electrolytes for batteries are known that contain a lithium phosphate compound, for example, at least one of lithium monofluorophosphate and lithium difluorophosphate as an additive (see, for example, Patent Document 1).
Lithium borate compounds are also used as additives, and for example, electrolytes for lithium ion batteries containing lithium bis(oxalato)borate are known (see, for example, Patent Document 2). Further, for example, an electrolytic solution for lithium ion batteries containing lithium difluoro(oxalato)borate is also known (see, for example, Patent Document 3).
Lithium boron phosphate compounds are also used as additives, and for example, electrolytes for lithium ion batteries containing compounds such as LiBF ₃ (PO ₂ F ₂ ) are known (for example, see Patent Document 4).

Patent No. 3439085 Patent No. 3730855 Patent No. 3722685 Patent No. 5544748

An object of one aspect of the present disclosure is to provide a novel lithium boron phosphate compound and an additive for lithium secondary batteries containing the lithium boron phosphate compound.
Another object of the present disclosure is to provide a non-aqueous electrolyte for a lithium secondary battery that can reduce battery resistance and battery swelling due to gas generation (also referred to as "gas swelling") in a high-temperature environment; Another object of the present invention is to provide a lithium secondary battery precursor containing the non-aqueous electrolyte for lithium secondary batteries, a lithium secondary battery, and a method for manufacturing a lithium secondary battery using the lithium secondary battery precursor.

Means for solving the above problems include the following aspects.
<1>
A lithium boron phosphate compound containing a repeating structure represented by the following formula (I).

[In formula (I), n represents an integer of 1 or more. ]

<2>
The lithium boron phosphate compound according to <1>, which has a number average molecular weight (Mn) of 150 to 100,000.

<3>
The lithium boron phosphate compound according to <1> or <2>, wherein the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) is 1.0 or more and 3.0 or less.

<4>
An additive for lithium secondary batteries comprising the lithium boron phosphate compound according to any one of <1> to <3>.
<5>
A nonaqueous electrolyte for a lithium secondary battery, comprising an electrolyte that is a lithium salt containing fluorine, a nonaqueous solvent, and the lithium boron phosphate compound according to any one of <1> to <3>.
<6>
The nonaqueous boron phosphate lithium compound according to <5>, wherein the content of the lithium boron phosphate compound is 0.1% by mass to 5.0% by mass based on the total amount of the nonaqueous electrolyte for lithium secondary batteries. Water electrolyte.
<7>
The nonaqueous electrolyte for a lithium secondary battery according to <5> or <6>, further containing vinylene carbonate.
<8>
The case includes a positive electrode, a negative electrode, a separator, and an electrolyte that are housed in the case, the positive electrode being a positive electrode capable of intercalating and deintercalating lithium ions, and the negative electrode being a positive electrode capable of intercalating and deintercalating lithium ions. A lithium secondary battery precursor, which is a possible negative electrode, and the electrolyte is the nonaqueous electrolyte for a lithium secondary battery according to any one of <5> to <7>.
<9>
The lithium secondary battery precursor according to claim 8, wherein the positive electrode contains a lithium-containing composite oxide represented by the following general formula (C1) as a positive electrode active material.
_LiNia Co _b Mn _c O ₂ ... General formula (C1)
[In general formula (C1), a, b and c are each independently greater than 0 and less than 1, and the sum of a, b and c is 0.99 to 1.00. ]
<10>
A step of preparing a lithium secondary battery precursor according to <8> or <9>, and a step of obtaining a lithium secondary battery by subjecting the lithium secondary battery precursor to an aging treatment. A method for producing a lithium secondary battery, wherein the aging treatment includes charging and discharging the lithium secondary battery precursor in an environment of 30°C to 70°C.
<11>
The case includes a positive electrode, a negative electrode, a separator, and an electrolyte that are housed in the case, the positive electrode being a positive electrode capable of intercalating and deintercalating lithium ions, and the negative electrode being a positive electrode capable of intercalating and deintercalating lithium ions. The electrolyte is a non-aqueous electrolyte containing an electrolyte that is a fluorine-containing lithium salt and a non-aqueous solvent, and at least a part of the surface of the negative electrode is formed by the following formula (I). A negative electrode coating containing a component derived from the electrolyte and a lithium boron phosphate compound having the repeating structure represented by the formula (I) is formed on at least a portion of the surface of the positive electrode, and the repeating structure represented by the following formula (I) is A lithium secondary battery comprising a positive electrode coating containing a lithium boron phosphate compound having a structure and a component derived from the electrolyte.

[In formula (I), n represents an integer of 1 or more. ]

According to one aspect of the present disclosure, a novel lithium boron phosphate compound and an additive for lithium secondary batteries containing the lithium boron phosphate compound are provided.
Further, according to another aspect of the present disclosure, a non-aqueous electrolyte for a lithium secondary battery that can reduce battery resistance and battery swelling due to gas generation (also referred to as "gas swelling") in a high-temperature environment; Furthermore, a lithium secondary battery precursor containing the above non-aqueous electrolyte for a lithium secondary battery, a lithium secondary battery, and a method for manufacturing a lithium secondary battery using the lithium secondary battery precursor are provided.

1 is a schematic cross-sectional view showing an example of a lithium secondary battery precursor according to an embodiment of the present disclosure.

In this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits.
In this specification, if there are multiple substances corresponding to each component in the composition, unless otherwise specified, the amount of each component in the composition refers to the total amount of the multiple substances present in the composition. means.
In this specification, the term "process" is used not only to refer to an independent process, but also to include any process that is not clearly distinguishable from other processes as long as the intended purpose of the process is achieved. It will be done.

[Lithium boron phosphate compound]
The lithium boron phosphate compound of the present disclosure is a novel lithium boron phosphate compound containing a repeating structure "(hereinafter also referred to as "repeating structure (I)")" represented by the following formula (I).

The lithium boron phosphate compound of the present disclosure preferably contains the repeating structure (I) as a main component. Here, the term "main component" means that the proportion of the "repeating structure (I)" is 50% by mass or more, preferably 80% by mass, based on the total amount of the lithium boron phosphate compound of the present disclosure. or more, and more preferably 90% by mass or more.

The repeating structure (I) can have a linear structure that may have a terminal group. When the repeating structure (I) has a terminal group, the terminal group is preferably a hydroxyl group. Moreover, the repeating structure (I) can also have a cyclic structure without a terminal group.

In formula (I), n represents an integer of 1 or more. Further, the upper limit of n is not particularly limited, but is preferably 1000, more preferably 100. When n in formula (I) is 1, the lithium boron phosphate compound of the present disclosure has a structure represented by formula (II) below.
Note that the lithium boron phosphate compound of the present disclosure may include multiple types of structures with different n (repetition numbers).

The molecular weight of the lithium boron phosphate compound of the present disclosure is not particularly limited, but the preferred molecular weight is 150 to 100,000, preferably 200 to 100,000 in polystyrene equivalent number average molecular weight (Mn) determined by GPC measurement. 10,000 is more preferable, and 300 to 5,000 is even more preferable.

In the lithium boron phosphate compound of the present disclosure, the ratio (Mw/Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) is preferably 1.0 or more and 3.0 or less, and 1.1 or more. More preferably, it is 2.7 or less.

[Method for producing lithium boron phosphate compound]
An example of the method for producing the lithium boron phosphate compound of the present disclosure (also referred to as "Production Method X") will be shown below. However, the method for producing the lithium boron phosphate compound of the present disclosure is not limited to Production Method X.

Production method By reacting the compound in a solvent, the lithium boron phosphate compound of the present disclosure (i.e., the lithium boron phosphate compound containing the repeating structure (I); hereinafter also simply referred to as "lithium boron phosphate compound (X)") It includes a reaction step to obtain.

Examples of the lithium salt compound in the reaction step include lithium carbonate, lithium hydroxide, lithium methoxide, lithium ethoxide, lithium-t-butoxide, and lithium carbonate or lithium hydroxide are preferred, with lithium carbonate being more preferred. preferable.

Examples of the phosphoric acid compound in the reaction step include phosphoric acid, pyrophosphoric acid, triphosphoric acid, polyphosphoric acid, and diphosphorous pentoxide. Phosphoric acid, pyrophosphoric acid, and triphosphoric acid are preferable, and among them, phosphoric acid and pyrophosphoric acid are more preferable. preferable.

Examples of the boron trifluoride compound in the reaction step include gaseous boron trifluoride and boron trifluoride complexes. Examples of boron trifluoride complexes include boron trifluoride diethyl ether complex, boron trifluoride tetrahydrofuran complex, boron trifluoride dimethyl ether complex, boron trifluoride dibutyl ether complex, and boron trifluoride diethyl ether complex. Complexes are preferred.

Examples of the solvent in the reaction step include acetone, ethyl acetate, acetonitrile, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, pentane, hexane, heptane, octane, nonane, decane, toluene, xylene (i.e., ortho-xylene, meta-xylene, or paraxylene), ethylbenzene, butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, propylbenzene, isopropylbenzene (also known as cumene), cyclohexylbenzene, tetralin, mesitylene, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane , cyclononane, and other non-aqueous solvents.

