WO2013065478A1 - Batterie secondaire aux ions-lithium et son procédé de fabrication - Google Patents

Batterie secondaire aux ions-lithium et son procédé de fabrication Download PDF

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WO2013065478A1
WO2013065478A1 PCT/JP2012/076753 JP2012076753W WO2013065478A1 WO 2013065478 A1 WO2013065478 A1 WO 2013065478A1 JP 2012076753 W JP2012076753 W JP 2012076753W WO 2013065478 A1 WO2013065478 A1 WO 2013065478A1
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Prior art keywords
electrode
foil
binder
lithium ion
solvent
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PCT/JP2012/076753
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English (en)
Japanese (ja)
Inventor
昌作 石原
菊池　廣
桂司 佐藤
千恵美 窪田
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株式会社日立製作所
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Priority claimed from JP2011238186A external-priority patent/JP5723746B2/ja
Priority claimed from JP2012007632A external-priority patent/JP2013149407A/ja
Application filed by 株式会社日立製作所 filed Critical 株式会社日立製作所
Priority to CN201280052544.1A priority Critical patent/CN104025340A/zh
Publication of WO2013065478A1 publication Critical patent/WO2013065478A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/049—Manufacturing of an active layer by chemical means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a lithium ion secondary battery and a manufacturing method thereof.
  • hybrid electric vehicles that use an engine and a motor as a power source and electric vehicles that use only a motor as a power source have been developed and commercialized.
  • the development of fuel cell hybrid vehicles using fuel cells instead of engines has also become active.
  • a secondary battery capable of repeatedly charging and discharging electricity is an essential technology as an energy source for the hybrid electric vehicle and the electric vehicle.
  • lithium ion secondary batteries are powerful batteries because of their high operating voltage and easy to obtain high output, and are increasingly important as power sources for hybrid and electric vehicles.
  • the importance in applications such as photovoltaic power generation and power storage for effective use of nighttime power has been increasing, and higher capacities have been demanded.
  • Patent Document 1 As a general manufacturing method of a lithium ion secondary battery, as shown in Patent Document 1, an electrode film slurry is applied to a collector foil and dried to manufacture an electrode film.
  • the solid members constituting the battery are an electrode film, a current collector foil, and a separator, but as the electrode film becomes thicker, the volume ratio of the electrode film to the current collector foil and the separator increases, and the electrode film volume occupies the battery volume. In other words, the battery capacity can be increased by increasing the active material ratio.
  • the binder in the electrode film is unevenly distributed in the thickness direction of the electrode film, and the binder is not present on the electrode film surface side compared to the electrode film collector foil side.
  • the degree of non-uniform distribution becomes more remarkable as the thick electrode film is made thicker.
  • the electrode film thickness is 100 ⁇ m
  • the binder amount on the electrode film surface side is about twice that of the current collector foil
  • the electrode film thickness is 200 ⁇ m.
  • the electrode film thickness is 500 ⁇ m, it is about 4 times. Since the required amount of the binder is determined from the adhesion strength of the electrode film to the current collector foil, the amount of the binder added must be increased when the electrode film is thickened. As a result, the ratio of the active material in the electrode film is reduced, which hinders the increase in capacity.
  • An object of the present invention is to provide a lithium ion secondary battery and a method of manufacturing the same, in which the capacity of the electrode film is increased by suppressing the non-uniform distribution of the binder in the electrode film.
  • the present invention comprises an electrode film formed on the surface of a current collector foil, and a binder for bonding the current collector foil and the electrode film, the electrode film on the side of the current collector foil.
  • the lithium ion secondary battery is characterized in that the binder concentration is higher than the binder concentration on the opposite side of the current collector foil.
  • the present invention also includes a first step of applying a liquid electrode material paste to the surface of the current collector foil, and contacting a solidified liquid containing a liquid component different from the liquid component contained in the electrode material paste with the electrode material paste. And performing a second step of solidifying the electrode material paste and a third step of removing a liquid component from the electrode material paste solidified in the second step and drying the lithium ion A method for manufacturing a secondary battery is provided.
  • the present invention it is possible to provide a lithium ion secondary battery and a method for manufacturing the lithium ion secondary battery that realize a high capacity electrode film.
  • Example 5 of this invention It is a figure explaining the solidification apparatus structure of the spray system in Example 5 of this invention. It is a figure explaining the apparatus structure of the double-sided continuous application type electrode manufacturing method in Example 6 of this invention. It is a figure explaining the apparatus structure of the double-sided batch application type electrode manufacturing method in Example 7 of this invention. It is a figure explaining the apparatus structure of the double-sided batch application type electrode manufacturing method using the direct processing solidification apparatus in Example 8 of this invention.
  • FIGS. 1-12 Embodiments of the present invention will be described with reference to FIGS. 1-12.
  • the structure of the lithium ion battery in this embodiment will be described.
  • the lithium ion secondary battery is wound or stacked via a separator that prevents contact between the positive electrode plate and the negative electrode plate.
  • the electrolytic solution is injected into the outer container.
  • the structure of the positive electrode plate and the negative electrode plate will be described with reference to FIG.
