WO2020128699A1 - 正極活物質および二次電池 - Google Patents

正極活物質および二次電池 Download PDF

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WO2020128699A1
WO2020128699A1 PCT/IB2019/060418 IB2019060418W WO2020128699A1 WO 2020128699 A1 WO2020128699 A1 WO 2020128699A1 IB 2019060418 W IB2019060418 W IB 2019060418W WO 2020128699 A1 WO2020128699 A1 WO 2020128699A1
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Prior art keywords
positive electrode
active material
electrode active
secondary battery
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English (en)
French (fr)
Japanese (ja)
Inventor
斉藤丞
三上真弓
門馬洋平
落合輝明
高橋辰義
成田和平
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Semiconductor Energy Laboratory Co Ltd
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Semiconductor Energy Laboratory Co Ltd
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Priority to KR1020217017264A priority Critical patent/KR102943001B1/ko
Priority to US17/413,160 priority patent/US12278366B2/en
Priority to CN201980079070.1A priority patent/CN113165908A/zh
Priority to JP2020560635A priority patent/JP7529570B2/ja
Priority to DE112019006253.0T priority patent/DE112019006253T5/de
Publication of WO2020128699A1 publication Critical patent/WO2020128699A1/ja
Anticipated expiration legal-status Critical
Priority to JP2024119467A priority patent/JP7785866B2/ja
Priority to US19/023,705 priority patent/US20250158054A1/en
Priority to JP2025225433A priority patent/JP2026026286A/ja
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Definitions

  • lithium-ion secondary batteries with high output and high energy density are used in mobile information terminals such as mobile phones, smartphones, tablets, and notebook computers, portable music players, digital cameras, medical equipment, next-generation clean energy vehicles (hybrid Vehicles (HEVs), electric vehicles (EVs), plug-in hybrid vehicles (PHEVs), etc.)
  • HEVs Hybrid Vehicles
  • EVs electric vehicles
  • PHEVs plug-in hybrid vehicles
  • X-ray diffraction is one of the methods used to analyze the crystal structure of the positive electrode active material.
  • XRD data can be analyzed by using ICSD (Inorganic Crystal Structure Database) introduced in Non-Patent Document 5.
  • Non-Patent Document 6 and Non-Patent Document 7 by using the first principle calculation, the energy according to the crystal structure, composition, etc. of the compound can be calculated.
  • aluminum is used in the TEM-EDX analysis in the first region where the distance from the surface of the particles is 20 nm or more and 200 nm or less.
  • the number of atoms is 0.04 times or more and less than 1.6 times the number of atoms of cobalt, and the distance from the surface of the particles is 1 ⁇ m or more and 3 ⁇ m or less in the second region, aluminum atoms are analyzed by TEM-EDX.
  • the number is preferably less than 0.03 times the number of cobalt atoms.
  • Another embodiment of the present invention is an aggregate of particles, which has a first particle group and a second particle group, has lithium, cobalt, oxygen, and aluminum, and is powder X-ray diffraction by CuK ⁇ 1 ray.
  • the crystal structure has a space group of R-3m
  • the number of magnesium atoms by ICP-MS, GD-MS or elemental analysis of atomic absorption is Mg1
  • the number of atoms of cobalt is Co1
  • Mg1/Co1 is 0.001 or more and 0.06 or less
  • the particle size distribution of the first particle group has the first maximum peak and the particle size of the second particle group.
  • the distribution has a second maximum peak, a first maximum peak has a maximum value of 9 ⁇ m or more and 25 ⁇ m or less, and a second maximum peak is a positive electrode active material having a maximum value of 0.1 ⁇ m or more and less than 9 ⁇ m. is there.
  • the intensity of the maximum value of the first maximum peak is I1
  • the intensity of the maximum value of the second maximum peak is I2
  • I1/I2 is preferably 0.01 or more and 0.6 or less. ..
  • one embodiment of the present invention includes a positive electrode including the positive electrode active material described in any one of the above, a negative electrode, and an electrolyte solution, which is charged and discharged once, and then discharged to the first discharge.
  • the capacity is obtained, and thereafter, charging and discharging are alternately performed 50 times, and the second discharging capacity is obtained from the last discharging.
  • the second discharging capacity is 90% or more times the first discharging capacity. It is a battery.
  • the heating temperature in the second step is preferably 700° C. or higher and 920° C. or lower.
  • a pseudo spinel type crystal structure included in a composite oxide containing lithium and a transition metal is a space group R-3m, which is not a spinel type crystal structure, but has ions such as cobalt and magnesium. It is a crystal structure that occupies oxygen 6-coordinate position and has a cation arrangement similar to that of spinel type.
  • a light element such as lithium may occupy the oxygen 4-coordinate position, and in this case also, the ion arrangement has a symmetry similar to that of the spinel type.
  • a non-equilibrium phase change means a phenomenon that causes a non-linear change in a physical quantity. For example, before and after the peak in the dQ/dV curve obtained by differentiating the capacity (Q) with the voltage (V) (dQ/dV), it is considered that a non-equilibrium phase change occurs and the crystal structure is largely changed. ..
