WO2014132333A1 - Batterie secondaire au lithium-ion entièrement solide - Google Patents

Batterie secondaire au lithium-ion entièrement solide Download PDF

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WO2014132333A1
WO2014132333A1 PCT/JP2013/054931 JP2013054931W WO2014132333A1 WO 2014132333 A1 WO2014132333 A1 WO 2014132333A1 JP 2013054931 W JP2013054931 W JP 2013054931W WO 2014132333 A1 WO2014132333 A1 WO 2014132333A1
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solid electrolyte
particles
solid
active material
secondary battery
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PCT/JP2013/054931
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English (en)
Japanese (ja)
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純 川治
良幸 高森
心 ▲高▼橋
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株式会社 日立製作所
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Priority to PCT/JP2013/054931 priority Critical patent/WO2014132333A1/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
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 an all solid lithium ion secondary battery.
  • Ceramic electrolyte materials include sulfide electrolytes that contain lithium-sulfur, phosphorus-sulfur, and transition metal-sulfur bonds in the polyanion, and oxide electrolytes that contain lithium-oxygen, phosphorus-oxygen, and transition metal-oxygen bonds. Is promising.
  • Sulfide-based electrolytes are suitable for conduction of lithium migration because of the large atomic radius of sulfur and high polarizability. Moreover, it is easy to deform
  • sulfide-based electrolytes are very unstable in the atmosphere and have further problems such as decomposition by moisture absorption and generation of toxic gas, hydrogen sulfide.
  • oxide-based electrolytes are highly safe because they are stable in the air and have excellent heat resistance.
  • the problems are low lithium ion conductivity in the electrolyte particles and high ion resistance (grain boundary resistance) between the electrolyte particles and between the electrolyte particles and the positive and negative electrode particles. As a result, the output characteristics and rate characteristics are reduced due to the increase in resistance of the battery.
  • Patent Document 1 JP-A-2001-243984 (Patent Document 1), attention is paid to the contact resistance between an electrode and a solid electrolyte, and in order to increase the contact area between the active material particles and the solid electrolyte, the active material particles and the particle binding material are used.
  • a unipolar side electrode composed of a porous structure, a solid electrolyte layer composed of an ion conductive material deposited on the surface of the void of the porous structure, and the void of the porous structure filled A solid electrolyte battery having another active material and another polar side electrode made of a filling material is disclosed. However, a reduction in resistance within the electrode is not considered.
  • Patent Document 2 in order to secure a lithium ion path in an electrode, all solid lithium in which an active material is disposed in a solid electrolyte network structure sintered in advance as a porous body. An ion secondary battery is disclosed.
  • the resistance between the current collector and the active material layer may increase, and it is expected that it is difficult to fill the porous material with the active material at a high density.
  • Patent Document 3 pays attention to the particle size of the solid electrolyte, includes a solid electrolyte layer composed of a laminate of electrolyte layers having different average particle diameters, and lithium metal deposited between the positive and negative electrodes.
  • a battery provided with a space that can be accommodated is disclosed.
  • such a structural change does not contribute to improvement of lithium ion conductivity in the electrode.
  • An object of the present invention is to reduce the lithium ion conduction resistance in the electrode and improve the rate characteristics of the all-solid battery.
  • a feature of the present invention that solves the above problems is an all-solid lithium ion secondary battery comprising a positive electrode and a negative electrode capable of inserting and extracting lithium ions, and a solid electrolyte layer provided between the positive electrode and the negative electrode, At least one of the positive electrode and the negative electrode includes active material particles, solid electrolyte particles made of an oxide capable of conducting lithium ions, and a current collector, and the solid electrolyte particles having different average particle diameters are used for the electrodes. There is that. When particles having different average particle sizes are mixed, the particle size distribution has two or more peaks.
  • a solid electrolyte having a large average particle diameter exists between the active material particles, and is arranged so as to fill the voids between the active materials.
  • the electrode configuration is preferably changed from the surface in contact with the electrolyte layer to the surface in contact with the current collector so that the solid electrolytic mass increases.
  • the solid electrolyte particle diameter in the vicinity of the interface between the solid electrolyte layer and the electrode is larger than that of other portions of the electrode.
  • the above configuration can provide an all-solid battery with high rate characteristics.
  • a lithium ion secondary battery is an electrochemical device that stores and releases by lithium storage and desorption with electron transfer in two electrode layers containing an active material capable of storing and desorbing lithium ions. Since lithium ions as charge carriers have a small atomic weight and a high ionization tendency, they have higher volume energy density and weight energy density than other secondary batteries. Therefore, it is widely used as a power source for portable devices such as mobile phones and notebook PCs, a power source for hybrid and electric vehicles, and a power storage power source for power generation systems using renewable energy such as solar power generation and wind power generation. .