The reaction in the reaction step can be carried out either under normal pressure or under reduced pressure.
The reaction in the reaction step is carried out under an inert atmosphere (e.g., under a nitrogen atmosphere, under an argon atmosphere, etc.) from the viewpoint of preventing the contamination of components (e.g., moisture) that inhibit the production of the lithium boron phosphate compound (X). It is preferable.

The reaction temperature in the reaction step is preferably 60°C to 150°C, more preferably 70°C to 120°C, even more preferably 80°C to 110°C.
When the reaction temperature is 60° C. or higher, the production of the lithium boron phosphate compound (X) is likely to be promoted.
When the reaction temperature is 150° C. or lower, decomposition of the produced lithium boron phosphate compound (X) is suppressed, and the production rate tends to improve.

The reaction time in the reaction step is preferably 30 minutes to 12 hours, more preferably 1 hour to 8 hours, from the viewpoint of efficiently proceeding the reaction between the dicarboxylic acid compound, lithium salt compound, and boric acid compound. preferable.

After the reaction step, there is no particular restriction on the method for removing the lithium boron phosphate compound (X).
For example, if the lithium boron phosphate compound (X) is obtained as a solid containing only the target component (i.e., the lithium boron phosphate compound (X) itself) through the reaction process, the solid may be subjected to special treatment. It can be taken out without any problems.
In addition, when a slurry in which the lithium boron phosphate compound (X) is dispersed in a solvent is obtained through the reaction process, the lithium boron phosphate compound (X) can be obtained by separating the solvent from the slurry and drying it. It can be taken out.
In addition, if a solution in which the lithium boron phosphate compound (X) is dissolved in a solvent is obtained through the reaction process, the lithium boron phosphate compound (X) can be dissolved by distilling off the solvent from the solution by heating concentration or the like. can be taken out.
In addition, if a solution in which the lithium boron phosphate compound (X) is dissolved in a solvent is obtained through the reaction process, phosphorus can be phosphorused by adding a solvent in which the lithium boron phosphate compound (X) is not dissolved to the solution. The lithium boron phosphate compound (X) can also be taken out by precipitating the lithium boron acid compound (X), then separating the solvent from the solution, and drying it.

Methods for drying the taken out lithium boron phosphate compound (X) include: stationary drying method using a tray dryer; fluidized drying method using a conical dryer; drying using a device such as a hot plate or an oven. A method of supplying warm air or hot air with a dryer such as a dryer; etc. can be applied.

The pressure at which the extracted lithium boron phosphate compound (X) is dried may be either normal pressure or reduced pressure.
The temperature at which the extracted lithium boron phosphate compound (X) is dried is preferably 20°C to 150°C, more preferably 50°C to 140°C, and more preferably 80°C to 130°C. is even more preferable.
Drying efficiency is excellent when the temperature is 20°C or higher. When the temperature is 150° C. or lower, decomposition of the generated lithium boron phosphate compound (X) is suppressed, and it is easy to stably take out the lithium boron phosphate compound (X).

The extracted lithium boron phosphate compound (X) may be used as it is, for example, may be used after being dispersed or dissolved in a solvent, or may be used after being mixed with other solid substances.

The lithium boron phosphate compound (X) of the present disclosure is an additive for lithium batteries (preferably an additive for lithium secondary batteries, more preferably an additive for nonaqueous electrolytes of lithium secondary batteries), a reaction reagent, It can be usefully used in applications such as synthesis reaction catalysts, electrolytes for various electrochemical devices, doping agents, and lubricating oil additives.

[Additive for lithium secondary batteries]
The secondary battery additive of the present disclosure contains the above-mentioned lithium boron phosphate compound (X). The additive for secondary batteries of the present disclosure is particularly suitable as an additive for non-aqueous electrolytes of lithium secondary batteries.

[Nonaqueous electrolyte for lithium secondary batteries]
A nonaqueous electrolyte for a lithium secondary battery according to an embodiment of the present disclosure (hereinafter also simply referred to as "nonaqueous electrolyte of the present embodiment") includes an electrolyte that is a lithium salt containing fluorine, and a nonaqueous solvent. ,
The above-mentioned lithium boron phosphate compound (X) is contained.

According to the non-aqueous electrolyte of the present embodiment, battery resistance and battery swelling due to gas generation (also referred to as "gas swelling") can be suppressed in a high-temperature environment.

The non-aqueous electrolyte (hereinafter also simply referred to as "non-aqueous electrolyte") of the present embodiment contains a lithium boron phosphate compound (X).
By containing the lithium boron phosphate compound (X), the non-aqueous electrolyte of the present disclosure can suppress an increase in battery resistance and gas expansion in a high-temperature environment.

The reason why the above effects are achieved is presumed as follows. However, the non-aqueous electrolyte of this embodiment is not limited by the following reasons.

When manufacturing a lithium secondary battery using the non-aqueous electrolyte of this embodiment, in the manufacturing process (for example, the aging process described below), a lithium boron phosphate compound ( It is thought that a reaction product of X) and LiF produced from the electrolyte is produced, and further a component that is a decomposition product of the reaction product is produced. It is thought that during the manufacturing process, this component moves to the vicinity of the positive electrode surface and the negative electrode surface, adheres to the positive electrode surface and the negative electrode surface, and forms a positive electrode coating and a negative electrode coating. This increases the stability of the battery in high-temperature environments (for example, suppresses the elution of metal elements in the positive electrode active material), and as a result, suppresses battery resistance and gas blistering in high-temperature environments. Conceivable.

For the above reasons, it is thought that the non-aqueous electrolyte of this embodiment can suppress battery resistance and gas swelling in a high-temperature environment.

The above-mentioned adhesion of components to the positive electrode surface and negative electrode surface (i.e., formation of the positive electrode film and negative electrode film) continues even during the storage period when the lithium secondary battery is stored after manufacturing the lithium secondary battery. It is thought that then.
Therefore, when the lithium secondary battery is stored, the rate of increase in the battery resistance of the lithium secondary battery with respect to the storage period of the lithium secondary battery is considered to be reduced.

The non-aqueous electrolyte of the present disclosure may contain only one kind of the above-mentioned lithium boron phosphate compound (X), or may contain two or more kinds.
The nonaqueous electrolyte of the present disclosure may contain the lithium boron phosphate compound (X) as a battery additive or as an electrolyte supply source.

The content of the lithium boron phosphate compound (X) in the nonaqueous electrolyte of the present disclosure is not particularly limited, but is preferably 0.1% by mass to 5.0% by mass with respect to the total amount of the nonaqueous electrolyte. be.
When the content of the lithium boron phosphate compound (X) with respect to the total amount of the non-aqueous electrolyte is 0.1% by mass or more, the effects of the non-aqueous electrolyte of the present disclosure are more effectively exhibited. The content of the lithium boron phosphate compound (X) relative to the total amount of the non-aqueous electrolyte is more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, and still more preferably 0.5% by mass. % by mass or more.
When the content of the lithium boron phosphate compound (X) based on the total amount of the non-aqueous electrolyte is 5.0% by mass or less, the chemical stability of the non-aqueous electrolyte is further improved.
The content of the lithium boron phosphate compound (X) relative to the total amount of the nonaqueous electrolyte is more preferably 3.0% by mass or less, still more preferably 2.0% by mass or less, and even more preferably 1.0% by mass. % by mass or less.

When the nonaqueous electrolyte of the present disclosure contains the lithium boron phosphate compound (X) as an electrolyte supply source, the concentration of the electrolyte is preferably 0.1 mol/L to 3 mol/L, and preferably 0.5 mol/L to 3 mol/L. 2 mol/L is more preferable.

Furthermore, even when the non-aqueous electrolyte sampled after actually disassembling the battery was analyzed, the amount of the lithium boron phosphate compound (X) was reduced compared to the amount added to the non-aqueous electrolyte. There are cases. Therefore, if the lithium boron phosphate compound (X) can be detected even in a small amount in the non-aqueous electrolyte taken out from the battery, it is included in the scope of the non-aqueous electrolyte of the present disclosure.
In addition, even if the above-mentioned lithium boron phosphate compound (X) cannot be detected from the non-aqueous electrolyte, there is a possibility that the decomposition product of the above-mentioned lithium boron phosphate compound (X) may be present in the non-aqueous electrolyte or in the electrode coating. is also considered to be within the scope of the non-aqueous electrolyte of the present disclosure.
These handlings are the same for compounds other than the above-mentioned lithium boron phosphate compound (X) that may be contained in the non-aqueous electrolyte.

<Electrolyte>
The nonaqueous electrolyte of the present embodiment contains at least one electrolyte that is a fluorine-containing lithium salt (hereinafter also referred to as "fluorine-containing lithium salt").
Examples of the fluorine-containing lithium salt include;
Inorganic acid anions such as lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium hexafluoride arsenate (LiAsF ₆ ), lithium hexafluorotantalate (LiTaF ₆ ), etc. salt;
Lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ), lithium bis(trifluoromethanesulfonyl)imide (Li(CF ₃ SO ₂ ) ₂ N), lithium bis(pentafluoroethanesulfonyl)imide (Li(C ₂ F ₅ SO _{2 )} ) ₂ N) and other organic acid anion salts;
etc.
As the fluorine-containing lithium salt, LiPF ₆ is particularly preferred.

