WO2020026525A1 - Batterie primaire au lithium - Google Patents

Batterie primaire au lithium Download PDF

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Publication number
WO2020026525A1
WO2020026525A1 PCT/JP2019/014861 JP2019014861W WO2020026525A1 WO 2020026525 A1 WO2020026525 A1 WO 2020026525A1 JP 2019014861 W JP2019014861 W JP 2019014861W WO 2020026525 A1 WO2020026525 A1 WO 2020026525A1
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WIPO (PCT)
Prior art keywords
additive
positive electrode
lithium
mass
general formula
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PCT/JP2019/014861
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English (en)
Japanese (ja)
Inventor
岳志 室谷
泰久 服部
堂太 水田
慎二 藤井
清水　敏之
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パナソニックＩｐマネジメント株式会社
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Publication of WO2020026525A1 publication Critical patent/WO2020026525A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte

Definitions

  • the present invention relates to a lithium primary battery.
  • Lithium primary batteries are used in many electronic devices because of their high energy density and low self-discharge. Lithium primary batteries have an extremely long storage life and can be stored for a long period of time of 10 years or more at room temperature, and thus are widely used as a main power supply for various meters and a memory backup power supply.
  • Patent Literature 1 discloses a lithium battery using an electrolyte containing LiBF 4 . According to Patent Literature 1, thereby, gas generation in a high-temperature environment is suppressed.
  • Patent Literature 2 discloses a lithium battery using an electrolyte containing phthalimide. According to Patent Document 2, this suppresses an increase in internal resistance when stored at a high temperature.
  • LiBF 4 open circuit voltage
  • a lithium primary battery used for a TPMS may be exposed to a high temperature of, for example, 125 ° C. or more.
  • the OCV of the lithium primary battery placed under a high temperature as by the addition of LiBF 4 rises more greatly.
  • phthalimide no change is observed in OCV.
  • One aspect of the present disclosure is a negative electrode including metal lithium and / or a lithium alloy as a negative electrode active material, a positive electrode including manganese dioxide as a positive electrode active material, a separator interposed between the negative electrode and the positive electrode, A conductive electrolyte, wherein the electrolyte comprises a first additive and a second additive, wherein the first additive comprises phthalimide, phthalimidine, tetrahydrophthalimide and derivatives thereof. At least one selected from the group, wherein the second additive is a tetrafluoroborate compound, and the content of the first additive in the electrolytic solution is 0.1% by mass or more and 1% by mass. %, And the content of the second additive in the electrolyte is 2.5% by mass or more and 5% by mass or less.
  • the progress of corrosion of the positive electrode case can be suppressed.
  • FIG. 1 is a longitudinal sectional view schematically showing a lithium primary battery according to one embodiment of the present invention. It is a graph which shows the result of having measured OCV in an initial stage and after high-temperature preservation in an example of an experiment. It is a graph which shows the result of having measured OCV in an example at the time of an initial stage, and after high-temperature preservation.
  • the lithium primary battery according to the embodiment of the present invention includes a negative electrode containing metallic lithium and / or a lithium alloy as a negative electrode active material, a positive electrode containing manganese dioxide as a positive electrode active material, and a separator interposed between the negative electrode and the positive electrode. And a lithium ion conductive electrolyte.
  • the electrolytic solution contains at least one first additive selected from the group consisting of phthalimide, phthalimidine, tetrahydrophthalimide and derivatives thereof, and a second additive which is a tetrafluoroborate compound.
  • the content of the first additive in the electrolytic solution is 0.1% by mass or more and 1% by mass or less
  • the content of the second additive in the electrolytic solution is 2.5% by mass or more and 5% by mass or less. % By mass or less.
  • the reason why the OCV increases due to the addition of the second additive is not clear, but is considered as follows.
  • the second additive causes a decomposition reaction of a non-aqueous solvent (for example, 1,2-dimethoxyethane) in the electrolytic solution to generate a decomposition product having high oxidizing power.