  • the solid electrolyte is a solid that can move ions inside.
  • Ceramic materials that conduct lithium ions are composed of a polyanion skeleton having a Li ion serving as a carrier and a void serving as a passage for the Li ion, and are classified into sulfide-based electrolytes, oxide electrolytes, etc. depending on the constituent elements and structure of the polyanion skeleton. .
  • oxide-based electrolytes have (1) low lithium ion conduction in electrolyte particles, (2 )
  • the ion resistance (grain boundary resistance) between adjacent particles is high in the solid electrolyte layer, the positive electrode, and the negative electrode.
  • the solid electrolyte particles are dispersed small in the electrode to increase the contact area between the solid electrolyte and the active material, it passes through many solid electrolyte grain boundaries before lithium is transferred from the active material to the solid electrolyte layer.
  • the grain boundary resistance increases the resistance of the entire electrode, resulting in a decrease in the output characteristics and rate characteristics of the battery.
  • the present invention relates to an active material-solid electrolyte, solid electrolyte particle-solid electrolyte particle ion, by controlling the particle size and distribution of the electrolyte particles introduced into the electrode for an all-solid lithium battery using oxide ceramics as an electrolyte.
  • oxide ceramics as an electrolyte.
  • the present inventors paid attention to the particle diameter of the solid electrolyte with respect to the positive electrode active material and measured the resistance of the electrode to which the solid electrolyte having various particle size distributions was applied. By introducing it into the electrode, we succeeded in dramatically reducing the ionic resistance in the electrode. As a result, an all-solid-state lithium ion battery with reduced lithium ion conduction resistance in the electrode can be provided.
  • An all-solid lithium secondary battery is an all-solid lithium ion secondary battery configured such that a positive electrode and a negative electrode are stacked so as to sandwich a solid electrolyte layer, and at least one of the positive electrode and the negative electrode
  • the electrode includes active material particles capable of inserting and extracting lithium ions, solid electrolyte particles made of an oxide capable of conducting lithium ions, and a current collector.
  • the solid electrolyte particles are particles having different average particle sizes. It is characterized by comprising.
  • the lithium conduction path from the active material particles to the solid electrolyte particles is increased, and the grain boundary during lithium conduction between the solid electrolyte particles is reduced.
  • an electrode corresponding to a high rate with a low lithium conduction resistance can be provided.
  • the solid electrolyte particles having a small particle size have the effect of increasing the contact area with the electrode active material.
  • Solid electrolyte particles having a large particle size have a small number of grain boundaries when lithium ions move by a certain distance, and the total grain boundary resistance is reduced. Therefore, a solid electrolyte having a large particle size is disposed between the active materials, and is used to conduct lithium ions desorbed and inserted from the active material in the electrode thickness direction.
  • the method for measuring the particle size distribution of the solid electrolyte is not particularly limited.
  • the particle size of a plurality of solid electrolyte particles can be measured from a cross-sectional SEM or TEM observation image of the electrode.
  • the particle diameter is the equivalent circle diameter when the particle cross-sectional shape is assumed to be a circle.
  • the particle size distribution of the solid electrolyte particles has two or more peaks.
  • the smaller one is preferably 10% or less of the average particle size of the active material, and the larger one is preferably 40% or less of the average particle size of the active material.
  • the solid electrolyte particles having a small particle size provide a sufficient contact area with the active material surface, and the gaps between the active material particles are effectively filled with the solid electrolyte having a large particle size.
  • the solid electrolyte particles having a small average particle diameter are disposed on or near the surface of the electrode active material, and the solid electrolyte particles having a large average particle diameter are disposed so as to fill the voids of the active material particles.
  • the solid electrolyte particles having a small average particle diameter are preferably brought into physical contact with the active material or deposited along the surface shape, and the solid electrolyte particles having a large average particle diameter are formed in a gap formed by a plurality of active materials. It exists and is in contact with two or more active material particles, or solid electrolyte particles on the surface thereof.
  • the solid electrolyte particles having a small average particle size contribute to an increase in the contact area with the active material, and the solid electrolyte particles having a large average particle size both improve lithium ion conductivity as a result of reducing the amount of grain boundaries.
  • Another configuration is to increase the proportion of the solid electrolyte particles contained in the electrode on the surface in contact with the current collector, rather than the proportion of the solid electrolyte particles contained in the electrode on the surface in contact with the solid electrolyte layer.
  • the solid electrolyte particles are ceramic particles having a metal oxide as a main skeleton.
