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WO2016098215A1 - Dispositif électrique - Google Patents

Dispositif électrique Download PDF

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Publication number
WO2016098215A1
WO2016098215A1 PCT/JP2014/083481 JP2014083481W WO2016098215A1 WO 2016098215 A1 WO2016098215 A1 WO 2016098215A1 JP 2014083481 W JP2014083481 W JP 2014083481W WO 2016098215 A1 WO2016098215 A1 WO 2016098215A1
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WO
WIPO (PCT)
Prior art keywords
active material
electrode active
positive electrode
negative electrode
material layer
Prior art date
Application number
PCT/JP2014/083481
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English (en)
Japanese (ja)
Inventor
渡邉　学
智裕 蕪木
洋一 吉岡
寛和 小松
千葉　啓貴
山本　伸司
Original Assignee
日産自動車株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 日産自動車株式会社 filed Critical 日産自動車株式会社
Priority to JP2016564522A priority Critical patent/JP6380553B2/ja
Priority to PCT/JP2014/083481 priority patent/WO2016098215A1/fr
Publication of WO2016098215A1 publication Critical patent/WO2016098215A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 electrical device.
  • the electric device according to the present invention is used, for example, as a secondary battery, a capacitor or the like as a driving power source or auxiliary power source for motors of vehicles such as electric vehicles, fuel cell vehicles, and hybrid electric vehicles.
  • Motor drive secondary batteries are required to have extremely high output characteristics and high energy compared to consumer lithium ion secondary batteries used in mobile phones and notebook computers. Therefore, lithium ion secondary batteries having the highest theoretical energy among all the batteries are attracting attention, and are currently being developed rapidly.
  • a lithium ion secondary battery includes a positive electrode in which a positive electrode active material or the like is applied to both surfaces of a positive electrode current collector using a binder, and a negative electrode in which a negative electrode active material or the like is applied to both surfaces of a negative electrode current collector using a binder.
  • a positive electrode in which a positive electrode active material or the like is applied to both surfaces of a positive electrode current collector using a binder
  • a negative electrode in which a negative electrode active material or the like is applied to both surfaces of a negative electrode current collector using a binder.
  • it has the structure connected through an electrolyte layer and accommodated in a battery case.
  • a battery using a material that is alloyed with Li for the negative electrode is expected as a negative electrode material for vehicle use because the energy density is improved as compared with a conventional carbon / graphite negative electrode material.
  • a lithium ion secondary battery using a material that is alloyed with Li for the negative electrode has a large expansion and contraction in the negative electrode during charge and discharge.
  • the volume expansion is about 1.2 times in graphite materials
  • Si materials when Si and Li are alloyed, transition from the amorphous state to the crystalline state causes a large volume change. (Approximately 4 times), there was a problem of reducing the cycle life of the electrode.
  • the capacity and the cycle durability are in a trade-off relationship, and there is a problem that it is difficult to improve the cycle durability while exhibiting a high capacity.
  • an invention that aims to provide a non-aqueous electrolyte secondary battery having a negative electrode pellet having a high capacity and excellent cycle life is disclosed.
  • a silicon-containing alloy obtained by mixing silicon powder and titanium powder by a mechanical alloying method and wet-pulverizing the first phase mainly composed of silicon and a silicide of titanium (such as TiSi 2 ) ) Containing a second phase containing) is disclosed as a negative electrode active material.
  • a silicon-containing alloy obtained by mixing silicon powder and titanium powder by a mechanical alloying method and wet-pulverizing the first phase mainly composed of silicon and a silicide of titanium (such as TiSi 2 ) ) Containing a second phase containing) is disclosed as a negative electrode active material.
  • at least one of these two phases is amorphous or low crystalline.
  • the present invention provides sufficient cycle durability while fully utilizing the high capacity characteristics that are characteristic of a solid solution cathode active material in an electrical device such as a lithium ion secondary battery having a cathode using a solid solution cathode active material.
  • An object is to provide means that can be realized.