  • Each of the positive electrode plate and the negative electrode plate is coated with an electrode film paste on the surface of the current collector foil 4 serving as a battery electrode, and the applied electrode film has an active material 1 for charging / discharging and the electric conductivity in the electrode film. It has a conductive material 2 to be enhanced and a solvent 3 containing a binder. By drying the applied electrode film, the solvent 3 evaporates, and the electrode film and the current collector foil 4 are bonded by the binder.
  • a second step of bringing the electrode material paste into contact with the electrode material paste to solidify the electrode material paste, and a third step of removing the liquid component from the electrode material paste solidified in the second step and drying The electrode film is manufactured to solve the conventional problems. By these steps, each of the positive electrode plate and the negative electrode plate is formed.
  • a separator made of a porous insulating material that allows lithium ions to pass through is sandwiched between the positive electrode plate and the negative electrode plate while preventing contact between the positive electrode plate and the negative electrode plate, and the positive electrode plate, the separator, and the negative electrode plate are wound.
  • the electrode winding body which consists of the wound positive electrode plate, separator, and negative electrode plate can be formed.
  • electrolyte solution is inject
  • a lithium ion secondary battery can be manufactured by cap-sealing an exterior container.
  • FIG. 6 shows an apparatus configuration for manufacturing a conventional single-side coated electrode.
  • Positive and negative electrode pastes for lithium ion batteries are generally high viscosity slurry liquids in which active material powder, conductive material powder, binder material for binding these powders, etc. are dispersed in an organic solvent such as NMP. is there.
  • a coating means 6-2 such as a die coater installed in the coating section 6-1
  • the paste in the paste was heated in a hot air drying furnace shown as a drying chamber 6-5.
  • the solvent component is heated and evaporated to dry and solidify the paste.
  • the electrode foil roll 6-6 wound with the solidified electrode foil is supplied to the next step. In normal electrode foil manufacture, this process is repeated twice for the front and back surfaces of the electrode foil to manufacture an electrode foil coated on both sides.
  • the liquid electrode material paste applied to the current collector foil 4 is introduced into the drying chamber as it is and dried, whereas in the manufacturing method of this embodiment, the liquid electrode material paste is solidified. In addition, the solidified electrode material is dried.
  • the distribution of the binder in the electrode film becomes non-uniform because the solvent 3 in the coated electrode film evaporates and dries in the drying process of the coated electrode film.
  • the solvent 3 evaporates from the surface of the coated electrode film. That is, since the solvent 3 evaporates from the electrode film surface, the solvent 3 on the current collector foil 4 side moves to the electrode film surface side and evaporates from the surface.
  • the binder dissolved in the solvent 3 also moves to the electrode film surface side together with the solvent 3. The moved solvent 3 evaporates from the surface, but the dissolved binder remains. By this mechanism, the binder is concentrated on the electrode film surface side. As shown in FIG.
  • the binder is increased on the electrode film surface side (opposite side of the current collector foil 4) as compared with the current collector foil 4 side of the electrode film.
  • the concentration part 5 will be formed.
  • a binder concentration analysis method a scanning electron microscope (SEM), an energy dispersive X-ray analyzer (EDX), or the like can be used.
  • the binder solidifying means for preventing the concentration on the surface side of the binder accompanying the solvent drying of the present embodiment is carried out on the coating film held on the current collector foil 4 containing the first solvent of the present embodiment.
  • Any liquid tank may be used as long as it has a function of depositing a binder by contacting the second solvent in the form and replacing the first solvent in the coating film with the second solvent.
  • the binder distribution is basically the same as the binder distribution in the coating electrode film liquid when the solidification is instantaneous. That is, the binder is uniformly distributed in the electrode film, but the actual solidification of the binder proceeds from the electrode film surface (opposite side of the current collector foil 4) to the current collector foil 4 side, so solidification does not proceed from the electrode film surface side.
  • the binder moves to the current collector foil 4 side, and the amount of the binder increases on the current collector foil 4 side.
  • This binder distribution is opposite to that of the conventional binder on the electrode film surface side (opposite side of the current collector foil 4), and is distributed as shown in FIG. Therefore, since the adhesive strength between the electrode film and the current collector foil 4 is maintained, it is not necessary to increase the amount of the binder even when the film thickness is increased.
  • the amount of binder added on the electrode film current collector foil side in the conventional manufacturing method is 2.4%, so the amount of binder added is Whereas 1.7 times is required, in this embodiment, the amount of binder on the current collector foil side is 4.4%, so the amount of binder added may be about 0.9 times.
  • the heating rate in a general drying process of a coated electrode film having a thickness of about 100 ⁇ m is about 2 to 4 ° C./second, and the drying time is about 1 to 5 minutes.
  • the slower the drying the smaller the non-uniformity of the binder described above, and by setting the rate of temperature rise to about 1 ° C./second, the amount of binder on the electrode film surface side is approximately when the electrode film thickness is 100 ⁇ m.