The non-aqueous electrolyte of this embodiment may contain an electrolyte that is a fluorine-free lithium salt.
Examples of fluorine-free lithium salts include lithium perchlorate (LiClO ₄ ), lithium aluminate tetrachloride (LiAlCl ₄ ), lithium decachlorodecaborate (Li ₂ B ₁₀ Cl ₁₀ ), and the like.

The proportion of the fluorine-containing lithium salt in the entire electrolyte contained in the nonaqueous electrolyte of the present embodiment is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, More preferably, it is 80% by mass to 100% by mass.

The proportion of LiPF ₆ in the entire electrolyte contained in the nonaqueous electrolyte of the present embodiment is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably is 80% by mass to 100% by mass.

The concentration of the electrolyte in the non-aqueous electrolyte of the present embodiment is preferably 0.1 mol/L to 3 mol/L, more preferably 0.5 mol/L to 2 mol/L.

The concentration of LiPF ₆ in the non-aqueous electrolyte of this embodiment is preferably 0.1 mol/L to 3 mol/L, more preferably 0.5 mol/L to 2 mol/L.

<Non-aqueous solvent>
The non-aqueous electrolyte of this embodiment contains at least one non-aqueous solvent.
Examples of the nonaqueous solvent include cyclic carbonates, fluorine-containing cyclic carbonates, chain carbonates, fluorine-containing chain carbonates, aliphatic carboxylic acid esters, fluorine-containing aliphatic carboxylic acid esters, and γ-lactones. , fluorine-containing γ-lactones, cyclic ethers, fluorine-containing cyclic ethers, chain ethers, fluorine-containing chain ethers, nitriles, amides, lactams, nitromethane, nitroethane, sulfolane, trimethyl phosphate, dimethyl sulfoxide , dimethyl sulfoxide phosphoric acid, and the like.

Examples of cyclic carbonates include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and the like.
Examples of the fluorine-containing cyclic carbonates include fluoroethylene carbonate (FEC).
Examples of chain carbonates include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), dipropyl carbonate (DPC), and the like. can be mentioned.
Examples of aliphatic carboxylic acid esters include methyl formate, methyl acetate, methyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethylbutyrate, ethyl formate, ethyl acetate, ethyl propionate, ethyl butyrate, ethyl isobutyrate, and trimethyl. Examples include ethyl butyrate.
Examples of γ-lactones include γ-butyrolactone, γ-valerolactone, etc. Examples of cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, and 4-methyl- Examples of chain ethers include 1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, etc. Examples of chain ethers include 1,2-ethoxyethane (DEE), ethoxymethoxyethane (EME), and diethyl ether. , 1,2-dimethoxyethane, 1,2-dibutoxyethane, and the like.
Examples of nitriles include acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, and the like.
Examples of amides include N,N-dimethylformamide and the like.
Examples of the lactams include N-methylpyrrolidinone, N-methyloxazolidinone, N,N'-dimethylimidazolidinone, and the like.

The nonaqueous solvent preferably contains at least one selected from the group consisting of cyclic carbonates, fluorine-containing cyclic carbonates, chain carbonates, and fluorine-containing chain carbonates.
In this case, the total proportion of cyclic carbonates, fluorine-containing cyclic carbonates, chain carbonates, and fluorine-containing chain carbonates in the nonaqueous solvent is preferably 50% by mass to 100% by mass, It is more preferably 60% by mass to 100% by mass, and even more preferably 80% by mass to 100% by mass.

Moreover, it is preferable that the non-aqueous solvent contains at least one selected from the group consisting of cyclic carbonates and chain carbonates.
In this case, the total proportion of cyclic carbonates and chain carbonates in the nonaqueous solvent is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and Preferably it is 80% by mass to 100% by mass.

The proportion of the nonaqueous solvent in the nonaqueous electrolyte of this embodiment is preferably 60% by mass or more, more preferably 70% by mass or more.
The upper limit of the proportion of the nonaqueous solvent in the nonaqueous electrolyte of this embodiment depends on the content of other components (lithium boron phosphate compound (X), electrolyte, etc.), but the upper limit is, for example, 99% It is mass %, preferably 97 mass %, and more preferably 90 mass %.

The intrinsic viscosity of the nonaqueous solvent is preferably 10.0 mPa·s or less at 25° C. from the viewpoint of further improving the dissociation properties of the electrolyte and the mobility of ions.

<Cyclic carbonate ester having unsaturated bond>
The non-aqueous electrolyte of the present embodiment may contain at least one type of cyclic carbonate having an unsaturated bond from the viewpoint of further improving the chemical stability of the non-aqueous electrolyte.
Generally, when the non-aqueous electrolyte contains a cyclic carbonate having an unsaturated bond, the internal resistance of the battery tends to increase.
However, since the nonaqueous electrolyte of the present embodiment contains the lithium boron phosphate compound (X), even when it further contains a cyclic carbonate ester having an unsaturated bond, the internal resistance of the battery cannot be reduced. I can do it.
Rather, when the non-aqueous electrolyte of the present embodiment contains a cyclic carbonate having an unsaturated bond, there is an advantage that the internal resistance can be improved over a wide range by adding the lithium boron phosphate compound (X).

Examples of the cyclic carbonate having an unsaturated bond include vinylene carbonate compounds, vinylethylene carbonate compounds, and methylene ethylene carbonate compounds.

Examples of vinylene carbonate-based compounds include vinylene carbonate (also known as 1,3-dioxol-2-one), methyl vinylene carbonate (also known as 4-methyl-1,3-dioxol-2-one), and ethyl vinylene carbonate (also known as 4-methyl-1,3-dioxol-2-one). Other names: 4-ethyl-1,3-dioxol-2-one), 4,5-dimethyl-1,3-dioxol-2-one, 4,5-diethyl-1,3-dioxol-2-one, 4 -fluoro-1,3-dioxol-2-one, 4-trifluoromethyl-1,3-dioxol-2-one, and the like.

Examples of vinyl ethylene carbonate compounds include vinyl ethylene carbonate (also known as 4-vinyl-1,3-dioxolan-2-one), 4-methyl-4-vinyl-1,3-dioxolan-2-one, and 4-vinyl-1,3-dioxolan-2-one. -Ethyl-4-vinyl-1,3-dioxolan-2-one, 4-n-propyl-4-vinyl-1,3-dioxolan-2-one, 5-methyl-4-vinyl-1,3-dioxolan -2-one, 4,4-divinyl-1,3-dioxolan-2-one, 4,5-divinyl-1,3-dioxolan-2-one, and the like.

Examples of methylene ethylene carbonate compounds include 4-methylene-1,3-dioxolan-2-one, 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one, 4,4-diethyl-5- Examples include methylene-1,3-dioxolan-2-one, and the like.

As the cyclic carbonate having an unsaturated bond, vinylene carbonate is particularly preferred.

When the non-aqueous electrolyte of the present embodiment contains a cyclic carbonate ester having an unsaturated bond, the content of the cyclic carbonate ester having an unsaturated bond is preferably 0.1 with respect to the total amount of the non-aqueous electrolyte. The content is from 10% by weight, more preferably from 0.2% to 5.0% by weight, and even more preferably from 0.3% to 3.0% by weight.

When the non-aqueous electrolyte of the present embodiment contains vinylene carbonate, the content of vinylene carbonate is preferably 0.1% by mass to 5.0% by mass, more preferably is 0.2% by mass to 4.0% by mass, more preferably 0.3% by mass to 3.0% by mass, even more preferably 0.3% by mass to 2.0% by mass.

When the non-aqueous electrolyte of this embodiment contains vinylene carbonate, the value obtained by dividing the content mass of the lithium boron phosphate compound (X) by the content mass of vinylene carbonate (hereinafter referred to as "content mass ratio [lithium boron phosphate compound (X)/vinylene carbonate]) is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1.0 or more.
When the content mass ratio [lithium boron phosphate compound (X)/vinylene carbonate] is 0.1 or more, increase in internal resistance of the lithium secondary battery after storage can be further suppressed.

The upper limit of the content mass ratio [lithium boron phosphate compound (X)/vinylene carbonate] is not particularly limited, but from the viewpoint of more effectively obtaining the effect of vinylene carbonate, it is preferably 10 or less, more preferably 5 It is as follows.

<Other ingredients>
The non-aqueous electrolyte of this embodiment may contain at least one component other than the components mentioned above.
Other components include sultone (ie, cyclic sulfonic acid ester), acid anhydride, and the like.

The intrinsic viscosity of the nonaqueous electrolyte of this embodiment is preferably 10.0 mPa·s or less at 25° C. from the viewpoint of further improving the dissociation properties of the electrolyte and the mobility of ions.

<Method for manufacturing non-aqueous electrolyte>
There is no particular limitation on the method for manufacturing the non-aqueous electrolyte of this embodiment. The nonaqueous electrolyte of this embodiment may be manufactured by mixing each component.

As a method for manufacturing the non-aqueous electrolyte of this embodiment, for example,
Obtaining a solution by dissolving the electrolyte in a non-aqueous solvent;
A step of adding and mixing lithium boron phosphate compound (X) (and other additives as necessary) to the obtained solution to obtain a non-aqueous electrolyte;
Examples of manufacturing methods include:
In the manufacturing method according to this example, it is preferable that the electrical conductivity of the obtained non-aqueous electrolyte is lower than the electrical conductivity of the solution (before adding the lithium boron phosphate compound (X)). . According to the nonaqueous electrolyte obtained by the manufacturing method of this aspect, the effect of the nonaqueous electrolyte described above (ie, the effect of reducing the internal resistance of the battery) is more effectively exhibited.