  • a non-aqueous solvent for example, 1,2-dimethoxyethane
  • manganese dioxide which is a positive electrode active material, is a non-stoichiometric compound, and may include manganese oxide having a divalent, trivalent, or tetravalent oxidation number.
  • the manganese oxide having a divalent or trivalent oxidation number is oxidized by a decomposition product of the non-aqueous solvent.
  • tetravalent manganese relatively increases and OCV increases.
  • the first additive suppresses the decomposition reaction of the non-aqueous solvent. Therefore, by using the first additive and the second additive in appropriate amounts in combination, it is possible to suppress gas generation at a high temperature and to suppress an increase in OCV. In particular, an increase in OCV (hereinafter, referred to as OCV after high-temperature storage) of a lithium battery placed at high temperature is effectively suppressed.
  • the first additive is at least one selected from the group consisting of phthalimide, phthalimidine, tetrahydrophthalimide and derivatives thereof.
  • the phthalimide or phthalimide derivative is represented by, for example, the following general formula (1).
  • X 1 to X 4 each independently represent H (hydrogen atom), F (fluorine atom), Cl (chlorine atom), Br (bromine atom), I (iodine atom), It is an alkyl group having 1 to 3 atoms, and Y 1 is H or K (potassium atom).
  • X 1 to X 4 may be H.
  • X 1 may be a methyl group or F
  • X 2 to X 4 may be H.
  • @Phthalimidine or a derivative of phthalimidine is represented, for example, by the following general formula (2).
  • X 5 to X 8 are each independently H, F, Cl, Br, I or an alkyl group having 1 to 3 carbon atoms, and Y 2 is H or K is there.
  • X 5 to X 8 may be H.
  • X 5 may be a methyl group or F, and X 6 to X 8 may be H.
  • Tetrahydrophthalimide or a derivative of tetrahydrophthalimide is represented, for example, by the following general formula (3).
  • Y 3 is H or K.
  • the derivative of phthalimide is also represented, for example, by the following general formula (4).
  • X 9 to X 12 and Y 4 are each independently H, F, Cl, Br, I or an alkyl group having 1 to 3 carbon atoms.
  • X 9 to X 12 may be H.
  • X 9 may be a methyl group or F, and
  • X 10 to X 12 may be H.
  • Y 4 may be H or a methyl group.
  • the derivative of phthalimidine is also represented, for example, by the following general formula (6).
  • X 13 to X 16 and Y 5 are each independently H, F, Cl, Br, I or an alkyl group having 1 to 3 carbon atoms.
  • X 13 to X 16 may be H.
  • Y 5 may be H or a methyl group.
  • the derivative of tetrahydrophthalimide is also represented, for example, by the following general formula (7).
  • Y 6 is H, F, Cl, Br, I or an alkyl group having 1 to 3 carbon atoms. Y 6 may be H or a methyl group.
  • the first additive may be phthalimide or a phthalimide derivative. Of these, phthalimide is preferred.
  • the content C1 of the first additive in the electrolytic solution is 0.1% by mass or more and 1% by mass or less. From the viewpoint of pulse discharge characteristics at low temperatures, the content C1 of the first additive may be 0.1% by mass to 0.8% by mass.
  • C1 / C2 is not particularly limited. From the viewpoint of suppressing the OCV increase after high-temperature storage, C1 / C2 may be, for example, from 0.01 to 0.5, from 0.02 to 0.3, from 0.025 to 0. It may be 25.
  • the second additive is a tetrafluoroborate compound.
  • the tetrafluoroboric acid compound is, for example, represented by the following general formula (5): Z- (BF 4 ) n It is represented by
  • Z is, Li, K, Na, NR 1 4, Zn, Sn, H, Ag, an NO 2 or R 2 N 2
  • R 1 are each, independently, H, or carbon
  • R 2 is an alkyl group having 1 to 3 atoms
  • R 2 is an aryl group having 6 to 8 carbon atoms.
