WO2021214946A1 - リチウムイオン二次電池及びその製造方法 - Google Patents

リチウムイオン二次電池及びその製造方法 Download PDF

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Publication number
WO2021214946A1
WO2021214946A1 PCT/JP2020/017529 JP2020017529W WO2021214946A1 WO 2021214946 A1 WO2021214946 A1 WO 2021214946A1 JP 2020017529 W JP2020017529 W JP 2020017529W WO 2021214946 A1 WO2021214946 A1 WO 2021214946A1
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Prior art keywords
secondary battery
ion secondary
lithium ion
electrode layer
green sheet
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English (en)
French (fr)
Japanese (ja)
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吉田　俊広
勝田　祐司
佐藤　洋介
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NGK Insulators Ltd
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NGK Insulators Ltd
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Priority to JP2022516584A priority Critical patent/JP7423760B2/ja
Priority to PCT/JP2020/017529 priority patent/WO2021214946A1/ja
Publication of WO2021214946A1 publication Critical patent/WO2021214946A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a lithium ion secondary battery and a method for manufacturing the same.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2009-193940
  • the surface of lithium cobalt oxide is coated with lithium niobate to provide interfacial resistance. It is disclosed that the reduction of Reduction of interfacial resistance leads to improvement of charge / discharge characteristics.
  • the battery disclosed in Patent Document 1 is an all-solid-state battery using a green compact, and is an electrode when pores remain between particles or a conductive auxiliary agent for ensuring electron conduction between active materials is added. Energy density decreases.
  • Patent Document 2 (WO2019 / 093222A1) contains an oriented positive electrode plate which is a lithium composite oxide sintered body plate having a void ratio of 10 to 50%, Ti, and 0.4 V (vs. Li / Li). + )
  • An all-solid-state lithium battery is disclosed, which comprises a negative electrode plate capable of inserting and removing lithium ions and a solid electrolyte having a melting point of the oriented positive electrode plate or the negative electrode plate or a melting point lower than the decomposition temperature.
  • Such a solid electrolyte can permeate into the voids of the electrode plate as a melt, and strong interfacial contact can be realized. As a result, it is said that the battery resistance and the rate performance at the time of charging / discharging can be remarkably improved, and the yield of battery manufacturing can be significantly improved.
  • Patent Document 3 (WO2019 / 221140A1) includes a positive electrode layer composed of a sintered body of a lithium composite oxide (for example, lithium cobalt oxide) and a titanium-containing sintered body (for example, lithium titanate).
  • a lithium ion secondary battery comprising a negative electrode layer, a ceramic separator, and an electrolyte impregnated in the ceramic separator is disclosed.
  • the positive electrode layer, the ceramic separator, and the negative electrode layer form one integrally sintered plate as a whole, whereby the positive electrode layer, the ceramic separator, and the negative electrode layer are bonded to each other.
  • Patent Document 4 Japanese Unexamined Patent Publication No. 2014-116156
  • Patent Document 4 Japanese Unexamined Patent Publication No. 2014-116156
  • Batteries are disclosed, and it is described that these plurality of laminated batteries are stacked via a positive electrode current collecting foil and a negative electrode current collecting foil, and are electrically connected in parallel.
  • the positive electrode member, the low melting point solid electrolyte (for example, 3LiOH / Li 2 SO 4 ), and the negative electrode member are stacked so as to be arranged in the order of the current collector layer / positive electrode plate / solid electrolyte / negative electrode plate / current collector layer.
  • the obtained laminate is heated to melt the low melting point solid electrolyte, and the positive electrode plate and the negative electrode plate are impregnated with the electrolyte to form a unit cell in which the battery components are integrated.
  • a plurality of these unit cells are produced.
  • a stacked cell is formed by stacking a plurality of unit cells.
  • such a manufacturing process has the following problems.
  • the present inventors have now impregnated an integrally sintered body including a plurality of unit laminates including a positive electrode layer, a ceramic separator, and a negative electrode layer together with a current collecting layer with a molten electrolyte having a melting point of 600 ° C. or lower.
  • the laminated battery can be manufactured more efficiently without the above-mentioned problems. That is, it was found that a laminated battery type lithium ion secondary battery having a plurality of unit cells can be manufactured with a significantly small number of steps and a high yield while being a method suitable for improving energy density.
  • an object of the present invention is to manufacture a laminated battery type lithium ion secondary battery having a plurality of unit cells, while using a method suitable for improving energy density, with a significantly small number of steps and a high yield. It is in.
  • the process of firing the green sheet laminate to form an integrally sintered body A step of impregnating the integrally sintered body with a molten electrolyte having a melting point of 600 ° C. or lower to obtain a lithium ion secondary battery.
  • a method for manufacturing a lithium ion secondary battery including the above is provided.
  • a plurality of unit cells including a positive electrode layer composed of a lithium composite oxide sintered body, a ceramic separator, and a negative electrode layer composed of a titanium-containing oxide sintered body in order.
  • the current collector layers arranged on both sides of the unit cell and At least an electrolyte having a melting point of 600 ° C. or less impregnated in the ceramic separator and
  • the plurality of unit cells are laminated in series or in parallel via the current collector layer to form a cell laminate, and the portion of the cell laminate other than the electrolyte is integrally fired as a whole.