  • Lithium-oxygen, phosphorus-oxygen, oxide electrolytes containing transition metal-oxygen bonds are known, Specifically, NASICON (Na super ion conductor) type Li 1 + x Al x Ti 2-x (PO 4 ) 3 , Li 1 + x Al x Ge 2-x (PO 4 ) 3 (x is 0 or more) 1 or less) Li 14 Zn (GeO 4 ) 4 of a LISICON (Li super ion conductor) type, Li 3x La 2 / 3-x TiO 3 having a perovskite structure (x is 0 or more and 2/3 or less), and having a garnet structure Examples thereof include Li 5 La 3 Nb 2 O 12 , Li 5 La 3 Ta 2 O 12 , Li 7 La 3 Zr 2 O 12 , Li 6.25 La 3 Zr 2 Ga 0.25 O 12 and the like. Moreover, you may coat
  • the active material particles and the solid electrolyte particles are mixed and sintered, they are pulverized, and further, the solid electrolyte particles having a larger average particle diameter than that added in the previous stage to the mixture of the pulverized active material and the solid electrolyte particles Are mixed and sintered again.
  • a precursor of solid electrolyte particles may be used.
  • the active material particles and the precursor of the solid electrolyte particles can be mixed and fired to form solid electrolyte particles on the surface of the active material particles. Then, this is grind
  • FIG. 1 and 2 are cross-sectional schematic views of a conventional all-solid lithium ion secondary battery.
  • 101 is a negative electrode
  • 102 is a solid electrolyte layer
  • 103 is a positive electrode.
  • Charging / discharging of the negative electrode 101 and the positive electrode 103 proceeds through the current collecting material 104.
  • FIG. 2 schematically shows the configuration of the electrode in the all solid lithium ion secondary battery.
  • the configuration of the positive electrode and the negative electrode is common, and includes an active material (201), a conductive additive (202), a solid electrolyte (203), a solid electrolyte layer (220), a current collector (230), and the like. .
  • an active material, a solid electrolyte, and a conductive additive are uniformly mixed in the electrode, and lithium ions are conducted through a path in which the solid electrolyte particles are in continuous contact.
  • the solid electrolyte and the conductive aid are smaller than the active material, and the contact area between the active material and each particle is increased.
  • the number of particle interfaces increases, and the lithium conduction resistance in the electrode film thickness direction increases due to the grain boundary resistance.
  • FIG. 3 shows a schematic cross-sectional view of the all-solid-state lithium ion secondary battery of the present invention.
  • the solid electrolyte group (303a) having a small particle size is mixed with the solid electrolyte group (303b) having a large particle size as compared with 303a, and the solid electrolyte group (303a) having a small particle size is composed of the active material (301). Easy to touch the surface.
  • the solid electrolyte group (303b) having a large particle size is in contact with at least two or more of the active material or solid electrolyte particles in contact with the active material, the particle size is large, and lithium ions move smoothly through the particles. Therefore, lithium ion conduction in the electrode thickness direction is promoted.
  • the electrolyte (303a) in contact with the solid electrolyte is as small a crystal particle as possible in order to increase the contact area.
  • the average particle diameter of the active material is D, it is preferably D ⁇ 0.2 or less, more preferably D ⁇ 0.1 or less. If the particle size is larger than these, not only the contact area is insufficient, but also the electrode bulk density is lowered and the energy and output density are lowered. The smaller the particle size, the better.
  • the particle size is so small that the crystallinity cannot be maintained, lithium ion conduction is inhibited, which is not desirable.
  • the thickness is 10 nm or less, the crystallinity is easily impaired, which is not desirable.
  • the solid electrolyte (303b) disposed between the active materials is preferably large in order to reduce the amount of grain boundaries and promote lithium ion conduction in the electrode.
  • the electrode density is extremely impaired (FIG. 4).
  • the contact area with other particles is reduced. Therefore, when the average particle diameter of the active material is D, D ⁇ 0.4 or less is desirable.
  • the particle size of D ⁇ 0.4 is close to a particle diameter that can enter a gap in a fine-structure sphere when the active material particles are assumed to be spheres. Even if these particles are too small, they are arranged between the particles.
  • the positive electrode active material a known positive electrode active material capable of occluding and releasing lithium ions can be used.
  • LiMO 2 M is at least one transition metal, such as Ni, Co, Mn, Fe, Ti, Zr, Al, Mg, Cr, and V
  • LiMO 2 that is, lithium manganate, lithium cobaltate, nickel acid
  • a material obtained by substituting a part of manganese, cobalt, or nickel such as lithium with one or two transition metals, or a metal element such as magnesium or aluminum can be used.
