WO2017082153A1 - Batterie secondaire au lithium-ion - Google Patents

Batterie secondaire au lithium-ion Download PDF

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Publication number
WO2017082153A1
WO2017082153A1 PCT/JP2016/082727 JP2016082727W WO2017082153A1 WO 2017082153 A1 WO2017082153 A1 WO 2017082153A1 JP 2016082727 W JP2016082727 W JP 2016082727W WO 2017082153 A1 WO2017082153 A1 WO 2017082153A1
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Prior art keywords
negative electrode
binder
secondary battery
ion secondary
current collector
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PCT/JP2016/082727
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English (en)
Japanese (ja)
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栄二 關
尚貴 木村
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日立オートモティブシステムズ株式会社
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Publication of WO2017082153A1 publication Critical patent/WO2017082153A1/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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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

Definitions

  • the present invention relates to a lithium ion secondary battery.
  • Patent Documents 1 and 2 polyamide, polyamideimide, and polyimide are used for the binder to improve the capacity reduction due to expansion and contraction of the negative electrode active material.
  • JP 2013-191330 A JP-A-10-261404
  • a first aspect of a lithium ion secondary battery according to the present invention is a lithium ion secondary battery comprising a positive electrode and a negative electrode having a current collector plate on which a negative electrode mixture layer containing a negative electrode active material and a binder is formed.
  • the breaking strength of the binder is 80 MPa or more and 400 MPa or less, and the breaking strength of the current collector plate is 600 MPa or more and 1100 MPa or less.
  • a second aspect of the lithium ion secondary battery according to the present invention is a lithium ion secondary battery comprising: a positive electrode; and a negative electrode having a current collector plate on which a negative electrode mixture layer containing a negative electrode active material and a binder is formed.
  • the binder includes at least one of polyimide and polyamideimide, and the current collector plate is formed of Fe or stainless steel.
  • a third aspect of the lithium ion secondary battery according to the present invention is a lithium ion secondary battery comprising a positive electrode and a negative electrode having a current collector plate on which a negative electrode mixture layer containing a negative electrode active material and a binder is formed.
  • the discharge capacity of the negative electrode is Q (Ah / kg)
  • the breaking strength of the binder is A (MPa)
  • the elongation at break is B (%), 3 ⁇ Q ⁇ A ⁇ B ⁇ 10 ⁇ Q Fulfill.
  • a lithium ion secondary battery having excellent cycle characteristics can be provided.
  • FIG. 1 is an exploded perspective view showing an example of a lithium ion secondary battery.
  • FIG. 2 is an exploded perspective view showing a laminated structure of the laminated electrode group.
  • FIG. 3 is a diagram schematically showing a part of the negative electrode cross section.
  • FIG. 4 is a diagram for explaining a decrease in cycle capacity maintenance rate due to soot.
  • FIG. 5 is a diagram showing the physical property values of the binder and the physical property values of the negative electrode current collector plate in Examples and Comparative Examples.
  • FIG. 6 is a diagram showing the measurement results of the negative electrode discharge capacity.
  • FIG. 7 is a diagram showing the measurement results of the capacity retention rate after 100 cycles.
  • FIG. 8 is a diagram showing a chemical formula of polyamideimide.
  • FIG. 1 shows an example of a lithium ion secondary battery, and is an exploded perspective view of a laminated lithium ion secondary battery cell (hereinafter referred to as a laminate cell).
  • a laminated laminate cell will be described as an example.
  • the present invention applies to lithium ion secondary batteries having other configurations, for example, those having a wound structure or sealed in a metal can. Can be applied.
  • the laminate cell 11 is one in which a laminated electrode group 9 and an electrolyte solution are enclosed in laminate films 8 and 10.
  • the laminated electrode group 9 is sandwiched between the laminate films 8 and 10, and the three sides of the laminate films 8 and 10 are heat-sealed and sealed.
  • the positive electrode terminal 1 and the negative electrode terminal 2 of the multilayer electrode group 9 are projected from one side not thermally welded to the outside. And after inject
  • FIG. 2 is an exploded perspective view showing a laminated structure of the laminated electrode group 9.