  • a lithium ion secondary battery is provided in which the positive electrode layer, the ceramic separator, the negative electrode layer, and the current collector layer are bonded to each other.
  • the present invention relates to a method for manufacturing a laminated battery type lithium-ion secondary battery including a plurality of unit cells.
  • FIG. 1 conceptually shows the layer structure of the unit cell 12
  • FIG. 2 conceptually shows an example of the layer structure of the lithium ion secondary battery 10 manufactured by the method of the present invention.
  • the lithium ion secondary battery 10 includes a plurality of unit cells 12, current collector layers 20 arranged on both sides of the unit cells 12, and an electrolyte (not shown).
  • the unit cell 12 includes, in order, a positive electrode layer 14 made of a lithium composite oxide sintered body, a ceramic separator 16, and a negative electrode layer 18 made of a titanium-containing oxide sintered body.
  • the current collector layer 20 is arranged on both sides of the unit cell 12.
  • the electrolyte is a low melting point electrolyte having a melting point of 600 ° C. or lower, and is impregnated at least in the ceramic separator 16 and typically also in the positive electrode layer 14 and / or the negative electrode layer 18. Therefore, the electrolyte is not shown in FIGS. 1 and 2 because it cannot be visualized by itself.
  • a plurality of unit cells 12 are laminated in parallel or in series via the current collector layer 20 to form a cell laminate. That is, although FIG. 2 shows a form in which the unit cells 12 are stacked in parallel, even in a form in which the unit cells 12 are stacked in series as in the lithium ion secondary battery 10'shown in FIG. good.
  • the parts of the cell laminate other than the electrolyte form one integral sintered body as a whole, whereby the positive electrode layer 14, the ceramic separator 16, the negative electrode layer 18, and the current collector layer 20 are mutually formed. It is combined. According to such an integrally sintered body type battery, both high discharge capacity and excellent charge / discharge cycle performance can be achieved.
  • the lithium ion secondary battery 10 includes (1) formation of the green sheet laminate 22 and (2) firing of the green sheet laminate 22. It can be produced through the formation of the integrally sintered body 24 according to the above and (3) impregnation of the molten electrolyte 26 into the integrally sintered body 24.
  • the green sheet laminate 22 is a unit laminate of a plurality of unit laminates 12'containing a positive electrode green sheet 14', a separator green sheet 16', and a negative electrode green sheet 18' in order.
  • the current collector layers 20 are arranged on both sides of the body 12'and laminated in series or in parallel.
  • the manufacturing process according to the conventional method of stacking a plurality of unit cells to form a laminated cell has the following problems. i) Since the number of manufacturing processes increases in proportion to the number of unit cells, the number of processes inevitably increases. ii) Since it is necessary to carefully handle the thin and fragile electrode plates one by one, the handleability is inferior, and the yield is lowered. iii) Since the thickness of the electrode plate tends to vary or warp, it is necessary to thicken the solid electrolyte layer in order to avoid a short circuit between positive and negative, and the energy density is reduced by that amount. These problems are conveniently solved according to the present invention.
  • the green sheet laminate 22 provided with the plurality of unit laminates 12 ′′ together with the current collector layer 20 is fired in advance and melted into the obtained integrally sintered body 24. Since a battery having a plurality of unit cells 12 can be formed only by impregnating the electrolyte 26, the number of steps can be significantly reduced. That is, it is not necessary to go through the complicated process by the conventional method as described above.
  • the positive electrode green sheet 14', the separator green sheet 16', the negative electrode green sheet 18', and the current collector layer 20 are integrally fired without firing the electrode plates one by one.
  • the positive electrode and the negative electrode can be laminated in the form of a green sheet and converted into the integrally sintered body 24, the thickness of the electrode plate that is likely to occur by firing the electrode layer for each sheet. The problem of unevenness and warpage can be effectively suppressed. Therefore, even if the solid electrolyte layer is formed thinly, a short circuit between the positive and negative electrodes can be sufficiently avoided, and as a result, the energy density can be improved.
  • Green Sheet Laminated Body a plurality of unit laminated bodies 12'provided with a positive electrode green sheet 14', a separator green sheet 16', and a negative electrode green sheet 18' in order are connected in series.
  • the green sheet laminate 22 is formed by laminating in parallel.
  • the green sheet laminate 22 is formed while the current collector layers 20 are arranged on both sides of the unit laminate 12'. For example, if the unit laminates 12'are stacked while interposing one current collector layer 20 between the unit laminates 12', and finally the current collector layers 20 are formed on both the upper and lower surfaces of the green sheet laminate 22. good.
  • the unit laminates 12'with the current collector layers 20 formed on both sides may be stacked.
  • the two current collector layers 20 are interposed between the unit laminates 12'.
  • the method for producing or forming the positive electrode green sheet 14', the negative electrode green sheet 18', the separator green sheet 16', and the current collector layer 20 is as follows.
  • the positive electrode green sheet 14' is a green sheet capable of forming a lithium composite oxide sintered body by firing.