  • the voltage of the positive electrode generally rises as the charging voltage of the secondary battery rises.
  • the positive electrode active material of one embodiment of the present invention has a stable crystal structure even at high voltage. Since the crystal structure of the positive electrode active material is stable during charging, it is possible to suppress a decrease in capacity due to repeated charging and discharging.
  • the metal serving as a carrier ion more specifically, lithium is desorbed, so that the lattice constant is changed or the layer is displaced. May occur and the crystal structure may be easily broken.
  • the desorption of the metal may significantly change the lattice constant in the direction perpendicular to the layer.
  • high charging voltage may, for example, 4.55V (vs Li / Li + ) or higher, more preferably 4.6V (vs Li / Li +) or higher, more preferably 4.65V (vs Li / Li +) or higher Is.
  • the concentration of the surface layer portion is higher than the concentration of the region deeper than the surface layer portion.
  • the processing can be performed by FIB, for example.
  • nickel may have a higher concentration measured by ICP-MS, GD-MS, or the like than the concentration measured by XPS or the like.
  • the positive electrode active material 100 may include particles 102 containing, as a main component, one or more of magnesium, aluminum and nickel. Further, for example, the particles 102 may be in contact with the surface of the particles 101.
  • FIG. 3 shows an example of a cross section of the positive electrode.
  • FIG. 3 illustrates an example in which the positive electrode active material layer 109 including the particles 101 and the particles 102 is formed over the current collector 108.
  • the positive electrode active material layer and the current collector will be described in detail later.
  • the positive electrode active material of one embodiment of the present invention is stable even at a high charge voltage, the charge capacity can be increased, and as a result, the discharge capacity of the secondary battery can be increased. Therefore, the capacity per volume of the secondary battery may be sufficiently high without increasing the density of the positive electrode active material excessively.
  • the density of the positive electrode active material layer can be increased by reducing the proportion of materials other than the positive electrode active material, such as a conductive additive and a binder.
  • the relative value of the number of halogen atoms such as fluorine is preferably 0.05 or more and 1.5 or less, more preferably 0.3 or more and 1.00 or less.
  • the peak showing the binding energy of fluorine and other elements is preferably 682 eV or more and less than 685 eV, and more preferably about 684.8 eV. This is a value different from 686 eV which is the binding energy of magnesium fluoride. That is, when the positive electrode active material 100 has fluorine, it is preferably a bond other than magnesium fluoride.
  • the peak showing the binding energy between magnesium and another element is preferably 1302 eV or more and less than 1304 eV, and more preferably about 1303 eV. This is a value different from the binding energy of magnesium fluoride, 1305 eV, and a value close to the binding energy of magnesium oxide. That is, when the positive electrode active material 100 has magnesium, it is preferable that the positive electrode active material 100 has a bond other than magnesium fluoride.
  • EDX surface analysis extracting data of a linear region from the surface analysis of EDX and evaluating the distribution of the atomic concentration in the positive electrode active material particles.
  • the number of aluminum atoms in the EDX analysis is equal to the number of cobalt atoms. It is preferably 0.04 times or more and less than 1.6 times. Further, in the second region in which the distance from the surface of the particle 101 is 1 ⁇ m or more and 3 ⁇ m or less, the number of aluminum atoms in EDX analysis is preferably less than 0.03 times the number of cobalt atoms.
  • the positive electrode active material shown in FIG. 5 is lithium cobalt oxide (LiCoO 2 ) to which halogen and magnesium are not added by the manufacturing method described later. As described in Non-Patent Document 1 and Non-Patent Document 2 and the like, the lithium cobalt oxide shown in FIG. 5 changes in crystal structure depending on the charging depth.
  • the charge depth is 1, it has a crystal structure of space group P-3m1, and one CoO 2 layer exists in the unit cell. Therefore, this crystal structure may be called an O1-type crystal structure.
  • FIG. 1 An example of the crystal structure of the positive electrode active material 100 before and after charging and discharging is shown in FIG.
  • Laminar rock salt type crystals and anions of rock salt type crystals have cubic close-packed structure (face centered cubic lattice structure). It is presumed that the pseudo-spinel type crystal also has an anion with a cubic close-packed structure. When these are in contact with each other, there is a crystal plane in which the directions of the cubic close-packed structure composed of anions are aligned.
  • the space group of the layered rock salt type crystal and the pseudo spinel type crystal is R-3m
  • the space group of the rock salt type crystal is Fm-3m (general rock salt type crystal space group) and Fd-3m (the simplest symmetry).
  • the crystal structure is less likely to collapse even if charging and discharging are repeated at a high voltage.
  • magnesium concentration is increased to a desired value or higher, the effect on stabilizing the crystal structure may be reduced. It is considered that magnesium enters the cobalt site in addition to the lithium site.
  • ⁇ 25 ⁇ m thick polypropylene can be used for the separator.
  • lithium fluoride LiF is prepared as the fluorine source
  • magnesium fluoride MgF 2 is prepared as the fluorine source and the magnesium source.
  • LiF:MgF 2 65:35 (molar ratio)
  • the effect of lowering the melting point becomes the highest (Non-Patent Document 4).