  • the laminated electrode group 9 is obtained by laminating a plate-like positive electrode 5 and a belt-like negative electrode 6 with a separator 7 interposed therebetween.
  • the positive electrode 5 is obtained by forming a positive electrode mixture layer on the front and back surfaces of the positive electrode current collector plate.
  • a part of the positive electrode current collector plate is the positive electrode uncoated portion 3 where the positive electrode mixture layer is not formed.
  • the negative electrode 6 is obtained by forming a negative electrode mixture layer on both front and back surfaces of a negative electrode current collector plate.
  • a part of the negative electrode current collector plate is the negative electrode uncoated portion 4 where the negative electrode mixture layer is not formed.
  • a metal foil is used for the positive current collector and the negative current collector.
  • each positive electrode 5 is bundled and ultrasonically welded to the positive electrode terminal 1.
  • the negative electrode uncoated portion 4 of each negative electrode 6 is bundled and ultrasonically welded to the negative electrode terminal 2.
  • the welding method may be other welding methods such as resistance welding.
  • the positive terminal 1 and the negative terminal 2 may be preliminarily coated with or attached to a sealing portion of the terminal in order to more reliably seal the inside and outside of the battery.
  • FIG. 3 is a diagram schematically showing a part of the negative electrode cross section.
  • the particulate negative electrode active material 611 contained in the negative electrode mixture layer 61 formed on the surface of the negative electrode current collector plate 60 is bound to each other by a binder 612 interposed therebetween.
  • the binder 612 binds the negative electrode active materials 611 to each other as described above, and binds them by interposing a gap between the particulate negative electrode active material 611 and the negative electrode current collector plate 60.
  • the negative electrode active material When the negative electrode active material repeatedly expands and contracts with repeated charge and discharge, when the breaking strength of the binder 612 is small, the expansion and contraction causes binding between the negative electrode active materials 611 and the negative electrode active material 611 and the negative electrode current collector plate 60. The bond is easily broken. As a result, the negative electrode mixture layer 61 is cracked or the negative electrode mixture is peeled off, and the cycle capacity retention rate is lowered. Therefore, in the above-described conventional technology, polyamide, polyimide, and polyamideimide are used for the binder, so that an imide group is added to the binder 612 to increase the breaking strength of the binder 612, and the negative electrode mixture layer 61 is cracked or mixed. I try to suppress the exfoliation.
  • the present inventor has found that when the breaking strength of the binder 612 is excessively increased, soot is generated in the negative electrode current collector plate 60 and the cycle capacity retention rate is reduced.
  • the breaking strength of the binder 612 that binds the negative electrode active material 611 and the negative electrode current collector plate 60 increases, the degree of adhesion between the negative electrode mixture layer 61 and the negative electrode current collector plate 60 increases. As a result, it is considered that a force acts on the current collector plate 60 due to expansion and contraction of the negative electrode active material 611 and wrinkles are generated.
  • FIG. 4 is a diagram for explaining a decrease in cycle capacity maintenance rate when wrinkles occur in the negative electrode current collector plate 60.
  • FIG. 4A schematically shows the shapes of the positive electrode 5 and the negative electrode 6 disposed with the separator 7 interposed therebetween when no wrinkles are generated on the negative electrode current collector plate 60.
  • the positive electrode mixture layer 51 and the negative electrode mixture layer 61 are opposed to each other with the separator 7 interposed therebetween.
  • An electrolyte solution exists in the gap between the positive electrode mixture layer 51 and the negative electrode mixture layer 61 and the separator 7.
  • the positive electrode mixture layer 51 is also formed on both the front and back surfaces of the positive electrode current collector plate 50.
  • FIG. 4B shows a case where wrinkles are generated on the surface of the negative electrode current collector plate 60 due to the expansion and contraction of the negative electrode mixture layer 61. Due to the generation of wrinkles, the surface 600 of the negative electrode current collector plate 60 has an uneven shape. Therefore, an uneven shape also appears on the surface 610 of the negative electrode mixture layer 61 formed on the surface 600. As a result, it is considered that the battery capacity changes due to the change in the distance ⁇ between the positive electrode mixture layer 51 and the negative electrode mixture layer 61, leading to a decrease in cycle characteristics (cycle capacity retention rate).
