WO2019187132A1 - Complexe d'électrode, batterie et bloc-batterie - Google Patents

Complexe d'électrode, batterie et bloc-batterie Download PDF

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Publication number
WO2019187132A1
WO2019187132A1 PCT/JP2018/013925 JP2018013925W WO2019187132A1 WO 2019187132 A1 WO2019187132 A1 WO 2019187132A1 JP 2018013925 W JP2018013925 W JP 2018013925W WO 2019187132 A1 WO2019187132 A1 WO 2019187132A1
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active material
negative electrode
electrode
battery
containing layer
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PCT/JP2018/013925
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English (en)
Japanese (ja)
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圭吾 保科
政典 田中
大典 高塚
康宏 原田
高見　則雄
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株式会社 東芝
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Priority to PCT/JP2018/013925 priority Critical patent/WO2019187132A1/fr
Priority to JP2020508897A priority patent/JP7068439B2/ja
Publication of WO2019187132A1 publication Critical patent/WO2019187132A1/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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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

  • Embodiments of the present invention relate to an electrode composite, a battery, and a battery pack.
  • a porous separator is disposed between the positive electrode and the negative electrode in order to avoid contact between the positive electrode and the negative electrode.
  • a self-supporting film separate from the positive electrode and the negative electrode is used.
  • An example of this is a polyolefin resin porous film. Since a separator made of a resin film needs to have mechanical strength so as not to be broken at the time of manufacturing a battery, it is difficult to make the separator thin beyond a certain level. Since the positive electrode and the negative electrode are stacked or wound with a separator interposed therebetween, if the separator is thick, the number of positive electrode and negative electrode layers that can be stored per unit volume of the battery is limited. As a result, the battery capacity is reduced. In addition, a resin film separator is poor in durability, and when used in a secondary battery, the battery deteriorates in cycle performance due to deterioration of the separator during repeated charging and discharging.
  • This invention is made in view of the said situation, and is providing the electrode composite body which can implement
  • an electrode composite including an electrode and an insulating layer.
  • the electrode includes an active material-containing layer.
  • the insulating layer covers at least part of the surface of the active material-containing layer.
  • the insulating layer has an opening and includes insulating particles.
  • a battery is provided.
  • the battery includes the electrode assembly according to the embodiment.
  • a battery pack is provided.
  • the battery pack includes the battery according to the embodiment.
  • FIG. 4 is a schematic plan view of the electrode assembly shown in FIG. 3. Sectional drawing which shows the electrode group containing the electrode composite_body
  • an electrode composite includes an electrode including an active material-containing layer and an insulating layer covering at least a part of the surface of the active material-containing layer.
  • the insulating layer contains insulating particles and has one or more openings. According to such an electrode composite, it is possible to suppress the separation of the insulating layer from the active material-containing layer even if a volume change occurs in the active material-containing layer due to a charge / discharge reaction or the like. Moreover, the impregnation property of electrolyte solution is also favorable. Therefore, the electrode composite contributes to the improvement of the battery life performance.
  • the active material-containing layer can contain a niobium titanium composite oxide as an active material.
  • the niobium titanium composite oxide can realize a high-capacity electrode, but has a large volume change amount due to expansion and contraction associated with insertion and extraction of lithium ions. Since the insulating layer has a plurality of openings in the portion covering the surface of the active material-containing layer, the insulating layer can be deformed following the volume change of the active material-containing layer. Therefore, an electrode composite can suppress that an insulating layer peels from an active material content layer at the time of long-term use, such as a charge-and-discharge cycle, when providing an active material containing niobium titanium complex oxide. As a result, the electrode composite can improve the cycle life performance when the active material containing the niobium titanium composite oxide is provided.
  • the electrode assembly according to the first embodiment may include a current collector. That is, the electrode included in the electrode composite can include a current collector and an active material-containing layer formed on the main surface of the current collector.
  • the active material-containing layer may be formed on one main surface of the current collector, or may be formed on both main surfaces.
  • the current collector can include a portion that does not carry the active material-containing layer. This part can serve as an electrode tab.
  • the electrode may further include an electrode tab that is separate from the current collector.
  • a sheet containing a material having high electrical conductivity can be used.
  • an aluminum foil or an aluminum alloy foil can be used as the current collector.
  • the thickness is preferably 20 ⁇ m or less.
  • the aluminum alloy foil can contain magnesium, zinc, silicon and the like.
  • the aluminum alloy foil may contain a transition metal.
  • the content of the transition metal in the aluminum alloy foil is preferably 1% by weight or less. Examples of the transition metal include iron, copper, nickel, or chromium.
  • the active material-containing layer includes active material particles and a binder.
  • the active material-containing layer may further contain a conductive agent.
  • the active material particles may be a positive electrode active material or a negative electrode active material.
  • the active material particles can include a titanium-containing oxide.
  • the titanium-containing oxide include monoclinic niobium titanium composite oxide, orthorhombic titanium-containing composite oxide, lithium titanate having a ramsdellite structure (for example, Li 2 + y Ti 3 O 7 , 0 ⁇ y ⁇ 3) Lithium titanate having a spinel structure (for example, Li 4 + x Ti 5 O 12 , 0 ⁇ x ⁇ 3), monoclinic titanium dioxide (TiO 2 (B)), anatase titanium dioxide, rutile titanium dioxide Hollandite-type titanium composite oxide and the like.
  • the titanium-containing oxide may be one type of compound or a mixture of two or more types of compounds.
  • the titanium-containing oxide may contain Li in advance, but can also contain Li by a charge / discharge reaction or the like. Therefore, the amount of Li contained in the titanium-containing oxide can vary due to charge / discharge reactions and the like.
  • Examples of the monoclinic niobium titanium composite oxide include compounds represented by Li x Ti 1-y M1 y Nb 2 -z M2 z O 7 + ⁇ .
  • M1 is at least one selected from the group consisting of Zr, Si, and Sn.
  • M2 is at least one selected from the group consisting of V, Ta, and Bi.
  • the subscripts in the composition formula are 0 ⁇ x ⁇ 5, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 2, and ⁇ 0.3 ⁇ ⁇ ⁇ 0.3.
  • a specific example of the monoclinic niobium titanium complex oxide is Li x Nb 2 TiO 7 (0 ⁇ x ⁇ 5).
  • M3 is at least one selected from Mg, Fe, Ni, Co, W, Ta, and Mo.
  • the subscripts in the composition formula are 0 ⁇ x ⁇ 5, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 2, and ⁇ 0.3 ⁇ ⁇ ⁇ 0.3.
  • Examples of the tetragonal titanium-containing composite oxide include a compound represented by Li 2 + a M (I) 2 -b Ti 6 -c M (II) d O 14 + ⁇ .
  • M (I) is at least one selected from the group consisting of Sr, Ba, Ca, Mg, Na, Cs, Rb and K.
  • M (II) is at least one selected from the group consisting of Zr, Sn, V, Nb, Ta, Mo, W, Y, Fe, Co, Cr, Mn, Ni, and Al.
  • the subscripts in the composition formula are 0 ⁇ a ⁇ 6, 0 ⁇ b ⁇ 2, 0 ⁇ c ⁇ 6, 0 ⁇ d ⁇ 6, and ⁇ 0.5 ⁇ ⁇ ⁇ 0.5.