  • spinel system, olivine system, layered oxide system, Li-excess layered solid solution system, silicate system, vanadium oxide system, etc. are exemplified.
  • the negative electrode active material a known negative electrode active material capable of occluding and releasing lithium ions can be used.
  • a carbon material typified by graphite
  • an alloy material such as a TiSn alloy or a TiSi alloy, a nitride such as LiCoN, or an oxide such as Li 4 Ti 5 O 12 or LiTiO 4
  • an all-solid battery having the structure shown in FIG. 3 can be fabricated using a lithium metal foil for the negative electrode and the positive electrode.
  • the conductive auxiliary material (302) is additionally used for the electrode as necessary.
  • a typical example is carbon black such as ketjen black or acetylene black.
  • metal powders such as gold, silver, copper, nickel, aluminum, and titanium can be used, and Sb-doped SnOx, TiOx, TiNx, and the like can also be used in the oxide.
  • the solid electrolyte is preferably a nonflammable inorganic solid electrolyte from the viewpoint of safety among solid materials that conduct lithium ions.
  • oxide glass represented by Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 , LiAlGe (PO 4 ) 3 , Li 3.4 V 0.6 Si 0.4 O 4 , Li 2 P 2 O 6 , Li 0.34 Perovskite oxides typified by La 0.51 TiO 2.94 , garnet oxides typified by LiLaZrO 2, etc.
  • Lithium halides such as LiCl and LiI may be contained in the solid electrolyte made of an oxide.
  • the ratio of the active material particles and the solid electrolyte particles in the electrode may not be constant.
  • An example in which the ratio of the active material and the solid electrolyte changes continuously or stepwise in the electrode film thickness direction is conceivable.
  • the volume fraction of the solid electrolyte particles with respect to the active material particles is increased from the surface side in contact with the solid electrolyte layer to the surface side in contact with the current collector.
  • the local lithium conductivity is increased at a position away from the electrolyte layer, that is, at a position where the lithium movement distance is large, the difference in reaction rate with the active material close to the electrolyte layer can be kept small, and current concentration is prevented.
  • the difference in volume fraction between the solid electrolyte side and the current collector side is not particularly limited.
  • the volume fraction on the current collector side is 1.
  • the structure which is 5 times can be mentioned.
  • the size of the solid electrolyte is preferably a configuration in which the solid electrolyte (303b) disposed between the active materials is increased on the current collector side.
  • FIG. 5 is a diagram showing a configuration example in which the particle diameter of the solid electrolyte particles changes in the electrode.
  • the ratio of the solid electrolyte (503b) having a larger particle diameter than that in the vicinity of the interface with the current collector is increased, and the average particle diameter of the solid electrolyte particles is increased.
  • the porosity in the vicinity of the interface increases.
  • the expansion and contraction in the in-plane direction of the electrode during charging / discharging can be suppressed, which is desirable.
  • the vicinity of the interface with the solid electrolyte layer refers to an electrode region within 5 ⁇ m from the boundary between the two confirmed by cross-sectional observation.
  • FIG. 6A is a diagram showing a configuration in which the surface of the solid electrolyte particles is covered with an amorphous oxide glass material.
  • the amorphous glass material is not particularly limited and has a void enough to conduct lithium ions. Since the oxide glass material does not have a specific crystal orientation, Li ions are conducted three-dimensionally and promote lithium conduction at the contact between the particles. Compared to Li ion conduction in solid electrolyte particles, the problem is that ion conduction between particles is low, but by covering the glass material, the contact area between adjacent solid electrolyte particles increases, and ions between solid electrolyte particles As a result of the enhanced conduction, the internal resistance of the battery is reduced.
  • FIG. 6B is a diagram showing a configuration in which the surface of the active material particles is covered with an amorphous oxide glass material.
  • the amorphous glass material is not particularly limited and has a void enough to conduct lithium ions. Since the oxide glass material does not have a specific crystal orientation, Li ions are conducted three-dimensionally and promote lithium conduction at the contact between the particles.
  • the term “between particles” here refers to both between the active material particles and the active material particles and between the active material particles and the solid electrolyte particles.
  • the glass material that can be used for the coating of the active material particles and the solid electrolyte particles in FIG. 6 is particularly limited as long as it is softened or melted at a relatively low temperature and has a diffusion path through which Li ions can be conducted.
  • the softening point is desirably 500 ° C. or lower, and more desirably 400 ° C. or lower.
  • the oxide glass described here includes, in addition to what is called amorphous ordinary glass, crystallized glass in which crystals are precipitated in an amorphous glass matrix.