  • the electrode film thickness is 200 ⁇ m, it is improved by about 2 times, and when the electrode film thickness is 500 ⁇ m, it is improved by about 3 times. Therefore, it becomes an obstacle to supplying an inexpensive lithium ion secondary battery to the market.
  • the lower limit of the contact time required for solidification generally requires time for the first solvent and the second solvent to mutually diffuse and replace in the coating film, but the electrode film thickness is 1 mm or less. If present, the contact time is preferably 1 to 100 seconds, more preferably 2 to 50 seconds, and even more preferably 5 to 20 seconds.
  • Binder distribution when the immersion time is 5 seconds is as shown in FIG.
  • the difference in the binder amount between the current collector foil and the surface side at that time is as shown in FIG. % Or less.
  • the binder amount difference between the current collector foil 4 side and the surface side (opposite side of the current collector foil 4) can be 50% or less. Accordingly, it is not necessary to increase the binder concentration even when the electrode film is thickened. Therefore, it is possible to suppress a decrease in the concentration of the active material that contributes to charging and discharging, and it is possible to realize a high capacity.
  • the above-described step of drying after solidifying the binder is not limited to either the positive electrode film or the negative electrode film of the electrode curtain of the lithium ion secondary battery, but can be applied to both. .
  • the drying means after solidifying the binder according to the present embodiment is not limited to general hot air drying because the binder does not move due to drying.
  • a heating method that irradiates electromagnetic waves such as infrared rays, far-infrared rays, or visible light may be used, or a dielectric heating method that uses a high-frequency electric field, or an induction heating method that uses a change in magnetic flux may be used.
  • a contact heating method using a heating roll or a hot plate incorporating a heater can also be used.
  • the positive electrode active material used for the positive electrode among the active materials of the lithium ion battery used in this embodiment includes lithium cobaltate, lithium-containing composite oxide having a spinel structure containing manganese, or nickel, cobalt, and manganese. Or a olivine-type compound represented by olivine-type iron phosphate, but is not limited thereto. Since the lithium-containing composite oxide having a spinel structure containing manganese is excellent in thermal stability, for example, a highly safe battery can be configured. As the positive electrode active material, only a lithium-containing composite oxide having a spinel structure containing manganese may be used, but another positive electrode active material may be used in combination.
  • Examples of such other positive electrode active materials include olivine type compounds represented by Li1 + xMO2 ( ⁇ 0.1 ⁇ x ⁇ 0.1, M: Co, Ni, Mn, Al, Mg, Zr, Ti, etc.) Is mentioned.
  • Specific examples of the lithium-containing transition metal oxide having a layered structure include LiCoO2 and LiNi1-xCox-yAlyO2 (0.1 ⁇ x ⁇ 0.3, 0.01 ⁇ y ⁇ 0.2), and at least Co.
  • An oxide containing Ni and Mn (LiMn1 / 3Ni1 / 3Co1 / 3O2, LiMn5 / 12Ni5 / 12Co1 / 6O2, LiNi3 / 5Mn1 / 5Co1 / 5O2, etc.) can be used.
  • the negative electrode active material used for the negative electrode includes, for example, graphite materials such as natural graphite (flaky graphite), artificial graphite, and expanded graphite; and easy graphite such as coke obtained by firing a pitch.
  • graphite materials such as natural graphite (flaky graphite), artificial graphite, and expanded graphite
  • easy graphite such as coke obtained by firing a pitch.
  • Carbonaceous materials carbon materials such as non-graphitizable carbonaceous materials such as amorphous carbon obtained by low-temperature firing of furfuryl alcohol resin (PFA), polyparaphenylene (PPP) and phenol resin .
  • lithium or a lithium-containing compound can also be used as the negative electrode active material.
  • the lithium-containing compound include a lithium alloy such as Li—Al, and an alloy containing an element that can be alloyed with lithium such as Si and Sn.
  • oxide-based materials such as Sn oxide and Si oxide can also be used.
  • the conductive material used in the present embodiment is usually used as an electron conduction aid to be contained in the positive electrode mixture layer.
  • carbon materials such as carbon black, acetylene black, ketjen black, graphite, carbon fiber, and carbon nanotube are used. Is preferred.
  • acetylene black or ketjen black is particularly preferable from the viewpoints of the amount of addition and conductivity, and the productivity of the positive electrode mixture layer-containing composition (described later).
  • Such a conductive material may be included in the negative electrode mixture and may be preferable.
  • the solidifying material of this embodiment can also use the binder component as the solidifying material of this embodiment, the following binders can be used.
  • the binder of this embodiment preferably also contains a binder for binding the active material and the conductive material.
  • a binder for example, a polyvinylidene fluoride polymer (a polymer of a fluorine-containing monomer group containing 80% by mass or more of vinylidene fluoride as a main component monomer), a rubber polymer, and the like are preferably used. Two or more of the above polymers may be used in combination.
  • the binder of this embodiment is preferably provided in the form of a solution dissolved in a solvent.
  • Examples of the fluorine-containing monomer group for synthesizing the polyvinylidene fluoride-based polymer include vinylidene fluoride; a mixture of vinylidene fluoride and other monomers, and a monomer mixture containing 80% by mass or more of vinylidene fluoride; Can be mentioned.