[Lithium secondary battery precursor]
A lithium secondary battery precursor according to an embodiment of the present disclosure (hereinafter also simply referred to as "battery precursor of this embodiment") includes:
case and
A positive electrode, a negative electrode, a separator, and an electrolyte contained in a case,
Equipped with
The positive electrode is a positive electrode capable of intercalating and deintercalating lithium ions,
The negative electrode is a negative electrode capable of intercalating and deintercalating lithium ions,
The electrolytic solution is a lithium secondary battery precursor which is the non-aqueous electrolytic solution of this embodiment described above.

Here, the lithium secondary battery precursor means a lithium secondary battery before being charged and discharged.
In the lithium secondary battery of this embodiment, which will be described later, a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte are housed in a case to produce a lithium secondary battery precursor, and the resulting lithium secondary battery precursor is , charging and discharging (preferably aging treatment including charging and discharging).

The battery precursor of this embodiment includes the non-aqueous electrolyte of this embodiment.
Therefore, the battery precursor of this embodiment provides the same effects as the non-aqueous electrolyte of this embodiment.

<Case>
The case for the battery precursor of this embodiment is not particularly limited, and examples thereof include known cases for lithium secondary batteries.
Examples of the case include a case containing a laminate film, a case consisting of a battery can and a battery can lid, and the like.

<Positive electrode>
The positive electrode in the battery precursor of this embodiment is a positive electrode capable of intercalating and deintercalating lithium ions.
The positive electrode in the battery precursor of the present embodiment preferably includes at least one positive electrode active material capable of intercalating and deintercalating lithium ions.
The positive electrode in the battery precursor of this embodiment more preferably includes a positive electrode current collector and a positive electrode composite layer containing a positive electrode active material and a binder.
The positive electrode composite material layer is provided on at least a portion of the surface of the positive electrode current collector.

(Cathode active material)
The positive electrode active material is not particularly limited as long as it is a material capable of intercalating and deintercalating lithium ions, and may be a positive electrode active material commonly used in lithium secondary batteries.
As the positive electrode active material, for example;
An oxide containing lithium (Li) and nickel (Ni) as constituent metal elements;
An oxide containing Li, Ni, and at least one metal element other than Li and Ni (for example, a transition metal element, a typical metal element, etc.) as a constituent metal element;
etc.
In the oxide, metal elements other than Li and Ni are preferably contained in a proportion equal to or smaller than Ni in terms of the number of atoms.
Metal elements other than Li and Ni include, for example, Co, Mn, Al, Cr, Fe, V, Mg, Ca, Na, Ti, Zr, Nb, Mo, W, Cu, Zn, Ga, In, Sn, and La. and Ce. These positive electrode active materials may be used alone or in combination.

The positive electrode active material preferably includes a lithium-containing composite oxide (hereinafter also referred to as "NCM") represented by the following general formula (C1).
The lithium-containing composite oxide (C1) has the advantages of high energy density per unit volume and excellent thermal stability.

_LiNia Co _b Mn _c O ₂ ... General formula (C1)
[In general formula (C1), a, b and c are each independently greater than 0 and less than 1, and the sum of a, b and c is 0.99 to 1.00. ]

Specific examples of NCM include LiNi _0.33 Co _0.33 Mn _0.33 O ₂ , LiNi _0.5 Co _0.3 Mn _0.2 O ₂ , LiNi _0.6 Co _0.2 Mn _0.2 O ₂ , LiNi _0.8 Co _0.1 Mn _0.1 O ₂ and the like.

The positive electrode active material may include a lithium-containing composite oxide (hereinafter also referred to as "NCA") represented by the following general formula (C2).

Li _t Ni _1-x-y Co _x Al _y O ₂ ... General formula (C2)
(In general formula (C2), t is 0.95 or more and 1.15 or less, x is 0 or more and 0.3 or less, y is 0.1 or more and 0.2 or less, x and The sum of y is less than 0.5.)

Specific examples of NCAs include LiNi _0.8 Co _0.15 Al _0.05 O ₂ and the like.

When the positive electrode in the battery precursor of this embodiment includes a positive electrode current collector and a positive electrode composite layer containing a positive electrode active material and a binder, the content of the positive electrode active material in the positive electrode composite layer is The amount is, for example, 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, particularly preferably 70% by mass or more, based on the total amount of the composite material layer.
Further, the content of the positive electrode active material in the positive electrode composite material layer is, for example, 99.9% by mass or less, preferably 99% by mass or less.

(binder)
Examples of the binder that can be contained in the positive electrode composite layer include polyvinyl acetate, polymethyl methacrylate, nitrocellulose, fluororesin, rubber particles, and the like.
Examples of the fluororesin include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), vinylidene fluoride-hexafluoropropylene copolymer, and the like.
Examples of the rubber particles include styrene-butadiene rubber particles and acrylonitrile rubber particles.
Among these, fluororesin is preferred from the viewpoint of improving the oxidation resistance of the positive electrode composite material layer.
One type of binder can be used alone, or two or more types can be used in combination as necessary.

The content of the binder in the positive electrode composite layer is set to 0.00000000000 with respect to the positive electrode composite material layer, from the viewpoint of achieving both the physical properties of the positive electrode composite material layer (for example, electrolyte permeability, peel strength, etc.) and battery performance. It is preferably 1% by mass to 4% by mass.
When the content of the binder is 0.1% by mass or more, the adhesiveness of the positive electrode composite material layer to the positive electrode current collector and the binding property between positive electrode active materials are further improved.
When the content of the binder is 4% by mass or less, the amount of the positive electrode active material in the positive electrode composite layer can be increased, so that the battery capacity can be further improved.

(conductive aid)
When the positive electrode in the battery precursor of this embodiment includes a positive electrode current collector and a positive electrode composite material layer, the positive electrode composite material layer preferably contains a conductive additive.
As the conductive aid, a known conductive aid can be used.

As the conductive aid, a known conductive aid can be used.
Known conductive additives are not particularly limited as long as they are conductive carbon materials, but include graphite, carbon black, conductive carbon fibers (carbon nanotubes, carbon nanofibers, carbon fibers), fullerenes, etc. They can be used alone or in combination of two or more.
Commercially available carbon blacks include, for example, Toka Black #4300, #4400, #4500, #5500 (manufactured by Tokai Carbon Co., Ltd., Furnace Black), Printex L, etc. (manufactured by Degussa Corporation, Furnace Black), Raven 7000, 5750, etc. 5250, 5000ULTRAIII, 5000ULTRA, etc., Conductex SC ULTRA, Conductex 975ULTRA, etc., PUER BLACK100, 115, 205, etc. (manufactured by Columbian, furnace black), #2350, #2400B, #2600B, # 30050B, #3030B, #3230B, # 3350B, #3400B, #5400B, etc. (manufactured by Mitsubishi Chemical Corporation, furnace black), MONARCH1400, 1300, 900, VulcanXC-72R, BlackPearls2000, LITX-50, LITX-200, etc. (manufactured by Cabot Corporation, furnace black), Ensaco250 G, Ensaco260G , Ensaco350G, Super-P (manufactured by TIMCAL), Ketjen Black EC-300J, EC-600JD (manufactured by Akzo), Denka Black, Denka Black HS-100, FX-35 (manufactured by Denka, acetylene black), etc. Can be mentioned.
Examples of graphite include, but are not limited to, artificial graphite, natural graphite (for example, scaly graphite, lumpy graphite, earthy graphite, etc.).

(Other ingredients)
When the positive electrode in the battery precursor of this embodiment includes a positive electrode current collector and a positive electrode composite material layer, the positive electrode composite material layer may contain other components in addition to the above-mentioned components.
Other components include thickeners, surfactants, dispersants, wetting agents, antifoaming agents, and the like.

(Positive electrode current collector)
Various materials can be used as the positive electrode current collector, and for example, metals or alloys are used.
More specifically, examples of the positive electrode current collector include aluminum, nickel, SUS, and the like. Among these, aluminum is preferred from the viewpoint of balance between high conductivity and cost. Here, "aluminum" means pure aluminum or aluminum alloy.
As the positive electrode current collector, aluminum foil is particularly preferred.
The aluminum foil is not particularly limited, but examples include A1085 material and A3003 material.

(Method for forming positive electrode composite layer)
The positive electrode composite material layer can be formed, for example, by applying a positive electrode composite slurry containing a positive electrode active material and a binder onto the surface of the positive electrode current collector and drying the slurry.
The solvent contained in the positive electrode material slurry is preferably an organic solvent such as N-methyl-2-pyrrolidone (NMP).

When applying the positive electrode mixture slurry to the positive electrode current collector and drying it, the application method and drying method are not particularly limited.
Examples of the coating method include slot die coating, slide coating, curtain coating, and gravure coating.
Examples of the drying method include drying with warm air, hot air, and low humidity air; vacuum drying; and drying with infrared rays (for example, far infrared rays) irradiation.
The drying time and drying temperature are not particularly limited, but the drying time is, for example, 1 minute to 30 minutes, and the drying temperature is, for example, 40°C to 80°C.
The method for producing the positive electrode composite layer is to apply a positive electrode mixture slurry onto a positive electrode current collector, dry it, and then apply pressure using a mold press, roll press, etc. to reduce the porosity of the positive electrode active material layer. It is preferable to include a step of lowering the .

