WO2012101693A1 - Collecteur d'électrode négative pour batteries au lithium-ion et batterie au lithium-ion - Google Patents

Collecteur d'électrode négative pour batteries au lithium-ion et batterie au lithium-ion Download PDF

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WO2012101693A1
WO2012101693A1 PCT/JP2011/005768 JP2011005768W WO2012101693A1 WO 2012101693 A1 WO2012101693 A1 WO 2012101693A1 JP 2011005768 W JP2011005768 W JP 2011005768W WO 2012101693 A1 WO2012101693 A1 WO 2012101693A1
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negative electrode
lithium ion
material layer
ion battery
battery
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PCT/JP2011/005768
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English (en)
Japanese (ja)
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一樹 遠藤
藤川　万郷
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パナソニック株式会社
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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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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 battery having improved safety against an internal short circuit, and a negative electrode current collector used in the battery.
  • the lithium ion battery includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a nonaqueous electrolyte.
  • a separator having a shutdown function for blocking the ionic current by blocking pores due to heat generated when an internal short circuit occurs in the battery is used.
  • the short-circuit current stops flowing due to the shutdown function, and the heat generation stops.
  • the separator is melted before the shutdown functions, thereby causing a melt-down that opens a large hole in the separator.
  • the positive electrode and the negative electrode are short-circuited due to meltdown, further overheating is caused. In some cases, the battery ignites or smokes, which is very dangerous.
  • Patent Document 1 Since heat-resistant resins such as aramid do not melt even at high temperatures, it is considered that using the technique of Patent Document 1 has a high ability to maintain insulation between positive and negative electrodes even in an overheated environment.
  • porous film made of a heat-resistant resin itself exhibits high heat resistance in the prior art disclosed in Patent Document 1, if the film breaks during short-circuiting, it is easily dragged by the melting or shrinking of the underlying separator, and this causes the short-circuit location to expand. May cause further overheating.
  • the method of suppressing the electric current at the time of a short circuit is proposed by forming the resistor layer (it consists of a mixture of carbon powder and a polyimide resin) which has high resistance on the collector surface (refer patent document 2). .
  • the resistor layer it consists of a mixture of carbon powder and a polyimide resin
  • the resistance value of the short-circuited portion is low, it is considered that if the technique of Patent Document 2 is used, the resistance value increases even if an internal short-circuit occurs, and thus overheating is suppressed. .
  • Patent Document 3 and Patent Document 4 in order to reduce the weight of the current collector without reducing the strength of the current collector, the conductivity of the metal is deposited by vapor deposition on both surfaces of a resin film such as PET or PP.
  • a resin film such as PET or PP.
  • a method of using a sheet on which a thin film is formed as a current collector has been proposed. According to this current collector, the resin film of the current collector at the short-circuit portion is melted by heat due to the heat generated at the time of the short circuit, and the current is interrupted by the heat-melted resin film.
  • a resin is used as the base material of the current collector, a metal is used as the base material. Since the resin has flexibility as compared with the case of using, the resin is deformed during rolling to relieve the stress, and as a result, it is difficult to increase the density of the active material.
  • the present invention has been made in view of such problems, has excellent load characteristics, is filled with a negative electrode active material at a high density, and even when an internal short circuit occurs, the battery temperature is excessive.
  • An object of the present invention is to provide a highly safe lithium ion battery capable of suppressing the increase.
  • the negative electrode current collector for a lithium ion battery according to the first aspect of the present invention comprises a base material layer made of a metal or an alloy having a melting point of 120 ° C. or higher and 800 ° C. or lower, and contact or non-contact with both surfaces of the base material layer. And a metal layer containing Cu or Ni.
  • a lithium ion battery includes a negative electrode plate having a negative electrode active material layer formed on the surface of the negative electrode current collector, and a positive electrode active material layer formed on the surface of the positive electrode current collector.
  • the positive electrode plate has an electrode group wound or laminated via a separator, and the electrode group is housed in a metal outer can, and one of the metal outer can and the two electrode plates Are electrically connected.