  • Examples of other monomers include vinyl fluoride, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, and fluoroalkyl vinyl ether.
  • Examples of the rubber polymer include styrene butadiene rubber (SBR), ethylene propylene diene rubber, and fluorine rubber.
  • SBR styrene butadiene rubber
  • ethylene propylene diene rubber examples include fluorine rubber.
  • the content of the binder in the electrode film after drying the positive and negative electrodes is 0.1% by mass or more, more preferably 0.3% by mass or more based on the electrode agent after drying, and 10% by mass or less. More preferably, the content is 5% by mass or less. If the binder content is too small, not only is the solidification in the solidification step of the present embodiment insufficient, but the mechanical strength of the electrode film after drying is insufficient and the electrode film peels off from the current collector foil 4. There is. Moreover, when there is too much content of a binder, there exists a possibility that the quantity of the active material 1 in an electrode film may reduce and battery capacity may become low.
  • the solidifying material of the present embodiment is the same as the above binder or a mixture thereof. That is, there are a case where the binder itself is solidified as a solidifying material and a case where the binder is not solidified as a solidifying material but a mixture contained in the binder is solidified as a solidifying material. Moreover, it is also possible in this embodiment to add and use the component which does not have the performance as a binder but has the performance as a solidification material.
  • the application of this embodiment can employ various application methods including, for example, an extrusion coater, a reverse roller, a doctor blade, an applicator, and the like.
  • the current collector foil used in the present embodiment is representatively shown, and is not limited to a sheet-like foil.
  • the substrate include pure metals such as aluminum, copper, stainless steel, and titanium, or
  • the alloy conductive material is used as the shape, such as a net, a punched metal, a foam metal, or a foil processed into a plate shape.
  • As the thickness of the current collector foil 4 for example, 5 to 30 ⁇ m, more preferably 8 to 16 ⁇ m is selected.
  • the thickness of the electrode film formed on the surface of the current collector foil is the thickness after pressing following the drying step, and can be selected, for example, from 10 to 500 ⁇ m, more preferably from 30 to 250 ⁇ m.
  • the solvent of this embodiment is used by appropriately selecting the first solvent and the second solvent.
  • a solvent should be selected from the solubility of the solidified material of this embodiment or the binder component that also serves as the solidified material, and the mutual solubility of the solvent.
  • the first solvent N-methylpyrrolidone, dimethyl sulfoxide, propylene carbonate, dimethyl
  • An aprotic polar solvent typified by formamide, ⁇ -butyrolactone or a mixture thereof can be selected.
  • the second solvent must be a solvent that solidifies the binder component, and can be selected from a protic solvent represented by water, ethanol, isopropyl alcohol, acetic acid, or a mixture thereof. It is not limited to the examples.
  • aliphatic saturated hydrocarbons, aliphatic amines, esters, ethers, various halogen-based solvents, and the like can be selected as the second solvent. Further, in some cases, it is possible to select to exchange the first solvent and the second solvent.
  • the selection of the solvent in this embodiment depends on the selection of the solidifying component used for the electrode material and the combination of the two types of solvents that match the selection.
  • the solidifying means of the present embodiment brings the second solvent of the present embodiment into contact with the coating film held on the current collector foil containing the first solvent of the present embodiment, and the first solvent in the coating film As long as it has a function of substituting the second solvent with the second solvent, a method of passing the coating film held on the current collector foil in the liquid tank storing the second solvent, Examples include, but are not limited to, a method in which the second solvent is sprayed on the coating film and a method in which the second solvent is supplied while flowing down.
  • Example 1- 4 The lithium ion secondary battery having the electrode film in which the binder according to this embodiment is uniformly distributed and the manufacturing method thereof have been described above. The results of manufacturing and evaluating the lithium ion secondary battery will be described below as Example 1- 4 is described.
  • the slurry of the positive electrode film coating mixture was prepared by the following method.
  • As the active material lithium manganese cobalt nickel composite oxide powder of lithium transition metal composite oxide was used.
  • a positive electrode mixture was prepared by mixing 9 parts by weight of graphite powder and 2 parts by weight of carbon black as conductive material 2 with respect to 85 parts by weight of this lithium manganese cobalt nickel composite oxide.
  • NMP N-methyl-2-pyrrolidone
  • PVDF polyvinylidene fluoride
  • the coated electrode film coated with the positive electrode mixture slurry (electrode material paste) prepared above on the surface of the aluminum current collector foil 4 using a die coater is immersed in pure water for 5 seconds to solidify the binder, and then dried with hot air
  • the electrode film was dried at 120 ° C. in a furnace at a heating rate of 3 ° C./second.
  • the positive electrode film produced above was roller-pressed while heating to produce a 200 ⁇ m thick electrode.
  • the amount of binder on the surface side of the prepared electrode film was 3.8%, and the amount of binder on the current collector foil 4 side of the electrode film was 4.3%, 13% higher.