  • the positive electrode green sheet 14' can be produced as follows. First, a raw material powder composed of a lithium composite oxide is prepared. Examples of the raw material powder include LiCoO 2 powder and Li (Ni 0.5 Co 0.2 Mn 0.3 ) O 2 powder. The volume-based D50 particle size of the raw material powder is preferably 0.3 to 30 ⁇ m. The raw material powder is mixed with a dispersion medium and various additives (binder, plasticizer, dispersant, etc.) to form a slurry.
  • a lithium compound (for example, lithium carbonate) other than the lithium composite oxide is excessively added to the slurry in an amount of about 0.5 to 30 mol% for the purpose of promoting grain growth or compensating for volatile matter during the firing step described later. May be good. It is preferable that the slurry is stirred under reduced pressure to defoam and the viscosity is adjusted to 4000 to 10000 cP. The obtained slurry is molded into a sheet to obtain a lithium composite oxide-containing green sheet. Sheet molding is preferably performed using a molding method capable of applying a shearing force to the plate-shaped particles in the raw material powder.
  • the average inclination angle of the primary particles can be set to more than 0 ° and 30 ° or less with respect to the sheet surface.
  • the doctor blade method is suitable as a molding method capable of applying a shearing force to the plate-shaped particles.
  • the thickness of the lithium composite oxide-containing green sheet may be appropriately set so as to be the desired thickness as described above after firing.
  • the negative electrode green sheet 18' is a green sheet capable of forming a titanium-containing oxide sintered body by firing.
  • the titanium-containing green sheet as the negative electrode green sheet 18' may be produced by any method.
  • the production of a green sheet containing lithium titanate Li 4 Ti 5 O 12 (hereinafter, LTO) can be carried out as follows. First, a raw material powder (LTO powder) composed of lithium titanate Li 4 Ti 5 O 12 is prepared. As the raw material powder, a commercially available LTO powder may be used, or may be newly synthesized.
  • a powder obtained by hydrolyzing a mixture of titanium tetraisopropoxyalcohol and isopropoxylithium may be used, or a mixture containing lithium carbonate, titania and the like may be calcined.
  • the volume-based D50 particle size of the raw material powder is preferably 0.05 to 5.0 ⁇ m, more preferably 0.1 to 2.0 ⁇ m.
  • pulverization treatment for example, pot mill pulverization, bead mill pulverization, jet mill pulverization, etc.
  • pulverization treatment for example, pot mill pulverization, bead mill pulverization, jet mill pulverization, etc.
  • the raw material powder is mixed with a dispersion medium and various additives (binder, plasticizer, dispersant, etc.) to form a slurry.
  • a lithium compound other than LiMO 2 for example, lithium carbonate
  • the slurry is stirred under reduced pressure to defoam and the viscosity is adjusted to 4000 to 10000 cP.
  • the obtained slurry is formed into a sheet to obtain an LTO-containing green sheet.
  • Sheet molding can be performed by various well-known methods, but it is preferably performed by the doctor blade method.
  • the thickness of the LTO-containing green sheet may be appropriately set so as to be the desired thickness as described above after firing.
  • Separator Green Sheet 16' is a green sheet capable of forming a ceramic separator by firing.
  • the separator green sheet 16' can be produced as follows. First, a MgO, Al 2 O 3, ZrO 2, SiC, Si 3 N 4, AlN, MgAl 2 O 4, mullite, and at least one ceramic powder is selected from cordierite. Glass frit may be added to this ceramic powder.
  • the volume-based D50 particle size of the raw material powder is preferably 0.05 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m. When the particle size of the raw material powder is large, the pores tend to be large.
  • pulverization treatment for example, pot mill pulverization, bead mill pulverization, jet mill pulverization, etc.
  • the raw material powder is mixed with a dispersion medium and various additives (binder, plasticizer, dispersant, etc.) to form a slurry.
  • the slurry is stirred under reduced pressure to defoam and the viscosity is adjusted to 4000 to 10000 cP.
  • the obtained slurry is formed into a sheet to obtain a separator green sheet 16'.
  • Sheet molding can be performed by various well-known methods, but it is preferably performed by the doctor blade method.
  • the thickness of the separator green sheet 16' may be appropriately set so as to have a desired thickness as described above after firing.
  • the current collector layer 20 is not particularly limited as long as it is a layer containing a conductive material, but it is preferable that the current collector layer 20 forms a metal layer by firing.
  • the current collecting layer 20 may be formed by applying a metal paste (for example, Ag paste, Au paste, Pt paste or Pd paste) to one side of the positive electrode green sheet 14'and / or the negative electrode green sheet 18'.
  • the metal paste may be applied by any method, but it is preferable to apply the metal paste by printing because the current collector layer 20 having a thickness controlled with high accuracy can be formed with high productivity.
  • the pressing may be performed by a known method and is not particularly limited, but is preferably performed by a uniaxial press or a CIP (cold isotropic pressurization method).
  • a preferable press pressure is 10 to 5000 kgf / cm 2 , and more preferably 50 to 3000 kgf / cm 2 .
  • the sheets may be appropriately heated at the time of pressing to improve the crimping property between the sheets. It is preferable to punch the green sheet laminate thus crimped into a desired shape (for example, coin shape or chip shape) or size with a punching die.