  • Glass containing vanadium oxide as a main component is desirable as a coating material because it has higher electron conductivity than other glass materials and a relatively high Li diffusion coefficient.
  • a component of vanadium oxide it contains at least one oxide selected from tellurium or phosphorus.
  • the low melting point oxide glass of the present invention is characterized by containing oxides of iron, manganese, tungsten, molybdenum, barium, cobalt, silver, etc. in order to control crystallinity, softening point, and coefficient of thermal expansion.
  • This oxide glass has a softening point of 500 ° C. or lower, more preferably a softening point of 400 ° C. or lower.
  • Li which is a conductive carrier
  • the amount of oxide glass added to the active material or solid electrolyte is preferably 5% by volume or more and 30% by volume or less in terms of volume.
  • the volume is 5% by volume or more with respect to the total volume of the active material and the solid electrolyte, the surface of the active material particles and the solid electrolyte particles can be sufficiently covered.
  • the volume is 30% by volume or less, the amount of the active material and the solid electrolytic mass are reduced. It is possible to prevent a decrease in charge / discharge capacity and charge / discharge rate due to the decrease.
  • Active material particles capable of occluding and releasing lithium ions and solid electrolyte particles having a particle size of 10% or less of the particle size are mixed in a solvent, slurried, dried, sintered, powdered, and formed on the surface of the active material particles. Place solid electrolyte particles, sufficiently smaller than that.
  • a spray dryer device By drying with a spray dryer device, a fine powder is obtained, and this is subjected to a high temperature treatment, whereby the bonding between the active material particles during drying and sintering can be suppressed.
  • the active material particles with a solid electrolyte thus obtained are mixed with a solid electrolyte having a large particle diameter and formed into a sheet on a current collector to obtain a desired structure.
  • active material particles are impregnated in a sol that is a precursor of a solid electrolyte, and precursor metal ions are adsorbed on the surface thereof, followed by drying and a condensation reaction.
  • active material particles having fine solid electrolyte particles attached to the surface can be obtained.
  • a desired structure can be obtained by mixing with solid electrolyte particles having a large particle size and forming into a sheet.
  • the positive electrode green sheet and the solid electrolyte green sheet were combined so that their centers coincided, and hot pressing was performed under conditions of 10 kN and 160 ° C.
  • hot pressing not only the positive electrode and the electrolyte are pressure-bonded, but also the PET film is peeled off from the electrolyte green sheet to form a positive electrode-electrolyte layer laminate.
  • the laminate was fired at 500 ° C. in the air for 1 hour to remove the binder component, and then heated and fired at 600 ° C. in a nitrogen atmosphere. Furthermore, the side surface of the laminate was masked with an insulator. Subsequently, a polyethylene oxide film containing lithium salt and a lithium foil were laminated on the electrolyte layer side, and a CR2025 type coin battery was fabricated by incorporating this (Comparative Example 1 battery).
  • Comparative Example 2 A laminate and a coin battery were produced in the same manner as in Comparative Example 1 except that LATP powder having an average particle size of 4.3 ⁇ m was used (Comparative Example 2 battery).
  • Example 1 The LATP powder with an average particle diameter of 0.8 ⁇ m is mixed with the LiCoO 2 powder with an average particle diameter of 12 ⁇ m at a weight ratio of 75:25, terpineol solvent is added, and the mixture is dried and pulverized. I let you. SEM observation of the obtained powder (powder A) confirmed that the LATP powder was fixed to the LiCoO 2 powder.
  • LATP powder having an average particle size of 4.3 ⁇ m and Ketjen black as a conductive additive were mixed in a mortar at a weight ratio of 80:10:10.
  • the weight ratio of LiCoO 2 , LATP, and ketjen black in this mixture is 60:30:10, which is the same as in Comparative Examples 1 and 2.
  • Example 1 battery The ethylcellulose solution was added to the mixed powder so that the binder ratio to the powder was 7: 3 and mixed to prepare a positive electrode paste B, and a laminate and a coin battery were manufactured in the same manner as in Comparative Examples 1 and 2. (Example 1 battery).
  • Example 2 In this example, a battery similar to that in Example 1 was manufactured by a different manufacturing method.
  • LiCoO 2 powder having an average particle size of 12 ⁇ m was impregnated with a solution containing a precursor of Li, Al, Ti, and P, and LATP was fixed to the surface by a sol-gel method. After removing the solvent and firing, SEM observation of the obtained powder confirmed that the LATP powder was fixed in the form of LiCoO 2 powder. The weight of the powder after the treatment is increased by 33% compared to the weight before the treatment, and the weight ratio of LiCoO 2 and LATP produced by the sol-gel method is considered to be about 75:25. From SEM observation, the particle size of the surface LATP powder was measured at 50 points, and it was confirmed that the average particle size was 1.1 ⁇ 0.3 ⁇ m.