  • Specific examples of the tetragonal titanium-containing composite oxide include Li 2 + a Na 2 Ti 6 O 14 (0 ⁇ a ⁇ 6).
  • the titanium-containing oxide includes, for example, single primary particles, secondary particles, Alternatively, it may be included in the active material-containing layer in a mixed form of primary particles and secondary particles.
  • the secondary particles here are aggregates in which a plurality of primary particles are aggregated.
  • the active material may include a carbon-containing layer formed on at least a part of the surface of the titanium-containing oxide particles.
  • the electrode assembly can obtain good conductivity.
  • composite particles in which a carbon-containing layer is formed on the particle surface of a niobium titanium composite oxide as a titanium-containing oxide can be suitably used.
  • the coating amount of the carbon-containing layer is desirably 0.1 to 3 parts by weight with respect to 100 parts by weight of the niobium titanium composite oxide particles.
  • the coating amount by the carbon-containing layer is small, it is difficult to improve the conductive path between the niobium titanium composite oxide particles.
  • the coating amount is large, due to the bulkiness of the carbon-containing layer, the compactability in the pressing process during electrode production is poor, and the electrode density is difficult to increase even when pressing is performed at a high pressing pressure. Therefore, high energy density cannot be achieved.
  • the carbon-containing layer is allowed to contain inevitable impurities such as hydrogen atoms and oxygen atoms. Further, the carbon-containing layer may be layered, granular, or have a mixed form of layered and granular.
  • the crystallinity of the carbon-containing layer can be determined.
  • the G band observed near 1580 cm ⁇ 1 is a peak derived from the graphite structure
  • the D band observed near 1330 cm ⁇ 1 is a peak derived from the defect structure of carbon. It is. G band and D band is due to various factors, from 1580 cm -1 and 1330 cm -1, it is possible that each shifted about ⁇ 50 cm -1.
  • Carbon-containing layer the ratio I G / I D between the peak intensity I D of the peak intensity I G and D bands G band is 0.8 to 1.2 in the Raman chart has a good crystallinity of the graphite Means that.
  • Such a carbon material can have excellent conductivity.
  • the carbon-containing layer can exist in various forms.
  • the carbon-containing layer may cover the entire titanium-containing oxide particle, or may be supported on a part of the surface of the titanium-containing oxide particle.
  • the existence state of the carbon-containing layer can be confirmed by, for example, observation by transmission electron microscope (TEM) observation and mapping by energy dispersive X-ray spectroscopy (EDX) analysis.
  • TEM transmission electron microscope
  • EDX energy dispersive X-ray spectroscopy
  • a micro Raman measurement apparatus As a technique for quantitatively evaluating the crystallinity of the carbon component contained in the carbon-containing layer, a micro Raman measurement apparatus can be used.
  • the micro Raman apparatus for example, Thermo Fisher Scientific ALMEGA can be used.
  • the measurement conditions can be, for example, a wavelength of the measurement light source of 532 nm, a slit size of 25 ⁇ m, a laser intensity of 10%, an exposure time of 5 s, and an integration count of 10 times.
  • Raman spectroscopy can be performed, for example, according to the procedure described below.
  • the battery When evaluating the active material particles incorporated in the battery, first, the battery is completely discharged in order to completely remove the lithium ions. However, a small amount of lithium ions may remain even in a discharged state.
  • the battery is disassembled in a glove box filled with argon, and the electrode is washed with an appropriate solvent. At this time, for example, ethyl methyl carbonate may be used.
  • the active material-containing layer is peeled off from the cleaned electrode, and a sample is collected.
  • Raman spectroscopy measurement is performed under the conditions described above.
  • the presence or absence of Raman activity and the peak position of other components contained in the current collector and the mixture such as the conductive agent and the binder are known.
  • a plurality of peaks are overlapped, it is necessary to separate peaks relating to components other than the active material.
  • the active material-containing layer when the active material (for example, when the carbon-containing layer is coated on the surface of the niobium titanium composite oxide particles) is mixed with a conductive agent, the carbon material contained in the active material and the conductive material It can be difficult to distinguish between carbon materials incorporated as agents.
  • a method for distinguishing between the two for example, a method of dissolving and removing the binder with a solvent and then performing centrifugation to extract an active material having a high specific gravity can be considered. According to such a method, since the active material and the conductive agent can be separated, the carbon material contained in the active material can be subjected to measurement while being contained in the active material. it can.
  • mapping is performed from the spectral component derived from the active material by mapping by microscopic Raman spectroscopy to separate the conductive agent component from the active material component, and then only the Raman spectrum corresponding to the active material component is extracted. It is also possible to take an evaluation method.
  • the active material may contain another active material (hereinafter referred to as a second active material) instead of the titanium-containing oxide.
  • a second active material examples include Li u MeO 2 having a layered structure (Me is at least one selected from the group consisting of Ni, Co, and Mn).
  • lithium nickel composite oxide for example, Li u NiO 2
  • lithium cobalt composite oxide for example, Li u CoO 2
  • lithium nickel cobalt composite oxide for example, Li u Ni 1-s Co s O 2
  • lithium manganese cobalt composite oxide e.g., Li u Mn s Co 1- s O 2
  • lithium-nickel-cobalt-manganese composite oxide e.g., Li u Ni 1-st Co s Mn t O 2
  • lithium nickel cobalt aluminum Complex oxides for example, Li u Ni 1-st Co s Al t O 2
  • lithium manganese complex oxides for example, Li u Ni 1-st Co s Al t O 2
  • lithium manganese complex oxides for example, Li u Ni 1-st Co s Al t O 2
  • lithium manganese complex oxides for example, Li u Ni 1-st Co s Al t O 2
  • lithium manganese complex oxides for example, Li u Ni 1-st Co
  • a spinel type lithium manganese composite oxide such as Li u Mn 2 O 4 or Li u Mn 2 -s Al s O 4 may be used alone, or a plurality of compounds may be used in combination. .
  • Lithium-manganese composite oxides Li u Mn 2 O 4 and Li u Mn 2 -s Al s O 4
  • lithium cobalt composite oxides that have a spinel structure because they can easily achieve high input / output performance and excellent lifetime performance
  • Li u CoO 2 lithium nickel cobalt composite oxide (Li u Ni 1-s Co s O 2), lithium manganese cobalt composite oxide (Li u Mn s Co 1- s O 2), lithium-nickel-cobalt-manganese composite oxides (e.g., Li u Ni 1-st Co s Mn t O 2), or lithium phosphates having an olivine structure (e.g., Li u FePO 4, Li u MnPO 4, Li u Mn 1-s Fe s PO 4 , Li u CoPO 4 ).
  • 0 ⁇ u ⁇ 1, 0 ⁇ s ⁇ 1, and 0 ⁇ t ⁇ 1 are preferable.
  • binder examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine-based rubber, styrene-butadiene rubber (SBR), carboxymethylcellulose (CMC), and acrylic.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • SBR styrene-butadiene rubber
  • CMC carboxymethylcellulose
  • acrylic examples thereof include a resin or a copolymer thereof, polyacrylic acid, and polyacrylonitrile.
  • the binder one of these may be used alone, or a plurality of binders may be used.
  • the active material-containing layer can further contain a conductive agent.
  • a conductive agent include carbonaceous materials such as acetylene black, carbon black, graphite, carbon nanofiber, and carbon nanotube.