  • the deviation between the positive electrode layer 14 and the negative electrode layer 18 can be eliminated.
  • the end face of the positive electrode layer 14 and the end face of the negative electrode layer 18 are aligned, so that the capacity of the battery can be maximized.
  • the green sheet laminated body 22 is calcined to obtain an integrally sintered body 24.
  • the green sheet laminate 22 is degreased and then fired.
  • Degreasing is preferably carried out by holding at 300 to 600 ° C. for 0.5 to 20 hours.
  • the firing is preferably carried out at 650 to 1000 ° C. for 0.01 to 20 hours, more preferably at 800 to 950 ° C. for 0.5 to 10 hours.
  • the rate of temperature rise during firing is preferably 50 to 1500 ° C./h, more preferably 200 to 1300 ° C./h.
  • an integrally sintered body 24 including a plurality of unit laminates 12 ′′ including the positive electrode layer 14, the ceramic separator 16 and the negative electrode layer 18 together with the current collector layer 20 is obtained. If the punching process is not performed at the stage of the green sheet laminated body 22 described above, a shift between the positive electrode layer 14 and the negative electrode layer 18 may occur in the integrally sintered body 24 in the final form. In this case, it is preferable to finish the end face of the integrally sintered body 24 by a method such as laser processing, cutting, or polishing to minimize or eliminate the deviation. As a result, the end face of the positive electrode layer 14 and the end face of the negative electrode layer 18 are aligned, so that the capacity of the battery can be maximized.
  • the integrally sintered body 24 is impregnated with the molten electrolyte 26 to obtain a lithium ion secondary battery 10. It is preferable that the integrally sintered body 24 is impregnated with the electrolyte 26 by putting the integrally sintered body 24 in the container 28 in advance and impregnating the molten electrolyte 26 therein.
  • the integrally sintered body 24 may be impregnated with the electrolyte 26 by pouring the molten electrolyte 26 into the container 28, or the molded body of the solid electrolyte may be placed adjacent to the integrally sintered body 24 (for example, integrally baked).
  • the integrally sintered body 24 may be impregnated with the electrolyte 26 by arranging it above and / or below the body 24 and melting the solid electrolyte by raising the temperature. As shown in FIG. 4C, the integrally sintered body 24 is immersed in the electrolyte 26 with the positive electrode layer 14, the ceramic separator 16, the negative electrode layer 18, and the current collecting layer 20 arranged side by side. It is preferable because it is easy to dispose.
  • the upper surface of the integrally sintered body 24 (the ends of the positive electrode layer 14, the ceramic separator 16, the negative electrode layer 18, and the current collector layer 20 are exposed) was melted by a method such as masking. It is preferable that the electrolyte 26 is absent. However, the integrally sintered body 24 may be immersed in the electrolyte 26 with the positive electrode layer 14, the ceramic separator 16, the negative electrode layer 18, and the current collector layer 20 arranged vertically.
  • the electrolyte 26 is preferably a solid electrolyte obtained by heating it to a temperature equal to or higher than the melting point and melting it.
  • the melting point of this solid electrolyte is 600 ° C. or lower, preferably 250 to 550 ° C., more preferably 275 to 500 ° C., and even more preferably 300 to 450 ° C. Having such a melting point allows the solid electrolyte to be melted and filled in the pores of the ceramic separator 16 and, if desired, in the pores of the positive electrode layer 14 and / or the negative electrode layer 18.
  • the low melting point solid electrolyte described above is preferably a LiOH / Li 2 SO 4 system solid electrolyte. Details of the LiOH / Li 2 SO 4 system solid electrolyte will be described later.
  • the integrally sintered body 24 that is, the lithium ion secondary battery 10) impregnated with the electrolyte 26 is taken out from the container 28 and subjected to final processing such as arrangement of terminals and an external circuit 30. , The final form of the battery.
  • the container 28 may be used as it is as a battery container without removing the integrally sintered body 24 from the container 28.
  • the integrally sintered body 24 impregnated with the electrolyte 26 is allowed to cool or cooled, and the molten electrolyte 26 is solidified. After the electrolyte 26 is solidified, it is preferable to scrape off the solid electrolyte adhering to the end face of the battery to expose the current collector layer 20 to the surface.
  • the lithium ion secondary battery 10 manufactured by the method of the present invention has a plurality of unit cells 12 and a current collecting layer 20 arranged on both sides of the unit cells 12. And an electrolyte 26 (shown only in FIG. 4; not shown in FIGS. 1-3).
  • the unit cell 12 includes, in order, a positive electrode layer 14 made of a lithium composite oxide sintered body, a ceramic separator 16, and a negative electrode layer 18 made of a titanium-containing oxide sintered body.
  • the current collector layer 20 is arranged on both sides of the unit cell 12.
  • the electrolyte is a low melting point electrolyte having a melting point of 600 ° C.
  • a plurality of unit cells 12 are laminated in parallel or in series via the current collector layer 20 to form a cell laminate.
  • the parts of the cell laminate other than the electrolyte form one integral sintered body as a whole, whereby the positive electrode layer 14, the ceramic separator 16, the negative electrode layer 18, and the current collector layer 20 are bonded to each other.
