Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0567—Liquid materials characterised by the additives
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/058—Construction or manufacture
  • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
• • 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
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the present invention relates to a non-aqueous electrolyte secondary battery having a positive electrode containing a lithium composite oxide, a negative electrode that absorbs and releases lithium, and an electrolyte.
• LiPF is generally used as an electrolyte salt of a lithium ion battery. Also,
• LiBF is also used as another electrolyte salt, and LiPF can be mixed with LiPF.
• LiFOB represented by the formula (1) or LiB OB represented by the formula (2) has been proposed as a lithium salt containing boron.
• Patent Document 1 JP 2004-103433 A
• the problem is that the battery swells when left unattended, and the output characteristics (charge / discharge cycle life characteristics) associated with the charge / discharge cycle are greatly reduced. In particular, deterioration of charge / discharge cycle life characteristics is a serious problem. Also, LiFOB or LiBOB can be changed to LiPF
• an object of the present invention is to provide a non-aqueous electrolyte secondary battery that can suppress deterioration of charge / discharge cycle life characteristics and battery swelling when left at high temperature.
• the present invention also relates to biphenyl, cyclohexylbenzene, 2,4 difluoroaromol, 2-fluorobiphenyl, tertiary amylbenzene, toluene, ethylbenzene, 4-fluorophenyl ether, and triphenyl.
• Addition of one or more aromatic compounds selected from the group consisting of Ruphosphate to the electrolyte reduces the charge / discharge cycle life characteristics without causing problems in the non-aqueous electrolyte secondary battery, and
• Another object is to provide a non-aqueous electrolyte secondary battery that can suppress battery swelling when left at high temperatures.
• the present invention is 0.1 mass of the total mass of the electrolyte 0 / is 0 or more than 2 mass%, vinylene carbonate, Bulle ethylene carbonate, Hue - Le ethylene carbonate, and from cyclic carboxylic acid anhydrides
• Another object is to provide a non-aqueous electrolyte secondary battery that can reduce the initial battery thickness by containing one or more kinds of compounds selected from the group consisting of:
• the present invention increases the electrochemical stability of the electrolyte by containing LiBF.
• Another object is to provide a non-aqueous electrolyte secondary battery with improved battery performance.
• the present invention relates to LiBF having a total mass of the electrolyte of 0.01% to 2% by mass,
• An object of the present invention is to provide a non-aqueous electrolyte secondary battery that can suppress a decrease in battery life and battery swelling when left at high temperatures.
• the present invention is 0.1 mass of the total mass of the electrolyte 0 / is 0 or more than 2 mass%, vinylene carbonate, Bulle ethylene carbonate, Hue - Le ethylene carbonate, and from cyclic carboxylic acid anhydrides
• Another object is to provide a non-aqueous electrolyte secondary battery that can reduce the initial battery thickness by containing one or more kinds of compounds selected from the group consisting of:
• the present invention relates to LiBF having a total mass of the electrolyte of 0.01% to 2% by mass,
• 4 and solution quality total mass of 0.1 mass% or more and 4 wt% or less of aromatic compounds is less 0.1 wt 0/0 over 2 mass 0/0 of the total weight of the electrolyte, Bulle ethylene carbonate, Hue -By containing one or more kinds of compounds selected from the group power consisting of lutylene carbonate and cyclic carboxylic acid anhydrides, the degradation of charge / discharge cycle life characteristics and the swelling of batteries when left at high temperatures are suppressed.
• Another object is to provide a nonaqueous electrolyte secondary battery that can reduce the initial battery thickness.
• the non-aqueous electrolyte secondary battery according to the first invention has a composition formula of Li MO or Li M O (however,
• M is a non-aqueous solution having one or more transition metals, a positive electrode containing a composite oxide represented by 0 ⁇ x ⁇ l, 0 ⁇ y ⁇ 2), a negative electrode that absorbs and releases lithium, and an electrolyte.
• the electrolyte is composed of a compound represented by the formula (1) and a compound represented by the formula (2) that are 0.1% by mass or more and 2% by mass or less of the total mass of the electrolyte. 1 or a plurality of types of compounds selected from the group, and an aromatic compound in an amount of 0.1% by mass to 4% by mass of the total mass of the electrolyte.
• the non-aqueous electrolyte secondary battery according to the second invention is the non-aqueous electrolyte secondary battery according to the first invention, wherein the aromatic compound is biphenyl, cyclohexylenobenzene, 2, 4 diphenololeol, 2 phenololebiphenol, It is characterized by being one or more kinds of compounds selected from the group consisting of tertiary amylbenzene, toluene, ethylbenzene, 4-fluorophenyl ether, and triphenyl phosphate.
• the aromatic compound is biphenyl, cyclohexylenobenzene, 2, 4 diphenololeol, 2 phenololebiphenol, It is characterized by being one or more kinds of compounds selected from the group consisting of tertiary amylbenzene, toluene, ethylbenzene, 4-fluorophenyl ether, and triphenyl phosphate.
• the non-aqueous electrolyte secondary battery according to the third invention in the first or second invention, wherein the electrolyte is not more than 2 mass 0/0 0.1 mass 0/0 or more of the total weight of the electrolyte, It is characterized by containing one or more kinds of compounds selected from the group consisting of vinylene carbonate, butyl ethylene carbonate, vinyl ethylene carbonate, and cyclic carboxylic acid anhydrides.
• the nonaqueous electrolyte secondary battery according to the fourth invention is any one of the first to third inventions, wherein the electrolyte is LiBF.
• the nonaqueous electrolyte secondary battery according to the fifth invention has a composition formula LiMO or LiMO (wherein
• M includes one or more kinds of transition metals, including complex oxides represented by 0 ⁇ x ⁇ l, 0 ⁇ y ⁇ 2)
• the electrolyte comprises 0.01% by mass or more and 2% by mass or less of LiBF, and an electrolyte. 0.1% or more and 4% or less bifoil by weight, 2, 4 gif
• It is characterized by containing one or more kinds of compounds selected from the group consisting of fluoraninol, 2 fluorobiphenyl, tonolene, ethylbenzene, 4 fluorodiphenyl ether and triphenyl phosphate.
• the electrolyte is a the total mass of the electrolyte 0.1 mass 0/0 over 2 mass 0/0 or less
• One or more kinds of compounds selected from the group consisting of vinylene carbonate, vinylethylene carbonate, vinyl ethylene carbonate, and cyclic carboxylic acid anhydride are characterized.
• the nonaqueous electrolyte secondary battery according to the seventh invention has a composition formula of Li MO or Li M O (where x 2 y 2 4
• M is a non-aqueous electrolyte having one or more kinds of transition metals, a positive electrode containing a composite oxide represented by 0 ⁇ x ⁇ l, 0 ⁇ y ⁇ 2), a negative electrode that absorbs and releases lithium, and an electrolyte.