  • a metal layer having Cu or Ni is formed on both surfaces of a base material layer made of metal or alloy in contact or non-contact, so that the load characteristics of the lithium ion battery are excellent and the negative electrode of the negative electrode plate
  • the active material can be filled with high density.
  • the base material layer is made of a metal or alloy having a melting point of 120 ° C. or higher and 800 ° C. or lower, even when an internal short circuit occurs, it melts due to heat generation and interrupts the current. Can be suppressed.
  • FIG. 1 is a cross-sectional view of a negative electrode current collector 800 for a lithium ion battery according to this embodiment.
  • the negative electrode current collector 800 for a lithium ion battery includes a base layer 100 and a metal layer 110, and the metal layer 110 is formed on both surfaces of the base layer 100.
  • a negative electrode active material layer 120 is formed on the surface of the metal layer 110.
  • the base material layer 100 is made of a metal or alloy having a melting point of 120 to 800 ° C. Since the base material layer 100 is formed of a metal or alloy having a melting point in the above range, even when an internal short circuit of the battery occurs, the current can be interrupted by melting by heat generation. That is, when the melting point of the metal or alloy forming the base material layer 100 is less than 120 ° C., there is a risk of breakage at a location where current is concentrated, such as a lead weld, when a large current such as high output charge / discharge flows.
  • the melting point of the metal or alloy is 120 to 800 ° C. Preferably, it is 200 to 700 ° C.
  • the base material layer 100 is not particularly limited, but for example, Al, 72Ag-28Cu (BAg-8), Sn, 58Bi-42Sn, etc. can be used from the above-mentioned conditions, and preferably Al.
  • the electric conductivity of the base material layer 100 is preferably 10 6 S / m or more. This is because if the electrical conductivity is less than 10 6 S / m, the electrical conductivity may decrease.
  • the thickness of the base material layer 100 is not particularly limited, but is preferably 1 to 100 ⁇ m, and more preferably 5 to 20 ⁇ m. When the thickness is less than 5 ⁇ m, it becomes difficult to process into a foil shape, and at the same time, the strength tends to be insufficient and the productivity may be lowered. When the thickness is 20 ⁇ m or more, the current interruption effect at the time of short circuit may be reduced, and the current occupying ratio in the battery becomes high, so that the energy density tends to decrease.
  • the metal layer 110 is not particularly limited as long as it does not alloy with Li, react with the electrolytic solution, or dissolve in the anode in the potential region used as the negative electrode, but is made of, for example, Cu or Ni. It can also be formed of a Cu alloy such as Au, a Ni alloy such as Ni—Fe, or an alloy containing Cu and Ni such as Cu—Ni.
  • the thickness of the metal layer 110 is not particularly limited, but is preferably 0.1 to 2 ⁇ m. When the thickness is smaller than 0.1 ⁇ m, it becomes difficult to uniformly cover the surface of the base material layer 100, and the surface of the base material layer 100 is partially exposed. Side reactions such as Li alloying may occur. When the thickness is larger than 2 ⁇ m, the ratio of the metal layer 110 in the negative electrode current collector becomes high, and the current blocking effect at the time of short circuit may be reduced.
  • the method for laminating the metal layer 110 on the base material layer 100 is not particularly limited, and for example, electroplating, electroless plating, vapor deposition, or the like can be suitably used.
  • FIG. 2 is a cross-sectional view schematically showing the configuration of the lithium ion battery 900.
  • the lithium ion battery 900 for example, a cylindrical lithium ion secondary battery as shown in FIG. 2 can be adopted.
  • This lithium ion secondary battery is provided with a safety valve mechanism that releases gas to the outside of the battery when the pressure in the battery increases due to the occurrence of an abnormality such as an internal short circuit.
  • an electrode group 104 in which a positive electrode 101 and a negative electrode 102 are wound through a separator 103 is housed in a battery case 107 together with a non-aqueous electrolyte. Insulating plates 109 and 119 are arranged above and below the electrode group 104, the positive electrode 101 is joined to the filter 112 via the positive electrode lead 105, and the negative electrode 102 is also connected to the negative electrode terminal via the negative electrode lead 106. Is joined to the bottom.