  • carbonaceous material one of these may be used alone, or a plurality of carbonaceous materials may be used.
  • the contents of the active material, the conductive agent, and the binder are 70% by mass to 96% by mass, 2% by mass to 28% by mass, and 2%, respectively. % Or more and 28% by mass or less is preferable.
  • the active material-containing layer in which the active material includes the second active material the active material, the conductive agent, and the binder are 80% by mass to 95% by mass, 3% by mass to 18% by mass, and 2% by mass, respectively. It is preferable to blend at a ratio of 17% by mass or less.
  • the thickness of the active material-containing layer (one side) can be 10 ⁇ m or more and 120 ⁇ m or less.
  • the total thickness of the active material containing layer can be 20 ⁇ m or more and 240 ⁇ m or less.
  • the electrode can be produced, for example, by the following method. First, an active material, a conductive agent, and a binder are suspended in a solvent to prepare a slurry. This slurry is applied to one surface or both surfaces of the current collector, and the coating film is dried. Next, the active material-containing layer can be obtained by subjecting the dried coating film to a press.
  • the insulating layer may include an aggregate in which insulating particles are bound together by, for example, a binder.
  • the opening portion of the insulating layer may be either a penetration type or a non-penetration type.
  • the through-type opening can enhance the electrolyte impregnation property of the electrode.
  • the non-penetrating opening can be easily deformed following the volume change of the active material-containing layer without reducing the strength of the insulating layer. It is also possible to provide both the through-type opening and the non-through-type opening in the insulating layer.
  • the shape of the opening is not particularly limited, and can be various shapes such as a circle, an ellipse, a triangle, a quadrangle, a polygon, and an indeterminate shape.
  • the shape of the opening may be only one type or a plurality of types.
  • the opening ratio by an opening part is 3% or more and 30% or less. If the aperture ratio is small, the insulating layer is not flexible enough that the insulating layer cannot be deformed following the volume change of the active material-containing layer, and the insulating layer is easily peeled off from the active material-containing layer. On the other hand, when the aperture ratio is large, there is a concern that the strength of the insulating layer is reduced, or that a separator is required in addition to the insulating layer to insulate the electrode and the counter electrode. A more preferable range is 4% or more and 20% or less. The opening ratio is performed on the electrode assembly taken out from the battery by the following procedure.
  • the battery is discharged at a constant current in a constant temperature bath at 25 ° C. until it reaches 1.5 V at a current value [A] corresponding to 0.2 C. Thereafter, constant voltage discharge is performed at 1.5 V for 1 hour.
  • the battery is disassembled in an argon glove box.
  • the electrode group is taken out from the exterior member in the glove box, and the electrode (for example, the negative electrode) is taken out together with the insulating layer.
  • the electrode connected to the negative electrode terminal of the battery is the negative electrode and the electrode connected to the positive electrode terminal of the battery is the positive electrode.
  • the taken-out electrode and the insulating layer are immersed in ethyl methyl carbonate for 10 minutes, taken out and dried.
  • the electrode length is sufficiently long and the electrode width is 5 cm or more, 10 samples of 5 cm ⁇ 5 cm are randomly cut out, the aperture ratio is determined for 10 sheets, and the average aperture ratio is determined.
  • the electrode length is short and the electrode width is less than 5 cm, 10 samples of 2 cm ⁇ 2 cm are randomly cut out, the aperture ratio is determined for 10 sheets, and the average aperture ratio is determined.
  • the insulating particles contained in the insulating layer may include non-Li conductive inorganic particles, solid electrolyte particles exhibiting Li conductivity, or the like.
  • Examples of inorganic particles that do not exhibit conductivity with respect to Li (lithium) include aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), magnesium oxide (MgO), barium oxide (BaO), and calcium oxide (CaO).
  • Beryllium oxide (BeO) lithium oxide (Li 2 O), sodium oxide (Na 2 O), potassium oxide (K 2 O), zinc oxide (ZnO), antimony oxide (Sb 2 O 5 ), strontium oxide (SrO) ),
  • Metal oxides such as zirconium oxide (ZrO 2 ), indium oxide (In 2 O 3 ), and sulfates such as barium sulfate, arsenic oxide (As 4 O 6 ), boron oxide (B 2 O 3 ), oxidation Particles of one or more compounds selected from the group consisting of silicon (SiO 2 ) can be used.
  • the above-mentioned metal oxide can show the outstanding stability with respect to the nonaqueous electrolyte which
  • Examples of the solid electrolyte exhibiting conductivity with respect to Li include a garnet-type oxide solid electrolyte.
  • An oxide solid electrolyte having a garnet structure has advantages of high reduction resistance and a wide electrochemical window.
  • Examples of the garnet-type oxide solid electrolyte include La 5 + x A x La 3-x M 2 O 12 (A is at least one element selected from the group consisting of Ca, Sr and Ba, M is Nb and / Or Ta, x is preferably in the range of 0.5 or less (including 0).), Li 3 M 2-x L 2 O 12 (M is Nb and / or Ta, L includes Zr, x is 0 0.5 or less (including 0) is preferable), Li 7-3x Al x La 3 Zr 3 O 12 (x is preferably 0.5 or less (including 0)), Li 7 La 3 Zr 2 O 12 is included.
  • Examples of the solid electrolyte having lithium ion conductivity include a lithium phosphate solid electrolyte having a NASICON type structure.
  • Examples of the lithium phosphate solid electrolyte of NASICON type structure include LiM1 2 (PO 4 ) 3 , where M1 is one or more elements selected from the group consisting of Ti, Ge, Sr, Zr, Sn, and Al. included.
  • Preferable examples include Li 1 + x Al x Ge 2-x (PO 4 ) 3 , Li 1 + x Al x Zr 2-x (PO 4 ) 3 , and Li 1 + x Al x Ti 2-x (PO 4 ) 3 .
  • x is preferably in the range of 0 to 0.5.
  • each of the exemplified solid electrolytes has high ionic conductivity and high electrochemical stability.
  • Both a lithium phosphate solid electrolyte having a NASICON type structure and an oxide solid electrolyte having a garnet type structure may be used as the solid electrolyte having lithium ion conductivity.
  • the solid electrolyte one type of compound may be used, or two or more types of compounds may be used in combination.
  • non-Li conductive inorganic particles and solid electrolyte particles can be used in combination as the insulating particles.
  • the form of the insulating particles can be, for example, granular or fibrous.
  • the average particle diameter of the insulating particles can be, for example, 0.3 ⁇ m or more and 5 ⁇ m or less.
  • the content of the insulating particles in the insulating layer is desirably in the range of 80% by weight to 99.9% by weight. Thereby, the insulation of an insulating layer can be made high.
  • the insulating layer can include a binder.
  • the binder that can be included in the insulating layer include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine-based rubber, styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), or a mixture thereof. It is done.
  • the content of the binder in the insulating layer is desirably in the range of 0.01% by weight to 20% by weight.
  • the thickness of the insulating layer can be, for example, 1 ⁇ m or more and 30 ⁇ m or less.
  • the electrode composite can be manufactured, for example, as follows.
  • a slurry containing an active material (hereinafter referred to as slurry I) is applied to at least one of the front and back surfaces of the current collector. Thereafter, the slurry I is dried to form an active material-containing layer.