  • Comparative Example 1 the coating electrode film obtained by applying the mixture layer slurry of Example 1 using a die coater is dried in a warm air drying furnace at a temperature rising rate of 3 ° C./second and at 120 ° C. without passing through the step of solidifying the binder. Then, a 200 ⁇ m-thick electrode film was produced by roller pressing, and the amount of binder was measured.
  • the amount of binder on the surface side of the electrode film was 5.6%
  • the amount of binder on the current collector foil 4 side of the electrode film was 2.2%, 61% less.
  • a positive electrode mixture slurry for coating was prepared and applied onto the aluminum current collector foil 4 in the same manner as in Example 1, and then the coated electrode film was immersed in pure water for 5 seconds to solidify the binder, The electrode film was dried at 120 ° C. at a temperature rising rate of 3 ° C./second in a wind drying furnace.
  • the positive electrode film prepared above was roller-pressed while heating to prepare an electrode film having a thickness of 500 ⁇ m.
  • the amount of binder on the surface side of the electrode film of the fabricated electrode film was 3.7%, and the amount of binder on the current collector foil 4 side of the electrode film was 4.5%, which was 22% more.
  • Example 2 the coated electrode film obtained by applying the positive electrode mixture layer slurry of Example 2 using a die coater was not subjected to the step of solidifying the binder at 120 ° C. at a temperature rising rate of 3 ° C./second in a warm air drying furnace.
  • the electrode film having a thickness of 500 ⁇ m was prepared by drying and roller pressing, and the amount of the binder was measured.
  • the binder amount on the surface side of the electrode film in this comparative example was 6.3%, and the binder amount on the current collector foil 4 side of the electrode film was 1.8%, which was 71% less.
  • Example 2 In the same manner as in Example 1, a positive electrode mixture slurry for coating was prepared and coated on an aluminum current collector foil. After the coated electrode film was immersed in pure water for 5 seconds to solidify the binder, The electrode film was dried at 120 ° C. in a drying furnace at a rate of temperature increase of 6 ° C./second.
  • the positive electrode film prepared above was roller-pressed while heating to prepare an electrode film having a thickness of 500 ⁇ m.
  • the amount of binder on the electrode surface side of the fabricated electrode film was 3.7%, and the amount of binder on the current collector foil 4 side was 4.5%, which was 22% more.
  • Example 3 the coated electrode film obtained by applying the positive electrode mixture layer slurry of Example 3 using a die coater was not subjected to a step of solidifying the binder at 120 ° C. at a temperature rising rate of 6 ° C./second in a warm air drying furnace.
  • the electrode film having a thickness of 500 ⁇ m was prepared by drying and roller pressing, and the amount of the binder was measured.
  • the binder amount on the surface side of the electrode film was 6.5%, and the binder amount on the current collector foil 4 side of the electrode film was 1.7%, which was 74% less.
  • the negative electrode mixture slurry was prepared by the following method.
  • a negative electrode mixture was prepared by mixing 2 parts by weight of carbon black with respect to 93 parts by weight of amorphous carbon powder as active material 1.
  • a binder solution was added to the negative electrode mixture so that PVDF was 5 parts by weight and dispersed in NMP to form a slurry.
  • the negative electrode mixture slurry prepared above was applied to the surface of the copper current collector foil using a die coater, the coated electrode film was immersed in pure water for 5 seconds to solidify the binder, and then heated in a hot air drying furnace. The electrode film was dried at 120 ° C. at a rate of temperature increase of 3 ° C./second.
  • the produced positive electrode film was roller-pressed while heating to produce a negative electrode film having a thickness of 500 ⁇ m.
  • the amount of binder on the surface side of the prepared electrode film was 4.7%, and the amount of binder on the current collector foil 4 side of the electrode film was 5.5% and 17% (Comparative Example 4).
  • the coated electrode film obtained by applying the negative electrode mixture slurry of Example 4 using a die coater is dried in a warm air drying furnace at a temperature rising rate of 3 ° C./second without a step of solidifying the binder at 120 ° C.
  • a roller press was performed to produce an electrode film having a thickness of 500 ⁇ m, and the amount of the binder was measured.
  • the binder amount on the surface side of the electrode film was 7.6%, and the binder amount on the current collector foil 4 side of the electrode film was 68%, which was 2.4%.
  • the electrode film manufacturing method of the present invention will be described in detail in Example 5-8.
  • the liquid electrode material paste coated on the surface of the electrode current collector foil is directly introduced into the drying chamber and dried, whereas in the manufacturing method of the present invention, the step of solidifying the liquid electrode material paste is performed. In addition, the solidified electrode material is dried.
  • FIG. 7 shows an apparatus configuration for manufacturing a single-side coated electrode in this example.
  • the coating means 7-2 such as a die coater in which the paste of this embodiment is installed in the coating section 7-1
  • the paste is thinly and evenly applied on the electrode foil supplied from the current collecting electrode foil roll 7-3.
  • Apply. Using the roller transport system 7-4 for transporting the electrode foil at a constant speed while being in contact with the back surface of the electrode foil coated with such paste, the electrode foil is carried into the solidification chamber 7-5, and this embodiment is applied to the electrode paste.