• the electrolyte includes 0.01% by mass to 2% by mass of LiBF and 0.1% by mass to 4% by mass of an aromatic compound of the total mass of the electrolyte.
• It contains one or more kinds of compounds.
• LiFOB or LiBOB When LiFOB or LiBOB is added to the electrolyte, the salt is oxidized and decomposed to form a film having a high lithium ion migration resistance on the surface of the positive electrode active material, and thus the polarization of the positive electrode is increased.
• LiFOB or LiBOB generates oxalic acid and HF when the salt undergoes oxidative decomposition. Therefore, the positive electrode active material is dissolved and deactivated. Then, the metal ions eluted from the positive electrode active material force are reduced at the negative electrode, and a high-resistance film is formed on the negative electrode, which promotes the decomposition of the electrolyte at the negative electrode and promotes the depletion of the electrolyte. .
• Such deterioration of the positive and negative electrodes due to the oxidative decomposition of the salt causes a problem that the charge / discharge cycle life characteristics are deteriorated.
• aromatic compounds have lower acidity potential than LiFOB and LiBOB, the oxidation of the salt is difficult. It acts as an inhibitor, can suppress the deterioration of the positive and negative electrodes due to the acid decomposition of the salt, and suppress the deterioration of the charge / discharge cycle life characteristics.
• the negative electrode film formed by the aromatic compound alone is unstable, but when mixed with LiFOB or LiBOB, LiFOB or LiBOB and the aromatic compound coexist and are stabilized. Therefore, when both LiFOB or LiBOB and an aromatic compound are added to the electrolyte, the charge / discharge cycle life characteristics are improved as compared with the case where only one of them is added.
• LiFOB and LiBOB When at least one of LiFOB and LiBOB is added in excess of 2% by mass of the total mass of the electrolyte, excess LiFOB and LiBOB in the electrolyte react with the positive electrode, resulting in reduced charge / discharge cycle life characteristics.
• the amount of addition should be 2% by mass or less because the battery is liable to swell when left at high temperature.
• the amount of LiFOB and LiBOB added is less than 0.1% by mass of the total mass of the electrolyte, the effect of LiFOB and LiBOB added will hardly occur, so the amount of applied force of LiFOB and LIB OB Is 0.1% by mass or more.
• the amount of aromatic compound added When the amount of added force of LiFOB and LiBOB is increased, the amount of aromatic compound added must be increased in order to suppress the reaction between LiFOB and LiBOB and the positive electrode. However, if the amount of aromatic compound added is greater than 4% by mass of the total mass of the electrolyte, a polymer is formed when excess aromatic compound is oxidized on the positive electrode, causing clogging of the separator. For Charge / discharge characteristics such as discharge cycle life characteristics deteriorate, and hydrogen is generated when left at high temperatures, causing battery swelling, so the amount of aromatic compound added should be 4% by mass or less. Also, if the amount of aromatic compound added is less than 0.1% by mass of the total mass of the electrolyte, the effect of adding aromatic compound is less likely to occur, so the amount of aromatic compound added is 0. 1Must be more than mass%.
• biphenyl, cyclohexyl benzene, 2,4 difluoro alcohol, 2-fluoro biphenyl, tartaramyl benzene, toluene, ethylbenzen, 4 fluorophenyl ether, and triphenyl Since one or more aromatic compounds selected from the group consisting of Ruphosphate are added to the electrolyte, the charge / discharge cycle life characteristics are reduced without causing problems in the non-aqueous electrolyte secondary battery, and they are left at high temperatures. The battery swelling at the time can be suppressed. In addition, when triphenyl phosphate is added, it is possible to suppress the swelling of the battery when left at high temperature better than when other compounds are added.
• the electrolyte contains one or more kinds of compounds selected from the group consisting of, the hydrogen gas generated during initial charging is suppressed, and the initial battery thickness can be reduced.
• the addition amount is larger than 2% by mass, the film resistance of the negative electrode becomes high, irreversible metallic lithium is deposited on the negative electrode, and the initial capacity is lowered. Therefore, the addition amount is made 2% by mass or less. If the addition amount is less than 0.1% by mass, the effect of addition hardly occurs, so the addition amount should be 0.1% by mass or more.
• LiBF having a content of 0.01 mass% or more and 2 mass% or less of the total mass of the electrolyte
• ff3 ⁇ 4 can be.
• the polarization of the positive electrode increases.
• the positive electrode active material is dissolved and deactivated.
• the metal ions eluted in the positive electrode active material force are reduced at the negative electrode, and a high-resistance film is formed on the negative electrode, whereby the decomposition of the electrolyte at the negative electrode is promoted and the electrolyte is exhausted.
• the acid / acid potential is lower than 4, it can be used as an antioxidant for the salt to suppress the generation of gas due to the acid / acid decomposition of the salt, thereby suppressing battery swelling when left at high temperature.
• the negative electrode film formed by the triphosphate alone is unstable and mixed with LiBF, a stable negative electrode film is formed.
• the amount of addition should be 2% by mass or less because this is likely to occur.
• the amount of LiBF added should be 2% by mass or less because this is likely to occur.
• the addition amount of LiBF should be 0.01 mass% or more.
• the addition amount of the compound such as biphenyl is more than 4% by mass of the total mass of the electrolyte, a polymer is formed when excess compound such as biphenyl is oxidized on the positive electrode. In order to induce clogging of the battery, the charge / discharge characteristics such as the charge / discharge cycle life characteristics are deteriorated, and hydrogen is generated when left at high temperature to cause the battery to swell. % Or less.
• the amount of the compound such as biphenyl is less than 0.1% by mass of the total mass of the electrolyte, the effect due to the addition of the compound such as biphenyl is less likely to occur. The amount of the compound is 0.1% by mass or more.
• the electrolyte from the total mass of the electrolyte is 0.1% by mass or more and 2% by mass or less, from vinylene carbonate, vinylene ethylene carbonate, phenylene ethylene carbonate, and cyclic carboxylic acid anhydride. Since the electrolyte contains one or more kinds of compounds selected from the group consisting of, the hydrogen gas generated during initial charging is suppressed, and the initial battery thickness can be reduced. When the addition amount is larger than 2% by mass, the film resistance of the negative electrode becomes high, irreversible metallic lithium is deposited on the negative electrode, and the initial capacity is lowered. Therefore, the addition amount is made 2% by mass or less. If the addition amount is less than 0.1% by mass, the effect of addition hardly occurs, so the addition amount should be 0.1% by mass or more.
• LiBF is not less than 0.01 mass% and not more than 2 mass% of the total mass of the electrolyte.