  • the positive electrode 101 includes a positive electrode current collector and a positive electrode active material layer carried thereon.
  • the positive electrode active material layer can contain a binder, a conductive agent, and the like in addition to the positive electrode active material.
  • the positive electrode 101 is prepared, for example, by mixing a positive electrode mixture composed of a positive electrode active material and an optional component with a liquid component to prepare a positive electrode mixture slurry, applying the obtained slurry to a positive electrode current collector, and drying the mixture. .
  • the negative electrode 102 for example, a negative electrode mixture composed of a negative electrode active material and an optional component is mixed with a liquid component to prepare a negative electrode mixture slurry, and the obtained slurry is applied to the negative electrode current collector 800 and dried.
  • the negative electrode active material is an element that can be alloyed with lithium, a silicon compound, a tin compound, or the like
  • the negative electrode active material layer may be formed by a vapor phase method. Examples of the vapor phase method include chemical vapor deposition (CVD), vacuum deposition, and sputtering.
  • a lithium composite metal oxide can be used as the positive electrode active material of the lithium ion battery 900.
  • M Na, Mg, Sc, Y , Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, and B.
  • x 0 to 1.2
  • y 0 to 0.9
  • z 2.0 to 2.3.
  • x value which shows the molar ratio of lithium is a value immediately after active material preparation, and increases / decreases by charging / discharging.
  • lithium-containing compounds may be substituted with a different element.
  • Surface treatment may be performed with a metal oxide, lithium oxide, a conductive agent, or the like, or the surface may be subjected to a hydrophobic treatment.
  • a positive electrode active material may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the positive electrode active material layer may be a stack of two or more layers having different compositions.
  • the negative electrode active material of the lithium ion battery of the present invention for example, metals, metal fibers, carbon materials, oxides, nitrides, tin compounds, silicon compounds, various alloy materials, and the like can be used.
  • the carbon material include carbon materials such as various natural graphites, cokes, graphitized carbon, carbon fibers, spherical carbon, various artificial graphites, and amorphous carbon.
  • the oxide for example, lithium titanate having a spinel crystal structure is used. Lithium titanate having a typical spinel crystal structure is represented by the formula: Li 4 Ti 5 O 12 . However, the general formula: Li x Ti 5-y M y O 12 + lithium titanate represented by z may be used as well.
  • M is composed of vanadium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, boron, magnesium, calcium, strontium, barium, zirconium, niobium, molybdenum, tungsten, bismuth, sodium, gallium, and rare earth elements.
  • x is a value of lithium titanate immediately after synthesis or in a completely discharged state, 3 ⁇ x ⁇ 5, 0.005 ⁇ y ⁇ 1.5, ⁇ 1 ⁇ z ⁇ 1.
  • a simple substance such as silicon (Si) or tin (Sn), or a silicon compound or tin compound such as an alloy, a compound, or a solid solution is preferable from the viewpoint of a large capacity density.
  • SiO x 0.05 ⁇ x ⁇ 1.95
  • any one of these may be B, Mg, Ni, Ti, Mo, Co, Ca, Cr, Cu, Fe, Mn, Nb
  • An alloy, a compound, a solid solution, or the like in which a part of Si is substituted with at least one element selected from the group consisting of Ta, V, W, Zn, C, N, and Sn can be used.
  • Ni 2 Sn 4 , Mg 2 Sn, SnO x (0 ⁇ x ⁇ 2), SnO 2 , SnSiO 3 or the like can be applied.
  • a negative electrode active material may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, you may laminate
  • the binder for the positive electrode 101 or the negative electrode 102 for example, PVDF, PTFE, polyethylene, polypropylene, and aramid resin can be used.
  • the conductive agent included in the electrode include natural graphite and artificial graphite graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, and other carbon blacks, carbon fibers and metal fibers.
  • Conductive fibers such as carbon powder, metal powders such as carbon fluoride and aluminum, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, organic conductive materials such as phenylene derivatives, etc. Is used.
  • the blending ratio of the positive electrode active material, the conductive agent and the binder is preferably in the range of 80 to 97% by weight of the positive electrode active material, 1 to 20% by weight of the conductive agent, and 1 to 10% by weight of the binder.