  • the amount of lithium fluoride is large, there is a concern that lithium will become excessive and the cycle characteristics will deteriorate.
  • the mixture 902 preferably has an average particle diameter (D50) of 600 nm or more and 20 ⁇ m or less, and more preferably 1 ⁇ m or more and 10 ⁇ m or less.
  • D50 average particle diameter
  • the mixture 902 pulverized in this way facilitates the uniform deposition of the mixture 902 on the surface of the particles of the composite oxide when mixed with a composite oxide containing lithium, a transition metal and oxygen in a later step. It is preferable that the mixture 902 be uniformly attached to the surfaces of the particles of the composite oxide, because halogen and magnesium are easily distributed to the surface layer of the composite oxide particles after heating. If there is a region that does not contain halogen and magnesium in the surface layer, the pseudo spinel type crystal structure described above may not be easily obtained in the charged state.
  • metal M for example, at least one of cobalt, manganese, and nickel can be used.
  • metal M source oxides, hydroxides and the like of the above metals exemplified as the metal M can be used.
  • cobalt source for example, cobalt oxide, cobalt hydroxide or the like can be used.
  • manganese source manganese oxide, manganese hydroxide or the like can be used.
  • nickel source nickel oxide, nickel hydroxide or the like can be used.
  • aluminum source aluminum oxide, aluminum hydroxide or the like can be used.
  • cooling to room temperature in step S23 is not essential. If there is no problem in performing the subsequent steps S24 and S31 to S33, the cooling may be performed to a temperature higher than room temperature.
  • step S24 a composite oxide containing metal A, metal M, and oxygen synthesized in advance as step S24 may be used. In this case, steps S21 to S23 can be omitted.
  • lithium cobalt oxide particles (trade name: Cell Seed C-10N) manufactured by Nippon Kagaku Kogyo Co., Ltd. can be used as the composite oxide synthesized in advance.
  • This has an average particle diameter (D50) of about 12 ⁇ m, and in the impurity analysis by glow discharge mass spectrometry (GD-MS), magnesium concentration and fluorine concentration are 50 ppm wt or less, calcium concentration, aluminum concentration and silicon concentration are 100 ppm wt.
  • lithium cobalt oxide having a nickel concentration of 150 ppm wt or less, a sulfur concentration of 500 ppm wt or less, an arsenic concentration of 1100 ppm wt or less, and other element concentrations other than lithium, cobalt and oxygen of 150 ppm wt or less.
  • lithium cobalt oxide particles (trade name: Cell Seed C-5H) manufactured by Nippon Kagaku Kogyo Co., Ltd. can be used.
  • This is a lithium cobalt oxide having an average particle diameter (D50) of about 6.5 ⁇ m and having an element concentration other than lithium, cobalt and oxygen in the impurity analysis by GD-MS which is about the same as or lower than C-10N. is there.
  • a magnesium source and a fluorine source may be further added to lithium cobalt oxide to which magnesium and fluorine have been added in advance.
  • the annealing temperature is preferably 600° C. or higher and 950° C. or lower.
  • the annealing time is, for example, preferably 3 hours or longer, more preferably 10 hours or longer, still more preferably 60 hours or longer.
  • the annealing temperature is preferably 600° C. or higher and 950° C. or lower.
  • the annealing time is preferably 1 hour or more and 10 hours or less, more preferably about 2 hours.
  • the temperature lowering time after annealing is preferably, for example, 10 hours or more and 50 hours or less.
  • step S34 the material annealed as described above is recovered to obtain a second composite oxide.
  • the composite oxide obtained in step S34 is further processed.
  • processing for adding the metal M2 is performed.
  • the concentration of the metal M2 in the particle surface layer portion of the positive electrode active material may be higher than that in the inside, which is preferable.
  • the addition of the metal M2 may be performed, for example, by mixing the material having the metal M2 together with the mixture 902 and the like in step S31. This case is preferable because the number of steps can be reduced and the process can be simplified.
  • sol-gel method is applied, and aluminum isopropoxide is used as the metal source and isopropanol is used as the solvent (step S41 in FIG. 10).
  • the mixed solution of the alcohol solution of metal alkoxide and the particles of lithium cobalt oxide is stirred in an atmosphere containing water vapor.
  • the stirring can be performed, for example, with a magnetic stirrer.
  • the stirring time may be a time sufficient for the water and metal alkoxide in the atmosphere to undergo hydrolysis and polycondensation reaction, for example, 4 hours, 25° C., 90% RH (Relative Humidity, relative humidity) conditions You can do it below.
  • the stirring may be performed in an atmosphere in which humidity control and temperature control are not performed, for example, in an air atmosphere in the draft chamber. In such a case, it is preferable to make the stirring time longer, for example, 12 hours or more at room temperature.
  • the sol-gel reaction By reacting water vapor and metal alkoxide in the atmosphere, the sol-gel reaction can proceed more slowly than when liquid water is added. Further, by reacting the metal alkoxide with water at room temperature, the sol-gel reaction can proceed more slowly than in the case of heating at a temperature above the boiling point of the alcohol of the solvent. By slowly advancing the sol-gel reaction, a coating layer having a uniform thickness and good quality can be formed.