  • the aryl group may have a substituent (for example, an alkyl group such as a methyl group, a hydroxyl group, an alkoxy group, and the like).
  • n is 1 or 2. From the viewpoint of suppressing side reactions, Z is Li, and n may be 1.
  • the content C2 of the second additive in the electrolytic solution is 2.5% by mass or more and 5% by mass or less. From the viewpoint of internal resistance, the content C2 of the second additive may be 3% by mass to 5% by mass.
  • the shape of the lithium primary battery can be appropriately selected from various shapes such as a cylindrical type, a square type, a sheet type, a flat type, and a stacked type, in addition to a coin type, depending on the use or the like.
  • the positive electrode contains manganese dioxide as a positive electrode active material.
  • the positive electrode may be, for example, a pellet obtained by pressing a positive electrode mixture containing a positive electrode active material into a disk shape.
  • the positive electrode is prepared by dispersing or dissolving the positive electrode mixture in a suitable liquid component such as water or N-methyl-2-pyrrolidone (NMP) and then collecting the resulting slurry with a current collector such as aluminum (Al) foil. It may be applied to the surface of the body (core material) or embedded in a lath material such as stainless steel or a mesh material and dried.
  • the positive electrode active material in addition to manganese dioxide, various active materials known in the field of lithium primary batteries may be included. Specifically, fluorocarbon or a metal compound can be used. Examples of the metal compound include oxides such as MoO 3 , V 2 O 5 and Mn 2 O 4, and metal sulfides such as TiS 2 and MoS 2 . These may be used alone or in combination of two or more.
  • the positive electrode mixture optionally contains additives such as a conductive agent and a binder.
  • the negative electrode contains lithium metal or a lithium alloy as a negative electrode active material.
  • the lithium alloy an alloy such as Li-Al, Li-Sn, Li-Ni-Si, or Li-Pb is used, and a Li-Al alloy is preferable.
  • the content of the metal element other than lithium contained in the lithium alloy may be 0.1% by mass or more and 5% by mass or less from the viewpoint of securing the discharge capacity and stabilizing the internal resistance.
  • the metallic lithium and / or lithium alloy is formed into an arbitrary shape and thickness according to the shape, dimensions, standard performance, and the like of the finally obtained lithium primary battery. You.
  • metallic lithium and / or a lithium alloy may be formed into a disk having a diameter of about 3 mm to 25 mm and a thickness of about 0.2 to 2.0 mm.
  • a porous sheet formed of an insulating material having resistance to the internal environment of the lithium primary battery may be used.
  • a nonwoven fabric made of a synthetic resin, a microporous film made of a synthetic resin, and the like can be given.
  • the electrolyte is lithium ion conductive.
  • the electrolytic solution includes a non-aqueous solvent, a lithium salt dissolved in the non-aqueous solvent, a first additive, and a second additive.
  • the non-aqueous solvent is not particularly limited.
  • the non-aqueous solvent for example, propylene carbonate (PC), ethylene carbonate, 1,2-dimethoxyethane (DME), ⁇ -butyrolactone, and the like can be used. These may be used alone or in combination of two or more. For example, a combination of a PC and a DME may be used.
  • lithium salts examples include lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), and lithium bistrifluoromethylsulfonimide (LiN ( SO 2 CF 3 ) 2 ) or lithium bispentafluoroethylsulfonimide (LiN (SO 2 C 2 F 5 ) 2 ) is used. These may be used alone or in combination of two or more.
  • the concentration of the lithium salt in the electrolytic solution may be, for example, 0.25 mol / L or more and 3.5 mol / L or less.
  • the lithium salt concentration is the sum of the dissociated lithium salt concentration and the undissociated lithium salt concentration.
  • the concentration of the anion in the electrolyte may be not less than 0.25 mol / L and not more than 3.5 mol / L.