<Negative electrode>
The negative electrode in the battery precursor of this embodiment is a negative electrode capable of intercalating and deintercalating lithium ions.
The negative electrode in the battery precursor of the present embodiment preferably contains at least one negative electrode active material capable of intercalating and deintercalating lithium ions.
The negative electrode in the battery precursor of this embodiment more preferably includes a negative electrode current collector and a negative electrode composite material layer containing a negative electrode active material and a binder.
The negative electrode composite material layer is provided on at least a portion of the surface of the negative electrode current collector.

(Negative electrode active material)
The negative electrode active material is not particularly limited as long as it can absorb and release lithium ions, but examples include metallic lithium, lithium-containing alloys, metals or alloys that can be alloyed with lithium, and lithium ion doped materials. At least one member selected from the group consisting of oxides that can be dedoped, transition metal nitrides that can be doped and dedoped with lithium ions, and carbon materials that can be doped and dedoped with lithium ions. (or a mixture containing two or more of these) can be used.
Among these, carbon materials that can be doped and dedoped with lithium ions are preferred.
Examples of the carbon material include carbon black, activated carbon, graphite materials (eg, artificial graphite, natural graphite, etc.), amorphous carbon materials, and the like.
The carbon material may be in any of fibrous, spherical, potato-like, and flake-like forms.
The particle size of the carbon material is not particularly limited, but is, for example, 5 μm to 50 μm, preferably 20 μm to 30 μm.

Specific examples of the amorphous carbon material include hard carbon, coke, mesocarbon microbeads (MCMB) fired at 1500° C. or lower, and mesophase pitch carbon fiber (MCF).

Examples of graphite materials include natural graphite and artificial graphite.
As the artificial graphite, graphitized MCMB, graphitized MCF, etc. are used.
Further, as the graphite material, one containing boron can also be used.
Further, as the graphite material, those coated with metals such as gold, platinum, silver, copper, and tin, those coated with amorphous carbon, and those coated with a mixture of amorphous carbon and graphite can also be used.

These carbon materials may be used alone or in combination of two or more.

(conductive aid)
When the negative electrode in the battery precursor of this embodiment includes a negative electrode current collector and a negative electrode composite material layer, it is preferable that the negative electrode composite material layer contains a conductive additive.
As the conductive aid, a known conductive aid can be used.
Specific examples of the conductive additive that can be included in the negative electrode composite layer are the same as the aforementioned specific examples of the conductive additive that can be included in the positive electrode composite layer.

(Other ingredients)
When the negative electrode in the battery precursor of this embodiment includes a negative electrode current collector and a negative electrode composite material layer, the negative electrode composite material layer may contain other components in addition to the above-mentioned components.
Other components include thickeners, surfactants, dispersants, wetting agents, antifoaming agents, and the like.

(Method for forming negative electrode composite material layer)
The negative electrode composite material layer can be formed, for example, by applying a negative electrode composite material slurry containing a negative electrode active material and a binder onto the surface of the negative electrode current collector and drying the slurry.
It is preferable to use water as the solvent contained in the negative electrode composite material slurry, but if necessary, for example, a liquid medium that is compatible with water may be used to improve the coating properties on the current collector. It's okay.
Liquid media that are compatible with water include alcohols, glycols, cellosolves, amino alcohols, amines, ketones, carboxylic acid amides, phosphoric acid amides, sulfoxides, carboxylic acid esters, and phosphoric acid esters. ethers, nitriles, etc., and may be used within a range that is compatible with water.

A preferred embodiment of the method for forming the negative electrode composite material layer is the same as the preferred embodiment of the method for forming the positive electrode composite material layer described above.

<Separator>
Examples of the separator in the battery precursor of this embodiment include porous flat plates containing resins such as polyethylene (PE), polypropylene (PP), polyester, cellulose, and polyamide. Moreover, as a separator, the nonwoven fabric containing the said resin is also mentioned.
A preferred example is a porous resin sheet having a single layer or multilayer structure mainly composed of one or more types of polyolefin resin.
The thickness of the separator can be, for example, 5 μm to 30 μm.
The separator is preferably placed between the positive electrode and the negative electrode.

<Electrolyte>
The electrolytic solution in the battery precursor of this embodiment is the non-aqueous electrolytic solution of this embodiment described above.
Preferred aspects of the non-aqueous electrolyte of this embodiment are as described above.

<Method for manufacturing battery precursor>
There is no particular limitation on the method for manufacturing the battery precursor of this embodiment.
An example of a method for manufacturing the battery precursor of this embodiment includes a step of housing a positive electrode, a negative electrode, a separator, and an electrolyte in a case.
The above example preferably includes:
A step of accommodating a positive electrode, a negative electrode, and a separator in a case;
Injecting an electrolyte into a case containing a positive electrode, a negative electrode, and a separator;
including.

<Example of lithium secondary battery precursor>
An example of the lithium secondary battery precursor of this embodiment will be described below with reference to FIG. 1, but the lithium secondary battery precursor of this embodiment is not limited to the following example.

FIG. 1 is a schematic cross-sectional view showing a lithium secondary battery precursor 1, which is an example of the lithium secondary battery precursor of this embodiment.
The lithium secondary battery precursor 1 is an example of a stacked lithium secondary battery.
In addition to this stacked lithium secondary battery, the lithium secondary battery precursor of the present embodiment may have a structure in which a positive electrode, a separator, a negative electrode, and a separator are stacked in this order and wound in a layered manner. A wound type lithium secondary battery may also be mentioned.

As shown in FIG. 1, the lithium secondary battery precursor 1 has a structure in which a battery element 10 to which a positive electrode lead 21 and a negative electrode lead 22 are attached is sealed inside an exterior body 30 formed of a laminate film. are doing.
In the lithium secondary battery precursor 1, the positive electrode lead 21 and the negative electrode lead 22 are led out in opposite directions from the inside of the exterior body 30 to the outside.
The positive electrode lead 21 and the negative electrode lead 22 can be attached to a positive electrode current collector and a negative electrode current collector, which will be described later, by, for example, ultrasonic welding or resistance welding.
Although not shown, the positive electrode lead and the negative electrode lead may be led out in the same direction from the inside of the exterior body to the outside.

As shown in FIG. 1, the battery element 10 includes a positive electrode 11 in which a positive electrode composite layer 11B is formed on both main surfaces of a positive electrode current collector 11A, a separator 13, and a negative electrode current collector 12A. It has a structure in which a negative electrode 12 having a negative electrode composite material layer 12B formed on the main surface is stacked.
In this structure, a positive electrode composite layer 11B is formed on one main surface of the positive electrode current collector 11A of the positive electrode 11, and a positive electrode composite layer 11B is formed on one main surface of the negative electrode current collector 12A of the negative electrode 12 adjacent to the positive electrode 11. The negative electrode composite material layer 12</b>B and the negative electrode composite material layer 12</b>B facing each other with the separator 13 interposed therebetween.

A non-aqueous electrolyte (not shown) of this embodiment is injected into the exterior body 30 of the lithium secondary battery precursor 1. The non-aqueous electrolyte of this embodiment is impregnated into the positive electrode mixture layer 11B, the separator 13, and the negative electrode mixture layer 12B.
In the lithium secondary battery precursor 1, one single cell layer 14 is formed by the adjacent positive electrode composite material layer 11B, separator 13, and negative electrode composite material layer 12B.
Note that the positive electrode and the negative electrode may each have an active material layer formed on one side of each current collector.

Note that, as an example of a lithium secondary battery according to an embodiment of the present disclosure described below, lithium secondary Examples include lithium secondary batteries in which a film is formed by charging and discharging the battery precursor 1.

[Method for manufacturing lithium secondary battery]
The method for manufacturing a lithium secondary battery according to the embodiment of the present disclosure (hereinafter also referred to as "the method for manufacturing a battery according to the present embodiment") includes:
A step of preparing the battery precursor of this embodiment (hereinafter also referred to as "preparation step"),
A step of obtaining a lithium secondary battery by subjecting a battery precursor to an aging treatment (hereinafter also referred to as "aging step");
including;
Aging treatment is a method for manufacturing a lithium secondary battery that includes charging and discharging a battery precursor in an environment of 30° C. to 70° C.

The aging treatment in the aging step preferably includes:
an initial holding phase in which the battery precursor is held in an environment of 30°C to 70°C (preferably 30°C to 60°C);
an initial charging phase in which the battery precursor after the initial holding phase is charged in an environment of 30° C. to 70° C. (preferably 30° C. to 60° C.);
a second holding phase in which the battery precursor after the initial charging phase is held in an environment of 30°C to 70°C (preferably 30°C to 60°C);
A charging/discharging phase in which the battery precursor after the second holding phase is subjected to a combination of charging and discharging one or more times in an environment of 30° C. to 70° C. (preferably 30° C. to 60° C.);
including.

According to the above preferred embodiment, the effect of suppressing battery resistance and gas expansion in a high temperature environment of a lithium secondary battery is more effectively exhibited.