  • the present inventors have conducted intensive research to solve the above problems. As a result, the inventors have found that the above problem can be solved by using a combination of a negative electrode containing a predetermined Si-containing alloy as a negative electrode active material and a positive electrode containing a predetermined solid solution positive electrode active material, and completed the present invention. I came to let you.
  • the present invention includes a positive electrode in which a positive electrode active material layer including a positive electrode active material is formed on the surface of a positive electrode current collector, and a negative electrode active material layer including a negative electrode active material on the surface of the negative electrode current collector.
  • the present invention relates to an electric device having a power generation element including a negative electrode and a separator.
  • the negative electrode active material layer has the following formula (1):
  • ⁇ represents the weight percent of each component in the negative electrode active material layer, and 40 ⁇ ⁇ 98.
  • the negative electrode active material represented by these is contained.
  • the positive electrode active material layer has the following formula (2):
  • e represents the weight percent of each component in the positive electrode active material layer, and 80 ⁇ e ⁇ 98.
  • the positive electrode active material represented by these is contained.
  • the Si-containing alloy has a structure in which a silicide phase containing a silicide of a transition metal is dispersed in a parent phase mainly composed of amorphous or low crystalline silicon.
  • A is an inevitable impurity
  • M is one or more transition metal elements
  • the solid solution positive electrode active material has the following formula (3):
  • FIG. 1 is a schematic cross-sectional view showing the basic configuration of a non-aqueous electrolyte lithium ion secondary battery that is not a flat type (stacked type) bipolar type, which is an embodiment of the electrical device according to the present invention. It is a perspective view showing the appearance of a flat lithium ion secondary battery which is a typical embodiment of an electric device according to the present invention. It is a chart which shows the X-ray-diffraction pattern of the solid solution positive electrode active material C0 which does not contain Ti. 2 is a chart showing an X-ray diffraction pattern of the solid solution positive electrode active material C1 obtained in Example 1.
  • a positive electrode in which a positive electrode active material layer containing a positive electrode active material is formed on the surface of a positive electrode current collector;
  • a negative electrode in which a negative electrode active material layer containing a negative electrode active material is formed on the surface of the negative electrode current collector;
  • a separator An electrical device having a power generation element comprising:
  • the negative electrode active material layer has the following formula (1):
  • ⁇ represents the weight percent of each component in the negative electrode active material layer, and 40 ⁇ ⁇ 98. Containing a negative electrode active material represented by The positive electrode active material layer has the following formula (2):
  • e represents the weight percent of each component in the positive electrode active material layer, and 80 ⁇ e ⁇ 98.
  • a positive electrode active material represented by In this case, the Si-containing alloy has a structure in which a silicide phase containing a silicide of a transition metal is dispersed in a parent phase mainly composed of amorphous or low crystalline silicon. I):
  • A is an inevitable impurity
  • M is one or more transition metal elements
  • the value (B / A) of the diffraction peak intensity B of the transition metal silicide in the range of ⁇ 45 ° is 0.41 or more
  • the said solid solution positive electrode active material is following formula (3):
  • An electrical device comprising a solid solution having a composition represented by: According to the present invention having such a configuration, when the value of B / A in the negative electrode active material (Si-containing alloy) is a value within the above-described range, an amorphous state when Si and Li are alloyed is obtained.
  • Crystal phase transition (crystallization to Li 15 Si 4 ) is suppressed.
  • contraction of the Si containing alloy which comprises the negative electrode active material in the charge / discharge process of an electrical device are suppressed.
  • the electrical device according to the present invention can realize sufficient cycle durability while fully utilizing the high capacity characteristics that are characteristic of the solid solution positive electrode active material.
  • a lithium ion secondary battery will be described as an example of an electric device.
  • the lithium ion secondary battery using the electric device according to the present invention the voltage of the cell (single cell layer) is large, and high energy density and high output density can be achieved. Therefore, the lithium ion secondary battery of the present embodiment is excellent as a vehicle driving power source or an auxiliary power source. As a result, it can be suitably used as a lithium ion secondary battery for a vehicle driving power source or the like. In addition to this, the present invention can be sufficiently applied to lithium ion secondary batteries for portable devices such as mobile phones.