  • the positive electrode layer 14 is composed of a lithium composite oxide sintered body.
  • the fact that the positive electrode layer 14 is made of a sintered body means that the positive electrode layer 14 does not contain a binder or a conductive auxiliary agent. This is because even if the green sheet contains a binder, the binder disappears or burns out during degreasing and firing. Since the positive electrode layer 14 does not contain a binder, a high capacity and good charge / discharge efficiency can be obtained by increasing the packing density of the positive electrode active material.
  • the lithium composite oxide is Li x MO 2 (0.05 ⁇ x ⁇ 1.10, M is at least one transition metal, and M is typically one or more of Co, Ni and Mn. Is an oxide represented by).
  • Lithium composite oxide has a layered rock salt structure.
  • the layered rock salt structure is a crystal structure in which a lithium layer and a transition metal layer other than lithium are alternately laminated with an oxygen layer sandwiched between them, that is, a transition metal ion layer and a lithium single layer are alternately laminated via oxide ions.
  • lithium composite oxides are Li x CoO 2 (lithium cobaltate), Li x NiO 2 (lithium nickelate), Li x MnO 2 (lithium manganate), Li x NimnO 2 (lithium nickel manganate).
  • Li x NiCoO 2 lithium nickel cobaltate
  • Li x CoNiMnO 2 cobalt, nickel, lithium manganate
  • Li x ComnO 2 lithium cobalt manganate
  • cobalt, nickel, Lithium manganate eg Li (Ni 0.5 Co 0.2 Mn 0.3 ) O 2
  • Li x CoO 2 lithium cobaltate, typically LiCoO 2
  • Lithium composite oxides include Mg, Al, Si, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, Ag, Sn, Sb, Te, Ba. , Bi, and W may contain one or more elements selected from. Further, LiMPO 4 having an olivine structure (M is at least one selected from Fe, Co, Mn and Ni in the formula) and the like can also be preferably used.
  • the positive electrode layer 14 preferably contains pores.
  • the "pores" in the positive electrode layer 14 mean an internal space that is confirmed when the positive electrode layer 14 is evaluated as a simple substance that does not contain other constituent components.
  • the inclusion of pores, especially open pores, in the sintered body allows the electrolyte 26 to penetrate into the sintered body when incorporated into the battery as a positive electrode plate, resulting in improved lithium ion conductivity. be able to.
  • the positive electrode layer 14, that is, the lithium composite oxide sintered body preferably has a porosity of 20 to 60%, more preferably 25 to 55%, still more preferably 30 to 50%, and particularly preferably 30 to 45%. be.
  • the stress release effect due to the pores and the increase in capacity can be expected, and the mutual adhesion between the primary particles 11 can be further improved, so that the rate characteristics can be further improved.
  • the porosity of the sintered body is calculated by polishing the cross section of the positive electrode layer by CP (cross section polisher) polishing, observing the SEM at a magnification of 1000, and binarizing the obtained SEM image.
  • the average pore diameter of the positive electrode layer 14, that is, the lithium composite oxide sintered body is preferably 0.1 to 15.0 ⁇ m, more preferably 0.2 to 10.0 ⁇ m, and further preferably 0.3 to 5. It is 0 ⁇ m. Within the above range, the occurrence of local stress concentration in large pores is suppressed, and the stress in the sintered body is easily released uniformly.
  • the thickness of the positive electrode layer 14 is preferably 60 to 450 ⁇ m, more preferably 70 to 350 ⁇ m, and even more preferably 90 to 300 ⁇ m. Within such a range, the active material capacity per unit area is increased to improve the energy density of the lithium ion secondary battery 10, and the battery characteristics are deteriorated (particularly, the resistance value is increased) due to repeated charging and discharging. Can be suppressed.
  • the negative electrode layer 18 is made of a titanium-containing sintered body.
  • the titanium-containing sintered body preferably contains lithium titanate Li 4 Ti 5 O 12 (hereinafter, LTO) or niobium-titanium composite oxide Nb 2 TiO 7 , and more preferably contains LTO.
  • LTO lithium titanate Li 4 Ti 5 O 12
  • Nb 2 TiO 7 niobium-titanium composite oxide
  • LTO is typically known to have a spinel-type structure
  • other structures may be adopted during charging / discharging.
  • LTO reacts in a two-phase coexistence of Li 4 Ti 5 O 12 (spinel structure) and Li 7 Ti 5 O 12 (rock salt structure) during charging and discharging. Therefore, LTO is not limited to the spinel structure.
  • the negative electrode layer 18 is made of a sintered body means that the negative electrode layer 18 does not contain a binder or a conductive auxiliary agent. This is because even if the green sheet contains a binder, the binder disappears or burns out during firing. Since the negative electrode layer does not contain a binder, a high capacity and good charge / discharge efficiency can be obtained by increasing the packing density of the negative electrode active material (for example, LTO or Nb 2 TiO 7).
  • the negative electrode active material for example, LTO or Nb 2 TiO 7
  • the thickness of the negative electrode layer 18 is preferably 70 to 500 ⁇ m, preferably 85 to 400 ⁇ m, and more preferably 95 to 350 ⁇ m.