• the total mass of 0.1 mass% or more and 4 wt% or less of an aromatic compound of the electrolyte is less 0.1 wt 0/0 over 2 mass 0/0 of the total weight of the electrolyte, vinyl ethylene carbonate, Since it contains one or more kinds of compounds selected from the group strength of fluoroethylene carbonate and cyclic carboxylic anhydride, it is the same as that of the fifth and sixth inventions described above. Suppresses deterioration of positive and negative electrodes due to decomposition, and suppresses deterioration of charge / discharge cycle life characteristics.
• the deterioration of the charge / discharge cycle life characteristics and the expansion of the battery when left at high temperature are achieved. This can be suppressed.
• the second invention it is possible to suppress the deterioration of the charge / discharge cycle life characteristics without causing a problem in the nonaqueous electrolyte secondary battery, and the swelling of the battery when left at high temperature.
• the initial battery thickness can be reduced.
• the electrochemical stability of the electrolyte can be increased.
• the initial battery thickness can be reduced.
• the seventh invention it is possible to suppress the deterioration of the charge / discharge cycle life characteristics and the expansion of the battery when left at high temperature, and to reduce the initial battery thickness.
• FIG. 1 is a cross-sectional view showing a configuration example of a nonaqueous electrolyte secondary battery according to the present invention.
• FIG. 3 is a table showing measurement results obtained by extracting and rearranging a part of FIG.
• FIG. 8 is a table showing the measurement results of capacity retention rate, thickness increment and recovery rate of a battery in which LiFOB was added to the electrolyte.
• FIG. 9 is a table showing measurement results obtained by extracting and rearranging a part of FIG.
• FIG. 10 is a table showing the measurement results of the initial capacity, initial battery thickness, capacity retention, thickness increment, and recovery rate of a battery with LiFOB added to the electrolyte.
• FIG. 11 is a table showing the measurement results of the initial capacity, initial battery thickness, capacity retention, thickness increment, and recovery rate of a battery with LiFOB added to the electrolyte.
• FIG. 12 is a table showing measurement results of initial capacity, initial battery thickness, capacity retention, thickness increment, and recovery rate of a battery in which LiFOB was added to the electrolyte.
• FIG. 13 is a table showing measurement results of initial capacity, initial battery thickness, capacity retention rate, thickness increment, and recovery rate of a battery in which LiFOB was added to the electrolyte.
• FIG. 14 is a table showing the measurement results of capacity retention rate, thickness increment and recovery rate of a battery in which LiBOB was added to the electrolyte.
• FIG. 15 is a table showing measurement results obtained by extracting and rearranging a part of FIG.
• FIG. 16 is a table showing measurement results of initial capacity, initial battery thickness, capacity retention, thickness increment, and recovery rate of a battery in which LiBOB was added to the electrolyte.
• FIG. 17 is a table showing the measurement results of the initial capacity, initial battery thickness, capacity retention, thickness increment, and recovery rate of a battery with LiBOB added to the electrolyte.
• FIG. 18 is a table showing measurement results of initial capacity, initial battery thickness, capacity retention, thickness increment, and recovery rate of a battery in which LiBOB was added to the electrolyte.
• FIG. 19 is a table showing the measurement results of the initial capacity, initial battery thickness, capacity retention, thickness increment, and recovery rate of a battery with LiBOB added to the electrolyte.
• FIG. 1 is a cross-sectional view showing a configuration example of a nonaqueous electrolyte secondary battery according to the present invention.
• 1 is a rectangular nonaqueous electrolyte secondary battery (hereinafter referred to as a battery)
• 2 is an electrode group
• 3 is a negative electrode
• 4 is a positive electrode
• 5 is a separator
• 6 is a battery case
• 7 is a battery lid.
• 8 is a safety valve
• 9 is a negative terminal
• 10 is a negative lead.
• the electrode group 2 is obtained by winding a negative electrode 3 and a positive electrode 4 in a flat shape with a separator 5 interposed therebetween.
• the electrode group 2 and the electrolyte (electrolyte) are stored in the battery case 6, and the opening of the battery case 6 is hermetically sealed by laser welding the battery lid 7 provided with the safety valve 8.
• the negative electrode terminal 9 is connected to the negative electrode 3 via the negative electrode lead 10, and the positive electrode 4 is connected to the inner surface of the battery case 6.
• the positive electrode 4 includes 90% by weight of LiCoO as an active material and acetylene black 5 as a conductive auxiliary agent.
• a paste was prepared by mixing 5% by weight with 5% by weight of polyvinylidene fluoride as a binder and dispersing it in N-methyl 2-pyrrolidone.
• the prepared paste was 20 m thick. It was produced by uniformly applying to an aluminum current collector, drying, and then compressing with a roll press.
• the negative electrode 3 was prepared by mixing 95% by weight of graphite as a negative electrode active material, 3% by weight of carboxymethyl cellulose and 2% by weight of styrene butadiene rubber as a binder, and adding and dispersing distilled water as appropriate. Apply the prepared slurry evenly to a 15 m thick copper current collector, dry it, and dry it at 100 ° C for 5 hours, then the density of the negative electrode active material layer consisting of the binder and active material 1. It was produced by compression molding with a roll press so that it would be 40 g / cm 3 .
• a microporous polyethylene film having a thickness of 20 ⁇ m was used as the separator.
• a battery was prepared in the same manner as in Example 1 except that BP added to the electrolytic solution was 0.5% by mass.
• a battery was manufactured in the same manner as in Example 1 except that BP added to the electrolytic solution was 4% by mass.
• LiBF added to the electrolyte is 0.05% by mass and BP is 0.5% by mass.
• LiBF to be added to the electrolyte is 0.1% by mass, BP is 0.2% by mass, otherwise
• LiBF to be added to the electrolyte is 0.1% by mass, BP is 0.5% by mass, otherwise
• LiBF to be added to the electrolyte is 0.1% by mass
• BP is 1% by mass
• LiBF to be added to the electrolyte is 0.2% by mass, BP is 0.1% by mass.
• LiBF to be added to the electrolyte is 0.2% by mass
• BP is 0.2% by mass
• LiBF added to the electrolyte is 0.2% by mass and BP is 0.5% by mass.
• LiBF to be added to the electrolyte solution is 0.2% by mass, BP is 1% by mass, otherwise, Example 1
• LiBF to be added to the electrolyte solution is 0.2% by mass, BP is 2% by mass, otherwise, Example 1
• LiBF to be added to the electrolyte solution is 0.2% by mass and BP is 4% by mass.
• LiBF added to the electrolyte is 0.5% by mass, BP is 0.2% by mass.