  • ⁇ Analytical methods such as ultraviolet-visible-near-infrared spectroscopy are used for component analysis of the first additive and the second additive of the electrolytic solution.
  • FIG. 1 is a longitudinal sectional view schematically showing a coin-type lithium primary battery according to one embodiment of the present invention.
  • the coin-type lithium primary battery 10 includes a positive electrode 11, a negative electrode 12, and a separator 13 disposed between the positive electrode 11 and the negative electrode 12.
  • the positive electrode 11, the negative electrode 12, and the separator 13 are in contact with a non-aqueous electrolyte (not shown).
  • the positive electrode case 14 is a member that accommodates the positive electrode 11 and a separator 13 described below, and also serves as a positive electrode current collector and a positive electrode terminal.
  • a material for forming the positive electrode case 14 various materials known in the field of lithium primary batteries can be used. Specifically, for example, stainless steel is used.
  • the negative electrode case 15 is a member that contacts the negative electrode 12 and acts as a negative electrode current collector and a negative electrode terminal.
  • the negative electrode case 15 also serves as a sealing plate for a coin-type battery.
  • Examples of the material for forming the negative electrode case 15 include various materials known in the field of lithium primary batteries. Specific examples include iron, titanium, and stainless steel.
  • the gasket 16 insulates between the positive electrode case 14 and the negative electrode case 15.
  • the constituent material of the gasket 16 include synthetic resins such as polypropylene, polyphenylene sulfide (PPS), and polyether ether ketone. Among them, polypropylene is preferred.
  • the electrolytic solution was injected into the inside of the positive electrode case, and the positive electrode and the separator were brought into contact with the electrolytic solution. Thereafter, the opening of the positive electrode case was sealed with the negative electrode case. Specifically, the power generation element including the positive electrode, the negative electrode, and the separator was sealed by caulking the open end of the positive electrode case to the peripheral edge of the negative electrode case via a gasket.
  • a coin-type lithium primary battery (reference battery 1, outer diameter 20 mm, thickness 5 mm) shown in FIG. 1 was assembled.
  • the reference battery 1 was assembled in dry air having a dew point of ⁇ 50 ° C. or less.
  • Reference batteries 2 to 7 were produced in the same manner as reference battery 1 except that the amount of LiBF 4 added was 2.5% by mass to 8% by mass.
  • the OCV increases as the addition amount of the tetrafluoroborate compound increases.
  • the addition amount of the tetrafluoroborate compound exceeds 2.5% by mass, the OCV becomes 3.5 V or more, which increases the risk of corrosion of the positive electrode case after high-temperature storage.
  • Reference battery 1 was prepared in the same manner as in Reference battery 1, except that phthalimide (first additive A1 in Table 3) was added as a first additive in an amount of 0.1% by mass to 1% by mass, and LiBF 4 was added as a second additive in an amount of 4% by mass. Similarly, batteries X1 to X4 were produced.
  • Batteries Y1 to Y3 were produced in the same manner as Battery X1, except that phthalimide was added as a first additive in an amount of less than 0.1% by mass or more than 1% by mass.
  • Examples 5 to 8 The batteries X5 to X8 were prepared in the same manner as the battery X1, except that 0.5% by mass of phthalimide was added as the first additive and 2.5% to 5% by mass of LiBF 4 was added as the second additive. Produced.
  • Battery Y5 was made in the same manner as Battery X1, except that 0.5% by mass of phthalimide was added as the first additive, and LiBF 4 was not added as the second additive.
  • Comparative Examples 6 to 8 Except that phthalimide was added as 0.5% by mass as the first additive and LiBF 4 was added as less than 2.5% by mass or more than 5% by mass as the second additive in the same manner as the battery X1. And batteries Y6 to Y8.
  • the batteries Y6 and Y7 in which the addition amount of the second additive is less than 2.5% by mass the batteries expand and the internal resistance is significantly increased.