  • a slurry containing insulating particles (hereinafter referred to as slurry II) is applied to the surface of the active material-containing layer (the surface in contact with the current collector is the back surface) in a desired pattern, for example, stripe coating, and then the slurry II is dried. Thus, an insulating layer provided with an opening is formed. The obtained laminate is pressed to obtain an electrode composite.
  • the slurry I may be dried and then pressed. Further, simultaneously with applying the slurry I to the current collector, the slurry II may be applied in a desired pattern on the slurry I.
  • the coating apparatus 50 includes a tank 52 that stores the slurry I and a tank 53 that stores the slurry II, and is configured to simultaneously apply the slurry I and the slurry II to the substrate.
  • the width orthogonal to the coating direction at the discharge port of the slurry I corresponds to the coating width of the active material-containing layer. Further, the width orthogonal to the coating direction at the discharge port of the slurry I corresponds to the coating width of the first film.
  • the long current collector 2 a before being cut into a predetermined size is conveyed to the slurry discharge port of the coating apparatus 50 by the conveying roller 51. In FIG.
  • the slurry I discharge port 52a is located on the upstream side of the current collector with respect to the slurry II discharge port 53a.
  • the width orthogonal to the coating direction of the slurry I discharge port 52a is narrower than the width orthogonal to the coating direction of the slurry II discharge port 53a.
  • the slurry I is applied from the coating device 50 onto the current collector 2a except for both ends in the short side direction.
  • the slurry II is overcoated so as to protrude from the application area of the slurry I. Since the slurry II is repeatedly applied to the slurry I before the slurry I dries, the slurry II easily follows the surface shape of the slurry I.
  • the dried product is subjected to a roll press and cut into a predetermined size to obtain an electrode composite.
  • the opening of the insulating layer can be provided by applying the slurry II in a desired pattern shape. Or you may provide an opening part by the embossing etc. in the insulating layer on an electrode.
  • the electrode assembly according to the first embodiment includes an insulating layer that covers at least part of the surface of the active material-containing layer, has an opening, and includes insulating particles. Therefore, the life performance of the battery including the electrode composite and the electrode composite can be improved.
  • the battery according to the embodiment includes a negative electrode and a positive electrode.
  • the electrode composite according to the embodiment is used for at least one of the negative electrode and the positive electrode.
  • the battery according to the embodiment can be, for example, a lithium ion secondary battery or a lithium ion nonaqueous electrolyte secondary battery.
  • the battery may further include a separator disposed between the negative electrode and the positive electrode.
  • a negative electrode, a positive electrode, and a separator can comprise an electrode group.
  • the electrolyte can be held on the electrode group.
  • the positive electrode active material-containing layer and the negative electrode active material-containing layer can face each other via an insulating layer and a separator. Since the insulating layer is provided in the active material-containing layer, necessary insulating properties can be ensured even if the thickness of the separator is reduced.
  • the battery can further include an exterior member that accommodates the electrode group and the electrolyte, a negative electrode terminal electrically connected to the negative electrode, and a positive electrode terminal electrically connected to the positive electrode.
  • the negative electrode, the positive electrode, the separator, the electrolyte, the exterior member, the negative electrode terminal, and the positive electrode terminal will be described in detail.
  • the negative electrode may be an electrode composite according to an embodiment using an active material containing a titanium-containing oxide.
  • the positive electrode can be the electrode composite according to the embodiment using the active material containing the second active material.
  • the separator is not particularly limited as long as it has insulating properties, but a porous film or a nonwoven fabric made of a polymer such as polyolefin, cellulose, polyethylene terephthalate, and vinylon can be used.
  • a porous film or a nonwoven fabric made of a polymer such as polyolefin, cellulose, polyethylene terephthalate, and vinylon can be used.
  • One type of separator material may be used, or two or more types may be used in combination.
  • the separator preferably contains pores having a diameter of 10 ⁇ m or more and 100 ⁇ m or less. Moreover, it is preferable that the thickness of a separator is 2 micrometers or more and 30 micrometers or less.
  • the electrolyte examples include non-aqueous electrolytes.
  • the non-aqueous electrolyte includes, for example, a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • the non-aqueous electrolyte may contain a polymer.
  • non-aqueous solvents examples include propylene carbonate (PC), ethylene carbonate (EC), 1,2-dimethoxyethane (DME), ⁇ -butyrolactone (GBL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeHF) 1,3-dioxolane, sulfolane, acetonitrile (AN), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (MEC) and dipropyl carbonate (DPC).
  • PC propylene carbonate
  • EC ethylene carbonate
  • DME 1,2-dimethoxyethane
  • GBL ⁇ -butyrolactone
  • THF tetrahydrofuran
  • 2-MeHF 2-methyltetrahydrofuran
  • 1,3-dioxolane examples include sulfolane, sulfolane, acetonitrile (AN), diethyl carbonate
  • the electrolyte salt is, for example, an alkali salt, preferably a lithium salt.
  • the electrolyte salt include LiPF 6 , LiBF 4 , Li (CF 3 SO 2 ) 2 N (bistrifluoromethanesulfonylimide lithium; commonly known as LiTFSI), LiCF 3 SO 3 (commonly known as LiTFS), Li (C 2 F 5 SO 2 ) 2 N (bis pentafluoroethanesulfonyl amide lithium; called LiBETI), LiClO 4, LiAsF 6 , LiSbF 6, bisoxalato Lato lithium borate (LiB (C 2 O 4) 2 ( known as LiBOB)), difluoro (oxalato) borate Lithium oxide (LiF 2 BC 2 O 4 ), difluoro (trifluoro-2-oxide-2-trifluoro-methylpropionate (2-)-0,0) lithium borate (LiBF 2 (OCOOC (CF 3
  • electrolyte salts may be used alone or in combination of two or more.
  • LiPF 6 LiBF 4 , lithium bisoxalatoborate (LiB (C 2 O 4 ) 2 (commonly called LiBOB)), lithium difluoro (oxalato) borate (LiF 2 BC 2 O 4 ), difluoro (trifluoro-2 -Oxide-2-trifluoro-methylpropionate (2-)-0,0) lithium borate (LiBF 2 (OCOOC (CF 3 ) 2 ) (commonly known as LiBF 2 (HHIB))) and lithium difluorophosphate (LiPO At least one selected from the group consisting of 2 F 2 ) is preferred.
  • the electrolyte salt concentration is preferably in the range of 0.5M to 3.0M. Thereby, the performance when a high load current is passed can be improved.
  • the non-aqueous electrolyte may contain other components.
  • Other components are not particularly limited, for example, vinylene carbonate (VC), fluoro vinylene carbonate, methyl vinylene carbonate, fluoromethyl vinylene carbonate, ethyl vinylene carbonate, propyl vinylene carbonate, butyl vinylene carbonate, dimethyl vinylene carbonate, Examples thereof include diethyl vinylene carbonate, dipropyl vinylene carbonate, vinylene acetate (VA), vinylene butyrate, vinylene hexanate, vinylene crotonate, catechol carbonate, propane sultone and butane sultone.
  • VC vinylene carbonate
  • FVC fluoro vinylene carbonate
  • methyl vinylene carbonate fluoromethyl vinylene carbonate
  • ethyl vinylene carbonate fluoromethyl vinylene carbonate
  • ethyl vinylene carbonate propyl vinylene carbon
  • the negative electrode terminal and the positive electrode terminal can function as a conductor for electrons to move between the negative electrode and the external terminal by being partly connected to a part of the negative electrode.