  • the thickness of the negative electrode layer 18 can be obtained, for example, by measuring the distance between the layer surfaces observed substantially in parallel when the cross section of the negative electrode layer 18 is observed by an SEM (scanning electron microscope).
  • the negative electrode layer 18 preferably contains pores.
  • the "pore" in the negative electrode layer 18 means an internal space that is confirmed when the negative electrode layer 18 is evaluated as a simple substance that does not contain other constituent components.
  • the porosity of the negative electrode layer 18 is preferably 20 to 60%, more preferably 30 to 55%, and even more preferably 35 to 50%. Within such a range, both lithium ion conductivity and electron conductivity are likely to be compatible, which contributes to the improvement of rate performance.
  • the average pore diameter of the negative electrode layer 18 is preferably 0.1 to 15.0 ⁇ m, more preferably 0.2 to 10.0 ⁇ m, and even more preferably 0.3 to 5 ⁇ m. Within such a range, both lithium ion conductivity and electron conductivity are likely to be compatible, which contributes to the improvement of rate performance.
  • the ceramic separator 16 is a microporous ceramic film.
  • the ceramic separator 16 is not only excellent in heat resistance, but also has an advantage that it can be manufactured together with the positive electrode layer 14 and the negative electrode layer 18 as one integrally sintered plate as a whole.
  • the ceramic contained in the ceramic separator 16 is preferably at least one selected from MgO, Al 2 O 3 , ZrO 2 , SiC, Si 3 N 4 , AlN, MgAl 2 O 4, mulite, and cordierite. , More preferably at least one selected from MgO, Al 2 O 3 , and ZrO 2.
  • the thickness of the ceramic separator 16 is preferably 3 to 50 ⁇ m, more preferably 3 to 40 ⁇ m, still more preferably 5 to 35 ⁇ m, and particularly preferably 10 to 30 ⁇ m.
  • the porosity of the ceramic separator 16 is preferably 20 to 80%, preferably 30 to 80%, and more preferably 40 to 80%.
  • the average pore diameter of the ceramic separator 16 is preferably 0.1 to 15.0 ⁇ m, more preferably 0.2 to 10.0 ⁇ m, and even more preferably 0.3 to 5.0 ⁇ m.
  • the "pore" in the ceramic separator 16 means an internal space confirmed when the ceramic separator 16 is evaluated as a simple substance containing no other constituent components.
  • the ceramic separator 16 may contain a glass component from the viewpoint of improving the adhesiveness with the positive electrode layer 14 and the negative electrode layer 18.
  • the content ratio of the glass component in the ceramic separator 16 is preferably 0.1 to 50% by weight, more preferably 0.5 to 40% by weight, still more preferably 0.5, based on the total weight of the ceramic separator 16. ⁇ 30% by weight.
  • the addition of the glass component to the ceramic separator 16 is preferably performed by adding a glass frit to the raw material powder of the ceramic separator 16. However, if the desired adhesiveness between the ceramic separator 16 and the positive electrode layer 14 and the negative electrode layer 18 can be ensured, the inclusion of the glass component in the ceramic separator 16 is not particularly required.
  • Electrolyte The electrolyte 26 is not particularly limited as long as it is a low melting point solid electrolyte having a melting point of 600 ° C. or lower, preferably 250 to 550 ° C., more preferably 275 to 500 ° C., and further preferably 300 to 450 ° C. Has a melting point. Having such a melting point, the solid electrolyte can be filled in the pores of the ceramic separator 16 and, if desired, in the pores of the positive electrode layer 14 and / or the negative electrode layer 18 through pressurization, heating, or the like.
  • the low melting point solid electrolyte described above is a LiOH / Li 2 SO 4 system solid electrolyte.
  • LiOH ⁇ Li 2 SO 4 based solid electrolyte is a solid electrolyte which is identified as 3LiOH ⁇ Li 2 SO 4 by X-ray diffraction.
  • This preferred solid electrolyte contains 3LiOH ⁇ Li 2 SO 4 as the main phase.
  • Whether or not the solid electrolyte contains 3 LiOH / Li 2 SO 4 can be confirmed by identifying it using 032-0598 of the ICDD database in the X-ray diffraction pattern.
  • “3LiOH / Li 2 SO 4 " refers to a crystal structure that can be regarded as the same as that of 3LiOH / Li 2 SO 4, and the crystal composition does not necessarily have to be the same as that of 3LiOH / Li 2 SO 4.
  • the solid electrolyte of the present invention contains a dopant such as boron (for example, 3LiOH / Li 2 SO 4 in which boron is dissolved and the X-ray diffraction peak is shifted to the high angle side), the crystal structure is 3LiOH / Li 2 SO. As long as it can be regarded as the same as 4 , it is referred to herein as 3LiOH ⁇ Li 2 SO 4.
  • the solid electrolyte used in the present invention also allows the inclusion of unavoidable impurities.
  • the LiOH ⁇ Li 2 SO 4 based solid electrolyte which is the main phase other than 3LiOH ⁇ Li 2 SO 4, may be included heterophase.