  • the strength of the negative electrode current collector plate is not improved according to the characteristics of the binder 612 (breaking strength, breaking elongation, toughness, etc.) instead of simply improving the breaking strength of the binder 612 as in the prior art.
  • breaking strength, breaking elongation, etc. the breaking strength, breaking elongation, etc.
  • the generation of wrinkles in the negative electrode current collector plate 60 is suppressed, and the cycle characteristics are improved.
  • FIGS. 5 to 7 show examples.
  • FIG. 5 shows the physical property values of the binder and the physical property value of the negative electrode current collector plate in Examples and Comparative Examples.
  • FIGS. 6 and 7 show the measurement results when the physical property values shown in FIG. 5 are used, FIG. 6 shows the negative electrode discharge capacity, and FIG. 7 shows the capacity retention rate after 100 cycles.
  • negative electrode active material negative electrode binder, negative electrode current collector
  • an active material in which an active material containing Si and graphite were mixed at a weight ratio of 1: 1 was used.
  • active material containing Si materials such as Si alloy and Si oxide can be used. In the example shown in FIG. 5, Si alloy was used.
  • the Si alloy is usually in a state where fine particles of metal silicon (Si) are dispersed in each particle of other metal elements, or other metal elements are dispersed in each particle of Si. It is in a state. Any other metal element may be used as long as it contains at least one of Al, Ni, Cu, Fe, Ti, and Mn.
  • the Si alloy can be produced by mechanical synthesis by a mechanical alloy method, or by heating and cooling a mixture of Si particles and other metal elements. This time, a Si alloy synthesized by a mechanical alloy method was used.
  • the composition of the Si alloy is preferably such that the atomic ratio of Si to another metal element is 50:50 to 90:10, more preferably 60:40 to 80:20. This time, the atomic ratio was set to 70:30, and Si 70 Ti 30 was used, but Si 70 Ti 10 Fe 10 Al 10 , Si 70 Al 30 , Si 70 Ni 30 , Si 70 Cu 30 , Si 70 Fe 30 , Si 70 were used. Ti 30 , Si 70 Mn 30 , Si 70 Ti 15 Fe 15 , Si 70 Al 10 Ni 20 or the like may be used.
  • graphite materials such as natural graphite and artificial graphite can be used. Natural graphite is desirable from the viewpoint of cost, but the surface may be coated with non-graphitizable carbon. This time, natural graphite having d002 of 3.356 mm or less, Lc (002) of 1000 mm or more, and La (110) of 1000 mm or more was used as crystallinity.
  • polyamideimide was used as the binder, but it could be polyamide or polyimide, or a mixture of these, or a binder with other binders such as PVDF (polyvinylidene fluoride) or SBR (styrene butadiene rubber). It does not matter.
  • binders such as PVDF (polyvinylidene fluoride) or SBR (styrene butadiene rubber).
  • PVDF polyvinylidene fluoride
  • SBR styrene butadiene rubber
  • FIG. 8 shows the chemical formula of polyamideimide.
  • R1 is an alkylene group having 1 to 18 carbon atoms, an arylene group, benzene, or the like, and may contain nitrogen, oxygen, sulfur, or halogen.
  • R2 to R10 are hydrogen, an alkyl group or an aryl group.
  • the breaking strength of the negative electrode binder is the strength when the negative electrode binder is broken by pulling at a speed of 0.2 (m / min) using a tensile tester, and from [Tensile load ⁇ Cross sectional area of negative electrode binder piece].
  • the elongation at break (%) of the negative electrode binder is the elongation when the negative electrode binder is broken by pulling at a speed of 0.2 (m / min) using a tensile tester, [100 ⁇ (negative electrode binder after tension) It was calculated from [Negative electrode-Negative anode binder piece before tension) / Negative anode binder piece before tension].