  • the lithium ion secondary battery When the lithium ion secondary battery is distinguished by its form / structure, it can be applied to any conventionally known form / structure such as a stacked (flat) battery or a wound (cylindrical) battery. Is. By adopting a stacked (flat) battery structure, long-term reliability can be secured by a sealing technique such as simple thermocompression bonding, which is advantageous in terms of cost and workability.
  • a solution electrolyte type battery using a solution electrolyte such as a nonaqueous electrolyte solution for the electrolyte layer, a polymer battery using a polymer electrolyte for the electrolyte layer, etc. It can be applied to any conventionally known electrolyte layer type.
  • the polymer battery is further divided into a gel electrolyte type battery using a polymer gel electrolyte (also simply referred to as gel electrolyte) and a solid polymer (all solid) type battery using a polymer solid electrolyte (also simply referred to as polymer electrolyte). It is done.
  • FIG. 1 schematically shows the overall structure of a flat (stacked) lithium ion secondary battery (hereinafter also simply referred to as “stacked battery”), which is a typical embodiment of the electrical device of the present invention.
  • stacked battery a flat (stacked) lithium ion secondary battery
  • the stacked battery 10 of the present embodiment has a structure in which a substantially rectangular power generation element 21 in which a charge / discharge reaction actually proceeds is sealed inside a laminate sheet 29 that is an exterior body.
  • the positive electrode in which the positive electrode active material layer 13 is disposed on both surfaces of the positive electrode current collector 11, the electrolyte layer 17, and the negative electrode active material layer 15 is disposed on both surfaces of the negative electrode current collector 12. It has a configuration in which a negative electrode is laminated. Specifically, the negative electrode, the electrolyte layer, and the positive electrode are laminated in this order so that one positive electrode active material layer 13 and the negative electrode active material layer 15 adjacent thereto face each other with the electrolyte layer 17 therebetween. .
  • the adjacent positive electrode, electrolyte layer, and negative electrode constitute one unit cell layer 19. Therefore, it can be said that the stacked battery 10 shown in FIG. 1 has a configuration in which a plurality of single battery layers 19 are stacked and electrically connected in parallel.
  • the positive electrode current collector 13 on the outermost layer located on both outermost layers of the power generating element 21 is provided with the positive electrode active material layer 13 only on one side, but the active material layer may be provided on both sides. . That is, instead of using a current collector dedicated to the outermost layer provided with an active material layer only on one side, a current collector having an active material layer on both sides may be used as it is as an outermost current collector.
  • the outermost negative electrode current collector is positioned on both outermost layers of the power generation element 21, and one side of the outermost negative electrode current collector or A negative electrode active material layer may be disposed on both sides.
  • the positive electrode current collector 11 and the negative electrode current collector 12 are attached to a positive electrode current collector plate 25 and a negative electrode current collector plate 27 that are electrically connected to the respective electrodes (positive electrode and negative electrode), and are sandwiched between end portions of the laminate sheet 29. Thus, it has a structure led out of the laminate sheet 29.
  • the positive electrode current collector plate 25 and the negative electrode current collector plate 27 are ultrasonically welded to the positive electrode current collector 11 and the negative electrode current collector 12 of each electrode via a positive electrode lead and a negative electrode lead (not shown), respectively, as necessary. Or resistance welding or the like.
  • the lithium ion secondary battery according to this embodiment is characterized by the configuration of the positive electrode and the negative electrode.
  • main components of the battery including the positive electrode and the negative electrode will be described.
  • the active material layers (13, 15) contain an active material, and further contain other additives as necessary.
  • the positive electrode active material layer 13 includes at least a positive electrode active material (also referred to as “solid solution positive electrode active material” in the present specification) made of a solid solution material.
  • Solid solution positive electrode active material A solid solution positive electrode active material consists of a solid solution which has a composition represented by following formula (3).
  • this solid solution positive electrode active material was measured at 20-23 °, 35-40 ° (101), 42-45 ° (104) and 64-65 (108) / 65-66 (X-ray diffraction (XRD) measurement).