  • the heterogeneous phase may contain a plurality of elements selected from Li, O, H, S and B, or may consist only of a plurality of elements selected from Li, O, H, S and B. It may be.
  • Examples of the heterogeneous phase include LiOH, Li 2 SO 4 and / or Li 3 BO 3 derived from the raw material. In forming the 3LiOH ⁇ Li 2 SO 4 for these heterogeneous phase, although the unreacted starting materials are thought to have remained, because it does not contribute to the lithium ion conductive, non-Li 3 BO 3 is better the amount is less desirable.
  • a heterogeneous phase containing boron such as Li 3 BO 3
  • the solid electrolyte may be composed of a single phase of 3LiOH / Li 2 SO 4 in which boron is dissolved.
  • the LiOH / Li 2 SO 4 system solid electrolyte (particularly 3 LiOH / Li 2 SO 4 ) preferably further contains boron.
  • 3LiOH ⁇ Li 2 SO 4 by causing further contains boron in solid electrolyte identified as can significantly suppress a decrease in lithium ion conductivity even after holding at a high temperature for a long time. Boron is incorporated into one of the sites of the crystal structure of 3LiOH ⁇ Li 2 SO 4, is presumed to improve the stability against the temperature of the crystal structure.
  • the molar ratio (B / S) of boron B to sulfur S contained in the solid electrolyte is preferably more than 0.002 and less than 1.0, more preferably 0.003 or more and 0.9 or less, still more preferably.
  • the B / S is within the above range, the maintenance rate of lithium ion conductivity can be improved. Further, if the B / S is within the above range, the content of the unreacted heterogeneous phase containing boron becomes low, so that the absolute value of the lithium ion conductivity can be increased.
  • the current collector layer 20 is not particularly limited as long as it is a layer containing a conductive material, but the current collector layer 20 is at least one selected from the group consisting of Ag, Pt, Pd, Au and stainless steel. It is preferable to include seeds.
  • the thickness of the current collector layer 20 is preferably 5 to 50 ⁇ m, more preferably 7 to 40 ⁇ m, and even more preferably 10 to 30 ⁇ m.
  • the lithium ion secondary battery 10 may further contain an ionic liquid.
  • An ionic liquid is a salt that exists as a liquid in a wide temperature range (for example, normal temperature), and is typically a salt having a melting point of 100 ° C. or lower. It is impregnated in the gaps between the porous sintered plate and the molten electrolyte.
  • Ionic liquids include ionic liquid cations, ionic liquid anions and electrolytes.
  • Examples of the ionic liquid cation include imidazolium-based, pyridinium-based, pyrrolidinium-based, piperidinium-based, ammonium-based, and phosphonium-based cations, and examples thereof include 1-ethyl-3-methylimidazolium cation (EMI), 1 -Methyl-1-propylpyrrolidinium cation (MPPy), N-methyl-N-propylpyrrolidinium cation (P13), N-methyl-N-propylpiperidinium cation (PP13), N-butyl-N- Methylpyrrolidinium cation (BMP), N, N-diethyl-N-methyl-N (2-methoxyethyl) ammonium cation (DEME), tetraamyl (pentyl) ammonium cation, tetraethylammonium cation, N-butyl-N methylpyrroli
  • ionic liquid anions include bis (trifluoromethylsulfonyl) imide anions (TFSI), bis (fluorosulfonyl) imide anions (FSI), fluorine-inorganic anions, and combinations thereof.
  • electrolytes include bis (trifluoromethylsulfonyl) imide lithium salt (LiTFSI), bis (fluorosulfonyl) imide lithium salt (LiFSI), lithium hexafluoride phosphate, lithium bisoxalate borate, and lithium tetrafluoroborate. Lithium and combinations thereof can be mentioned. Further, as the grime-based ionic liquid, a mixed solution of an oligoether-based solvent (G3, G4, etc.) and LiTFSI can also be used.
  • LiNi x Co y Mn z O 2 with (x + y + z 1 ) and "NCM”, a Li 4 Ti 5 O 12 shall be referred to as "LTO”.
  • Example 1 (1) Preparation of NCM Green Sheet (Positive Green Sheet) First, the (Ni 0.5 Co 0.2 Mn 0.3 ) OH powder weighed so that the molar ratio of Li / (Ni + Co + Mn) was 1.15. (CorMax) and Li 2 CO 3 powder (manufactured by Honjo Chemical Co., Ltd.) are mixed, held at 750 ° C. for 10 hours, and the obtained powder is crushed with a pot mill so that the volume standard D50 is 10 ⁇ m. A powder composed of NCM particles was obtained.
  • a binder polyvinyl butyral: product number BM-2, manufactured by Sekisui Chemical Co., Ltd.
  • a plasticizer 4 parts by weight (DOP: Di (2-ethylhexyl) phthalate, manufactured by Kurokin Kasei Co., Ltd.) and 2 parts by weight of a dispersant (product name: Leodor SP-O30, manufactured by Kao Co., Ltd.) were mixed.
  • DOP Di (2-ethylhexyl) phthalate, manufactured by Kurokin Kasei Co., Ltd.
  • a dispersant product name: Leodor SP-O30, manufactured by Kao Co., Ltd.