  • step S43 a precipitate is collected from the mixed liquid that has undergone the above-described processing, and the collected residue is dried to obtain a mixture 904.
  • filtration, centrifugation, evaporation to dryness or the like can be applied.
  • the precipitate can be washed with the same alcohol as the solvent in which the metal alkoxide is dissolved.
  • vacuum or ventilation drying can be performed at 80° C. for 1 hour or more and 4 hours or less.
  • Step S44 Next, as step S44, the obtained mixture 904 is fired.
  • the prescribed temperature is preferably 500°C or higher and 1200°C or lower, more preferably 700°C or higher and 920°C or lower, and further preferably 800°C or higher and 900°C or lower. If the specified temperature is too low, the crystallinity of the compound having the metal M2 formed in the surface layer portion may be low. Alternatively, the diffusion of the metal M2 may be insufficient. Alternatively, organic matter may remain on the surface.
  • firing is performed in an atmosphere containing oxygen. If the oxygen partial pressure is low, Co may be reduced unless the firing temperature is lowered.
  • the temperature decrease time from the specified temperature to room temperature is 10 hours or more and 50 hours or less.
  • the firing temperature in step S44 is preferably lower than the firing temperature in step S33.
  • step S45 the cooled particles can be collected to manufacture the positive electrode active material 100 of one embodiment of the present invention. At this time, it is preferable to screen the recovered particles further.
  • This embodiment can be implemented in combination with any of the other embodiments as appropriate.
  • the positive electrode active material layer has at least a positive electrode active material.
  • the positive electrode active material layer may include other materials such as a coating film on the surface of the active material, a conductive additive, or a binder.
  • the positive electrode active material 100 described in the above embodiment can be used as the positive electrode active material.
  • a secondary battery with high capacity and excellent cycle characteristics can be obtained.
  • the conductive additive for example, natural graphite, artificial graphite such as mesocarbon microbeads, and carbon fiber can be used.
  • carbon fibers for example, carbon fibers such as mesophase pitch carbon fibers and isotropic pitch carbon fibers can be used.
  • carbon nanofibers or carbon nanotubes can be used as the carbon fibers.
  • the carbon nanotube can be produced by, for example, a vapor phase growth method.
  • carbon materials such as carbon black (acetylene black (AB) and the like), graphite (graphite) particles, graphene and fullerene can be used.
  • metal powder such as copper, nickel, aluminum, silver, gold, metal fiber, conductive ceramic material, or the like can be used.
  • the graphene compound may have excellent electrical properties of having high conductivity and excellent physical properties of having high flexibility and high mechanical strength. Further, the graphene compound has a planar shape. The graphene compound enables surface contact with low contact resistance. Further, even if it is thin, it may have very high conductivity, and a small amount can efficiently form a conductive path in the active material layer. Therefore, it is preferable to use a graphene compound as a conductive additive because the contact area between the active material and the conductive additive can be increased. It is preferable that the entire surface of the active material is covered with a spray drying apparatus to form a graphene compound as a conductive additive as a film. It is also preferable because the electric resistance may be reduced in some cases.
  • RGO refers to, for example, a compound obtained by reducing graphene oxide (GO).
  • FIG. 11A shows a vertical sectional view of the active material layer 200.
  • the active material layer 200 includes a granular positive electrode active material 100, a graphene compound 201 as a conductive additive, and a binder (not shown).
  • graphene or multi-graphene may be used as the graphene compound 201.
  • the graphene compound 201 preferably has a sheet shape.
  • the graphene compound 201 may have a sheet shape in which a plurality of multi-graphenes and/or a plurality of graphenes are partially overlapped with each other.
  • graphene oxide as the graphene compound 201, mix with an active material to form a layer to be the active material layer 200, and then reduce the layer.
  • the graphene oxide having extremely high dispersibility in a polar solvent for forming the graphene compound 201 the graphene compound 201 can be dispersed substantially uniformly inside the active material layer 200. Since the solvent is evaporated and removed from the dispersion medium containing the uniformly dispersed graphene oxide to reduce the graphene oxide, the graphene compounds 201 remaining in the active material layer 200 are partially overlapped and dispersed so that they are in surface contact with each other. By doing so, a three-dimensional conductive path can be formed.
  • the graphene oxide may be reduced by, for example, heat treatment or a reducing agent.
  • -Binders may be used by combining multiple of the above.
  • Method for producing positive electrode As an example of a method for manufacturing a positive electrode including the positive electrode active material of one embodiment of the present invention, a slurry is manufactured and an electrode can be manufactured by applying the slurry. An example of a method for producing a slurry used for producing an electrode will be described.
  • the positive electrode active material of one embodiment of the present invention may have a particle size distribution according to the mixing ratio of the first particle group and the second particle group. Further, depending on the ratio of each particle group, the intensity or area of the maximum peak corresponding to each particle group may have a value having a size corresponding to the ratio of the ratios.
  • the maximum peak of one particle group may be 1 or may be 2 or more. In the case of 2 or more, it may be sufficient to use the area of the sum of a plurality of maximum peaks.