  • the solidified liquid (not shown) which is the second solvent is contacted to solidify the paste.
  • the solidified liquid that is the second solvent of the present embodiment has the property of not dissolving the solidification material and the property of being mutually soluble with the first solvent. is necessary.
  • the second solvent When the second solvent is brought into contact with the coating film on the electrode foil, the second solvent penetrates into the coating film while replacing the first solvent in the coating film. If the concentration of the second solvent increases in the coating film, the solidification material becomes insufficient because the solubility of the solidification material becomes insufficient. At this time, the active material particles contained in the paste are bound together to form the entire coating film. Is solidified. Usually, such a solidification process occurs in a time much shorter than the time required for drying or the like, so that the distribution of various components in the coating film is fixed almost instantaneously.
  • this embodiment Due to the characteristics of this embodiment, it is possible to use a contact-type roller conveyance system that contacts the solidified coating film for conveying the electrode foil holding the solidified coating film.
  • the advantage of this embodiment is particularly excellent when the electrode films are applied on both sides and then the electrode films on both sides are dried together. That is, in this embodiment, since it is possible to use a contact type roller conveyance system that comes into contact with the solidified coating film, there is no need to use a complicated and expensive air floating conveyance system even when performing double-sided batch drying. An inexpensive drying room using a transport system can be used.
  • the electrode foil holding the paste solidified by the means of this embodiment is carried into the drying chamber 7-6, and the solvent component in the paste is heated and evaporated by a known method such as hot air drying to dry the paste.
  • the electrode foil roll 7-7 wound with the dried electrode foil is supplied to the next step.
  • the solidified paste may be dried instead of the liquid paste.
  • drying can be performed while preventing fluctuations in various compositions and film thickness that have been fluctuated in the past, so that rapid drying in a short time is possible.
  • Such a feature of the present embodiment is directly linked to an economic advantage that the drying equipment can be downsized.
  • the solvent in the paste is replaced with the second solvent in this example in the solidification step of this example. If a nonflammable solvent is selected as the second solvent, it is possible to eliminate the generation of flammable solvent vapor in the drying chamber. For this reason, it becomes possible to eliminate problems in facilities such as various safety measures and steam recovery equipment associated with handling of combustible steam. In this embodiment, it is possible to design a process that avoids the problems and restrictions of the manufacturing process.
  • the solidifying means of the present example brings the second solvent of the present example into contact with the coating film held on the electrode foil containing the first solvent of the present example, and the first solvent in the coated film is removed. What is necessary is just to have the function substituted by the 2nd solvent, and the system which passes the coating film hold
  • the solidifying device 8-1 of this example is a solidifying device provided with an overflow tank 8-5 and a circulation pump 8-6 using an electrode foil 8-3 coated with an electrode agent paste 8-2 using a roller transport system 8-4. Introduced in 8-1. In the overflow tank 8-5, the electrode agent paste 8-2 is solidified by being brought into contact with the solidifying liquid 8-7 of the present embodiment, and is transported to the next drying apparatus.
  • the solidifying device 8-1 of this embodiment can be provided with an air knife 8-8 for draining liquid.
  • the solidifying device 9-1 of the present embodiment is a solidifying device provided with a spray nozzle 9-5 and a circulation pump 9-6 using an electrode foil 9-3 coated with an electrode agent paste 9-2 using a roller transport system 9-4. 9-1.
  • the solidifying device 9-1 of the present embodiment can be provided with an air knife 9-8 for draining liquid.
  • the first solvent removed by substitution from the electrode paste accumulates in the second solvent, which is the solidification liquid of this embodiment, and the concentration thereof increases. become.
  • the second solvent which is the solidification liquid of this embodiment
  • concentration thereof increases.
  • the contact time required for solidification generally, a time for replacing the first solvent and the second solvent by interdiffusion in the coating film is required.
  • the upper limit of the contact time depends mainly on economic constraints. From this point of view, the contact time is preferably 1 to 100 seconds, more preferably 2 to 50 seconds, and further preferably 5 to 20 seconds.
  • the liquid transport means of this embodiment is preferably an inexpensive contact roller transport system, but this embodiment does not limit the use of an air floating transport system, and the use of a small amount reduces the overall productivity. Sometimes it improves.
  • the liquid drying means of the present embodiment is generally hot air drying, but is not limited thereto.
  • a heating method that irradiates electromagnetic waves such as infrared rays, far-infrared rays, or visible light may be used, or a dielectric heating method that uses a high-frequency electric field, or an induction heating method that uses a change in magnetic flux may be used.
  • a contact heating method using a heating roll and a hot plate incorporating a heater, or a heating method combining these can also be used.
  • a contact-type roller conveyance system that contacts the solidified coating film for conveying the electrode foil holding the solidified coating film.
  • Such an advantage of the present invention is particularly excellent when the electrode films are applied on both sides and then the electrode films on both sides are collectively dried. That is, in the present invention, since it is possible to use a contact type roller conveyance system that comes into contact with the solidified electrode material paste, it is not necessary to use a complicated and expensive air floating conveyance system even when performing double-sided batch drying. An inexpensive drying room using a transport system can be used.