  • the negative electrode terminal can be connected to, for example, a negative electrode current collector, particularly a negative electrode tab.
  • the positive electrode terminal can function as a conductor for electrons to move between the positive electrode and an external circuit by being electrically connected to a part of the positive electrode.
  • the positive electrode terminal can be connected to, for example, a positive electrode current collector, particularly a positive electrode tab.
  • the negative electrode terminal and the positive electrode terminal are preferably formed from a material having high electrical conductivity. When connecting to the current collector, these terminals are preferably made of the same material as the current collector in order to reduce contact resistance.
  • Exterior Member As the exterior member, for example, a metal container or a laminate film container can be used, but it is not particularly limited.
  • a metal container As the exterior member, a nonaqueous electrolyte battery excellent in impact resistance and long-term reliability can be realized.
  • a laminate film container As the exterior member, a non-aqueous electrolyte battery excellent in corrosion resistance can be realized, and the non-aqueous electrolyte battery can be reduced in weight.
  • the metal container for example, one having a plate thickness in the range of 0.2 mm to 5 mm can be used.
  • the plate thickness of the metal container is more preferably 0.5 mm or less.
  • the metal container preferably contains at least one metal element selected from the group consisting of Fe, Ni, Cu, Sn, and Al.
  • the metal container can be made of, for example, aluminum or an aluminum alloy.
  • the aluminum alloy is preferably an alloy containing elements such as magnesium, zinc, and silicon.
  • the alloy contains a transition metal such as iron, copper, nickel, or chromium, the content is preferably 1% by weight or less.
  • the thickness of the laminated film container is, for example, in the range of 0.1 mm to 2 mm.
  • the thickness of the laminate film is more preferably 0.2 mm or less.
  • the laminate film is composed of, for example, a multilayer film including a metal layer and a resin layer sandwiching the metal layer.
  • the metal layer preferably contains a metal including at least one selected from the group consisting of Fe, Ni, Cu, Sn, and Al.
  • the metal layer is preferably an aluminum foil or an aluminum alloy foil for weight reduction.
  • a polymer material such as polypropylene (PP), polyethylene (PE), nylon, and polyethylene terephthalate (PET) can be used.
  • PP polypropylene
  • PE polyethylene
  • nylon polyethylene terephthalate
  • the laminate film can be formed into the shape of an exterior member by sealing by heat sealing.
  • Examples of the shape of the exterior member include a flat type (thin type), a square type, a cylindrical type, a coin type, and a button type.
  • An exterior member can take various dimensions according to a use. For example, when a nonaqueous electrolyte battery is used for a portable electronic device, the exterior member can be made small in accordance with the size of the electronic device to be mounted. Further, when the nonaqueous electrolyte battery is loaded on a two-wheel or four-wheel automobile, a container for a large battery can be used.
  • FIG. 1 is a partially cutaway perspective view showing an example of a battery according to an embodiment.
  • FIG. 2 is an enlarged cross-sectional view of part A of the battery shown in FIG.
  • the battery 100 shown in FIGS. 1 and 2 includes a flat electrode group 1.
  • the flat electrode group 1 includes a negative electrode 2, a positive electrode 3, and a composite layer 4.
  • the composite layer 4 includes an insulating layer 8 and a separator 9.
  • the electrode group 1 has a structure in which a negative electrode 2 and a positive electrode 3 are wound in a spiral shape so as to have a flat shape with a composite layer 4 interposed therebetween.
  • the wound electrode group will be described here, the electrode group may be a stacked electrode group in which a plurality of negative electrodes 2, composite layers 4, and positive electrodes 3 are stacked.
  • the negative electrode 2 includes a negative electrode current collector 2a and a negative electrode active material-containing layer 2b supported on the negative electrode current collector 2a.
  • the positive electrode 3 includes a positive electrode current collector 3a and a positive electrode active material-containing layer 3b supported on the positive electrode current collector 3a.
  • the negative electrode active material-containing layer 2b has an insulating layer 8 bonded to the surface facing the positive electrode active material-containing layer 3b.
  • a separator 9 is interposed between the positive electrode active material-containing layer 3 b and the insulating layer 8. The separator 9 is in contact with the insulating layer 8. The separator 9 may or may not be joined to the insulating layer 8.
  • a strip-like negative electrode terminal 5 is electrically connected to the negative electrode 2. More specifically, the negative electrode terminal 5 is connected to the negative electrode current collector 2a.
  • a strip-like positive electrode terminal 6 is electrically connected to the positive electrode 3. More specifically, the positive electrode terminal 6 is connected to the positive electrode current collector 3a.
  • the battery 100 further includes an outer packaging container 7 made of a laminate film as a container. That is, the battery 100 includes an exterior member composed of an exterior container 7 made of a laminate film.
  • the electrode group 1 is accommodated in an outer packaging container 7 made of a laminate film. However, the end portions of the negative electrode terminal 5 and the positive electrode terminal 6 extend from the outer container 7.
  • a non-aqueous electrolyte (not shown) is accommodated in the outer packaging container 7 made of a laminate film. The nonaqueous electrolyte is impregnated in the electrode group 1.
  • the outer casing 7 is heat-sealed at the peripheral edge, thereby sealing the electrode group 1 and the non-aqueous electrolyte.
  • the electrode composite may include a current collecting tab.
  • FIGS. The electrode composite includes the negative electrode 2 and the insulating layer 8.
  • the negative electrode 2 includes a negative electrode current collector 2a, a negative electrode active material-containing layer 2b, and a negative electrode current collector tab 2c.
  • the negative electrode current collector 2a is a conductive sheet having a front surface and a back surface. One main surface of the negative electrode current collector 2a is the front surface, and the other main surface is the back surface.
  • the negative electrode current collecting tab 2c extends from one side (for example, long side, short side) of the negative electrode current collector 2a in a direction perpendicular to the side.
  • the negative electrode active material-containing layer 2b is held on each of the front surface and the back surface of the negative electrode current collector 2a excluding the part that becomes the negative electrode current collection tab 2c.
  • the insulating layer 8 includes a main surface of each of the negative electrode active material-containing layers 2b, a side surface 41 adjacent to the negative electrode current collecting tab 2c among the side surfaces of the negative electrode active material containing layer 2b, and a main surface of the negative electrode current collecting tab 2c.
  • the edge part 42 located adjacent to the negative electrode active material content layer 2b is coat
  • the insulating layer 8 may cover only one main surface of the negative electrode active material-containing layer 2b. Further, the insulating layer 8 may be coated on all four side surfaces of the negative electrode active material-containing layer 2b.
  • the insulating layer 8 is provided with a plurality of openings 8a to 8e as shown in FIG.
  • the openings 8a-8e can be through holes, grooves, or both through holes and grooves.
  • the opening 8a is a circular example
  • the opening 8b is an ellipse
  • the opening 8c is a triangle
  • the opening 8d is a quadrangle
  • the opening 8e is a slit
  • the opening 8f is a corrugated shape. It is an example.
  • the shape of the opening may be unified or may be composed of a plurality of patterns. Further, the arrangement of the openings may be regular or random.