• LiBF added to the electrolyte is 0.5% by mass
• BP is 0.5% by mass
• Example 1 The LiBF added to the electrolyte is 0.5% by mass, and BP is 1% by mass. Otherwise, Example 1
• LiBF to be added to the electrolyte is 2% by mass, BP is 0.1% by mass, otherwise, Example 1
• LiBF to be added to the electrolyte is 2% by mass, BP is 0.5% by mass, otherwise, Example 1
• the LiBF added to the electrolyte is 2% by mass and BP is 4% by mass.
• Example 20 Based on the total weight of the electrolyte solution, further 0.1 mass 0/0 of bi - Ren carbonate (VC) was added Caro, otherwise was produced in the same manner as the battery of Example 10.
• VC bi - Ren carbonate
• a battery was manufactured in the same manner as in Example 10 except that 0.5% by mass of VC was further added to the total mass of the electrolytic solution.
• a battery was manufactured in the same manner as in Example 10 except that 1.0% by mass of VC was further added to the total mass of the electrolytic solution.
• a battery was manufactured in the same manner as in Example 10 except that 1.5% by mass of VC was further added to the total mass of the electrolytic solution.
• a battery was manufactured in the same manner as in Example 10 except that 2.0% by mass of VC was further added to the total mass of the electrolytic solution.
• a battery was manufactured in the same manner as in Example 10 except that 0.5% by mass of VC and 0.5% by mass of VEC were further added to the total mass of the electrolytic solution.
• a battery was manufactured in the same manner as in Example 10 except that 1.0% by mass of phenylethylene carbonate (Ph EC) was further added to the total mass of the electrolytic solution.
• Ph EC phenylethylene carbonate
• a battery was manufactured in the same manner as in Example 10 except that 1.0% by mass of succinic anhydride was further added to the total mass of the electrolytic solution.
• a battery was manufactured in the same manner as in Example 11 except that 1.0% by mass of toluene (TOL) was added to the electrolyte instead of 1.0% by mass of BP.
• TOL toluene
• a battery was manufactured in the same manner as in Example 11 except that 1.0% by mass of ethylbenzene (EB) was added to the electrolyte instead of 1.0% by mass of BP.
• EB ethylbenzene
• a battery was prepared in the same manner as in Example 22 except that 0.5% by mass of CHB was added to the electrolyte instead of 5% by mass of BPO.
• a battery was prepared in the same manner as in Example 22 except that 0.5 mass% of 2,4FA was added to the electrolyte instead of 5 mass% of BPO. [0088] (Example 39)
• a battery was fabricated in the same manner as in Example 22 except that 0.5 mass% of 2FBP was added to the electrolyte instead of 5 mass% of BPO.
• a battery was manufactured in the same manner as in Example 22 except that 0.5% by mass of TAB was added to the electrolyte instead of 5% by mass of BPO.
• a battery was prepared in the same manner as in Example 22 except that 0.5% by mass of TOL was added to the electrolyte instead of 5% by mass of BPO.
• a battery was manufactured in the same manner as in Example 22 except that 0.5% by mass of EB was added to the electrolyte instead of 5% by mass of BPO.
• a battery was prepared in the same manner as in Example 22 except that 4FDPE was added in an amount of 0.5% by mass instead of 5% by mass of BPO.
• a battery was fabricated in the same manner as in Example 22 except that 0.5% by mass of TPP was added to the electrolyte instead of 5% by mass of BPO.
• a solvent for the electrolyte instead of a mixed solvent of ethylene carbonate (EC) and ethylmethyl carbonate (EMC) in a volume ratio of 3: 7, a volume ratio of EC and jetyl carbonate (DEC) of 3: 7 A battery was prepared in the same manner as in Example 22 except that the mixed solvent was used.
• EC ethylene carbonate
• EMC ethylmethyl carbonate
• DEC jetyl carbonate
• a mixed solvent of EC and dimethyl carbonate (DMC) in a volume ratio of 3: 7 was used instead of a mixed solvent of EC and EMC in a volume ratio of 3: 7.
• DMC dimethyl carbonate
• EC and EM A battery was prepared in the same manner as in Example 22 except that a mixed solvent of C: DEC in a volume ratio of 3: 5: 2 was used.
• the amount of LiPF dissolved in the electrolyte was changed from 1. ImolZL to 1.5 molZL.
• the amount of LiPF dissolved in the electrolyte was changed from 1. ImolZL to 0.7 molZL.
• a mixed solvent with a volume ratio of EC: propylene carbonate (PC) and EMC of 2: 1: 7 was used instead of a mixed solvent of EC: EMC with a volume ratio of 3: 7.
• PC propylene carbonate
• EMC EMC with a volume ratio of 3: 7.
• LiNiO was used instead of LiCoO. Otherwise, Example 22 and
• LiMn O was used instead of LiCoO.
• LiNi Co Mn O is used instead of LiCoO as the positive electrode active material.
• a battery was manufactured in the same manner as in Example 1 except that 0.1% by mass of the compound represented by formula 1 (LiFOB) was added.
• a battery was made in the same manner as in Example 54 except that BP added to the electrolytic solution was 1% by mass.
• a battery was made in the same manner as in Example 54 except that BP added to the electrolytic solution was 4% by mass.
• a battery was prepared in the same manner as in Example 54 except that LiFOB added to the electrolytic solution was 0.5% by mass and BP was 0.5% by mass.
• a battery was prepared in the same manner as in Example 54 except that LiFOB added to the electrolytic solution was 0.5 mass% and BP was 1 mass%.
• a battery was prepared in the same manner as in Example 54 except that LiFOB added to the electrolytic solution was 0.5% by mass and BP was 2% by mass.
• a battery was prepared in the same manner as in Example 54 except that LiFOB added to the electrolytic solution was 1% by mass and BP was 0.1% by mass.
• a battery was prepared in the same manner as in Example 54 except that LiFOB added to the electrolytic solution was 1% by mass and BP was 0.5% by mass. [0112] (Example 62)
• a battery was prepared in the same manner as in Example 54 except that LiFOB added to the electrolytic solution was 1% by mass and BP was 1% by mass.
• a battery was prepared in the same manner as in Example 54 except that LiFOB added to the electrolytic solution was 1 mass% and BP was 2 mass%.
• a battery was prepared in the same manner as in Example 54 except that LiFOB added to the electrolytic solution was 1% by mass and BP was 4% by mass.
• a battery was prepared in the same manner as in Example 54 except that LiFOB added to the electrolytic solution was 1.5% by mass and BP was 0.5% by mass.
• a battery was prepared in the same manner as in Example 54 except that LiFOB added to the electrolytic solution was 1.5 mass% and BP was 1 mass%.
• a battery was prepared in the same manner as in Example 54 except that LiFOB added to the electrolytic solution was 1.5% by mass and BP was 2% by mass.
• a battery was prepared in the same manner as in Example 54 except that LiFOB to be added to the electrolytic solution was 2 mass% and BP was 0.1 mass%.