  • LATP powder having an average particle size of 4.3 ⁇ m and ketjen black as a conductive aid were mixed in a mortar at a weight ratio of 80:10:10, respectively, with the powder obtained by firing.
  • the weight ratio of LiCoO 2 , LATP, and ketjen black in this mixture is the same as in Comparative Examples 1 and 2.
  • Example 2 In the same manner as in Example 1, an ethylcellulose solution was added to the mixed powder so that the binder ratio to the powder was 7: 3 and mixed to prepare a positive electrode paste, and a laminate and a coin battery were manufactured (Example 2). battery)
  • Example 3 the particle size of the solid electrolyte particles having a large particle size in Example 1 was changed.
  • the powder A obtained in Example 1 was mixed with LATP powder having an average particle size of 8.5 ⁇ m and ketjen black as a conductive additive in a mortar at a weight ratio of 80:10:10, respectively.
  • the weight ratio of LiCoO 2 , LATP, and ketjen black in this mixture is the same as in Comparative Examples 1 and 2.
  • Example 3 the ethylcellulose solution was added to the mixed powder so that the binder ratio to the powder was 7: 3 and mixed to prepare a positive electrode paste, and a laminate and a coin battery were prepared (Example 3). battery
  • Example 4 This example is an example having a positive electrode layer in which the mixing amount of solid electrolyte particles is changed stepwise.
  • a positive electrode paste F1 having a large amount of solid electrolyte particles was prepared.
  • a LATP powder with an average particle size of 0.8 ⁇ m is mixed with LiCoO 2 powder with an average particle size of 12 ⁇ m so that the weight ratio is 65:35, terpineol solvent is added, and the mixture is dried and ground. It was. SEM observation of the obtained powder confirmed that the LATP powder was fixed to the LiCoO 2 powder.
  • LATP powder having an average particle size of 4.3 ⁇ m and ketjen black as a conductive additive were mixed in a mortar at a weight ratio of 77:13:10, respectively.
  • the weight ratio of LATP to LiCoO 2 in this mixture is 0.8, which is higher than 0.5 in Comparative Examples 1 and 2.
  • the ethylcellulose solution was added to the mixed powder so that the binder ratio to the powder was 7: 3 and mixed to prepare a positive electrode paste F1.
  • a positive electrode paste F2 with a small amount of solid electrolyte particles mixed was produced.
  • a LATP powder with an average particle size of 0.8 ⁇ m is mixed with LiCoO 2 powder with an average particle size of 12 ⁇ m so that the weight ratio is 84:16, terpineol solvent is added, and the mixture is dried and ground. It was. SEM observation of the obtained powder confirmed that the LATP powder was fixed to the LiCoO 2 powder.
  • LATP powder having an average particle size of 4.3 ⁇ m and ketjen black as a conductive aid were mixed in a mortar at a weight ratio of 83: 7: 10, respectively.
  • the weight ratio of LATP to LiCoO 2 in this mixture is 0.29, which is lower than 0.5 in Comparative Examples 1 and 2.
  • the ethylcellulose solution was added to the mixed powder so that the binder ratio to the powder was 7: 3 and mixed to prepare a positive electrode paste F2.
  • the side surface of the obtained laminate was masked with an insulator, and a polyethylene oxide film containing lithium salt and a lithium foil were laminated on the electrolyte layer side, and a CR2025 type coin battery was fabricated by incorporating this (Example 4 battery) ).
  • Example 5 The present example is an example having a positive electrode layer in which the average particle size of the solid electrolyte particles is changed stepwise.
  • LATP powder with an average particle size of 4.3 ⁇ m and ketjen black as a conductive aid were mixed in a mortar at a weight ratio of 75:15:10, respectively.
  • the weight ratio of LiCoO 2 , LATP, and ketjen black in this mixture is 60:30:10, which is the same as in Comparative Examples 1 and 2.
  • the ethyl cellulose solution was added to the mixed powder so that the binder ratio to the powder was 7: 3, and mixed to prepare a positive electrode paste G.
  • the positive electrode paste obtained in the above step was applied onto a PET film, the positive electrode paste A prepared in Example 1 was applied onto an aluminum foil, the solvent was removed, and then the aluminum foil and the PET film coated with the paste were respectively applied. Bonding was performed so that the electrode surfaces face each other, and thermocompression bonding was performed. Thereafter, the PET film was peeled off, and the electrolyte sheet was thermocompression bonded from above. In this configuration, the average particle diameter of the electrolyte particles in the vicinity of the boundary between the solid electrolyte layer and the electrode layer is large.