[Lithium secondary battery]
A lithium secondary battery according to an embodiment of the present disclosure (hereinafter also referred to as "battery of this embodiment") includes:
case and
A positive electrode, a negative electrode, a separator, and an electrolyte contained in a case,
Equipped with
The positive electrode is a positive electrode capable of intercalating and deintercalating lithium ions,
The negative electrode is a negative electrode capable of intercalating and deintercalating lithium ions,
The electrolyte is a nonaqueous electrolyte containing an electrolyte that is a lithium salt containing fluorine and a nonaqueous solvent,
A negative electrode film containing a lithium boron phosphate compound containing a repeating structure represented by the following formula (I) and a component derived from the electrolyte is formed on at least a part of the surface of the negative electrode, and the surface of the positive electrode This is a lithium secondary battery in which a positive electrode coating containing a lithium boron phosphate compound containing a repeating structure represented by the following formula (I) and a component derived from the electrolyte is formed on at least a portion of the lithium secondary battery.

[In formula (I), n represents an integer of 1 or more. ]

Here, the component derived from the lithium boron phosphate compound containing the repeating structure represented by formula (I) and the electrolyte refers to, for example, the lithium boron phosphate compound containing the repeating structure represented by formula (I). It refers to a component containing at least one selected from a decomposition product, a reaction product of a lithium boron phosphate compound containing a repeating structure represented by formula (I) and an electrolyte, and a decomposition product of the reaction product.

The battery of this embodiment can be suitably manufactured by the method for manufacturing the battery of this embodiment described above.
Since the battery of this embodiment includes the negative electrode coating and the positive electrode coating, the same effects as those of the battery manufactured by the battery manufacturing method of this embodiment are achieved.

Preferred aspects of the case, positive electrode, negative electrode, and separator in the battery of this embodiment are the same as those of the case, positive electrode, negative electrode, and separator in the battery precursor of this embodiment described above.

A preferred embodiment of the non-aqueous electrolyte in the battery of this embodiment is the same as the preferred embodiment of the non-aqueous electrolyte of this embodiment, except that it is not limited to containing the lithium boron phosphate compound (X). It is.
The non-aqueous electrolyte in the battery of this embodiment may contain a lithium boron phosphate compound (X).
For example, when the battery of this embodiment is manufactured by the battery manufacturing method of this embodiment, the lithium boron phosphate compound (X) may be completely consumed by the aging treatment, or the lithium boron phosphate compound (X) may be completely consumed by the aging treatment. A part of X) may remain.

The additive for a lithium secondary battery of the present disclosure, the nonaqueous electrolyte for a lithium secondary battery of the present disclosure, the lithium secondary battery precursor of the present disclosure, the method for manufacturing a lithium secondary battery of the present disclosure, as described above, The lithium secondary battery of the present disclosure can be applied to, for example, electronic devices such as mobile phones and notebook computers; electric vehicles; hybrid vehicles; power sources for power storage; and the like.
The additive for lithium secondary batteries of the present disclosure, the non-aqueous electrolyte for lithium secondary batteries of the present disclosure, the lithium secondary battery precursor of the present disclosure, the method for manufacturing a lithium secondary battery of the present disclosure, and the lithium of the present disclosure Secondary batteries are particularly suitable for use in hybrid vehicles or electric vehicles.

Examples of the present disclosure will be shown below, but the present disclosure is not limited to the following examples.

[Example 1] Synthesis example of compound of formula (I) A 300 mL flask equipped with a stirring device, a thermometer, a gas introduction line, an exhaust line, and a Dean-Stark tube was prepared. The Deanstark tube was filled with toluene for removal of produced water.
After purging the above 300 mL flask with dry nitrogen gas, 33.6 g (0.30 mol) of phosphoric acid with a concentration of 87.5%, 11.08 g (0.15 mol) of lithium carbonate, and 60 g of water were added thereto. and stirred and mixed to obtain a homogeneous solution. 100 g of toluene was added thereto while stirring, and heating was started 30 minutes later to bring the toluene into a state of reflux at a temperature of 85 to 110°C. Heating, stirring, and toluene reflux were continued, and distilled water was separated from toluene in the Deanstark tube to be removed. When no water was distilled out from the refluxing toluene, heating was stopped, and the reaction solution was cooled to room temperature (25° C.). The reaction solution obtained above was a slurry in which solids were precipitated.

This slurry was filtered to remove solid content, and the slurry was heated and dried at 150° C. for 6 hours in a nitrogen atmosphere. This yielded 25.77 g (0.30 mol) of Intermediate A as white crystals. This intermediate A was then added to the original reaction flask along with 200 g of dimethyl carbonate and mixed with stirring to obtain a homogeneous slurry. 42.58 g (0.30 mol) of boron trifluoride diethyl ether complex was added thereto while stirring, and then heated to 90° C. and stirred for 2 hours under solvent reflux (reaction step). During this 2 hour stirring process, the slurry turned into a homogeneous solution. This reaction solution was cooled to room temperature and then dried under conditions of 10 kPa or less and 30° C. to obtain 46.10 g of a highly viscous liquid product with almost no fluidity.

The obtained product was dissolved in a heavy dimethyl sulfoxide solvent and subjected to ¹¹ B-NMR analysis, ¹⁹ F-NMR analysis, and ³¹ P-NMR analysis. The chemical shifts [ppm] of the spectra obtained by each NMR analysis were as follows.

^11B -NMR: -2.2 ppm.
^19F -NMR: -148.3ppm.
^31P -NMR: 0.2 ppm.

The obtained product was confirmed to have a trifluoroborate skeleton from the spectral patterns of ¹¹ B-NMR and ¹⁹ F-NMR, and was confirmed to be a phosphoric acid compound from ³¹ P-NMR. .

Further, the obtained product was dissolved in a dimethylformamide solvent, and the weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by GPC measurement. The GPC measurement was performed using two TSKgel Super AWM-H 9 μm (6.0φ×150 mm) columns in series, solvent: 10 mM LiBr/dimethylformamide, and column temperature: 40°C. The Mw value and Mn value are polystyrene equivalent values.

As a result of GPC measurement, Mw=1,700, Mn=1,500, and Mw/Mn≈1.13.
From the measurement results of Mw and Mn, n is considered to be 8 to 11.

As described above, it was confirmed that the product obtained by the synthesis of Example 1 was a type of lithium boron phosphate compound, that is, a lithium boron phosphate compound containing the repeating structure (I). Therefore, the results of Example 1 showed that a compound (n is 1 or more) containing the repeating structure (I) was obtained using the following reaction scheme.

[Examples 101-104, Comparative Examples 101-102]
<Preparation of non-aqueous electrolyte (sample 0 to sample 5)>
(Sample 0)
By mixing ethylene carbonate (hereinafter referred to as EC), dimethyl carbonate (hereinafter referred to as DMC), and methyl ethyl carbonate (EMC) at a ratio of EC:DMC:EMC=30:35:35 (volume ratio), a non-aqueous solvent can be obtained. A mixed solvent was prepared.
LiPF ₆ as an electrolyte was dissolved in the mixed solvent so that the concentration in the finally obtained non-aqueous electrolyte was 1 mol/liter.
Through the above steps, sample 0 was obtained.
Sample 0 is a non-aqueous electrolyte used in the battery of Comparative Example 101.

(Samples 1-2)
Furthermore, as an example of the lithium boron phosphate compound (X), the compound obtained in Example 1 (hereinafter also referred to as "compound (I)") was added to the total amount of the non-aqueous electrolyte finally obtained. Samples 1 to 2 were obtained in the same manner as Sample 0, except that the amounts were added so that the contents (mass%) were as shown in Table 1.
Samples 1 to 2 are non-aqueous electrolytes used in the batteries of Examples 101 to 102, respectively.

(Sample 3)
Furthermore, the same as sample 0 except that vinylene carbonate (VC) was added so that the content based on the total amount of the non-aqueous electrolyte finally obtained was the content (mass%) shown in Table 2. Sample 3 was obtained.
Sample 3 is a non-aqueous electrolyte used in the battery of Comparative Example 102.

(Samples 4-5)
Furthermore, Samples 1 and 2 were the same, except that vinylene carbonate (VC) was added so that the content (mass%) based on the total amount of the non-aqueous electrolyte finally obtained was as shown in Table 2. Samples 4 and 5 were obtained in the same manner as each sample.
Samples 4 to 5 are non-aqueous electrolytes used in the batteries of Examples 103 to 104, respectively.

<Production of lithium secondary battery>
A wound type battery (designed capacity 1 Ah) (hereinafter also simply referred to as "battery") as a lithium secondary battery was produced in the following manner.

(Preparation of positive electrode)
1. Preparation of positive electrode composite slurry A 5L planetary disperser was used to prepare the positive electrode composite slurry.
920 g of NCM523 (i.e., LiNi _0.5 Co _0.2 Mn _0.3 O ₂ ) as a positive electrode active material, 20 g of Super-P (conductive carbon manufactured by TIMCAL) as a conductive additive, and After 20 g of KS-6 (scaly graphite manufactured by TIMREX) was mixed for 10 minutes, 100 g of N-methylpyrrolidone (NMP) was added thereto and further mixed for 20 minutes.