  • the blending ratio of the negative electrode active material and the binder is preferably in the range of 93 to 99% by weight of the negative electrode active material and 1 to 10% by weight of the binder, respectively. Further, when the negative electrode active material layer is formed by a vapor phase method, the binder may not be included.
  • the positive electrode current collector a long porous conductive substrate or a nonporous conductive substrate is used.
  • the material used for the conductive substrate for example, stainless steel, Al, Ti or the like is used. It is more preferable to use Al from the viewpoint of imparting a current interruption effect at the time of a short circuit to the positive electrode current collector and reducing the weight.
  • the thickness of the positive electrode current collector is not particularly limited, but is preferably 1 to 100 ⁇ m, and more preferably 5 to 20 ⁇ m. By setting the thickness of the positive electrode current collector in the above range, it is possible to reduce the weight while maintaining the strength of the electrode plate.
  • the separator 103 interposed between the positive electrode 101 and the negative electrode 102 a microporous thin film, a woven fabric, a non-woven fabric or the like having a high ion permeability and having a predetermined mechanical strength and an insulating property is used.
  • a material of the separator 103 for example, polyolefin such as polypropylene and polyethylene is preferable from the viewpoint of safety of the lithium ion battery because it is excellent in durability and has a shutdown function.
  • the thickness of the separator 103 is generally 10 to 300 ⁇ m, but is preferably 40 ⁇ m or less. Further, the range of 15 to 30 ⁇ m is more preferable, and the more preferable range of the separator thickness is 20 to 25 ⁇ m.
  • the microporous film may be a single layer film made of one kind of material, or a composite film or multilayer film made of one kind or two or more kinds of materials.
  • the porosity of the separator 103 is preferably in the range of 30 to 70%.
  • the porosity indicates the volume ratio of the pores to the separator volume.
  • a more preferable range of the porosity of the separator 103 is 35 to 60%.
  • non-aqueous electrolyte a liquid, gel or solid (polymer solid electrolyte) substance can be used.
  • a liquid non-aqueous electrolyte (non-aqueous electrolyte) can be obtained by dissolving an electrolyte (for example, a lithium salt) in a non-aqueous solvent.
  • the gel-like non-aqueous electrolyte includes a non-aqueous electrolyte and a polymer material that holds the non-aqueous electrolyte.
  • this polymer material for example, PVDF, polyacrylonitrile, polyethylene oxide, polyvinyl chloride, polyacrylate, polyvinylidene fluoride hexafluoropropylene and the like are preferably used.
  • non-aqueous solvent for dissolving the electrolyte
  • a known non-aqueous solvent can be used.
  • the kind of this non-aqueous solvent is not specifically limited, For example, cyclic carbonate ester, chain
  • the cyclic carbonate include propylene carbonate (PC) and ethylene carbonate (EC).
  • the chain carbonate include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC) and the like.
  • the cyclic carboxylic acid ester include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
  • a non-aqueous solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • LiClO 4 , LiBF 4 , LiPF 6 , LiAlCl 4 , LiSbF 6 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , and LiB 10 Cl 10 are used.
  • LiClO 4 , LiBF 4 , LiPF 6 , LiAlCl 4 , LiSbF 6 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , and LiB 10 Cl 10 are used.
  • One electrolyte may be used alone, or two or more electrolytes may be used in combination.
  • the non-aqueous electrolyte may contain a material that can be decomposed on the negative electrode as an additive to form a film having high lithium ion conductivity and increase charge / discharge efficiency.
  • the additive having such a function include vinylene carbonate (VC), 4-methyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, and the like. These may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of vinylene carbonate, vinyl ethylene carbonate, and divinyl ethylene carbonate is preferable.
  • part of the hydrogen atoms may be substituted with fluorine atoms.
  • the amount of the electrolyte dissolved in the non-aqueous solvent is preferably in the range of 0.5 to 2 mol / L.
  • the non-aqueous electrolyte may contain a known benzene derivative that decomposes during overcharge to form a film on the electrode and inactivate the battery.