  • a mixture J is prepared by mixing a positive electrode active material in which the first particle group and the second particle group are mixed, a conductive auxiliary agent, a binder, and a solvent.
  • the mixing may be performed under normal pressure or under reduced pressure.
  • a kneader can be used.
  • a surface treatment may be performed on the current collector before applying the slurry.
  • the surface treatment include corona discharge treatment, plasma treatment, undercoat treatment and the like.
  • the undercoat is for the purpose of reducing the interfacial resistance between the active material layer and the current collector and for improving the adhesion between the active material layer and the current collector before applying the slurry onto the current collector.
  • the undercoat does not necessarily have to be in the form of a film, and may be formed in the shape of an island. Also, the undercoat may serve as an active material to develop the capacity.
  • a carbon material can be used.
  • the carbon material for example, graphite, carbon black such as acetylene black, Ketjen Black (registered trademark), carbon nanotube, or the like can be used.
  • the slurry can be applied by a slot die method, a gravure method, a blade method, a method combining them, or the like.
  • a continuous coater or the like may be used for coating.
  • the step of evaporating the solvent of the slurry may be carried out in a temperature range of 50°C or higher and 200°C or lower, preferably 60°C or higher and 90°C or lower.
  • the evaporation may be carried out, for example, under atmospheric pressure at atmospheric pressure or under reduced pressure.
  • the evaporation time may be shortened in some cases by performing it in a reduced pressure atmosphere. Alternatively, it may be possible to lower the evaporation temperature.
  • the evaporation process can be performed using a hot plate, a drying oven, etc.
  • the negative electrode has a negative electrode active material layer and a negative electrode current collector. Further, the negative electrode active material layer may have a conductive additive and a binder.
  • an element capable of performing a charge/discharge reaction by an alloying/dealloying reaction with lithium, a compound having the element, or the like may be referred to as an alloy-based material.
  • Examples of graphite include artificial graphite and natural graphite.
  • Examples of artificial graphite include mesocarbon microbeads (MCMB), coke-based artificial graphite, pitch-based artificial graphite, and the like.
  • MCMB mesocarbon microbeads
  • spherical graphite having a spherical shape can be used as the artificial graphite.
  • MCMB may have a spherical shape, which is preferable.
  • it is relatively easy to reduce the surface area of MCMB which may be preferable.
  • Examples of the natural graphite include scaly graphite and spheroidized natural graphite.
  • Graphite shows a potential as low as that of lithium metal when lithium ions are inserted into graphite (when a lithium-graphite intercalation compound is formed) (0.05 V or more and 0.3 V or less vs. Li / Li + ). Thereby, the lithium ion secondary battery can exhibit a high operating voltage. Further, graphite is preferable because it has advantages such as a relatively high capacity per unit volume, a relatively small volume expansion, a low cost, and a higher safety than lithium metal.
  • titanium dioxide TiO 2
  • lithium titanium oxide Li 4 Ti 5 O 12
  • lithium-graphite intercalation compound Li x C 6
  • niobium pentoxide Nb 2 O 5
  • oxidation An oxide such as tungsten (WO 2 ) or molybdenum oxide (MoO 2 ) can be used.
  • the positive electrode will be referred to as a "positive electrode” and the negative electrode will be referred to as a "negative electrode” or a “negative electrode”.
  • anode (anode) and cathode (cathode) related to the oxidation reaction and the reduction reaction are used, the charging time and the discharging time are reversed, which may cause confusion. Therefore, the terms anode (anode) and cathode (cathode) will not be used herein. If the terms anode (anode) and cathode (cathode) are used, indicate whether they are charging or discharging and also indicate whether they correspond to the positive electrode (positive electrode) or the negative electrode (negative electrode). To do.
  • the exterior body 509 is made of a metal such as aluminum, stainless steel, copper or nickel having excellent flexibility on a film made of a material such as polyethylene, polypropylene, polycarbonate, ionomer or polyamide.
  • a laminated film having a three-layer structure in which a thin film is provided and an insulating synthetic resin film of a polyamide resin, a polyester resin or the like is further provided on the metal thin film as the outer surface of the outer package can be used.
  • FIG. 23B shows an example of a cross-sectional structure of the laminated secondary battery 500.
  • FIG. 23A an example in which two current collectors are used for simplification is shown, but actually, as shown in FIG. 23B, a plurality of electrode layers are used.
  • a separator 214 is provided between the surface of the positive electrode 211a on which the positive electrode active material is formed and the surface of the negative electrode 211b on which the negative electrode active material is formed.
  • the separator 214 is indicated by a dotted line for easy viewing.
  • 27D is a cross section including the lead 212a, and corresponds to the cross section in the length direction of the secondary battery 250, the positive electrode 211a, and the negative electrode 211b. As shown in FIG. 27D, in the bent portion 261, it is preferable to have a space 273 between the ends of the positive electrode 211a and the negative electrode 211b in the length direction and the exterior body 251.
  • a secondary battery with a flexible shape along the inner or outer wall of a house or building, or along the curved surface of the interior or exterior of an automobile.
  • FIG. 30A shows an example of a mobile phone.