Next, 150 g of an 8% PVDF solution (PVDFW #7200 manufactured by Kureha dissolved in NMP) was added and kneaded for 30 minutes, and then 200 g of the above 8% PVDF solution was added and kneaded for 30 minutes. Next, 80 g of the above 8%-PVDF solution was added thereto and kneaded for 30 minutes. Thereafter, 27 g of NMP was added to adjust the viscosity and mixed for 30 minutes, followed by vacuum defoaming for 30 minutes.
Through the above steps, a positive electrode composite slurry having a solid content concentration of 60% was obtained.

2. Coating, Drying, and Pressing A die coater was used to apply the positive electrode composite slurry.
The above positive electrode composite slurry was applied to a part of one side of an aluminum foil (thickness 20 μm, width 200 mm) as a positive electrode current collector so that the applied mass after drying was 19.0 mg/cm ² and dried. . Next, the positive electrode composite slurry was applied to a part of the opposite side (uncoated side) of the aluminum foil so that the applied mass was 19.0 mg/cm ² and dried.
The thus obtained double-sided coated aluminum foil (38.0 mg/cm ² ) was dried in a vacuum drying oven at 130°C for 12 hours, and then, using a 35-ton press machine, the pressed density was 2.9 g/cm 2 . A positive electrode original fabric was obtained by compressing it to a size of cm ³ .
This positive electrode original fabric includes an aluminum foil as a positive electrode current collector, and positive electrode composite material layers provided on both sides of this aluminum foil. Both sides of the aluminum foil each include a region where the positive electrode composite material layer is formed and a region (i.e., a blank space) where the positive electrode composite material layer is not formed.

3. Slit By slitting the above positive electrode material, the front side includes a positive electrode composite material layer of 56 mm x 334 mm and a margin for tab welding, and the back side includes a positive electrode composite material layer of 56 mm x 408 mm. , and a tab welding margin, a positive electrode C-1 was obtained.

(Preparation of negative electrode)
1. Preparation of negative electrode composite material slurry A 5L planetary disperser was used to prepare the negative electrode composite material slurry.
1%-CMC aqueous solution (i.e., 1 mass of carboxymethyl cellulose (CMC)) per 960 g of natural graphite as a negative electrode active material and 10 g of Super-P (conductive carbon, BET specific surface area 62 m ² /g) as a conductive additive. % aqueous solution) was added and mixed for 30 minutes.
To the resulting mixture, 300 g of a 1% CMC aqueous solution was added and kneaded for 30 minutes, and then 250 g of a 1% CMC aqueous solution was added and kneaded for 30 minutes.
To the obtained kneaded material, 50 g of styrene butadiene rubber (SBR) (40% emulsion) was added and mixed for 30 minutes, followed by vacuum defoaming for 30 minutes.
As described above, a negative electrode composite slurry having a solid content concentration of 45% was prepared.

2. Coating, drying, and pressing A die coater was used to apply the negative electrode composite slurry.
The negative electrode composite slurry was applied to a part of one side of a copper foil (thickness: 10 μm) as a negative electrode current collector so that the applied mass after drying was 11.0 mg/cm ² and dried. Next, the negative electrode composite slurry was applied to a part of the opposite side (uncoated side) of this copper foil so that the applied mass was 11.0 mg/cm ² and dried.
The thus obtained double-sided coated copper foil (22.0 mg/cm ² ) was dried in a vacuum drying oven at 120°C for 12 hours, and then, using a small press machine, the pressed density was 1.45 g/cm. A negative electrode original fabric was obtained by compressing it so that it became ³ .
This negative electrode original fabric includes a copper foil as a negative electrode current collector, and negative electrode composite material layers provided on both sides of the copper foil. Both sides of the copper foil each include a region where the negative electrode composite material layer is formed and a region (ie, a blank space) where the negative electrode composite material layer is not formed.

3. Slit By slitting the above negative electrode original fabric, the front side includes a negative electrode composite material layer of 58 mm x 372 mm and a margin for tab welding, and the back side includes a negative electrode composite material layer of 58 mm x 431 mm. , and a tab welding margin, a negative electrode A-1 was obtained.

(Preparation of battery precursor)
As a separator, a porous resin sheet (porous polyethylene membrane with a porosity of 45% and a thickness of 25 μm) (60.5 mm×450 mm) was prepared.
A laminate was obtained by stacking the negative electrode A-1, the separator, and the positive electrode C-1 in such a direction that the back surface of the negative electrode A-1 was in contact with the separator and the back surface of the positive electrode C-1 was in contact with the separator. The obtained laminate was wound to obtain a wound body. The obtained wound body was press-molded to obtain a molded body.
Next, an aluminum positive electrode tab is bonded to the blank space of the positive electrode C-1 in the molded body using an ultrasonic bonding machine, and a nickel negative electrode tab is bonded to the blank space of the negative electrode A-1 in the molded body using an ultrasonic bonding machine. It was joined with The molded body in which the positive electrode tab and the negative electrode tab were joined was sandwiched between a pair of laminate sheets, and then three sides were heat-sealed to obtain a laminate body. At this time, the positive electrode tab and negative electrode tab were made to protrude from the remaining side of the laminate (the side that was not heat-sealed).

Next, the laminate was dried under reduced pressure at 70° C. for 12 hours using a vacuum dryer while drawing a vacuum. Next, while continuing to vacuum, a non-aqueous electrolyte (any one of samples 0 to 5) is injected into the laminate from the remaining side, and then the remaining side is heated. I sealed it. The amount of electrolyte injected was 4.7 g.
As described above, battery precursors (that is, lithium secondary battery precursors) of each Example and each Comparative Example were obtained.

(Battery production (aging treatment))
The batteries (ie, lithium secondary batteries) of each Example and each Comparative Example were obtained by subjecting the battery precursors of each Example and each Comparative Example to the aging treatment shown below. Details are shown below.

The battery precursor was held at an ambient temperature of 40° C. for 12 hours.
Next, under an ambient temperature of 40°C, the battery precursor was charged at a constant current of 0.05C to 3.0V, then charged to 3.4V at a charge rate of 0.1C, and then Constant current charging was performed to 3.7V at a charging rate of 0.2C.
Next, the battery precursor was allowed to rest for 24 hours at an ambient temperature of 40°C.
Next, the battery precursor was charged at a constant current and constant voltage (0.5C-CCCV) at a charging rate of 0.5C to 4.2V (SOC (State of Charge) 100%) at an ambient temperature of 40°C. , then rested for 30 minutes, and then subjected to constant current discharge (0.5C-CC) to 2.5V at a discharge rate of 0.5C. Next, the battery precursor was charged to 4.2V at 0.5C-CCCV and then discharged to 2.5V at 0.5C-CC.
Through the above steps, a test battery was obtained.

<Evaluation of battery resistance and resistance increase rate after high temperature storage>
Evaluation of the battery resistance and resistance increase rate of the battery after 4 weeks at high temperature was performed before storing the battery (after 0 weeks) and after charging the battery to 4.2V at 0.2C-CCCV in an environment of 60℃. Using the test battery stored for 4 weeks (after storage for 4 weeks), the following operations were performed at 25° C. and evaluated.

Regarding the test batteries before storing the batteries described above (after 0 week storage), the initial DCIR (Direct current internal resistance) of each battery was measured by the following method.

CCCV charging was performed to 3.7V at a charging rate of 0.5C.
Next, the battery was subjected to CC10s discharge at a discharge rate of 1C, and then CC10s charge was performed at a charge rate of 1C.
Next, the battery was subjected to CC10s discharge at a discharge rate of 2C, and then CC20s charge was performed at a charge rate of 1C.
Next, the battery was subjected to CC10s discharge at a discharge rate of 3C, and then CC30s charge was performed at a charge rate of 1C.
Next, the battery was subjected to CC10s discharge at a discharge rate of 4C, and then CC40s charge was performed at a charge rate of 1C.
Next, the battery was subjected to CC10s discharge at a discharge rate of 5C, and then CC50s charge was performed at a charge rate of 1C.

In addition, CCCV charging means charging with constant current constant voltage (Constant Current Constant Voltage), and CC10s discharge means discharging with constant current (Constant Current) for 10 seconds. means charging at a constant current for 10 seconds.

Each voltage drop amount due to "CC10s discharge" at the above discharge rate 1C to 5C (=voltage before discharge start - voltage 10 seconds after discharge start) and each current value (that is, each corresponding to discharge rate 1C to 5C) The DC resistance (Ω) was determined based on the current value).
Next, in each example, the rate of increase in resistance of the battery after 4 weeks at high temperature was determined. In calculating the resistance increase rate of the battery after 4 weeks at high temperature, the battery to be compared with the increase is the test battery before the battery was stored as described above (storage 0 weeks). In other words, the rate of increase in resistance of the battery after 4 weeks at high temperature is the DC resistance value of the battery after 4 weeks at high temperature measured by the method described above, and the DC resistance of the test battery before storing the battery (0 weeks of storage). It is divided by the value of the value.
The results are shown in Tables 1 and 2.
In addition, the values of the battery resistance after 4 weeks of storage and the resistance increase rate after 4 weeks of storage in a high temperature environment shown in Table 1 are the battery resistance after 4 weeks of storage in Comparative Example 101 and the values of the resistance increase rate after 4 weeks of storage, respectively. It is a relative value [%] in each example when the value of the resistance increase rate after storage is taken as 100%. In addition, the values of the battery resistance after 4 weeks of storage in a high temperature environment and the resistance increase rate after 4 weeks of storage shown in Table 2 are the battery resistance after 4 weeks of storage in Comparative Example 102 and the values of the resistance increase rate after 4 weeks of storage, respectively. It is a relative value [%] in each example when the value of the subsequent resistance increase rate is 100%.