  • the toughness (%) of the negative electrode binder was determined by the product of the breaking strength and the breaking elongation.
  • the negative electrode current collector plate has a single-layer structure (Examples 1, 2, Examples 5, 6, Examples 9 to 14, Comparative Examples 1 to 4) and a double-layer structure (Examples 3, 4, and 4). Examples 7 and 8) were used. Fe and stainless steel (SUS) were used for the 1st layer used as a board
  • the breaking strength of the negative electrode current collector plate was calculated from [tensile load / cross sectional area of the negative electrode binder piece] as the strength when the negative electrode binder was broken by pulling at a speed of 0.2 (m / min) using a tensile tester.
  • the breaking elongation (%) of the current collector plate is the elongation when the negative electrode binder is broken by pulling at a speed of 0.2 (m / min) using a tensile tester, [100 ⁇ (negative binder after tension) Piece minus negative electrode binder piece before tension) / negative electrode binder piece before tension].
  • the negative electrode was prepared by preparing a negative electrode mixture slurry, coating the negative electrode current collector plate, and pressing.
  • the negative electrode slurry uses acetylene black as a conductive material, and the weight ratio is 92: 5: 3 in order, and the viscosity is 5000 to 8000 mPa.
  • a slurry was prepared while mixing (methylpyrrolidone) solvent. Although NMP was used as a solvent this time, water, 2-butoxyethanol, butyl cellosolve, N, N-dimethylacetamide, diethylene glycol diethyl ether, or a mixture thereof may be used.
  • a planetary mixer was used for slurry preparation.
  • the drying temperature at the time of coating the negative electrode is 80 ° C. or more and 120 ° C. or less, and the effect is obtained, but the effect is most obtained if it is 90 ° C. or more and 100 ° C. or less.
  • the density of the coated negative electrode was adjusted with a roll press. The density was pressed so that the pores of the electrode were about 20 to 40%, and the negative electrode was produced at a density of 1.9 (g / cm 3 ). Thereafter, the polyamideimide was thermally cured in vacuum at 300 ° C. for 1 hour. In addition, it does not matter even if it exists in nitrogen and the hardening time of resin is not ask
  • the separator is not particularly limited as long as it is a material that does not allow lithium ions to pass through due to thermal contraction.
  • polyolefin is used.
  • Polyolefin is mainly characterized by containing at least one kind of polyethylene, polypropylene, etc., but may contain heat-resistant resin such as polyamide, polyamideimide, polyimide, polysulfone, polyethersulfone, polyphenylsulfone, polyacrylonitrile. Absent.
  • the inorganic filler layer may be applied to one side or both sides of the separator.
  • the inorganic filler layer is characterized by containing at least one of SiO 2 , Al 2 O 3 , montmorillonite, mica, ZnO, TiO 2 , BaTiO 3 , and ZrO 2. From the viewpoint of cost and performance, SiO 2 or Al 2 O 3 is most preferred. This time, a three-layer film having a thickness of 25 ⁇ m having polyethylene between polypropylenes was used.
  • electrolytes include, for example, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, methyl acetate, ethyl acetate, methyl propionate, tetrahydrofuran 2-methyltetrahydrofuran, 1,2-dimethoxyethane, 1-ethoxy-2-methoxyethane, 3-methyltetrahydrofuran, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, 1,3-dioxolane
  • LiPF 6 , LiBF 4 , LiClO 4 , LiN (C 2 F) can be used as the non-aqueous solvent
  • a known electrolyte used in a battery such as an organic electrolyte in which at least one lithium salt selected from SO 2 ) 2 or the like is dissolved, a solid electrolyte having a lithium ion conductivity, a gel electrolyte, or a molten salt; Can be used.
  • the negative electrode produced as described above was processed into a size of ⁇ 16 mm, a separator was sandwiched between them, a monopolar small cell having a counter electrode of Li was produced, and the discharge capacity of the negative electrode was measured.