• a battery was prepared in the same manner as in Example 54 except that LiFOB to be added to the electrolytic solution was 2 mass% and BP was 1 mass%.
• a battery was prepared in the same manner as in Example 54 except that LiFOB to be added to the electrolytic solution was 2 mass% and BP was 4 mass%.
• Example 71 Based on the total weight of the electrolyte solution, further 0.1 mass 0/0 of bi - Ren carbonate (VC) was added Caro, otherwise was produced in the same manner as the battery of Example 62.
• VC bi - Ren carbonate
• a battery was manufactured in the same manner as in Example 62, except that 0.5% by mass of VC was further added to the total mass of the electrolytic solution.
• a battery was manufactured in the same manner as in Example 62, except that 1.0% by mass of VC was further added to the total mass of the electrolytic solution.
• a battery was manufactured in the same manner as in Example 62, except that 2.0% by mass of VC was further added to the total mass of the electrolytic solution.
• a battery was manufactured in the same manner as in Example 62 excepting that 0.5% by mass of VC and 0.5% by mass of VEC were further added to the total mass of the electrolytic solution.
• a battery was manufactured in the same manner as in Example 62 excepting that 1.0% by mass of phenylethylene carbonate (Ph EC) was further added to the total mass of the electrolytic solution.
• Ph EC phenylethylene carbonate
• a battery was manufactured in the same manner as in Example 62 excepting that 1.0% by mass of succinic anhydride was further added relative to the total mass of the electrolytic solution.
• a battery was fabricated in the same manner as in Example 62 excepting that 1% by mass of cyclohexylbenzene (CHB) was added to the electrolyte instead of 1% by mass of biphenyl (BP).
• CHB cyclohexylbenzene
• a battery was prepared in the same manner as in Example 62 except that 1% by mass of 2-fluorobiphenyl (2FBP) was added to the electrolyte instead of 1% by mass of BP.
• 2FBP 2-fluorobiphenyl
• a battery was manufactured in the same manner as in Example 62 excepting that 1% by mass of tartaramylbenzene (TAB) was added to the electrolyte instead of 1% by mass of BP.
• TAB tartaramylbenzene
• a battery was prepared in the same manner as in Example 62 except that 1% by mass of toluene (TOL) was added to the electrolyte instead of 1% by mass of BP.
• TOL toluene
• a battery was fabricated in the same manner as in Example 62 except that 1% by mass of ethylbenzene (EB) was added to the electrolyte instead of 1% by mass of BP.
• EB ethylbenzene
• the electrolytic solution instead of BP1 mass 0/0, 4 Furuorojifue - adding ether a (4FDPE) 1 wt%, otherwise was produced in the same manner as the battery of Example 62.
• the electrolytic solution instead of BP1 mass 0/0, bird whistle - Rufosufeto (TPP) and 1 mass 0/0 added pressure to the otherwise was prepared in the same manner as the battery of Example 62.
• TPP bird whistle - Rufosufeto
• a battery was prepared in the same manner as in Example 73 except that 1% by mass of CHB was added to the electrolyte instead of 1% by mass of BP.
• a battery was manufactured in the same manner as in Example 73 except that 1% by mass of 2,4FA was added to the electrolyte instead of 1% by mass of BP.
• a battery was prepared in the same manner as in Example 73 except that 1% by mass of 2FBP was added to the electrolyte instead of 1% by mass of BP. [0140] (Example 90)
• a battery was prepared in the same manner as in Example 73 except that 1% by mass of TAB was added to the electrolyte instead of 1% by mass of BP.
• a battery was manufactured in the same manner as in Example 73 except that 1% by mass of TOL was added to the electrolyte instead of 1% by mass of BP.
• a battery was manufactured in the same manner as in Example 73 except that 1% by mass of EB was added to the electrolyte instead of 1% by mass of BP.
• a battery was prepared in the same manner as in Example 73 except that 1% by mass of 4FDPE was added to the electrolyte instead of 1% by mass of BP.
• a battery was manufactured in the same manner as in Example 73 except that 1% by mass of TPP was added to the electrolyte instead of 1% by mass of BP.
• a solvent for the electrolyte instead of a mixed solvent of ethylene carbonate (EC) and ethylmethyl carbonate (EMC) in a volume ratio of 3: 7, a volume ratio of EC and jetyl carbonate (DEC) of 3: 7 A battery was prepared in the same manner as in Example 73 except that the mixed solvent was used.
• EC ethylene carbonate
• EMC ethylmethyl carbonate
• DEC jetyl carbonate
• a mixed solvent of EC and dimethyl carbonate (DMC) in a volume ratio of 3: 7 was used instead of a mixed solvent of EC and EMC in a volume ratio of 3: 7.
• DMC dimethyl carbonate
• a mixed solvent of EC, EMC, and DEC in a volume ratio of 3: 5: 2 was used instead of a mixed solvent of EC: EMC in a volume ratio of 3: 7.
• a similar battery was produced.
• the amount of LiPF dissolved in the electrolyte was changed from 1. ImolZL to 0.7 molZL.
• a mixed solvent of EC: propylene carbonate (PC) and EMC with a volume ratio of 2: 1: 7 was used instead of a mixed solvent of EC: EMC with a volume ratio of 3: 7.
• PC propylene carbonate
• EMC propylene carbonate
• a battery similar to that of Example 73 was produced.
• LiNiO was used in place of LiCoO.
• LiMn 2 O was used instead of LiCoO.
• LiNi Co Mn O is used instead of LiCoO as the positive electrode active material.
• a battery was prepared in the same manner as in Example 1 except that 0.1% by mass of LiBOB represented by Formula 2 was added.
• a battery was made in the same manner as in Example 104 except that BP added to the electrolytic solution was 1% by mass.
• a battery was made in the same manner as in Example 104 except that BP added to the electrolytic solution was 4% by mass.
• a battery was manufactured in the same manner as in Example 104 except that LiBOB added to the electrolyte was 0.5 mass% and BP was 0.5 mass%.
• a battery was prepared in the same manner as in Example 04 except that LiBOB added to the electrolyte was 0.5 mass% and BP was 1 mass%.
• a battery was manufactured in the same manner as in Example 04 except that LiBOB added to the electrolyte solution was 0.5 mass% and BP was 2 mass%.
• a battery was prepared in the same manner as in Example 04 except that LiBOB added to the electrolyte was 1% by mass and BP was 0.1% by mass.
• a battery was prepared in the same manner as in Example 04 except that LiBOB added to the electrolyte was 1% by mass and BP was 0.5% by mass.
• Example 112 A battery was prepared in the same manner as in Example 104 except that LiBOB added to the electrolytic solution was 1% by mass and BP was 1% by mass.