  • FIG. 5 shows an example of an electrode group in which the electrode composite shown in FIG. 3 and a positive electrode are stacked.
  • the positive electrode 3 includes a positive electrode current collector 3a, a positive electrode active material-containing layer 3b, and a positive electrode current collector tab 3c.
  • the positive electrode current collector 3a is a conductive sheet having a front surface and a back surface. One main surface of the positive electrode current collector 3a is the front surface, and the other main surface is the back surface.
  • the positive electrode current collector tab 3c extends from one side (for example, long side, short side) of the positive electrode current collector 3a in a direction perpendicular to the side.
  • the positive electrode active material-containing layer 3b is held on each of the front surface and the back surface of the positive electrode current collector 3a excluding the portion that becomes the positive electrode current collection tab 3c.
  • the separator 9 is laminated on the side facing the positive electrode active material-containing layer 3b.
  • the main surface that does not face the positive electrode active material-containing layer 3b may not be covered with the insulating layer 8.
  • the shape of the negative electrode current collecting tab is not limited to the band shape illustrated in FIG.
  • the negative electrode active material-containing layer 2b is not provided at the end parallel to one side (for example, the long side or the short side) of the negative electrode current collector 2a, and this end is used as the negative electrode current collecting tab 2c. It may be used.
  • the insulating layer 8 includes the respective main surfaces of the negative electrode active material-containing layer 2b, side surfaces 41 adjacent to the negative electrode current collecting tab 2c among the side surfaces of the negative electrode active material containing layer 2b, and the negative electrode current collecting tab 2c. The end 42 located next to the negative electrode active material-containing layer 2b in the main surface is covered.
  • FIG. 9 is a partially cutaway perspective view showing another example of the battery according to the embodiment.
  • the battery 200 shown in FIG. 9 is different from the battery 100 shown in FIGS. 1 and 2 in that the exterior member is composed of a metal container 17a and a sealing plate 17b.
  • the flat electrode group 11 includes a negative electrode, a positive electrode, and a composite layer, similarly to the electrode group 1 in the battery 100 shown in FIGS. 1 and 2.
  • the electrode group 11 has the same structure as the electrode group 1. However, in the electrode group 11, in place of the negative electrode terminal 5 and the positive electrode terminal 6, a negative electrode tab 15a and a positive electrode tab 16a are connected to the negative electrode and the positive electrode, respectively, as described later.
  • such an electrode group 11 is accommodated in a metal container 17a.
  • the metal container 17a further stores an electrolyte (for example, an electrolytic solution) (not shown).
  • the metal container 17a is sealed with a metal sealing plate 17b.
  • the metal container 17a and the sealing plate 17b constitute, for example, an outer can as an outer member.
  • the negative electrode tab 15 a has one end electrically connected to the negative electrode current collector and the other end electrically connected to the negative electrode terminal 15.
  • One end of the positive electrode tab 16a is electrically connected to the positive electrode current collector, and the other end is electrically connected to the positive electrode terminal 16 fixed to the sealing plate 17b.
  • the positive terminal 16 is fixed to the sealing plate 17b via an insulating member 17c.
  • the positive electrode terminal 16 and the sealing plate 17b are electrically insulated by an insulating member 17c.
  • the battery according to the second embodiment includes the electrode assembly according to the first embodiment. Therefore, the battery according to the second embodiment can achieve excellent input / output performance and cycle life performance.
  • a battery pack is provided.
  • This battery pack includes the battery according to the second embodiment.
  • the battery pack according to the third embodiment can also include a plurality of batteries.
  • the plurality of batteries can be electrically connected in series or electrically connected in parallel.
  • a plurality of batteries can be connected in a combination of series and parallel.
  • the battery pack according to the third embodiment can include, for example, five batteries. These batteries can be connected in series. Moreover, the battery connected in series can comprise an assembled battery. That is, the battery pack according to the third embodiment can include an assembled battery.
  • the battery pack according to the third embodiment can include a plurality of assembled batteries.
  • the plurality of assembled batteries can be connected in series, parallel, or a combination of series and parallel.
  • FIG. 10 is an exploded perspective view showing an example of a battery pack according to the third embodiment.
  • 11 is a block diagram showing an example of an electric circuit of the battery pack shown in FIG.
  • the battery pack 20 shown in FIGS. 10 and 11 includes a plurality of unit cells 21.
  • the unit cell 21 may be an example flat battery 100 according to the embodiment described with reference to FIG.
  • the plurality of unit cells 21 are laminated so that the negative electrode terminal 5 and the positive electrode terminal 6 extending to the outside are aligned in the same direction, and are fastened with an adhesive tape 22 to constitute an assembled battery 23. These unit cells 21 are electrically connected to each other in series as shown in FIG.
  • the printed wiring board 24 is disposed so as to face the side surface where the negative electrode terminal 5 and the positive electrode terminal 6 of the unit cell 21 extend. As shown in FIG. 11, a thermistor 25, a protection circuit 26, and a terminal 27 for energizing external equipment are mounted on the printed wiring board 24. Note that an insulating plate (not shown) is attached to the printed wiring board 24 on the surface facing the assembled battery 23 in order to avoid unnecessary connection with the wiring of the assembled battery 23.
  • the positive electrode side lead 28 is connected to the positive electrode terminal 6 located in the lowermost layer of the assembled battery 23, and the tip thereof is inserted into the positive electrode side connector 29 of the printed wiring board 24 and electrically connected thereto.
  • the negative electrode side lead 30 is connected to the negative electrode terminal 5 located in the uppermost layer of the assembled battery 23, and the tip thereof is inserted into the negative electrode side connector 31 of the printed wiring board 24 and electrically connected thereto.
  • These connectors 29 and 31 are connected to the protection circuit 26 through wirings 32 and 33 formed on the printed wiring board 24.
  • the thermistor 25 detects the temperature of the unit cell 21, and the detection signal is transmitted to the protection circuit 26.
  • the protection circuit 26 can cut off the plus side wiring 34a and the minus side wiring 34b between the protection circuit 26 and the energization terminal 27 to the external device under a predetermined condition.
  • An example of the predetermined condition is when the temperature detected by the thermistor 25 is equal to or higher than a predetermined temperature.
  • Another example of the predetermined condition is when overcharge, overdischarge, overcurrent, or the like of the unit cell 21 is detected. This detection of overcharge or the like is performed for each individual cell 21 or the entire assembled battery 23. When detecting individual cells 21, the battery voltage may be detected, or the positive electrode potential or the negative electrode potential may be detected.
  • a lithium electrode used as a reference electrode is inserted into each unit cell 21.
  • a wiring 35 for voltage detection is connected to each unit cell 21. A detection signal is transmitted to the protection circuit 26 through these wirings 35.
  • Protective sheets 36 made of rubber or resin are disposed on the three side surfaces of the assembled battery 23 excluding the side surfaces from which the positive electrode terminal 6 and the negative electrode terminal 5 protrude.
  • the assembled battery 23 is stored in a storage container 37 together with each protective sheet 36 and the printed wiring board 24. That is, the protective sheet 36 is disposed on each of the inner side surface in the long side direction and one inner side surface in the short side direction of the storage container 37, and the printed wiring board 24 is disposed on the other inner side surface in the short side direction.
  • the assembled battery 23 is located in a space surrounded by the protective sheet 36 and the printed wiring board 24.