  • 110) preferably has a diffraction peak indicating a rock salt type layered structure. At this time, in order to surely obtain the effect of improving the cycle characteristics, those having substantially no peak attributed to other than the diffraction peak of the rock salt type layered structure are preferable. More preferably, one having three diffraction peaks at 35-40 ° (101) and one diffraction peak at 42-45 ° (104) is suitable.
  • the X-ray diffraction measurement shall employ the measurement method described in the examples described later.
  • the notation of 64-65 (108) / 65-66 (110) has two peaks close to 64-65 and 65-66.
  • one peak is broadly separated without being clearly separated. It is meant to include.
  • the solid solution positive electrode active material having the composition represented by the composition formula (3) preferably has a plurality of specific diffraction peaks in the X-ray diffraction (XRD) measurement.
  • the solid solution positive electrode active material having the above composition formula is a solid solution system of Li 2 MnO 3 and LiMnO 2.
  • the diffraction peak at 20-23 ° is characteristic of Li 2 MnO 3 .
  • the diffraction peaks of 36.5-37.5 ° (101), 44-45 ° (104) and 64-65 (108) / 65-66 (110) are usually in the rock salt type layered structure of LiMnO 2. It is characteristic.
  • the solid solution positive electrode active material of the present embodiment does not include those having a peak other than a diffraction peak showing a rock salt type layered structure, for example, other peaks derived from impurities or the like, in these angular ranges.
  • a structure other than the rock salt type layered structure is included in the positive electrode active material. If the structure other than the rock salt type layered structure is not included, the effect of improving the cycle characteristics can be surely obtained.
  • the solid solution positive electrode active material at least one of Ti, Zr, and Nb is dissolved in a transition metal layer made of Ni, Co, and Mn by substituting Mn 4+ to form a rock salt type It is considered that a layered structure is formed. Since at least one kind of Ti, Zr and Nb is dissolved, the crystal structure is stabilized, so that it is considered that elution of transition metals including Mn is suppressed during charging and discharging. As a result, even if charging / discharging is repeated, a reduction in battery capacity can be prevented, and excellent cycle characteristics can be achieved. In addition, battery performance itself and durability can be improved.
  • the diffraction peak showing the rock salt type layered structure in this embodiment is shifted to the low angle side. That is, the solid solution positive electrode active material according to the present embodiment is 20-23 °, 35.5-36.5 ° (101), 43.5-44.5 ° (104) in X-ray diffraction (XRD) measurement. And preferably have diffraction peaks at 64-65 (108) / 65-66 (110).
  • the shift of the diffraction peak to the lower angle side indicates that Ti and the like are more solid-dissolved in the positive electrode active material and substitutes Mn, which is considered to have a greater effect of suppressing Mn elution.
  • a + b + c + e satisfies 1.1 ⁇ [a + b + c + e] ⁇ 1.4.
  • nickel (Ni), cobalt (Co), and manganese (Mn) are known to contribute to capacity characteristics and output characteristics from the viewpoint of improving the purity of the material and improving the electronic conductivity.
  • Ti or the like partially substitutes Mn in the crystal lattice.
  • a is preferably 0 ⁇ a ⁇ 1.5, and more preferably 0.1 ⁇ a ⁇ 0.75.
  • a is in the above range, a secondary battery having a better capacity retention rate can be obtained.
  • a is not a ⁇ 0.75, the crystal structure is not stabilized because nickel is contained in the positive electrode active material within the above range d on condition that nickel (Ni) is divalent. There is.
  • a ⁇ 0.75 the crystal structure of the positive electrode active material tends to be a rock salt type layered structure.
  • b is preferably 0 ⁇ b ⁇ 1.5, and more preferably 0.2 ⁇ b ⁇ 0.9.
  • b is in the above range, an electric device having a better capacity retention rate can be obtained.
  • b does not satisfy b ⁇ 0.9, manganese is contained in the positive electrode active material within the above range d, provided that manganese is tetravalent, and nickel (Ni ), The crystal structure may not be stabilized.
  • b ⁇ 0.9 the crystal structure of the positive electrode active material tends to be a rock salt type layered structure.
  • c is preferably 0 ⁇ c ⁇ 1.5.
  • nickel and manganese are contained in the positive electrode active material within the above range d on condition that cobalt is trivalent.