  • the benzene derivative those having a phenyl group and a cyclic compound group adjacent to the phenyl group are preferable.
  • the cyclic compound group a phenyl group, a cyclic ether group, a cyclic ester group, a cycloalkyl group, a phenoxy group and the like are preferable.
  • Specific examples of the benzene derivative include cyclohexylbenzene, biphenyl, diphenyl ether and the like. These may be used alone or in combination of two or more. However, the content of the benzene derivative is preferably 10% by volume or less of the entire non-aqueous solvent.
  • the filter 112 is connected to the inner cap 113, and the protrusion of the inner cap 113 is joined to the metal valve plate 114. Further, the valve plate 114 is connected to a terminal plate 108 that also serves as a positive electrode terminal. The terminal plate 108, the valve plate 114, the inner cap 113, and the filter 112 are integrated to seal the opening of the battery case 107 via the gasket 111.
  • valve body 114 When an abnormality such as an internal short circuit occurs in the unit cell 100 and the pressure in the unit cell 100 increases, the valve body 114 swells toward the terminal plate 108, and the inner cap 113 and the valve body 114 are disconnected. The current path is interrupted. When the pressure in the unit cell 100 further increases, the valve body 114 is broken. As a result, the gas generated in the unit cell 100 is discharged to the outside through the through hole 112a of the filter 112, the through hole 113a of the inner cap 113, the tear of the valve body 114, and the opening 108a of the terminal plate 108. Is done.
  • FIG. 3 is a diagram for explaining a state before a foreign object is stuck in the negative electrode 102 produced by applying a slurry-like negative electrode mixture to a negative electrode current collector 800 for a lithium ion battery and drying it.
  • the metal layer 110 is formed on both surfaces of the base material layer 100, and the negative electrode active material layer 120 is formed on the surface of the metal layer 110.
  • the negative electrode active material layer 120 schematically describes negative electrode active material particles.
  • the thickness of the negative electrode active material layer 120 is not particularly limited, but is, for example, 100 ⁇ m or less, and preferably 10 to 100 ⁇ m.
  • the average particle diameter of the negative electrode active material particles in the negative electrode active material layer 120 is not particularly limited, but is, for example, 50 ⁇ m or less, preferably 30 ⁇ m or less, and more preferably 10 ⁇ m or less. Further, this is not the case when the negative electrode active material layer is formed by a vapor phase method.
  • FIG. 4 is a diagram for explaining a state in which the foreign material 200 is stuck in the negative electrode 102 described above.
  • a large foreign object 200 such as a nail is pierced through the negative electrode 102
  • an internal short circuit occurs between the negative electrode 102 and a positive electrode (not shown), and the short-circuited portion generates heat. To do.
  • FIG. 5 is a diagram illustrating a state where the short circuit portion of the negative electrode 102 generates heat and the base material layer 100 is melted.
  • the heat generation causes the base material layer 100 to melt, and a void 130 is generated in the base material layer 100. Since the gap 130 is generated, the internal short circuit current can be cut off, and an excessive increase in the battery temperature at the time of the short circuit can be suppressed.
  • gap part 130 among the metal layers 110 may lose
  • the negative electrode current collector 800 for a lithium ion battery is configured as a three-layer structure including the base material layer 100 and the metal layer 110 formed in contact with both surfaces thereof.
  • the scope of the present invention is not limited to such an embodiment.
  • a negative electrode current collector 800 for a lithium ion battery includes a base material layer 100 made of a metal or an alloy having a melting point of 120 to 800 ° C., and a metal layer 110 made of Cu or Ni formed in contact with both surfaces of the base material layer 100. And a conductive resin layer formed in contact with both surfaces of the metal layer 110 is also possible.
  • the conductive resin layer is formed of, for example, a conductive polymer, and polypyrrole, polyaniline, polyacetylene, polythiophene, polyparaphenylene, polyphenylene vinylene, or the like can be used as the conductive polymer.
  • the softening point of the conductive polymer is preferably 100 to 400 ° C., more preferably 200 to 300 ° C.
  • the thickness of the conductive resin layer is not particularly limited, but is preferably 0.1 to 2 ⁇ m.