  • the battery Y8 in which the amount of the second additive exceeds 5% by mass although the expansion of the battery is suppressed, the internal resistance is significantly increased.
  • Batteries X9 to X19 were prepared and evaluated in the same manner as battery X3, except that the first additives A2 to A4, B1 to B4, C1, C2, D1 or D2 shown in Table 3 were used instead of phthalimide. did.
  • Table 4 shows the evaluation results together with the battery Y1 and the battery X3.
  • the lithium primary battery according to the present invention is suitably used as a power source of an electronic device that requires high safety as well as excellent battery performance.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Primary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne une batterie primaire au lithium comprenant : une électrode négative contenant un métal lithium et/ou un alliage de lithium en tant que matériau actif d'électrode négative ; une électrode positive contenant du dioxyde de manganèse en tant que matériau actif d'électrode positive ; un séparateur situé entre l'électrode négative et l'électrode positive ; et une solution électrolytique conductrice d'ions lithium. La solution électrolytique contient un premier additif et un second additif. Le premier additif est au moins un élément choisi dans le groupe constitué par le phtalimide, la phtalimidine, le tétrahydrophtalimide, et leurs dérivés. Le second additif est un composé acide tétrafluoroborique. La teneur en premier additif dans la solution électrolytique est de 0,1 à 1 % en masse. La teneur en second additif dans la solution électrolytique est de 2,5 à 5% en masse.
PCT/JP2019/014861 2018-08-02 2019-04-03 Batterie primaire au lithium WO2020026525A1 (fr)

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JP2018-145960 2018-08-02
JP2018145960A JP2021180064A (ja) 2018-08-02 2018-08-02 リチウム一次電池

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021192440A1 (fr) * 2020-03-25 2021-09-30 パナソニックＩｐマネジメント株式会社 Batterie primaire au lithium et électrolyte non aqueux pour batterie primaire au lithium
WO2022176233A1 (fr) * 2021-02-18 2022-08-25 パナソニックＩｐマネジメント株式会社 Batterie primaire au lithium et solution électrolytique non aqueuse utilisée dans celle-ci
JP2022133085A (ja) * 2021-03-01 2022-09-13 プライムプラネットエナジー＆ソリューションズ株式会社 二次電池用電極および該電極の製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001041247A1 (fr) * 1999-11-29 2001-06-07 Matsushita Electric Industrial Co., Ltd. Cellule electrolytique non-aqueuse
JP2010262864A (ja) * 2009-05-08 2010-11-18 Panasonic Corp リチウム電池
JP2015149140A (ja) * 2014-02-05 2015-08-20 Fdk株式会社 リチウム一次電池用非水系有機電解液、およびリチウム一次電池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001041247A1 (fr) * 1999-11-29 2001-06-07 Matsushita Electric Industrial Co., Ltd. Cellule electrolytique non-aqueuse
JP2010262864A (ja) * 2009-05-08 2010-11-18 Panasonic Corp リチウム電池
JP2015149140A (ja) * 2014-02-05 2015-08-20 Fdk株式会社 リチウム一次電池用非水系有機電解液、およびリチウム一次電池

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021192440A1 (fr) * 2020-03-25 2021-09-30 パナソニックＩｐマネジメント株式会社 Batterie primaire au lithium et électrolyte non aqueux pour batterie primaire au lithium
WO2022176233A1 (fr) * 2021-02-18 2022-08-25 パナソニックＩｐマネジメント株式会社 Batterie primaire au lithium et solution électrolytique non aqueuse utilisée dans celle-ci
JP2022133085A (ja) * 2021-03-01 2022-09-13 プライムプラネットエナジー＆ソリューションズ株式会社 二次電池用電極および該電極の製造方法
JP7334201B2 (ja) 2021-03-01 2023-08-28 プライムプラネットエナジー＆ソリューションズ株式会社 二次電池用電極および該電極の製造方法

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