  • cobalt (Co) is contained in the positive electrode active material within the above range d on condition that nickel (Ni) is divalent and manganese (Mn) is tetravalent. Therefore, the crystal structure of the positive electrode active material may not be stabilized.
  • c ⁇ 0.6 the crystal structure of the positive electrode active material tends to be a rock salt type layered structure.
  • composition formula (3) 0.1 ⁇ d ⁇ 0.4.
  • d is not 0.1 ⁇ d ⁇ 0.4, the crystal structure of the positive electrode active material may not be stabilized.
  • the positive electrode active material tends to have a rock salt type layered structure.
  • the range of d is more preferably 0.15 ⁇ d ⁇ 0.35.
  • d is 0.1 or more, the composition is less likely to be close to Li 2 MnO 3 and charge / discharge is facilitated, which is preferable.
  • e 0.01 ⁇ e ⁇ 0.4.
  • the element cannot be uniformly dissolved in the crystal structure, and the crystal structure cannot be stabilized.
  • at least one of Ti, Zr, and Nb can sufficiently substitute Mn 4+ so that elution is suppressed. More preferably, e satisfies 0.02 ⁇ e ⁇ 0.3, more preferably 0.025 ⁇ e ⁇ 0.25, and particularly preferably 0.03 ⁇ e ⁇ 0.2.
  • the ionic radius of each element is Mn 4+ 0.540.5, Mn 4+ 0.54 ⁇ , Ti 4+ 0.61 ⁇ , Zr 4+ 0.72 ⁇ , Nb 5+ 0.64 ⁇ , and Ti, Zr and Nb are larger than Mn. ing. Therefore, as Mn 4+ in the positive electrode active material is replaced with Ti or the like, the crystal lattice expands, and the diffraction peak indicating the rock salt type layered structure shifts to a lower angle side. On the contrary, if the diffraction peak is shifted to a lower angle side, the substitution amount of Mn 4+ such as Ti is larger, and the crystal structure is easily stabilized. That is, elution of Mn at the time of charging / discharging is further suppressed, and the capacity reduction of the electric device can be more effectively prevented.
  • the specific surface area of the positive electrode active material is preferably 0.2 to 0.6 m 2 / g, and more preferably 0.25 to 0.5 m 2 / g.
  • a specific surface area of 0.2 m 2 / g or more is preferable because sufficient battery output can be obtained.
  • the specific surface area is 0.6 m 2 / g or less because elution of manganese can be further suppressed.
  • the value measured by the method of an Example shall be employ
  • the average particle diameter of the positive electrode active material is preferably 10 to 20 ⁇ m, and more preferably 12 to 18 ⁇ m. It is preferable that the average particle size is 10 ⁇ m or more because elution of manganese can be suppressed. On the other hand, when the average particle size is 20 ⁇ m or less, it is preferable that foil breakage, clogging, and the like can be suppressed in the application step to the current collector during the production of the positive electrode.
  • the average particle diameter is measured by a laser diffraction / scattering particle size distribution measuring device. The average particle diameter can be measured, for example, using a particle size distribution analyzer (model LA-920) manufactured by Horiba.
  • the solid solution positive electrode active material as described above can be prepared, for example, by the following method. That is, a first step of mixing at least one citrate of Ti, Zr and Nb with an organic acid salt of a transition metal having a melting point of 100 ° C. to 350 ° C., and a mixture obtained in the first step at 100 ° C. A second step of melting at ⁇ 350 ° C., a third step of pyrolyzing the melt obtained in the second step at a temperature higher than the melting point, and a second step of firing the pyrolyzate obtained in the third step. 4 steps. Hereinafter, each step will be described.
  • At least one citrate of Ti, Zr and Nb and an organic acid salt of a transition metal having a melting point of 100 ° C. to 350 ° C. are mixed.
  • At least one citrate of Ti, Zr and Nb is preferably mixed in the form of an aqueous citric acid complex solution.
  • the aqueous solution of at least one kind of citrate complex of Ti, Zr and Nb is not limited to the following, but it can be preferably prepared as follows.