  • the negative electrode current collector 800 for a lithium ion battery includes a base material layer 100 made of a metal or an alloy having a melting point of 120 to 800 ° C., a conductive resin layer formed in contact with both surfaces of the base material layer 100, A structure provided with a metal layer 110 made of Cu or Ni formed in contact with both surfaces of the conductive resin layer is also possible.
  • the base material layer 100 and the conductive resin layer are melted in the short-circuit portion at the time of short-circuit, so that the internal short-circuit current can be interrupted. And since the current collection of a negative electrode is performed from the base material layer 100, the metal layer 110, and a conductive resin layer, a load characteristic is good. Furthermore, since the base material layer 100 and the metal layer 110 make it difficult to relieve stress during rolling, a decrease in the density of the negative electrode active material hardly occurs.
  • the present invention is not limited to the above-described three layers and five layers as long as the substrate layer and the metal layer are provided, and the present invention may be applied to a four-layer or six-layer structure. Included in the range.
  • Example 1 Production of Negative Electrode 102 A metal layer 110 made of Cu having a thickness of 1 ⁇ m was formed on both surfaces by using an aluminum foil having a thickness of 10 ⁇ m as a base material layer 100 to produce a negative electrode current collector 800 for a lithium ion battery.
  • NMP N-methyl-pyrrolidone
  • This positive electrode mixture slurry was applied and dried on both sides of a 15 ⁇ m thick aluminum current collector, and rolled three times at a linear pressure of 1000 kg / cm. The thickness after rolling was 175 ⁇ m. This was cut into dimensions of 56 mm in width and 600 mm in length to produce the positive electrode 101. One end of the aluminum lead was connected to the portion of the positive electrode 101 where the positive electrode current collector was exposed.
  • a nonaqueous electrolyte was prepared by dissolving LiPF 6 at a concentration of 1 mol / L in a mixed solvent containing EC and EMC at a volume ratio of 1: 3.
  • a terminal plate 108 that supports the positive terminal was attached to the opening of the battery case 107, and the end of the opening was caulked toward the terminal plate 108 to seal the battery case 107.
  • a cylindrical lithium ion battery having a design capacity of 2000 mAh was produced. This is referred to as the battery of Example 1.
  • Example 2 For the battery of Example 1, except that the negative electrode current collector 800 for a lithium ion battery was formed by forming a metal layer 110 made of Cu having a thickness of 3 ⁇ m on both surfaces of an aluminum substrate layer 100 having a thickness of 6 ⁇ m. A lithium ion battery was produced in the same manner as in Example 1. The negative electrode thickness after rolling was 159 ⁇ m, and the negative electrode active material density was 1.57 g / cm 3 . This is referred to as the battery of Example 2.
  • Comparative Example 1 A lithium ion battery was fabricated in the same manner as in Example 1 except that a 10 ⁇ m thick copper foil was used for the negative electrode current collector for the lithium ion battery.
  • the negative electrode thickness after rolling was 157 ⁇ m, and the negative electrode active material density was 1.57 g / cm 3 . This is referred to as the battery of Comparative Example 1.
  • Example 2 The battery of Example 1 is the same as Example 1 except that a negative electrode current collector for a lithium ion battery is formed by forming a metal layer made of Cu having a thickness of 1 ⁇ m on both surfaces of a PET resin substrate having a thickness of 10 ⁇ m. Similarly, a lithium ion battery was produced.
  • a thickness of about 0.1 ⁇ m was formed by vapor deposition, and then the thickness was set to 1 ⁇ m by electroplating.
  • the negative electrode thickness after rolling was 176 ⁇ m, and the negative electrode active material density was 1.40 g / cm 3 . This is referred to as the battery of Comparative Example 2.
  • Comparative Example 3 For the battery of Comparative Example 2, Comparative Example 2 was used except that a negative electrode current collector for a lithium ion battery was formed by forming a metal layer made of Cu of 3 ⁇ m thickness on both sides of a PET resin substrate of 6 ⁇ m thickness. Similarly, a lithium ion battery was produced. The negative electrode thickness after rolling was 175 ⁇ m, and the negative electrode active material density was 1.41 g / cm 3 . This is referred to as the battery of Comparative Example 3.