  • the charge / discharge conditions were a negative electrode discharge capacity that was a constant current charge of 0.2 CA up to a lower limit voltage of 5 mV and a constant voltage charge of 2 h at a constant voltage of 0.2 CA up to an upper limit voltage of 2.0 V.
  • 1 CA is a current value at which charging or discharging of the battery capacity is completed in 1 hour
  • 0.2 CA is a current value at which charging or discharging of the battery capacity is completed in 5 hours.
  • the positive electrode has an aluminum foil as a positive electrode current collector foil.
  • a positive electrode mixture layer is formed on the aluminum foil.
  • the positive electrode active material mixture includes a positive electrode active material LiNi 1/3 Mn 1/3 Co 1/3 O 2 , a carbon material conductive material and a polyvinylidene fluoride (hereinafter abbreviated as PVDF) binder (binding). Material).
  • the weight ratios were 90: 5: 5 in order, and the mixture coating amount was 240 (g / m 2 ).
  • the positive electrode active material mixture is applied to the aluminum foil, the viscosity is adjusted with a dispersion solvent of N-methyl-2-pyrrolidone.
  • the positive electrode after coating was dried at 120 ° C., and the density was adjusted by a roll press. This time, the density was adjusted to 3.0 (g / cm 3 ).
  • FIG. 6 shows the result of measuring the discharge capacity of the negative electrode (negative electrode discharge capacity Q) and the designed capacity. From the results of FIG. 6, Examples 1 to 12, 14 and Comparative Examples 1, 3, and 4 were expressed as designed capacity, but the negative electrode discharge capacity Q of Example 13 and Comparative Example 2 was less than the designed capacity. I understood.
  • the physical properties of the binder (breaking strength, breaking elongation, toughness, elastic modulus) were changed by increasing the imide group. If the amount of imide groups in the binder is large, the breaking strength and breaking elongation increase. 5 is compared with the negative electrode discharge capacity Q in FIG. 6, it is estimated that the decrease in the discharge capacity of the negative electrode is caused by the imide group in the negative electrode binder. Is done. That is, since the amount of the imide group in the binder is large, Li is trapped in the imide group in the negative electrode binder, resulting in an irreversible capacity of the negative electrode and a low discharge capacity of the negative electrode.
  • the breaking strength of the binder is 400 MPa or less, the breaking elongation of the binder is 120% or less, and the toughness of the binder (toughness) ⁇ 10) If 3Q, it is considered that the negative electrode discharge capacity Q is developed as designed.
  • Example 13 the binder elongation at break is too large (toughness ⁇ 10)> 3Q, and in the case of Comparative Example 2, the binder has a too high breaking strength (toughness ⁇ 10). > 3Q.
  • FIG. 7 shows the results of capacity retention rate measurement after 100 cycles.
  • Examples 1 to 14 and Comparative Example 2 have a cycle capacity maintenance rate of 70% or more, and show a relatively good cycle capacity maintenance rate. However, all of Comparative Examples 1 and 3 have a cycle capacity retention rate of 50%, which is lower than that of the other examples.
  • FIG. 5 and FIG. 7 are compared.
  • Comparative Example 1 in which the cycle capacity retention rate was low, the fracture strength of the binder was too small as 70 MPa, and the toughness was less than 8000 MPa. In this case, it is considered that the cycle capacity retention rate is poor due to the peeling of the negative electrode mixture.
  • Comparative Example 3 the binder physical properties (breaking strength, breaking elongation) are the same as in Example 2 where the cycle capacity retention rate is relatively good, but the breaking strength of the negative electrode current collector plate is as small as 400 MPa. It is considered that the cycle capacity retention rate is lowered due to the influence of wrinkles on the negative electrode current collector plate due to the volume change of the negative electrode active material.
  • the breaking strength of the negative electrode current collector plate since the breaking strength of the negative electrode current collector plate was too large as 1200 MPa, electrode processing became difficult, and measurement data of the cycle capacity retention rate could not be obtained.
  • the cycle capacity retention rates of Examples 1 to 14 in which the breaking strength of the negative electrode current collector plate is in the range of 600 MPa to 1100 MPa, the cycle capacity retention rates of Examples 3, 4, 7, and 8 are 90 to 93.