  • the side surface of the obtained laminate was masked with an insulator, and a polyethylene oxide film containing lithium salt and a lithium foil were laminated on the electrolyte layer side, and this was incorporated to produce a CR2025 type coin battery (Example 5 battery) ).
  • an amorphous glass coating having Li conductivity is provided on the surface of the positive electrode active material and the solid electrolyte in the positive electrode.
  • lithium oxide (Li 2 O), vanadium oxide (V 2 O 5 ), phosphorus oxide (P 2 O 5 ), and iron oxide (Fe 2 O 3 ) are in a molar ratio of 10: 55: 25: 10.
  • Amorphous glass H was obtained by mixing and heating to quench the melt. It was 400 degreeC when the softening point of the glass obtained by the differential thermal analysis (DTA) method was investigated. Glass H was added to the paste B obtained in Example 1 and further mixed. The weight of the glass added at this time was set to 10% with respect to the weight of LiCoO 2 in the paste.
  • An electrode was applied using a positive electrode paste containing glass, and kept at a temperature of 410 ° C. above the softening point for 10 minutes. By the cross-sectional SEM, a configuration in which the periphery of the active material and the solid electrolyte is covered with the glass H in the obtained electrode can be confirmed.
  • a coin battery was made in the same manner as in Example 1 except that this electrode was used (Example 6 battery).
  • Example 1-6 were better than those of Comparative Examples 1 and 2 for both the 0.1 C rate and the 1 C rate. This is considered to be because the ionic conductivity in the electrode is improved by using solid electrolyte particles having a particle size distribution.
  • Example 2 has almost the same 0.1C rate as Example 1, but the characteristics of 1C rate are improved.
  • Example 1 and 2 there is no difference in the electrolytic mass in the electrode, but in Example 2, a solid electrolyte is directly formed on the active material surface using the sol-gel method, and the contact area between the active material and the solid electrolyte Therefore, it is considered that the lithium conduction at the interface is promoted, and as a result, the performance of the 1C rate is improved.
  • Example 3 Compared to Example 3, the performance of other examples is high.
  • the solid electrolyte used in Example 3 contains 8.5 ⁇ m, which is larger than the appropriate range, which means that ion path formation in the electrode is not satisfactorily formed. Therefore, the solid electrolyte particles are preferably 40% or less with respect to the particle diameter of the positive electrode active material particles.
  • Example 4 resulted in the best discharge characteristics. It is considered that the reaction uniformity in the electrode was maintained as a result of increasing the amount of active material in the vicinity of the solid electrolyte layer and reducing the solid electrolytic mass, and decreasing the amount of active material in the vicinity of the current collector layer and increasing the solid electrolytic mass. Therefore, it is preferable that the ratio of the solid electrolyte particles in the electrode is large on the current collector side and small on the solid electrolyte layer side. In the present example, two layers were formed, but further improvement in performance is expected by increasing the solid electrolytic mass stepwise from the electrolyte layer side toward the current collector side.
  • Example 5 almost the same performance as Example 1 was obtained.
  • Example 5 there is no change in the ratio of the amount of active material to the solid electrolytic mass in the electrode thickness direction, but the average particle diameter of the solid electrolyte in the electrode close to the solid electrolyte layer is large, and in the vicinity of the solid electrolyte layer-electrode layer interface. This increases the porosity.
  • expansion and contraction in the in-plane direction of the electrode during charging / discharging can be suppressed. Therefore, even if the charge / discharge cycle is repeated, the discharge capacity can be maintained over many cycles.
  • Example 6 in which the active material and the solid electrolyte were coated with an amorphous glass material having lithium conductivity was higher in both cases of 0.1 C rate and 1 C rate than uncoated Example 1. Discharge characteristics were obtained. It is considered that the capacity of the 0.1 rate is increased because the ion conduction path between the active material particles and the active material particles is increased between the active material particles and the solid electrolyte particles, and the amount of the active material that can be used for charging and discharging is increased in the electrode. Moreover, it is thought that the ionic conduction resistance between the particles was reduced by the coating of the Li conductive glass material and the internal resistance of the whole battery was reduced, which contributed to the performance improvement at the 1C rate.
  • Example disclosed by the Example is only a positive electrode, the same effect is seen also in a negative electrode.
  • the battery is the all-solid battery of the present invention can be determined by disassembling the all-solid battery and observing the cross-sectional image with an SEM or a TEM.
  • the present invention can be used for all-solid lithium secondary batteries using oxide ceramics, lithium-air batteries, and the like.