  • the present invention is characterized in that most of the solvent component in the paste to be removed in the drying chamber is not the first solvent used for preparing the paste, but the second solvent of the present invention. It is also an advantage of the present invention that various problems in production due to drying can be avoided by using a solvent different from the solvent in the paste as the solvent during drying.
  • the solvent in the paste is replaced with the second solvent in the present invention in the solidification step of the present invention.
  • a non-flammable solvent as the solvent, it is possible to eliminate the generation of the flammable solvent vapor in the drying chamber, so that it is possible to solve the problem on equipment for safety. It is possible to design a process that avoids the problems and limitations of the manufacturing process.
  • Example 6 A method for producing an electrode film in Example 6 will be described with reference to FIG. The description of the same configuration as that of the first embodiment is omitted.
  • the electrode material paste is applied to the surface of the electrode foil, the electrode material paste is applied to the electrode foil, the electrode material paste is solidified, and the electrode foil is dried. It is characterized by performing a step of applying a paste, a step of solidifying an electrode material paste, and a step of drying an electrode foil.
  • the positive and negative electrode pastes for the lithium battery according to the present embodiment are prepared as a high-viscosity slurry liquid, and the paste is applied to the coating unit 10-1 for the surface. 2 is applied thinly and uniformly onto the electrode foil supplied from the current collecting electrode foil roll 10-3.
  • the electrode foil is carried into the solidification chamber 10-5, and this example is applied to the electrode paste.
  • the solidified liquid (not shown) which is the second solvent is contacted to solidify the paste.
  • the electrode foil holding the paste solidified by the means of this embodiment is carried into the drying chamber 10-6, and the solvent component in the paste is heated and evaporated by a technique such as hot air drying to dry the paste.
  • the dried electrode foil is thinly and uniformly applied on the back surface of the electrode foil using a coating means 10-8 such as a die coater installed in the back surface coating section 10-7.
  • the electrode foil coated with such paste is carried into the solidification chamber 10-9 for the back surface, and the solidified liquid (not shown) as the second solvent of this example is brought into contact with the electrode paste to solidify the paste.
  • the electrode foil holding the paste solidified by the means of this example is carried into the drying chamber 10-10, and the solvent component in the paste is heated and evaporated by a technique such as hot air drying to dry the paste.
  • the electrode foil roll 10-11 wound with the dried electrode foil is supplied to the next step.
  • electrode formation on the front and back surfaces of the electrode foil is carried out by dividing the coating process on the front and back surfaces, solidification, and drying, making it easy to achieve both improvement in electrode quality and downsizing of the drying equipment. It can be done.
  • Example 7 A method for manufacturing an electrode film in Example 7 will be described with reference to FIG. The description of the same configuration as that of the first embodiment is omitted.
  • a positive and negative electrode paste for a lithium battery according to the present embodiment is prepared as a high-viscosity slurry liquid, and the surface coating means 11-2 such as a die coater in which the paste is installed in the coating section 11-1. And using the coating means 11-3 for the back surface, it is applied thinly and uniformly on both surfaces of the electrode foil supplied from the collecting electrode foil roll 11-4.
  • the electrode foil having the paste applied on both sides thereof is carried into the solidification chamber 11-5, and the electrode paste is brought into contact with both sides of the electrode foil with a solidification liquid (not shown) as the second solvent of this embodiment. , Solidify the paste.
  • the solidified paste can be transported using a roller transport system 11-6 for transporting the electrode foil at a constant speed while being in contact with the back surface of the electrode foil.
  • the electrode foil holding the paste solidified by the means of the present example is carried into the drying chamber 11-7, and the solvent components in the paste are heated and evaporated together on both sides by a technique such as hot air drying, and the paste is dried. To do.
  • the electrode foil roll 11-8 wound with the dried electrode foil is supplied to the next step.
  • the low-cost contact-type roller transport system that contacts the solidified coating film is used to transport the electrode foil that holds the solidified coating film. Can also be used.
  • Example 8 The manufacturing method of the electrode film in Example 8 will be described with reference to FIG. The description of the same configuration as that of the first embodiment is omitted.
  • a positive and negative electrode paste for a lithium battery according to the present embodiment is prepared as a high-viscosity slurry liquid, and the surface coating means 12-2 such as a die coater in which the paste is installed in the coating section 12-1. Then, using the back surface coating means 12-3, the electrode foil supplied from the current collecting electrode foil roll 10-4 is thinly and uniformly coated on both surfaces.
  • the electrode foil coated with the paste on both sides is carried into a solidification chamber 12-5 arranged vertically, and a solidification liquid (not shown) as the second solvent of this embodiment is supplied to the electrode paste by spraying or the like.
  • the electrode foil is conveyed from the top to the bottom (or from the bottom to the top) by vertical treatment, and the paste is solidified.
  • the solidified paste can be transported using a roller transport system 12-6 for transporting the electrode foil at a constant speed while in contact with the back surface of the electrode foil.
  • the electrode foil holding the paste solidified by the means of this example is carried into the drying chamber 12-7, and the solvent component in the paste is heated and evaporated by a technique such as hot air drying to dry the paste.