  • the lid 38 is attached to the upper surface of the storage container 37.
  • a heat shrink tape may be used for fixing the assembled battery 23.
  • protective sheets are arranged on both side surfaces of the assembled battery, the heat shrinkable tape is circulated, and then the heat shrinkable tape is heat shrunk to bind the assembled battery.
  • the 10 and 11 show a configuration in which the unit cells 21 are connected in series, but they may be connected in parallel in order to increase the battery capacity. Further, the assembled battery packs can be connected in series and / or in parallel.
  • the aspect of the battery pack according to the third embodiment is appropriately changed depending on the application.
  • a battery pack according to the third embodiment a battery pack in which cycle performance with high current performance is desired is preferable.
  • Specific applications include power supplies for digital cameras, and in-vehicle use such as two-wheel to four-wheel hybrid electric vehicles, two-wheel to four-wheel electric vehicles, and assist bicycles.
  • in-vehicle use is particularly suitable.
  • the battery pack according to the third embodiment includes the battery according to the second embodiment. Therefore, the battery pack according to the third embodiment can realize excellent input / output performance and cycle life performance.
  • Example 1 Carbon coating treatment
  • monoclinic TiNb 2 O 7 particles having a specific surface area of 10 m 2 / g by BET method using N 2 adsorption were prepared.
  • TiNb 2 O 7 contained a lot of secondary particles. 95% by weight of TiNb 2 O 7 particles and 5% by weight of carboxymethyl cellulose (CMC) were mixed, ethanol was added thereto, and the mixture was pulverized and uniformly mixed using a ball mill. The mixed particles are subjected to a heat treatment for 1 hour at a temperature of 700 ° C.
  • CMC carboxymethyl cellulose
  • the carbon-coated negative electrode Active material particles were obtained.
  • the carbon content in the carbon-coated negative electrode active material particles was 1% by weight.
  • the average primary particle diameter of this negative electrode active material particle was 1 micrometer, and the average secondary particle diameter was 10 micrometers.
  • NMP n-methylpyrrolidone
  • a negative electrode slurry was applied on both sides of an aluminum foil having a thickness of 15 ⁇ m with a basis weight of 80 g / m 2 and dried to form a negative electrode active material-containing layer.
  • the negative electrode active material content layer unsupported part was provided in one long side of the collector, and this part was made into the negative electrode current collection tab.
  • the thickness of each negative electrode active material content layer was 32 micrometers.
  • insulating layer slurry Al 2 O 3 particles having an average particle diameter of 1 ⁇ m were prepared as insulating particles. Insulating particles and PVdF were mixed at a weight ratio of 100: 4 to obtain a mixture. Next, the obtained mixture was dispersed in NMP to prepare an insulating layer slurry.
  • the surface (main surface) of the negative electrode active material-containing layer is covered with a mask having a pattern shape, and after spray-coating alumina-containing slurry thereon, the insulating layer is formed by drying to form the structure shown in FIG. An electrode composite was obtained.
  • the insulating layer contained 98% by weight of insulating particles and 2% by weight of a binder.
  • the insulating layer was provided with a plurality of circular through holes. Table 1 shows the thickness and aperture ratio of the insulating layer.
  • LiNi 0.33 Co 0.33 Mn 0.33 O 2 particles were prepared as a positive electrode active material, carbon black as a conductive agent, and polyvinylidene fluoride (PVdF) as a binder. These were mixed at a weight ratio of 90: 5: 5 to obtain a mixture. Next, the obtained mixture was dispersed in an n-methylpyrrolidone (NMP) solvent to prepare a positive electrode slurry. The positive electrode slurry was applied to both sides of an aluminum foil having a thickness of 15 ⁇ m and dried. Then, the roll press was performed and it cut
  • NMP n-methylpyrrolidone
  • each positive electrode active material-containing layer was 20 ⁇ m. Note that a portion not carrying the positive electrode active material-containing layer was provided on one long side of the current collector, and this portion was used as a positive electrode current collecting tab.
  • the produced electrode group was inserted into a metal can made of an aluminum alloy (Al purity 99%) having a thickness of 0.25 mm.
  • a liquid non-aqueous electrolyte was injected into the electrode group in the container, and the container was sealed to produce a rectangular secondary battery having a thickness of 13 mm, a width of 62 mm, and a height of 96 mm.
  • Example 2 ⁇ Production of negative electrode> No carbon coating
  • TiNb 2 O 7 particles having a monoclinic structure with a specific surface area of 10 m 2 / g by BET method by N 2 adsorption were prepared. TiNb 2 O 7 particles contained many primary particles. The average primary particle diameter of TiNb 2 O 7 was 0.9 ⁇ m.
  • the TiNb 2 O 7 particles, carbon black powder as a conductive agent, and polyvinylidene fluoride as a binder were prepared. These were mixed at a weight ratio of 95: 3: 2 to obtain a mixture. The obtained mixture was dispersed in an n-methylpyrrolidone (NMP) solvent and stirred using a ball mill at a rotation speed of 1000 rpm and a stirring time of 2 hours to prepare a negative electrode slurry.
  • NMP n-methylpyrrolidone
  • a negative electrode slurry was applied on both sides of an aluminum foil having a thickness of 15 ⁇ m with a basis weight of 80 g / m 2 and dried to form a negative electrode active material-containing layer.
  • the negative electrode active material content layer unsupported part was provided in one long side of the collector, and this part was made into the negative electrode current collection tab.
  • the thickness of each negative electrode active material-containing layer was 32 ⁇ m.
  • the surface (main surface) of the negative electrode active material-containing layer is covered with a mask having a pattern shape, and after spray-coating alumina-containing slurry thereon, the insulating layer is formed by drying to form the structure shown in FIG. An electrode composite was obtained.
  • the insulating layer was provided with a plurality of circular through holes. Table 1 shows the thickness and aperture ratio of the insulating layer.
  • a square secondary battery was produced in the same manner as in Example 1 except that the obtained electrode assembly was used.
  • Example 3 ⁇ Preparation of insulating layer slurry>
  • the insulating particles Li 7 La 3 Zr 2 O 12 solid electrolyte particles having an average particle diameter of 1 ⁇ m were prepared.
  • the solid electrolyte particles and carboxymethyl cellulose (CMC) as a binder were mixed at a ratio of 95% by weight: 5% by weight. Subsequently, these were dispersed in an aqueous solvent to prepare a solid electrolyte slurry.
  • CMC carboxymethyl cellulose
  • the surface (main surface) of the negative electrode active material-containing layer having the same composition as in Example 1 is covered with a mask having a pattern shape, and a solid electrolyte slurry is spray-coated thereon, followed by drying to form an insulating layer.
  • an electrode composite having the structure shown in FIG. 6 was obtained.
  • the insulating layer is provided with a plurality of slit-shaped through holes. Table 1 shows the thickness and aperture ratio of the insulating layer.
  • Example 4 The surface (main surface) of the negative electrode active material-containing layer having the same composition as that of Example 2 is covered with a mask having a pattern shape, and a solid electrolyte slurry having the same composition as that of Example 3 is spray-coated thereon, followed by drying. As a result, an insulating layer was formed to obtain an electrode composite having the structure shown in FIG.