  • anhydrous citric acid is dissolved in an organic solvent such as acetone, and at least one alkoxide of Ti, Zr and Nb is added to the solution.
  • the molar ratio of at least one of Ti, Zr and Nb to citric acid is preferably (at least one of Ti, Zr and Nb) / citric acid being 1/1 to 1/2.
  • the amount of water is appropriately added so that the concentration of the aqueous citric acid complex is 1 to 10% by mass in terms of at least one of Ti, Zr and Nb.
  • This aqueous solution is allowed to stand for one day, and the precipitate is filtered to obtain an aqueous solution of at least one citrate complex of Ti, Zr and Nb as a filtrate.
  • an organic acid salt of a transition metal having a melting point of 100 ° C. to 350 ° C. is added to the obtained aqueous solution of at least one kind of citric acid complex of Ti, Zr and Nb to obtain a mixture.
  • the organic acid salt of transition metal having a melting point of 100 ° C. to 350 ° C. preferably includes nickel acetate, manganese acetate, cobalt acetate, manganese citrate and the like.
  • an alkali metal organic acid salt is further mixed with the above-described aqueous solution of at least one kind of citric acid complex of Ti, Zr and Nb.
  • Preferred examples of the organic acid salt of alkali metal include lithium acetate and lithium citrate. It is preferable to mix an alkali metal organic acid salt at this stage because the production method is simple.
  • Second Step The mixture obtained in the first step is melted at 100 to 350 ° C., preferably 200 to 300 ° C.
  • the heated melt (slurry) obtained in the second step is pyrolyzed at a temperature equal to or higher than the melting point of the organic acid salt of the transition metal used in the first step to obtain a pyrolyzate that is a dry powder.
  • the melting points of the organic acid salts of a plurality of transition metals are different from each other, they are thermally decomposed at a temperature higher than the highest melting point. More specifically, the melt can be heated and sprayed at 200 to 600 ° C., more preferably 200 to 400 ° C., with a spray device.
  • the pyrolyzate obtained in the third step is calcined at 600 to 1200 ° C., more preferably 800 to 1100 ° C., for 5 to 20 hours, preferably 10 to 15 hours.
  • Temporary baking may be performed before baking, in which case the temporary baking may be performed at 200 to 700 ° C., more preferably 300 to 600 ° C. for 1 to 10 hours, more preferably 2 to 6 hours.
  • the positive electrode active material of this embodiment is obtained.
  • a positive electrode active material other than the solid solution positive electrode active material described above may be used in combination.
  • a lithium-transition metal composite oxide is used in combination as the positive electrode active material from the viewpoint of capacity and output characteristics.
  • other positive electrode active materials may be used.
  • the optimum particle size is different for expressing the unique effect of each active material, the optimum particle size may be blended and used for expressing each unique effect. It is not always necessary to make the particle diameter uniform.
  • the average particle diameter of the positive electrode active material contained in the positive electrode active material layer 13 is not particularly limited, but is preferably 1 to 30 ⁇ m and more preferably 5 to 20 ⁇ m from the viewpoint of increasing the output.
  • the “particle diameter” refers to the outline of the active material particles (observation surface) observed using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). It means the maximum distance among any two points.
  • the value of “average particle diameter” is the value of particles observed in several to several tens of fields using observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The value calculated as the average value of the particle diameter shall be adopted.
  • the particle diameters and average particle diameters of other components can be defined in the same manner.
  • the positive electrode active material layer contains a positive electrode active material (solid solution positive electrode active material) represented by the following formula (2).
  • e represents mass% of each component in the positive electrode active material layer, and 80 ⁇ e ⁇ 98.
  • the content of the solid solution positive electrode active material in the positive electrode active material layer is essential to be 80 to 98% by mass, but preferably 84 to 98% by mass.
  • the positive electrode active material layer preferably contains a binder and a conductive aid in addition to the solid solution positive electrode active material described above. Further, if necessary, it further contains other additives such as an electrolyte (polymer matrix, ion-conductive polymer, electrolyte solution, etc.) and a lithium salt for increasing the ion conductivity.