  • the resulting mixture was stirred under reduced pressure to defoam and the viscosity was adjusted to 4000 cP to prepare an LCO slurry.
  • the viscosity was measured with a Brookfield LVT viscometer.
  • the slurry thus prepared was formed into a sheet on a PET film by a doctor blade method to form an NCM green sheet.
  • the thickness of the NCM green sheet was set so that the thickness after firing was 100 ⁇ m.
  • the obtained negative electrode raw material mixture was stirred under reduced pressure to defoam, and the viscosity was adjusted to 4000 cP to prepare an LTO slurry.
  • the viscosity was measured with a Brookfield LVT viscometer.
  • the slurry thus prepared was formed into a sheet on a PET film by a doctor blade method to form an LTO green sheet.
  • the thickness of the LTO green sheet was set so that the thickness after firing was 140 ⁇ m.
  • MgO Green Sheet (Separator Green Sheet) Magnesium carbonate powder (manufactured by Konoshima Chemical Co., Ltd.) was heat-treated at 900 ° C. for 5 hours to obtain MgO powder. The obtained MgO powder and glass frit (manufactured by Nippon Frit Co., Ltd., CK0199) were mixed at a weight ratio of 4: 1.
  • the obtained raw material mixture was stirred under reduced pressure to defoam, and the viscosity was adjusted to 4000 cP to prepare a slurry.
  • the viscosity was measured with a Brookfield LVT viscometer.
  • the slurry thus prepared was formed into a sheet on a PET film by a doctor blade method to form a separator green sheet.
  • the thickness of the separator green sheet was set so that the thickness after firing was 25 ⁇ m.
  • NCM green sheet positive electrode green sheet
  • MgO green sheet separatator green sheet
  • LTO green sheet negative electrode green sheet
  • a unit is used, and a laminate obtained by stacking 4 units of the single units so that the same electrodes face each other (that is, in parallel stacking) is pressed at 200 kgf / cm 2 by CIP (cold isotropic pressure pressurization method). Then, the green sheets were crimped to each other.
  • the laminated body crimped in this way was punched into a 55 mm square plate shape with a punching die.
  • the obtained plate-shaped laminate was degreased at 450 ° C.
  • the obtained coagulated product was pulverized in an Ar atmosphere in a mortar to obtain a solid electrolyte powder having an average particle size D50 of 5 to 50 ⁇ m.
  • the obtained solid electrolyte powder was analyzed by an X-ray diffractometer (XRD, X-ray source: CuK ⁇ ray) to obtain an X-ray diffraction pattern.
  • Metallic Si powder was added as an internal standard to align the 2 ⁇ position.
  • the present invention is not limited to the above examples, and various modifications described below can be implemented.
  • the battery thus obtained can also be charged and discharged.
  • the battery can be produced in the same manner as in Example 1 except that Al 2 O 3 powder or ZrO 2 powder is used instead of MgO powder.
  • -A battery can be produced in the same manner as in Example 1 except that Pt paste or Pd paste is used instead of Ag paste in the formation of the current collector layer ((4) above).
  • -A battery can be manufactured in the same manner as in Example 1 except that the thickness, porosity, and / or pore diameter of the positive electrode and / or the negative electrode are changed.
  • -A battery can be produced in the same manner as in Example 1 except that a LiCoO 2 green sheet is produced instead of the NCM green sheet in the production of the positive electrode green sheet ((1) above).
  • a LiCoO 2 green sheet is produced instead of the NCM green sheet in the production of the positive electrode green sheet ((1) above).
  • the single units are stacked so that different poles face each other (that is, in series stacking) instead of facing the same poles to form a laminated body. Except for this, a battery can be manufactured in the same manner as in Example 1.

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024203869A1 (ja) * 2023-03-31 2024-10-03 日本碍子株式会社 リチウムイオン電池
WO2024203868A1 (ja) * 2023-03-31 2024-10-03 日本碍子株式会社 リチウムイオン電池のための電極およびリチウムイオン電池

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5773827B2 (ja) * 2011-09-30 2015-09-02 京セラ株式会社 二次電池
JP2018097982A (ja) * 2016-12-09 2018-06-21 Fdk株式会社 全固体電池の製造方法
JP6392576B2 (ja) * 2014-08-06 2018-09-19 日本特殊陶業株式会社 リチウム電池
JP2019192609A (ja) * 2018-04-27 2019-10-31 日本碍子株式会社 全固体リチウム電池及びその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5773827B2 (ja) * 2011-09-30 2015-09-02 京セラ株式会社 二次電池
JP6392576B2 (ja) * 2014-08-06 2018-09-19 日本特殊陶業株式会社 リチウム電池
JP2018097982A (ja) * 2016-12-09 2018-06-21 Fdk株式会社 全固体電池の製造方法
JP2019192609A (ja) * 2018-04-27 2019-10-31 日本碍子株式会社 全固体リチウム電池及びその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024203869A1 (ja) * 2023-03-31 2024-10-03 日本碍子株式会社 リチウムイオン電池
WO2024203868A1 (ja) * 2023-03-31 2024-10-03 日本碍子株式会社 リチウムイオン電池のための電極およびリチウムイオン電池

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