  • the mobile phone 7400 includes a display portion 7402 incorporated in a housing 7401, operation buttons 7403, an external connection port 7404, a speaker 7405, a microphone 7406, and the like.
  • the mobile phone 7400 includes a secondary battery 7407.
  • the secondary battery 7407 By using the secondary battery of one embodiment of the present invention for the secondary battery 7407, a lightweight and long-life mobile phone can be provided.
  • FIG. 30B shows a state in which the mobile phone 7400 is curved.
  • the secondary battery 7407 provided therein is also bent.
  • FIG. 30C shows the state of the secondary battery 7407 that is bent at that time.
  • the secondary battery 7407 is a thin storage battery.
  • the secondary battery 7407 is fixed in a bent state.
  • the secondary battery 7407 has a lead electrode electrically connected to the current collector.
  • the current collector is a copper foil, which is partly alloyed with gallium to improve the adhesion to the active material layer in contact with the current collector and to improve the reliability of the secondary battery 7407 in a bent state. It has a high configuration.
  • a part or all of the main surface of the housing or the secondary battery 7104 changes within the range of the radius of curvature of 40 mm or more and 150 mm or less.
  • the radius of curvature on the main surface of the secondary battery 7104 is in the range of 40 mm or more and 150 mm or less, high reliability can be maintained.
  • the mobile information terminal 7200 can execute various applications such as mobile phone, e-mail, text browsing and creation, music playback, Internet communication, and computer games.
  • the operation button 7205 can have various functions such as power on/off operation, wireless communication on/off operation, manner mode execution/cancellation, and power saving mode execution/cancellation in addition to time setting. ..
  • the function of the operation button 7205 can be freely set by the operating system incorporated in the portable information terminal 7200.
  • the secondary battery of one embodiment of the present invention as the secondary battery included in the display device 7300, a lightweight and long-life display device can be provided.
  • FIGS. 31A and 31B show an example of a tablet terminal that can be folded in two.
  • a tablet terminal 9600 illustrated in FIGS. 31A and 31B includes a housing 9630a, a housing 9630b, a movable portion 9640 that connects the housing 9630a and the housing 9630b, a display portion 9631 including a display portion 9631a and a display portion 9631b, and a switch 9625.
  • a switch 9627, a fastener 9629, and an operation switch 9628 By using a flexible panel for the display portion 9631, a tablet terminal having a wider display portion can be obtained.
  • FIG. 31A shows a state in which the tablet terminal 9600 is opened
  • FIG. 31B shows a state in which the tablet terminal 9600 is closed.
  • FIG. 31A illustrates an example in which the display areas of the display portion 9631a on the housing 9630a side and the display portion 9631b on the housing 9630b side are almost the same, the display areas of the display portion 9631a and the display portion 9631b are particularly
  • one size may be different from the other size, and the display quality may be different.
  • one may be a display panel that can display a higher definition than the other.
  • FIG. 31B shows a state in which the tablet terminal 9600 is closed in half, and the tablet terminal 9600 has a housing 9630, a solar cell 9633, and a charge/discharge control circuit 9634 including a DCDC converter 9636.
  • the power storage unit 9635 the power storage unit according to one embodiment of the present invention is used.
  • Electric power can be supplied to a touch panel, a display portion, a video signal processing portion, or the like by a solar cell 9633 attached to the surface of the tablet terminal 9600.
  • the solar cell 9633 can be provided on one side or both sides of the housing 9630, so that the power storage unit 9635 can be efficiently charged.
  • a lithium ion battery is used as the power storage unit 9635, there are advantages such as downsizing.
  • FIG. 31C illustrates the solar cell 9633, the power storage unit 9635, the DCDC converter 9636, the converter 9637, the switches SW1 to SW3, and the display portion 9631.
  • the power storage unit 9635, the DCDC converter 9636, the converter 9637, and the switches SW1 to SW3 are This is a portion corresponding to the charge/discharge control circuit 9634 shown in FIG. 31B.
  • the solar cell 9633 is shown as an example of a power generation unit, it is not particularly limited and a structure in which the power storage unit 9635 is charged by another power generation unit such as a piezoelectric element (piezo element) or a thermoelectric conversion element (Peltier element).
  • a non-contact power transmission module that wirelessly (contactlessly) transmits and receives electric power to charge the battery, or another charging means may be combined.
  • FIG. 32 shows examples of other electronic devices.
  • a display device 8000 is an example of an electronic device including a secondary battery 8004 according to one embodiment of the present invention.
  • the display device 8000 corresponds to a display device for receiving TV broadcast, and includes a housing 8001, a display portion 8002, a speaker portion 8003, a secondary battery 8004, and the like.
  • the secondary battery 8004 according to one embodiment of the present invention is provided inside the housing 8001.
  • the display device 8000 can be supplied with power from a commercial power source or can use power stored in the secondary battery 8004. Therefore, even when power cannot be supplied from a commercial power source due to a power failure or the like, the display device 8000 can be used by using the secondary battery 8004 of one embodiment of the present invention as an uninterruptible power source.
  • the secondary battery 8203 when the secondary battery 8203 is provided in both the indoor unit 8200 and the outdoor unit 8204, the secondary battery 8203 according to one embodiment of the present invention can be used even when power cannot be supplied from a commercial power source due to a power failure or the like.