  • the insulating layer is provided with a plurality of slit-shaped through holes. Table 1 shows the thickness and aperture ratio of the insulating layer.
  • Example 5 ⁇ Production of negative electrode> A tetragonal Li 2 Na 1.6 Ti 5.6 Nb 0.4 O 14 negative electrode active material particle having a carbon content of 1 wt% was prepared. The average primary particle size was 1 ⁇ m, and the average secondary particle size was 10 ⁇ m. 95: 3: 2 by weight of carbon-coated Li 2 Na 1.6 Ti 5.6 Nb 0.4 O 14 negative electrode active material particles, carbon black powder as a conductive agent, and PVdF as a binder. The resulting mixture was dispersed in an n-methylpyrrolidone (NMP) solvent and stirred using a ball mill at a rotation speed of 1000 rpm and a stirring time of 2 hours to prepare a slurry.
  • NMP n-methylpyrrolidone
  • a negative electrode slurry was applied on both sides of an aluminum foil having a thickness of 15 ⁇ m with a basis weight of 110 g / m 2 and dried to form a negative electrode active material-containing layer.
  • the negative electrode active material content layer unsupported part was provided in one long side of the collector, and this part was made into the negative electrode current collection tab.
  • the thickness of each negative electrode active material-containing layer was 46 ⁇ m.
  • the surface (main surface) of the negative electrode active material-containing layer is covered with a mask having a pattern shape, and an alumina-containing slurry having the same composition as that of Example 1 is spray coated thereon, followed by drying to form an insulating layer.
  • an electrode composite having the structure shown in FIG. 6 was obtained.
  • Table 1 shows the shape of the through hole provided in the insulating layer, the thickness of the insulating layer, and the aperture ratio.
  • a square secondary battery was produced in the same manner as in Example 1 except that the obtained electrode assembly was used.
  • Example 6 Li 2 Na 1.6 Ti 5.6 Nb 0.4 O 14 particles having a tetragonal structure with a specific surface area of 10 m 2 / g by BET method using N 2 adsorption were prepared.
  • the Li 2 Na 1.6 Ti 5.6 Nb 0.4 O 14 particles contained many primary particles.
  • the average primary particle diameter of the Li 2 Na 1.6 Ti 5.6 Nb 0.4 O 14 particles was 0.9 ⁇ m.
  • the Li 2 Na 1.6 Ti 5.6 Nb 0.4 O 14 particles, carbon black powder as a conductive agent, and polyvinylidene fluoride as a binder were prepared. These were mixed at a weight ratio of 95: 3: 2 to obtain a mixture.
  • the obtained mixture was dispersed in an n-methylpyrrolidone (NMP) solvent and stirred using a ball mill at a rotational speed of 1000 rpm and a stirring time of 2 hours to prepare a slurry.
  • NMP n-methylpyrrolidone
  • a negative electrode slurry was applied on both sides of an aluminum foil having a thickness of 15 ⁇ m with a basis weight of 110 g / m 2 and dried to form a negative electrode active material-containing layer.
  • the negative electrode active material content layer unsupported part was provided in one long side of the collector, and this part was made into the negative electrode current collection tab.
  • the thickness of each negative electrode active material-containing layer was 46 ⁇ m.
  • the surface (main surface) of the negative electrode active material-containing layer is covered with a mask having a pattern shape, and an alumina-containing slurry having the same composition as that of Example 1 is spray coated thereon, followed by drying to form an insulating layer.
  • an electrode composite having the structure shown in FIG. 6 was obtained.
  • Table 1 shows the shape of the through hole provided in the insulating layer, the thickness of the insulating layer, and the aperture ratio.
  • a square secondary battery was produced in the same manner as in Example 1 except that the obtained electrode assembly was used.
  • Example 7 ⁇ Production of negative electrode>
  • As negative electrode active material particles Li 4 Ti 5 O 12 particles having a spinel structure with a specific surface area of 12 m 2 / g by BET method using N 2 adsorption were prepared. Li 4 Ti 5 O 12 particles contained many primary particles. The average primary particle diameter of Li 4 Ti 5 O 12 was 0.9 ⁇ m.
  • the Li 4 Ti 5 O 12 particles, carbon black powder as a conductive agent, and polyvinylidene fluoride as a binder were prepared. These were mixed at a weight ratio of 95: 3: 2 to obtain a mixture. The obtained mixture was dispersed in an n-methylpyrrolidone (NMP) solvent and stirred using a ball mill at a rotation speed of 1000 rpm and a stirring time of 2 hours to prepare a negative electrode slurry.
  • NMP n-methylpyrrolidone
  • a negative electrode slurry was applied on both sides of an aluminum foil having a thickness of 15 ⁇ m with a basis weight of 80 g / m 2 and dried to form a negative electrode active material-containing layer.
  • the negative electrode active material content layer unsupported part was provided in one long side of the collector, and this part was made into the negative electrode current collection tab.
  • the thickness of each negative electrode active material-containing layer was 35 ⁇ m.
  • the surface (main surface) of the negative electrode active material-containing layer is covered with a mask having a pattern shape, and an alumina-containing slurry having the same composition as that of Example 1 is spray coated thereon, followed by drying to form an insulating layer.
  • an electrode composite having the structure shown in FIG. 6 was obtained.
  • Table 2 shows the shape of the through hole provided in the insulating layer, the thickness of the insulating layer, and the aperture ratio.
  • a square secondary battery was produced in the same manner as in Example 1 except that the obtained electrode assembly was used.
  • Example 1 A secondary battery was fabricated in the same manner as in Example 1 except that the insulating layer was not provided.
  • Example 2 A secondary battery was fabricated in the same manner as in Example 1 except that no opening was provided in the insulating layer.
  • Example 3 A secondary battery was fabricated in the same manner as in Example 7 except that the insulating layer was not provided.
  • Tables 1 and 2 show the results of displaying the discharge capacity after the cycle test, assuming the discharge capacity before the cycle test as 100%, as the charge / discharge cycle capacity maintenance rate.
  • an electrode assembly is provided. Since the electrode composite includes an insulating layer that covers at least part of the surface of the active material-containing layer, has an opening, and includes insulating particles, cycle performance and input / output performance can be improved.

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Abstract

Un mode de réalisation de la présente invention concerne un complexe d'électrode qui comprend une électrode et une couche isolante. L'électrode comprend une couche contenant un matériau actif. La couche isolante recouvre au moins une partie de la surface de la couche contenant un matériau actif. La couche isolante a également une ouverture et comprend des particules isolantes.
PCT/JP2018/013925 2018-03-30 2018-03-30 Complexe d'électrode, batterie et bloc-batterie WO2019187132A1 (fr)

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PCT/JP2018/013925 WO2019187132A1 (fr) 2018-03-30 2018-03-30 Complexe d'électrode, batterie et bloc-batterie
JP2020508897A JP7068439B2 (ja) 2018-03-30 2018-03-30 電極複合体、電池及び電池パック

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PCT/JP2018/013925 WO2019187132A1 (fr) 2018-03-30 2018-03-30 Complexe d'électrode, batterie et bloc-batterie

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JP2007027100A (ja) * 2005-06-14 2007-02-01 Matsushita Electric Ind Co Ltd 非水電解質二次電池
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113270276A (zh) * 2021-05-19 2021-08-17 河北科技大学 一种超级电容器电极的制备工艺

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