  • a binder and a conductive aid in addition to the solid solution positive electrode active material described above. Further, if necessary, it further contains other additives such as an electrolyte (polymer matrix, ion-conductive polymer, electrolyte solution, etc.) and a lithium salt for increasing the ion conductivity.
  • Binder Although it does not specifically limit as a binder used for a positive electrode active material layer, for example, the following materials are mentioned. Polyethylene, polypropylene, polyethylene terephthalate (PET), polyether nitrile, polyacrylonitrile, polyimide, polyamide, cellulose, carboxymethyl cellulose (CMC) and its salts, ethylene-vinyl acetate copolymer, polyvinyl chloride, styrene-butadiene rubber (SBR) ), Isoprene rubber, butadiene rubber, ethylene / propylene rubber, ethylene / propylene / diene copolymer, styrene / butadiene / styrene block copolymer and hydrogenated product thereof, styrene / isoprene / styrene block copolymer and hydrogenated product thereof.
  • Thermoplastic polymers such as products, polyvinylidene fluoride (P
  • the binder content in the positive electrode active material layer is preferably 1 to 10% by mass, more preferably 1 to 8% by mass.
  • the conductive assistant refers to an additive that is blended in order to improve the conductivity of the positive electrode active material layer or the negative electrode active material layer.
  • Examples of the conductive assistant include carbon black such as ketjen black and acetylene black.
  • the content of the conductive additive in the positive electrode active material layer is preferably 1 to 10% by mass, more preferably 1 to 8% by mass.
  • electrolyte salt examples include Li (C 2 F 5 SO 2 ) 2 N, LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 and the like.
  • Examples of the ion conductive polymer include polyethylene oxide (PEO) and polypropylene oxide (PPO) polymers.
  • the positive electrode (positive electrode active material layer) can be applied by any one of a kneading method, a sputtering method, a vapor deposition method, a CVD method, a PVD method, an ion plating method, and a thermal spraying method in addition to a method of applying (coating) a normal slurry. Can be formed.
  • the negative electrode active material layer 15 essentially contains a Si-containing alloy as a negative electrode active material.
  • the Si-containing alloy as the negative electrode active material has a structure in which a silicide phase containing a transition metal silicide is dispersed in a parent phase mainly composed of amorphous or low crystalline silicon. And having a predetermined composition.
  • the Si-containing alloy constituting the negative electrode active material in the present embodiment is first provided with a parent phase mainly composed of amorphous or amorphous silicon.
  • a parent phase mainly composed of amorphous or amorphous silicon.
  • the parent phase constituting the silicon-containing alloy is a phase containing silicon as a main component, and is preferably a Si single phase (phase consisting of only Si).
  • This parent phase (phase containing Si as a main component) is a phase involved in occlusion / release of lithium ions during operation of the electrical device (lithium ion secondary battery) of the present embodiment, and electrochemically reacts with Li. It is a possible phase.
  • the Si single phase it is possible to occlude and release a large amount of Li per weight and per volume.
  • the parent phase may contain a small amount of additive elements such as phosphorus and boron, transition metals, and the like.
  • this parent phase (phase containing Si as a main component) is made amorphousr than a silicide phase described later.
  • the negative electrode active material silicon-containing alloy
  • the parent phase is more amorphous than the silicide phase can be confirmed by electron beam diffraction analysis. Specifically, according to the electron diffraction analysis, a net pattern (lattice spot) of a two-dimensional dot arrangement is obtained for a single crystal phase, and a Debye-Scherrer ring (diffraction ring) is obtained for a polycrystalline phase, A halo pattern is obtained for the amorphous phase. By using this, the above confirmation becomes possible.
  • the silicon-containing alloy constituting the negative electrode active material in the present embodiment also includes a silicide phase containing a transition metal silicide (also referred to as silicide) dispersed in the parent phase in addition to the parent phase. It is out.
  • This silicide phase contains a transition metal silicide (eg, TiSi 2 ), so that it has excellent affinity with the parent phase, and can particularly suppress cracking at the crystal interface due to volume expansion during charging.
  • the silicide phase is superior in terms of electron conductivity and hardness compared to the parent phase. For this reason, the silicide phase plays a role of improving the low electron conductivity of the parent phase and maintaining the shape of the active material against the stress during expansion.