  • an uninterruptible power supply By using as an uninterruptible power supply, it becomes possible to use an air conditioner.
  • FIG. 32 illustrates a separate type air conditioner including an indoor unit and an outdoor unit
  • an integrated type air conditioner having the function of the indoor unit and the function of the outdoor unit in one housing
  • the secondary battery according to one embodiment of the present invention can be used.
  • an electric refrigerator-freezer 8300 is an example of an electronic device including a secondary battery 8304 according to one embodiment of the present invention.
  • the electric refrigerator-freezer 8300 includes a housing 8301, a refrigerator compartment door 8302, a freezer compartment door 8303, a secondary battery 8304, and the like.
  • a secondary battery 8304 is provided inside the housing 8301.
  • the electric refrigerator-freezer 8300 can be supplied with electric power from a commercial power source and can also use electric power stored in the secondary battery 8304. Therefore, even when power cannot be supplied from a commercial power source due to a power failure or the like, the electric refrigerator-freezer 8300 can be used by using the secondary battery 8304 of one embodiment of the present invention as an uninterruptible power source.
  • high-frequency heating devices such as microwave ovens and electronic devices such as electric rice cookers require high power in a short time. Therefore, by using the secondary battery of one embodiment of the present invention as an auxiliary power source for supplementing electric power that cannot be covered by the commercial power source, the breaker of the commercial power source can be prevented from dropping when the electronic device is used. ..
  • the electronic device when the electronic device is not used, particularly when the ratio of the amount of power actually used (called power usage rate) to the total amount of power that can be supplied by the commercial power supply source is low,
  • power usage rate the ratio of the amount of power actually used
  • the secondary battery 8304 By storing the electric power in the secondary battery, it is possible to prevent the power usage rate from increasing outside the above time period.
  • the electric refrigerator/freezer 8300 electric power is stored in the secondary battery 8304 at night when the temperature is low and the refrigerator compartment door 8302 and the freezer compartment door 8303 are not opened or closed. Then, by using the secondary battery 8304 as an auxiliary power source during the daytime when the temperature rises and the refrigerator door 8302 and the freezer door 8303 are opened and closed, the power usage rate during the daytime can be suppressed.
  • This embodiment can be implemented in combination with any of the other embodiments as appropriate.
  • the automobile 8500 illustrated in FIG. 33B can be charged by receiving power from an external charging facility by a secondary battery included in the automobile 8500 by a plug-in method, a contactless power feeding method, or the like.
  • FIG. 33B shows a state in which a charging device 8021 installed on the ground is charging a secondary battery 8024 mounted on an automobile 8500 via a cable 8022.
  • the charging method, the standard of the connector, etc. may be appropriately performed by a predetermined method such as CHAdeMO (registered trademark) or a combo.
  • the charging device 8021 may be a charging station provided in a commercial facility or may be a home power source.
  • the plug-in technology the secondary battery 8024 mounted on the automobile 8500 can be charged by external power supply. Charging can be performed by converting AC power into DC power via a converter such as an ACDC converter.
  • FIG. 33C is an example of a motorcycle using the secondary battery of one embodiment of the present invention.
  • the scooter 8600 illustrated in FIG. 33C includes a secondary battery 8602, a side mirror 8601, and a direction indicator light 8603.
  • the secondary battery 8602 can supply electricity to the direction indicator light 8603.
  • the scooter 8600 shown in FIG. 33C can store the secondary battery 8602 in the under-seat storage 8604.
  • the secondary battery 8602 can be stored in the under-seat storage 8604 even if the under-seat storage 8604 is small.
  • the secondary battery 8602 is removable, and when charging, the secondary battery 8602 may be carried indoors, charged, and stored before traveling.
  • the mixture 903 was put into an alumina crucible and annealed at 850° C. for 60 hours in a muffle furnace in an oxygen atmosphere (step S33). During the annealing, the alumina crucible was covered with a lid. The flow rate of oxygen was 10 L/min. The temperature was raised to 200° C./hr, and the temperature was lowered over 10 hours. The material after the heat treatment was collected and sieved to obtain a second composite oxide (step S34).
  • step S41 nickel was added, and steps S41 to S44 were performed again to add aluminum.
  • a sample was also prepared under the condition that steps S41 to S44 were not performed.
  • nickel hydroxide which is a metal source
  • the second composite oxide were ball-mill mixed.
  • the number of cobalt atoms was 100, they were mixed so that the number of nickel atoms would be the value shown in Table 1.
  • the mixing was performed with a ball mill using zirconia balls, and 150 rpm for 1 hour. After mixing, the mixture was passed through a 300 ⁇ m ⁇ sieve. Then, the obtained mixture was put into an alumina crucible, covered with a lid, and annealed at 850° C. for 2 hours in an oxygen atmosphere.
  • the solvent was evaporated. Then, after pressurizing at 210 kN/m, further pressurizing at 1467 kN/m. A positive electrode was obtained through the above steps. The amount of the positive electrode carried was about 7 mg/cm 2 .