  • Comparative Example 1 In the battery of Comparative Example 1 using a negative electrode current collector for a lithium ion battery made of only Cu, the battery surface temperature rose significantly due to overheating accompanying the expansion of the short-circuited portion. Further, Comparative Example 2 and Comparative Example 3 using a base material layer made of PET instead of the Al base material layer had a large decrease in load characteristics, although the battery surface temperature was lower than that of Comparative Example 1 due to the current blocking effect. . This is presumably because current collection at a large current becomes insufficient because current collection at the negative electrode depends only on Cu of the thin metal layer. Moreover, the negative electrode active material density in the same rolling conditions was also low. This is presumably because the base material layer made of PET resin has relaxed the stress during rolling.
  • Example 2 the battery surface temperature after the nail penetration test of Example 2 where the metal layer is thick is somewhat high, and the thickness of the metal layer is more preferably 2 ⁇ m or less.
  • the present invention can provide a lithium ion battery having excellent safety while preventing deterioration of the load characteristics of the battery, it is useful as a technique that can be developed not only for small power sources such as portable electronic devices but also for large power sources such as EVs. is there.

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

Cette invention concerne une batterie au lithium-ion haute sécurité qui peut être supprimée en cas d'augmentation excessive de la température de la batterie sans détériorer les caractéristiques du collecteur et la densité du matériau actif de l'électrode négative, même en cas de court-circuit dû à une matière étrangère piégée dans celle-ci. Un collecteur d'électrode négative pour batteries secondaires au lithium-ion selon l'invention, présente une structure à trois couches obtenue en formant des couches métalliques (110) à base de Cu ou de Ni sur les deux surfaces d'une couche de base (100) faite d'un métal ou d'un alliage dont le point de fusion va de 120 à 800˚C (inclus). Ladite couche de base (100) qui peut, par exemple, être à base d'Al, a une conductivité électrique supérieure ou égale à 106 S/m. L'épaisseur de la couche de base (100) va de 1 à 100 μm, par exemple.
PCT/JP2011/005768 2011-01-28 2011-10-14 Collecteur d'électrode négative pour batteries au lithium-ion et batterie au lithium-ion WO2012101693A1 (fr)

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JP2011017013 2011-01-28

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CN111707965A (zh) * 2020-05-26 2020-09-25 欣旺达电动汽车电池有限公司 锂离子电池短路测试的方法
CN112290079A (zh) * 2020-10-19 2021-01-29 江苏智泰新能源科技有限公司 一种快充锂离子电池
EP3951935A4 (fr) * 2020-03-20 2022-07-06 Contemporary Amperex Technology Co., Limited Languette d'électrode négative, batterie secondaire et dispositif comprenant la batterie secondaire
DE102022200908A1 (de) 2022-01-27 2023-07-27 Technische Universität Clausthal, Körperschaft des öffentlichen Rechts Lithium-Ionen-Batteriezelle

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Publication number Priority date Publication date Assignee Title
EP3951935A4 (fr) * 2020-03-20 2022-07-06 Contemporary Amperex Technology Co., Limited Languette d'électrode négative, batterie secondaire et dispositif comprenant la batterie secondaire
US11923537B2 (en) 2020-03-20 2024-03-05 Contemporary Amperex Technology Co., Limited Negative electrode plate, secondary battery, and apparatus contianing the secondary battery
CN111707965A (zh) * 2020-05-26 2020-09-25 欣旺达电动汽车电池有限公司 锂离子电池短路测试的方法
CN111707965B (zh) * 2020-05-26 2022-08-09 欣旺达电动汽车电池有限公司 锂离子电池短路测试的方法
CN112290079A (zh) * 2020-10-19 2021-01-29 江苏智泰新能源科技有限公司 一种快充锂离子电池
DE102022200908A1 (de) 2022-01-27 2023-07-27 Technische Universität Clausthal, Körperschaft des öffentlichen Rechts Lithium-Ionen-Batteriezelle

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