• a battery was prepared in the same manner as in Example 104 except that LiBOB added to the electrolytic solution was 1% by mass and BP was 2% by mass.
• a battery was prepared in the same manner as in Example 104 except that LiBOB added to the electrolytic solution was 1% by mass and BP was 4% by mass.
• a battery was prepared in the same manner as in Example 104, except that LiBOB added to the electrolytic solution was 1.5 mass% and BP was 0.5 mass%.
• a battery was manufactured in the same manner as in Example 104, except that LiBOB added to the electrolytic solution was 1.5 mass% and BP was 1 mass%.
• a battery was prepared in the same manner as in Example 104 except that LiBOB added to the electrolytic solution was 1.5 mass% and BP was 2 mass%.
• a battery was prepared in the same manner as in Example 104, except that LiBOB added to the electrolyte was 2% by mass and BP was 0.1% by mass.
• a battery was prepared in the same manner as in Example 104 except that LiBOB added to the electrolytic solution was 2 mass% and BP was 1 mass%.
• a battery was prepared in the same manner as in Example 104 except that LiBOB added to the electrolytic solution was 2% by mass and BP was 4% by mass.
• a battery was manufactured in the same manner as in Example 112 except that 0.5% by mass of VC was further added to the total mass of the electrolytic solution.
• a battery was manufactured in the same manner as in Example 112 except that 1.0% by mass of VC was further added to the total mass of the electrolytic solution.
• a battery was manufactured in the same manner as in Example 112 except that 2.0% by mass of VC was further added to the total mass of the electrolytic solution.
• a battery was manufactured in the same manner as in Example 112 excepting that 0.5% by mass of VC and 0.5% by mass of VEC were further added to the total mass of the electrolytic solution.
• a battery was manufactured in the same manner as in Example 112 excepting that 1.0% by mass of phenylethylene carbonate (Ph EC) was further added to the total mass of the electrolytic solution.
• Ph EC phenylethylene carbonate
• a battery was manufactured in the same manner as in Example 112 excepting that 1.0% by mass of succinic anhydride was further added relative to the total mass of the electrolytic solution.
• a battery was manufactured in the same manner as in Example 112, except that 1% by mass of cyclohexylbenzene (CHB) was added to the electrolyte instead of 1% by mass of biphenyl (BP).
• CHB cyclohexylbenzene
• a battery similar to Example 112 was fabricated except that 1% by mass of 2-fluorobiphenyl (2FBP) was added to the electrolyte instead of 1% by mass of BP.
• 2FBP 2-fluorobiphenyl
• a battery was manufactured in the same manner as in Example 112 except that 1% by mass of tartaramylbenzene (TAB) was added to the electrolyte instead of 1% by mass of BP.
• TAB tartaramylbenzene
• a battery was manufactured in the same manner as in Example 112 except that 1% by mass of toluene (TOL) was added to the electrolyte instead of 1% by mass of BP.
• TOL toluene
• a battery was manufactured in the same manner as in Example 112 except that 1% by mass of ethylbenzene (EB) was added to the electrolyte instead of 1% by mass of BP.
• EB ethylbenzene
• a battery was manufactured in the same manner as in Example 123 except that 1% by mass of CHB was added to the electrolyte instead of 1% by mass of BP.
• a battery was manufactured in the same manner as in Example 123 except that 1% by mass of 2,4FA was added to the electrolyte instead of 1% by mass of BP.
• a battery was prepared in the same manner as in Example 123 except that 1% by mass of 2FBP was added to the electrolyte instead of 1% by mass of BP.
• Example 140 A battery was prepared in the same manner as in Example 123 except that 1% by mass of TAB was added to the electrolyte instead of 1% by mass of BP.
• a battery was manufactured in the same manner as in Example 123 except that 1% by mass of TOL was added to the electrolyte instead of 1% by mass of BP.
• a battery was manufactured in the same manner as in Example 123 except that 1% by mass of EB was added to the electrolyte instead of 1% by mass of BP.
• a battery was prepared in the same manner as in Example 123 except that 1% by mass of 4FDPE was added to the electrolyte instead of 1% by mass of BP.
• a battery was manufactured in the same manner as in Example 123 except that 1% by mass of TPP was added to the electrolyte instead of 1% by mass of BP.
• a solvent for the electrolyte instead of a mixed solvent of ethylene carbonate (EC) and ethylmethyl carbonate (EMC) in a volume ratio of 3: 7, a volume ratio of EC and jetyl carbonate (DEC) of 3: 7 A battery was prepared in the same manner as in Example 123 except that the mixed solvent was used.
• EC ethylene carbonate
• EMC ethylmethyl carbonate
• DEC jetyl carbonate
• a mixed solvent of EC and dimethyl carbonate (DMC) in a volume ratio of 3: 7 was used instead of a mixed solvent of EC and EMC in a volume ratio of 3: 7.
• DMC dimethyl carbonate
• a mixed solvent having a volume ratio of EC, EMC, and DEC of 3: 5: 2 was used instead of a mixed solvent of EC: EMC, and a volume ratio of 3: 7.
• a battery similar to that described above was prepared.
• the amount of LiPF dissolved in the electrolyte was changed from 1. ImolZL to 0.7 molZL.
• a mixed solvent of EC: propylene carbonate (PC) and EMC with a volume ratio of 2: 1: 7 was used instead of a mixed solvent of EC: EMC with a volume ratio of 3: 7.
• PC propylene carbonate
• EMC propylene carbonate
• a battery similar to that of Example 123 was produced.
• LiNiO was used instead of LiCoO.
• LiMn O was used instead of LiCoO.
• LiNi Co Mn O is used instead of LiCoO as the positive electrode active material.
• LiBF and bifur (BP) are not added to the electrolyte, otherwise
• LiBF was not added to the electrolyte, and BP added to the electrolyte was 0.5% by mass.
• LiBF was not added to the electrolyte, and BP added to the electrolyte was 4% by mass.
• LiBF added to the electrolyte is 0.005% by mass and BP is 0.1% by mass.
• a battery similar to that of Example 1 was produced.
• LiBF added to the electrolyte is 0.005% by mass and BP is 0.5% by mass.
• LiBF added to the electrolyte is 0.005% by mass, BP is 4% by mass.
• a battery was prepared in the same manner as in Example 1 except that BP was not added to the electrolytic solution.
• a battery was prepared in the same manner as in Example 1 except that BP added to the electrolytic solution was 0.05% by mass.
• a battery was manufactured in the same manner as in Example 1 except that BP added to the electrolytic solution was 5% by mass.