  • a CR2032 type (20 mm diameter, 3.2 mm height) coin-type secondary battery was produced.
  • Lithium metal was used as the counter electrode.
  • FIG. 37 shows two conditions in which nickel and aluminum are both 0.25 or 0.5, and conditions in which steps S41 to S44 are not performed and nickel and aluminum are not added (in the figure legend, “Ni: ⁇ , Al :-)) and the discharge capacity maintenance ratio and discharge energy are shown in excerpt.
  • Table 5 shows the concentration of each element obtained by XPS.
  • This positive electrode was charged and discharged once for capacity confirmation, and then charged at 4.5V, 4.55V or 4.6V, and subjected to XRD analysis.
  • Charging for capacity confirmation was CCCV (0.2 C, 4.5 V, final current 0.05 C), and a rest time of 20 minutes was provided after charging.
  • the discharge was CC (0.2 C, 3 V), and a rest time of 20 minutes was provided after the discharge.
  • the manufacturing conditions are the following 5 conditions.
  • the first is under the condition that magnesium, nickel and aluminum are not added without performing steps S11 to S13 and steps S21 to S24 (described as "Mg:-, Ni:-, Al:-" in FIG. 42). is there.
  • the second condition is that the number of magnesium atoms is 1.0 when the number of cobalt atoms is 100, and nickel and aluminum are not added (Mg:1, Ni:-, Al:-).
  • the third condition is that the number of magnesium atoms is 1.0 and the number of nickel and aluminum atoms is 0.25 when the number of cobalt atoms is 100 (Mg:1, Ni:0.25, Al:0). .25).
  • a positive electrode active material was produced using lithium cobalt oxide manufactured by Aldrich as the composite oxide used in step S24.
  • the manufacturing conditions are the following two conditions. The first is a condition that magnesium, nickel and aluminum are not added without performing steps S11 to S13 and steps S21 to S24. The second condition is that the number of magnesium atoms is 0.5 when the number of cobalt atoms is 100, and nickel and aluminum are not added.
  • a secondary battery was produced with reference to the method of Example 1, and the cycle characteristics were evaluated. The temperature of the cycle test was 45° C., and the upper limit voltage of charging was 4.55V.
  • the characteristics of the secondary battery using the positive electrode active material of one embodiment of the present invention were evaluated.
  • step S24 cell seed 5H manufactured by Nippon Kagaku Kogyo Co., Ltd. was prepared as a composite oxide (step S24).
  • the result of the particle size distribution of 5H is shown in FIG.
  • step S31 the mixture 902 and the complex oxide were mixed (step S31).
  • the mixture 902 was weighed so that the number of magnesium atoms in the mixture 902 was 0.5 or 2.
  • the mixing was dry.
  • the mixing was performed with a ball mill using zirconia balls, and 150 rpm for 1 hour.
  • a condition was also prepared in which magnesium was not added.
  • the metal hydroxide, nickel hydroxide, and the second composite oxide were ball mill mixed. They were mixed so that the number of nickel atoms was 0.5 when the number of cobalt atoms was 100.
  • the mixing was performed with a ball mill using zirconia balls, and 150 rpm for 1 hour. After mixing, the mixture was passed through a 300 ⁇ m ⁇ sieve. Then, the obtained mixture was put into an alumina crucible, covered with a lid, and annealed at 850° C. for 2 hours in an oxygen atmosphere.
  • a coating layer containing aluminum was formed by the sol-gel method.
  • Al isopropoxide was used as the metal source and 2-propanol was used as the solvent.
  • the number of cobalt atoms was 100, they were mixed so that the number of aluminum atoms was 0.5.
  • the obtained mixture was put into an alumina crucible, covered with a lid, and annealed at 850° C. for 2 hours in an oxygen atmosphere. Then, the powder was recovered by sieving with a 53 ⁇ m ⁇ to obtain a positive electrode active material.
  • Each positive electrode was produced using the positive electrode active material obtained above.
  • a positive electrode (described as Mg:-, Ni:-, Al:- in FIG. 48) using cell seed 5H as a positive electrode active material was also manufactured.
  • the solvent was evaporated. Then, after pressurizing at 210 kN/m, further pressurizing at 1467 kN/m. A positive electrode was obtained through the above steps. The amount of the positive electrode carried was about 7 mg/cm 2 .
  • a CR2032 type (20 mm diameter, 3.2 mm height) coin-type secondary battery was produced.
  • Lithium metal was used as the counter electrode.
  • Charging for capacity confirmation was CCCV (0.2 C, 4.5 V, final current 0.02 C), and a rest period of 20 minutes was provided after charging.
  • the discharge was CV (0.2 C, 3 V), and a rest period of 20 minutes was provided after the discharge.

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JPWO2022038451A1 (https=) * 2020-08-20 2022-02-24
KR20230053598A (ko) 2020-08-20 2023-04-21 가부시키가이샤 한도오따이 에네루기 켄큐쇼 전극의 제작 방법, 이차 전지, 전자 기기, 및 차량
KR20230145368A (ko) 2021-02-12 2023-10-17 가부시키가이샤 한도오따이 에네루기 켄큐쇼 전극의 제작 방법
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