  • the cycle capacity retention rate of Examples 1, 2, 5, 6, 9 to 11 is in the range of 80 to 88%, and the cycle capacity retention rate of Examples 12 to 14 is 70 to 75%. It is a range.
  • Example 14 is a case where the elongation at break was increased to 55% by annealing stainless steel used for the negative electrode current collector plate.
  • the cycle capacity maintenance rate is inferior to that. This is presumed that when the breaking elongation of the negative electrode current collector plate is too large, wrinkles are easily generated, and the cycle capacity retention rate is lowered.
  • Example 12 since the breaking elongation of the binder is too small as 32% and the effect of suppressing the peeling of the negative electrode mixture is small, it is presumed that the cycle capacity maintenance rate is lowered.
  • the current collector plate has a two-layer structure, the first layer serving as the substrate is Fe or stainless steel, The second layer formed on the surface of one layer is Ni or Cu. It was found that the cycle characteristics were further improved by using such a two-layer structure.
  • the breaking strength of the binder is set to 80 MPa or more and 400 MPa or less, and the breaking strength of the current collector plate is 600 MPa. It is preferable that the pressure be 1100 MPa or less.
  • the breaking strength of the binder When the breaking strength of the binder is less than 80 MPa, the negative electrode mixture is peeled off due to expansion and contraction of the negative electrode active material, and the capacity is greatly reduced. On the other hand, if the breaking strength of the binder exceeds 400 MPa, the amount of imide groups in the binder increases, so that Li is trapped in the imide groups in the negative electrode binder, resulting in an irreversible capacity of the negative electrode, and a negative electrode discharge capacity. Lower. On the other hand, when the breaking strength of the negative electrode current collector plate is less than 600 MPa, wrinkles are generated in the negative electrode current collector plate due to expansion and contraction of the negative electrode active material, resulting in a large capacity reduction. On the other hand, when the breaking strength of the negative electrode current collector plate exceeds 1100 MPa, the strength of the negative electrode current collector is so high that the electrode processing becomes difficult.
  • the breaking elongation of the binder is preferably 50% or more and 120% or less, and the breaking elongation of the negative electrode current collector plate is preferably 1% or more and 45% or less.
  • the binder preferably contains at least one of polyimide and polyamideimide
  • the current collector foil used for the negative electrode current collector plate is preferably formed of Fe or stainless steel.
  • the current collector foil has a first layer serving as a substrate and a second layer formed on the surface of the first layer, the first layer is formed of Fe or stainless steel, the second layer is Ni and It is preferably formed of any of Cu.
  • the first layer serving as the substrate can secure breaking strength and suppress the occurrence of wrinkles on the negative electrode current collector plate.
  • the second layer is Ni or Cu used in a conventional lithium ion secondary battery, and can ensure the conductivity of the negative electrode current collector plate.
  • the negative electrode slurry at the time of preparing the negative electrode has a negative electrode active material / binder / conductive material weight ratio of 92: 5: 3, but the binder concentration in the negative electrode mixture layer is in the range of 3 to 15 wt%. Is preferred. By doing so, generation

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Abstract

L'invention concerne une batterie secondaire au lithium-ion ayant d'excellentes propriétés de cycle. La batterie secondaire au lithium-ion est dotée d'une électrode positive (5), et d'une électrode négative (6) ayant une plaque collectrice de courant sur laquelle est formée une couche de mélange d'électrode négative, qui comprend un matériau actif d'électrode négative et un liant. La résistance à la rupture du liant est de 80 MPa à 400 MPa, et la résistance à la rupture de la plaque collectrice de courant est de 600 MPa à 1 100 MPa.
PCT/JP2016/082727 2015-11-13 2016-11-04 Batterie secondaire au lithium-ion WO2017082153A1 (fr)

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JP7074701B2 (ja) * 2019-03-05 2022-05-24 株式会社豊田自動織機 蓄電モジュール及び蓄電装置

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