• LiBF added to the electrolyte is 0.2% by mass, BP is 0.05% by mass, otherwise
• LiBF to be added to the electrolyte solution is 0.2% by mass, BP is 5% by mass, otherwise, Example 1
• LiBF added to the electrolyte was 2% by mass
• a battery was manufactured in the same manner as in Example 1 except that LiBF added to the electrolytic solution was 2 mass% and BP was 0.05 mass%.
• a battery was manufactured in the same manner as in Example 1 except that LiBF added to the electrolytic solution was 2 mass% and BP was 5 mass%.
• a battery was manufactured in the same manner as in Example 1 except that LiBF added to the electrolytic solution was 3% by mass and BP was 0.1% by mass.
• a battery was manufactured in the same manner as in Example 1 except that LiBF added to the electrolytic solution was 3% by mass and BP was 0.5% by mass.
• a battery was manufactured in the same manner as in Example 1 except that LiBF added to the electrolyte was 3% by mass and BP was 4% by mass.
• a battery was manufactured in the same manner as in Example 10 except that 5.0% by mass of VC was further added to the total mass of the electrolytic solution.
• LiNiO was used instead of LiCoO as the positive electrode active material, and other than that of Comparative Example 10
• LiMn O was used instead of LiCoO.
• Comparative Example 10 Comparative Example 10
• LiNi Co Mn O is used instead of LiCoO as the positive electrode active material.
• LiBF is not added to the electrolyte, and the beef (BP) that is added to the electrolyte is 1
• a battery was prepared in the same manner as in Example 1 except for the mass%.
• BP added to the electrolyte is 0.1% by mass, and LiFOB is added to the electrolyte instead of LiBF.
• a battery was prepared in the same manner as in Example 1 except that 01% by mass was added.
• a battery was manufactured in the same manner as in Comparative Example 25 except that BP added to the electrolyte was 1% by mass.
• a battery was manufactured in the same manner as in Comparative Example 25 except that BP added to the electrolytic solution was 4% by mass.
• a battery was manufactured in the same manner as in Comparative Example 25, except that BP was not added to the electrolytic solution, and LiFOB added to the electrolytic solution was 0.1% by mass.
• a battery was prepared in the same manner as in Comparative Example 25, except that LiFOB added to the electrolyte was 0.1% by mass and BP was 0.05% by mass.
• a battery was prepared in the same manner as in Comparative Example 25 except that LiFOB added to the electrolytic solution was 0.1% by mass and BP was 5% by mass.
• a battery was manufactured in the same manner as in Comparative Example 25, except that BP was not added to the electrolytic solution, LiFOB added to the electrolytic solution was 1% by mass.
• LiFOB added to the electrolyte is 1% by mass and BP is 0.05% by mass.
• a battery similar to that of No. 25 was produced.
• a battery was manufactured in the same manner as in Comparative Example 25 except that LiFOB added to the electrolyte was 1% by mass and BP was 5% by mass.
• a battery was manufactured in the same manner as in Comparative Example 25, except that BP was not added to the electrolyte solution, and LiFOB added to the electrolyte solution was 2% by mass.
• a battery was manufactured in the same manner as in Comparative Example 25 except that LiFOB to be added to the electrolytic solution was 2 mass% and BP was 0.05 mass%.
• a battery was prepared in the same manner as in Comparative Example 25 except that LiFOB to be added to the electrolytic solution was 2 mass% and BP was 5 mass%.
• a battery was prepared in the same manner as in Comparative Example 25 except that LiFOB added to the electrolyte was 3% by mass and BP was 0.1% by mass.
• a battery was manufactured in the same manner as in Comparative Example 25 except that LiFOB to be added to the electrolyte was 3% by mass and BP was 1% by mass.
• a battery was manufactured in the same manner as in Comparative Example 25 except that LiFOB added to the electrolyte was 3% by mass and BP was 4% by mass.
• a battery was produced in the same manner as in Example 62, except that 5.0% by mass of VC was further added to the total mass of the electrolytic solution. [0246] (Comparative Example 42)
• LiNiO was used instead of LiCoO as the positive electrode active material, and other than that of Comparative Example 31
• LiMn O was used instead of LiCoO.
• LiNi Co Mn O is used instead of LiCoO as the positive electrode active material.
• a battery was prepared in the same manner as in Example 1 except that 0.01% by mass of LiBOB was added.
• a battery was manufactured in the same manner as in Comparative Example 45 except that BP added to the electrolytic solution was 1% by mass.
• a battery was manufactured in the same manner as in Comparative Example 45, except that the amount of BP added to the electrolyte was 4% by mass.
• a battery was prepared in the same manner as in Comparative Example 45, except that BP was not added to the electrolyte solution, and LiBOB added to the electrolyte solution was 0.1% by mass.
• a battery was prepared in the same manner as in Comparative Example 45, except that LiBOB added to the electrolytic solution was 0.1% by mass and BP was 0.05% by mass.
• a battery was prepared in the same manner as in Comparative Example 45 except that LiBOB added to the electrolytic solution was 0.1% by mass and BP was 5% by mass.
• Comparative Example 51 A battery was manufactured in the same manner as in Comparative Example 45, except that BP was not added to the electrolytic solution, LiBOB added to the electrolytic solution was 1% by mass.
• a battery was prepared in the same manner as in Comparative Example 45, except that LiBOB added to the electrolyte was 1% by mass and BP was 0.05% by mass.
• a battery was prepared in the same manner as in Comparative Example 45 except that LiBOB added to the electrolyte was 1% by mass and BP was 5% by mass.
• a battery was manufactured in the same manner as in Comparative Example 45, except that BP was not added to the electrolyte solution and LiBOB added to the electrolyte solution was 2% by mass.
• a battery was manufactured in the same manner as in Comparative Example 45, except that LiBOB added to the electrolytic solution was 2 mass% and BP was 0.05 mass%.
• a battery was manufactured in the same manner as in Comparative Example 45 except that LiBOB added to the electrolyte was 2% by mass and BP was 5% by mass.
• a battery was manufactured in the same manner as in Comparative Example 45 except that LiBOB added to the electrolyte was 3% by mass and BP was 0.1% by mass.
• a battery was manufactured in the same manner as in Comparative Example 45 except that LiBOB added to the electrolyte was 3% by mass and BP was 1% by mass.
• a battery was manufactured in the same manner as in Comparative Example 45 except that LiBOB added to the electrolyte was 3% by mass and BP was 4% by mass.
• a battery was manufactured in the same manner as in Example 112 except that 5.0% by mass of VC was further added to the total mass of the electrolytic solution.
• LiNiO was used instead of LiCoO as the positive electrode active material, and other than that of Comparative Example 51
• LiMn O was used instead of LiCoO.
• LiNi Co Mn O is used instead of LiCoO as the positive electrode active material.