  • the electrode foil roll 12-8 wound with the dried electrode foil is supplied to the next step.
  • the electrode foil was conveyed from the top to the bottom (or from the bottom to the top), but instead of or in addition to this, the electrode foil was dried in the step of drying the electrode foil. You may convey from the top to the bottom (or the bottom to the top).
  • the coating unit and the solidification chamber are arranged vertically as in this embodiment, it is possible to easily realize both improvement in electrode quality and downsizing of the drying equipment, as well as arrangement of manufacturing equipment. It is possible to expect an excellent effect of reducing the capital investment in the manufacturing apparatus, such as enabling a flexible layout and reducing the area of the installation plane of the manufacturing apparatus.
  • an example of the vertical arrangement of the coating unit and the solidifying chamber is shown, but this example does not limit the vertical arrangement of the drying chamber, but may be preferable.
  • the uneven distribution of the binder in the electrode film is eliminated. Thereby, it is not necessary to increase the binder concentration, the ratio of the active material 1 in the electrode film can be improved, and the capacity of the electrode film can be increased.
  • lithium manganese cobalt nickel composite oxide is exemplified as the lithium transition metal composite oxide of the positive electrode active material
  • amorphous carbon is exemplified as the negative electrode active material.
  • the present embodiment is not limited thereto. Is not to be done.
  • PVDF is exemplified as the binder
  • N-methyl-2-pyrrolidone is exemplified as the first solvent
  • distilled water is exemplified as the second solvent, but the present invention is not limited thereto.

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  • General Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
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Abstract

La présente invention vise à proposer : une batterie secondaires aux ions-lithium dans laquelle une augmentation de la capacité d'un film d'électrode a été atteinte par suppression d'une distribution irrégulière d'un liant dans le film d'électrode ; et un procédé de fabrication de la batterie secondaire aux ions-lithium. La présente invention porte sur une batterie secondaire aux ions-lithium qui est caractérisée en ce que la concentration en liant côté feuille de collecteur dans un film d'électrode, qui est formé sur la surface d'une feuille de collecteur, est supérieure à la concentration en liant sur le côté inverse du côté feuille de collecteur par introduction d'une étape de solidification de liant. La présente invention porte également sur un procédé de fabrication d'une batterie secondaire aux ions-lithium, qui comprend : une première étape dans laquelle une pâte de matière d'électrode dans un état liquide est appliquée à une surface de feuille d'électrode ; une deuxième étape dans laquelle la pâte de matière d'électrode est solidifiée en amenant la pâte de matière d'électrode en contact avec un liquide de solidification qui contient un composant liquide différent du composant liquide contenu dans la pâte de matière d'électrode ; et une troisième étape dans laquelle le composant liquide est retiré de la pâte de matière d'électrode solidifiée, séchant ainsi la pâte de matière d'électrode.
PCT/JP2012/076753 2011-10-31 2012-10-17 Batterie secondaire aux ions-lithium et son procédé de fabrication WO2013065478A1 (fr)

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WO2014141547A1 (fr) * 2013-03-13 2014-09-18 株式会社日立製作所 Dispositif et procédé de production d'une batterie secondaire au lithium-ion
US10195621B2 (en) 2013-07-19 2019-02-05 Graco Minnesota Inc. Pump changeover algorithm for spray system
JP2019071227A (ja) * 2017-10-10 2019-05-09 日産自動車株式会社 非水電解質二次電池用電極
CN112038567A (zh) * 2020-08-12 2020-12-04 北京化工大学 一种电极的连续生产装置及其生产工艺
CN113921883A (zh) * 2020-07-09 2022-01-11 丰田自动车株式会社 全固体电池的制造装置和全固体电池的制造方法

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JPH10270023A (ja) * 1997-03-27 1998-10-09 Japan Storage Battery Co Ltd 非水電解質二次電池用電極の製造方法
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Publication number Priority date Publication date Assignee Title
WO2014141547A1 (fr) * 2013-03-13 2014-09-18 株式会社日立製作所 Dispositif et procédé de production d'une batterie secondaire au lithium-ion
US10195621B2 (en) 2013-07-19 2019-02-05 Graco Minnesota Inc. Pump changeover algorithm for spray system
US11148152B2 (en) 2013-07-19 2021-10-19 Graco Minnesota Inc. Pump changeover algorithm for spray system
JP2019071227A (ja) * 2017-10-10 2019-05-09 日産自動車株式会社 非水電解質二次電池用電極
JP7133301B2 (ja) 2017-10-10 2022-09-08 日産自動車株式会社 非水電解質二次電池用電極
CN113921883A (zh) * 2020-07-09 2022-01-11 丰田自动车株式会社 全固体电池的制造装置和全固体电池的制造方法
CN113921883B (zh) * 2020-07-09 2024-03-15 丰田自动车株式会社 全固体电池的制造装置和全固体电池的制造方法
CN112038567A (zh) * 2020-08-12 2020-12-04 北京化工大学 一种电极的连续生产装置及其生产工艺

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