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Abstract

L'invention concerne une batterie secondaire au lithium-ion entièrement solide comprenant des électrodes positive et négative pouvant absorber et libérer des ions lithium et une couche d'électrolyte solide mise en sandwich entre les électrodes positive et négative. Dans la batterie secondaire au lithium-ion entièrement solide, au moins une des électrodes positive et négative est équipée de particules de matériau actif, de particules d'électrolyte solide constituées de particules d'oxyde pouvant conduire des ions lithium, et d'un collecteur. En particulier, les particules d'électrolyte solide présentant différents diamètres moyens de particule sont utilisées pour l'électrode. Les particules présentent différents diamètres moyens de particule, ce qui fait en sorte que la distribution de diamètre de particule présente deux crêtes ou plus lorsque les particules sont mélangées. Cela permet de fournir une batterie entièrement solide présentant des caractéristiques de rendement élevé.
PCT/JP2013/054931 2013-02-26 2013-02-26 Batterie secondaire au lithium-ion entièrement solide WO2014132333A1 (fr)

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CN110226255A (zh) * 2017-01-24 2019-09-10 日立造船株式会社 全固态电池及其制造方法
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CN107946639A (zh) * 2016-10-12 2018-04-20 松下知识产权经营株式会社 固体电解质以及使用该固体电解质的二次电池
CN107946639B (zh) * 2016-10-12 2022-02-08 松下知识产权经营株式会社 固体电解质以及使用该固体电解质的二次电池
CN107968220A (zh) * 2016-10-20 2018-04-27 现代自动车株式会社 活性材料复合颗粒、包括其的电极复合物及其制造方法
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EP3576192A4 (fr) * 2017-01-24 2020-11-11 Hitachi Zosen Corporation Procédé de fabrication d'électrode pour batterie totalement solide et procédé de fabrication de batterie totalement solide
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KR20190103353A (ko) * 2017-01-24 2019-09-04 히다치 조센 가부시키가이샤 전고체 전지용 전극의 제조방법 및 전고체 전지의 제조방법
CN110226255A (zh) * 2017-01-24 2019-09-10 日立造船株式会社 全固态电池及其制造方法
CN110226255B (zh) * 2017-01-24 2023-02-17 日立造船株式会社 全固态电池及其制造方法
JP2018120710A (ja) * 2017-01-24 2018-08-02 日立造船株式会社 全固体電池の製造方法
US11121403B2 (en) 2017-01-24 2021-09-14 Hitachi Zosen Corporation Production method of electrode for all-solid-state batteries and production method of all-solid-state battery
WO2018139449A1 (fr) * 2017-01-24 2018-08-02 日立造船株式会社 Procédé de fabrication d'électrode pour batterie totalement solide et procédé de fabrication de batterie totalement solide
JP2018152253A (ja) * 2017-03-13 2018-09-27 富士フイルム株式会社 固体電解質含有シートの製造方法および全固体二次電池の製造方法
JP2018160444A (ja) * 2017-03-23 2018-10-11 株式会社東芝 二次電池、電池パック、及び車両
CN111133610A (zh) * 2017-09-29 2020-05-08 罗伯特·博世有限公司 具有经涂覆的材料的固体复合电极
US11527754B2 (en) 2017-09-29 2022-12-13 Robert Bosch Gmbh Solid composite electrode with coated materials
WO2019063431A1 (fr) * 2017-09-29 2019-04-04 Robert Bosch Gmbh Électrode composite à l'état solide dotée de matériaux revêtus
JPWO2019074074A1 (ja) * 2017-10-12 2020-10-22 富士フイルム株式会社 固体電解質組成物、固体電解質含有シート及び全固体二次電池、並びに、固体電解質含有シート及び全固体二次電池の製造方法
WO2019074074A1 (fr) * 2017-10-12 2019-04-18 富士フイルム株式会社 Composition d'électrolyte solide, feuille contenant un électrolyte solide, batterie secondaire entièrement solide, et procédés de production de feuille contenant un électrolyte solide et de batterie secondaire entièrement solide
GB2580146A (en) * 2018-12-21 2020-07-15 Ilika Tech Limited Composite material
WO2020128505A1 (fr) * 2018-12-21 2020-06-25 Ilika Technologies Ltd Matériau composite
GB2611193A (en) * 2018-12-21 2023-03-29 Ilika Tech Ltd Composite material
GB2580146B (en) * 2018-12-21 2023-05-24 Ilika Tech Limited Composite material
GB2611193B (en) * 2018-12-21 2023-09-27 Ilika Tech Ltd Composite material
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