• the initial capacity (mAh) and the initial battery thickness (mm) were measured for the batteries of the above Examples and Comparative Examples. In addition, for each battery, the capacity retention rate (%) after repeated charging and discharging, the thickness increment after standing at high temperature (mm), and the capacity recovery rate (%) were measured.
• the initial capacity and initial battery thickness were measured by preparing 5 cells for each of the examples and comparative examples, and charging each battery with a constant current and constant voltage for 3 hours at a current of 600 mA up to 4.2 V. After that, the battery was discharged at a current of 600 mA up to 3 V, and the discharge capacity (initial capacity) and battery thickness (initial battery thickness) were measured to obtain an average value.
• the addition amount of 4 is preferably 0.01% by mass or more and 2% by mass or less, more preferably 0.1% by mass or more and 0.5% by mass or less.
• the addition amount of BP when the addition amount of BP is 0.05% by mass and when the addition amount is 5% by mass, the effect of adding BP is small.
• the addition amount is 0.1% by mass or more and 4% by mass or less. A good effect is obtained. Among them, a better effect is obtained when the addition amount is 0.2 mass% or more and 1 mass% or less.
• the amount of added BP is preferably 0.1% by mass or more and 4% by mass or less, more preferably 0.2% by mass or more and 1% by mass or less.
• VC biethylene carbonate
• VEC butyl ethylene carbonate
• PhEC phenol ethylene carbonate
• oxalic anhydride oxalic anhydride
• the thickness tends to decrease and the recovery rate tends to increase.
• the amount of VC added is preferably 0.1% by mass or more and 2% by mass or less, and more preferably 0.5% by mass or more and 2% by mass or less.
• additives other than VC have similar properties to VC, changes in the effect due to increase or decrease in the amount of addition are considered to show the same tendency as VC. It is also possible to use a mixture of VC and other additives. The For example, in the case of Example 26, the initial capacity and capacity retention are improved.
• the present invention can also be achieved by changing the solvent composition of the electrolyte or the concentration of LiPF.
• the effect of the present invention can be obtained even when the positive electrode active material is changed.
• the thickness increments of Examples 52 and 53 using Mn are well suppressed.
• Fig. 8 shows the measurement results of capacity retention rate, thickness increment, and recovery rate of the battery with LiFOB added to the electrolyte.
• Fig. 9 (a) shows a part of Fig. 8 extracted and rearranged. Shown in (d).
• Figures 10 to 13 show the measurement results of the initial capacity, initial battery thickness, capacity retention, thickness increment, and recovery rate of the battery with LiFOB added to the electrolyte.
• the addition amount of LiFOB is 0.01 mass and when the addition amount is 3% by mass, the effect of addition of LiFOB is small and good when the addition amount is 0.1% by mass or more and 2% by mass or less. The effect is acquired. Among them, a better effect is obtained when the addition amount is 0.5 mass% or more and 1.5 mass% or less.
• the amount of LiFOB added is preferably 0.1% by mass or more and 2% by mass or less, more preferably 0.5% by mass or more and 1.5% by mass or less.
• the addition amount of BP when the addition amount of BP is 0.05% by mass and when the addition amount is 5% by mass, the effect of adding BP is small.
• the addition amount is 0.1% by mass or more and 4% by mass or less. A good effect is obtained. In addition, a better effect is obtained when the addition amount is 0.5 mass% or more and 2 mass% or less.
• the additive amount of BP is preferably 0.1% by mass or more and 4% by mass or less, more preferably 0.5% by mass or more and 2% by mass or less.
• VC biethylene carbonate
• VE C butyl ethylene carbonate
• PhEC phenylene ethylene carbonate
• oxalic anhydride when added to the electrolyte, the initial battery The thickness tends to decrease and the initial capacity and recovery rate tend to increase.
• the amount of VC added is preferably 0.1% by mass or more and 2% by mass or less, and more preferably 0.5% by mass or more and 1% by mass or less.
• the present invention also applies when the solvent composition of the electrolyte or the concentration of LiPF is changed.
• the effect is obtained.
• the initial capacity is increased even in the electrolyte containing PC as in Example 100. This is thought to be because, in an electrolyte containing PC, the decomposition of PC is suppressed by the negative electrode film formed by LiFOB.
• the effect of the present invention can be obtained even when the positive electrode active material is changed. Among them, the thickness increments of Examples 102 and 103 using Mn are well suppressed.
• Fig. 14 shows the measurement results of capacity retention rate, thickness increment, and recovery rate of the battery with LiBOB added to the electrolyte.
• Fig. 15 (a) shows a part of Fig. 14 extracted and rearranged. Shown in (d).
• Figures 16 to 19 show the measurement results of the initial capacity, initial battery thickness, capacity retention, thickness increment, and recovery rate of the battery with LiBOB added to the electrolyte.
• the added amount of LiBOB is 0.01% by mass and when the added amount is 3% by mass, the effect of adding LiBOB is small.
• the added amount is 0.1% by mass to 2% by mass A good effect is obtained. Further, when the addition amount is 0.5 mass% or more and 1.5 mass% or less, a better effect is obtained.
• the amount of LiBOB added is preferably 0.1% by mass or more and 2% by mass or less, more preferably 0.5% by mass or more and 1.5% by mass or less.
• the addition amount of BP when the addition amount of BP is 0.05% by mass, and when the addition amount is 5% by mass, the effect of adding BP is small. A good effect is obtained. In addition, a better effect is obtained when the addition amount is 0.5 mass% or more and 2 mass% or less.
• the additive amount of BP is preferably 0.1% by mass or more and 4% by mass or less, more preferably 0.5% by mass or more and 2% by mass or less.
• VC biethylene carbonate
• VE C butyl ethylene carbonate
• PhEC phenylene ethylene carbonate
• oxalic anhydride oxalic anhydride
• the thickness tends to decrease and the initial capacity and recovery rate tend to increase.
• the amount of VC added is preferably 0.1% by mass or more and 2% by mass or less, and more preferably 0.5% by mass or more and 1% by mass or less.
• additives other than VC have similar properties to VC, changes in the effect due to changes in the amount of addition are considered to show the same tendency as VC. It is also possible to use a mixture of VC and other additives. For example, in the case of Example 126, the initial capacity, capacity retention rate, and recovery rate are improved.
• the present invention also applies when the solvent composition of the electrolyte or the concentration of LiPF is changed.
• the effect is obtained.
• the initial capacity is increased even in the electrolyte containing PC as in Example 150. This is because in electrolytes containing PC This is thought to be because the decomposition of PC is suppressed by the negative electrode film formed by LiBOB.
• the effect of the present invention is also obtained when the positive electrode active material is changed. Among them, the thickness increments of Examples 152 and 153 using Mn are well suppressed.
• LiBF, LiFOB, or LiBOB is used alone.
• the amount is preferably 2% or less of the total mass of the electrolyte.

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