<Gas expansion amount after high temperature storage>
The effect of suppressing gas swelling in the test battery was evaluated by comparing the thickness of the test battery before and after high-temperature storage. The evaluation procedure is shown below.
The produced test battery was measured using a specific gravity measuring device (SGM-300P, manufactured by Shimadzu Corporation) based on the Archimedes method, and the initial battery volume was determined as [cm ³ ]. Thereafter, the volume of the battery after the battery high temperature storage test was measured in the same manner, and this was taken as the battery volume after high temperature storage [cm ³ ], and the difference in battery volume after high temperature storage [cm 3 ] (volume increment) was determined. At this time, pure water was used as the immersion solvent, and the density of water used in calculating the battery volume was the value at 25°C (0.99704 g cm-3).

The initial battery volume [cm ³ ] and the battery volume after high-temperature storage [cm ³ ] were also measured for the test battery of Comparative Example 101, which will be described later, in the same manner as in the examples, and the difference in battery volume after high-temperature storage of Comparative Example 101 was determined. [cm3] was determined.

From the above results, the relative value [%] of the difference in battery volume after high temperature storage in each example, when the amount of gas swelling after high temperature storage in Comparative Example 101 is taken as 100%, can be calculated using the following formula. Gas bulge amount [relative value; %]"
The results are shown in Table 1.

Gas swelling amount after high temperature storage [relative value; %]
= (Difference in battery volume after high temperature storage in each example listed in Table 1/Difference in volume after high temperature storage in Comparative Example 101) x 100

In the same manner for Examples 103 to 104, the relative value [%] of the amount of gas swelling after high temperature storage in each example, when the amount of gas swelling after high temperature storage in Comparative Example 102 was taken as 100%, was calculated as "high temperature storage". It was calculated as "post-gas swelling amount [relative value; %]".
The results are shown in Table 2.

As shown in Table 1, in the examples using the lithium boron phosphate compound (X) of the present disclosure as an additive, compared to the comparative examples, battery resistance, battery resistance increase rate, and gas swelling in a high-temperature environment were higher. It can be seen that this has been reduced.

As shown in Table 2, in the examples in which the lithium boron phosphate compound (X) of the present disclosure is used as an additive in combination with VC, the battery resistance and It can be seen that the resistance increase rate and gas blistering are reduced.

<Evaluation of battery resistance after high temperature cycle>
For the batteries obtained in each example (i.e., test batteries), battery resistance was evaluated after high-temperature cycles (i.e., after charge-discharge cycles in a high-temperature environment). Details are shown below.

The following operations were performed at a temperature of 45°C.
The test battery was charged to SOC 100% at a charge rate of 0.5C, and then discharged at a discharge rate of 1C for 0 cycles and 700 cycles, respectively.
The battery resistance (Ω) of the test battery obtained after each cycle was measured by the method described above.
The results are shown in Table 3.
In addition, the value of battery resistance after 700 cycles shown in Table 3 is the value of battery resistance after 700 cycles in each example when the value of battery resistance after 700 cycles in Comparative Example 101 is taken as 100%. It is a relative value [%].

<Evaluation of battery resistance increase rate after high temperature cycle>
Evaluation of the resistance increase rate after 700 cycles in a high-temperature environment was performed using the test battery after 0 cycles as well as the battery after 700 cycles, and the following operations were performed at 25°C. ,evaluated.

Regarding the test batteries after the 0 cycle described above, the initial DCIR (Direct current internal resistance) of each battery (that is, before storage) was measured by the following method.

CCCV charging was performed to 3.7V at a charging rate of 0.5C.
Next, the battery was subjected to CC10s discharge at a discharge rate of 1C, and then CC10s charge was performed at a charge rate of 1C.
Next, the battery was subjected to CC10s discharge at a discharge rate of 2C, and then CC20s charge was performed at a charge rate of 1C.
Next, the battery was subjected to CC10s discharge at a discharge rate of 3C, and then CC30s charge was performed at a charge rate of 1C.
Next, the battery was subjected to CC10s discharge at a discharge rate of 4C, and then CC40s charge was performed at a charge rate of 1C.
Next, the battery was subjected to CC10s discharge at a discharge rate of 5C, and then CC50s charge was performed at a charge rate of 1C.

In addition, CCCV charging means charging with constant current constant voltage (Constant Current Constant Voltage), and CC10s discharge means discharging with constant current (Constant Current) for 10 seconds. means charging at a constant current for 10 seconds.

Each voltage drop amount due to "CC10s discharge" at the above discharge rate 1C to 5C (=voltage before discharge start - voltage 10 seconds after discharge start) and each current value (that is, each corresponding to discharge rate 1C to 5C) The DC resistance (Ω) was determined based on the current value).
Next, in each example, the rate of increase in resistance of the battery after 700 high temperature cycles was determined. In calculating the resistance increase rate of the battery after 700 cycles at high temperature, the battery to be compared with the increase is the test battery after 0 cycles as described above. In other words, the resistance increase rate after 700 high-temperature cycles is calculated by dividing the DC resistance value of the battery after 700 high-temperature cycles measured by the method described above by the DC resistance value of the test battery after 0 cycles. It is.
The results are shown in Table 3.
Note that the value of the resistance increase rate after 700 cycles shown in Table 3 is the battery resistance after 700 cycles in each example when the value of the battery resistance increase rate after 700 cycles in Comparative Example 101 is taken as 100%. It is the relative value [%] of the increase rate value.

As shown in Table 3, in the examples in which the lithium boron phosphate compound (X) of the present disclosure is used as an additive in combination with VC, the battery resistance and It can be seen that the rate of increase in battery resistance is reduced.

1 Lithium secondary battery precursor 10 Battery element 11 Positive electrode 11A Positive electrode current collector 11B Positive electrode composite layer 12 Negative electrode 12A Negative electrode current collector 12B Negative electrode composite layer 13 Separator 14 Cell layer 21 Positive electrode lead 22 Negative electrode lead 30 Exterior body

Claims (11)

A lithium boron phosphate compound containing a repeating structure represented by the following formula (I).


[In formula (I), n represents an integer of 1 or more. ] The lithium boron phosphate compound according to claim 1, which has a number average molecular weight of 150 to 100,000. The lithium boron phosphate compound according to claim 1 or 2, wherein the ratio of weight average molecular weight to number average molecular weight is 1.0 or more and 3.0 or less. An additive for lithium secondary batteries, comprising the lithium boron phosphate compound according to any one of claims 1 to 3. an electrolyte that is a lithium salt containing fluorine;
a non-aqueous solvent;
The lithium boron phosphate compound according to any one of claims 1 to 3,
A non-aqueous electrolyte for lithium secondary batteries containing The nonaqueous boron phosphate lithium compound according to claim 5, wherein the content of the lithium boron phosphate compound is 0.1% by mass to 5.0% by mass based on the total amount of the nonaqueous electrolyte for lithium secondary batteries. Water electrolyte. The non-aqueous electrolyte for a lithium secondary battery according to claim 5 or 6, further comprising vinylene carbonate. case and
A positive electrode, a negative electrode, a separator, and an electrolytic solution housed in the case;
Equipped with
The positive electrode is a positive electrode capable of intercalating and deintercalating lithium ions,
The negative electrode is a negative electrode capable of intercalating and deintercalating lithium ions,
A lithium secondary battery precursor, wherein the electrolyte is the nonaqueous electrolyte for a lithium secondary battery according to any one of claims 5 to 7. The lithium secondary battery precursor according to claim 8, wherein the positive electrode contains a lithium-containing composite oxide represented by the following general formula (C1) as a positive electrode active material.
_LiNia Co _b Mn _c O ₂ ... General formula (C1)
[In general formula (C1), a, b and c are each independently greater than 0 and less than 1, and the sum of a, b and c is 0.99 to 1.00. ] A step of preparing a lithium secondary battery precursor according to claim 8 or 9;
obtaining a lithium secondary battery by subjecting the lithium secondary battery precursor to an aging treatment;
including;
A method for producing a lithium secondary battery, wherein the aging treatment includes charging and discharging the lithium secondary battery precursor in an environment of 30°C to 70°C. case and
A positive electrode, a negative electrode, a separator, and an electrolytic solution housed in the case;
Equipped with
The positive electrode is a positive electrode capable of intercalating and deintercalating lithium ions,
The negative electrode is a negative electrode capable of intercalating and deintercalating lithium ions,
The electrolytic solution is a nonaqueous electrolyte containing an electrolyte that is a lithium salt containing fluorine and a nonaqueous solvent,
A negative electrode film containing a lithium boron phosphate compound containing a repeating structure represented by the following formula (I) and a component derived from the electrolyte is formed on at least a part of the surface of the negative electrode,
A lithium secondary battery, wherein a positive electrode coating containing a lithium boron phosphate compound containing a repeating structure represented by the following formula (I) and a component derived from the electrolyte is formed on at least a part of the surface of the positive electrode.

[In formula (I), n represents an integer of 1 or more. ]