  • a plurality of phases may exist in the silicide phase.
  • two or more phases for example, MSi 2 and MSi
  • two or more phases may exist by including a silicide with different transition metal elements.
  • the type of transition metal contained in the silicide phase is not particularly limited, but is preferably at least one selected from the group consisting of Ti, Zr, Ni, Cu, and Fe, and more preferably Ti or Zr. Yes, particularly preferably Ti.
  • These elements have a higher electron conductivity and higher strength than silicides of other elements when silicides are formed.
  • TiSi 2 which is silicide when the transition metal element is Ti is preferable because it exhibits very excellent electron conductivity.
  • the silicide phase is 50 mass% or more, preferably 80 mass% or more, More preferably, 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass is the TiSi 2 phase.
  • the size of the silicide phase is not particularly limited, but in a preferred embodiment, the size of the silicide phase is 50 nm or less. With such a configuration, the negative electrode active material (silicon-containing alloy) can have a higher capacity.
  • the silicon-containing alloy constituting the negative electrode active material has a composition represented by the following chemical formula (I).
  • A is an inevitable impurity
  • M is one or more transition metal elements
  • the “inevitable impurities” means an Si-containing alloy that exists in a raw material or is inevitably mixed in a manufacturing process. The inevitable impurities are originally unnecessary impurities, but are a very small amount and do not affect the characteristics of the Si alloy.
  • Ti is selected as an additive element (M; transition metal) to the negative electrode active material (silicon-containing alloy), and Sn is added as a second additive element as necessary.
  • M transition metal
  • Sn is added as a second additive element as necessary.
  • M is preferably titanium (Ti)
  • M is a ternary system of Si—Sn—Ti containing titanium. More preferably.
  • the amorphous-crystal phase transition is suppressed because, in the Si material, when Si and Li are alloyed, the amorphous state transitions to the crystalline state and a large volume change (about 4 times) occurs. This is because the particles themselves are broken and the function as an active material is lost. Therefore, by suppressing the amorphous-crystal phase transition, it is possible to suppress the collapse of the particles themselves, maintain the function as the active material (high capacity), and improve the cycle life. By selecting such an additive element, a Si alloy negative electrode active material having a high capacity and high cycle durability can be provided.
  • the composition ratio z of the transition metal M (particularly Ti) is preferably 7 ⁇ z ⁇ 100, more preferably 10 ⁇ z ⁇ 100, and 15 ⁇ z ⁇ 100. It is more preferable that 20 ⁇ z ⁇ 100.
  • the x, y, and z in the chemical formula (I) are represented by the following formula (1) or (2):
  • the content of the transition metal M is preferably in the range of more than 7% by mass. That is, the x, y, and z are represented by the following formula (3) or (4):
  • the x, y, and z are represented by the following formula (5) or (6):
  • the x, y, and z are expressed by the following formula (7):
  • A is an impurity (unavoidable impurity) other than the above three components derived from the raw materials and the manufacturing method.
  • the a is 0 ⁇ a ⁇ 0.5, and preferably 0 ⁇ a ⁇ 0.1.
  • the X-ray diffraction analysis for calculating the intensity ratio of the diffraction peaks is performed using the method described in the column of Examples described later.
  • a line segment ab is defined as a base line
  • the silicide of the transition metal is TiSi 2
  • diffraction peak intensity A of the Si (111) plane and the diffraction peak intensity B of the transition metal silicide are not particularly limited, but the diffraction peak intensity A of the Si (111) plane is not particularly limited. Is preferably 6000 to 25000 (cps), more preferably 6000 to 15000.
  • the diffraction peak intensity B of the transition metal silicide is preferably 9000 to 46000 (cps), more preferably 25000 to 46000 (cps).
  • the particle diameter of the silicon-containing alloy constituting the negative electrode active material in the present embodiment is not particularly limited, but the average particle diameter is preferably 0.1 to 20 ⁇ m, more preferably 0.2 to 10 ⁇ m.
  • a process for obtaining a mixed powder by mixing raw materials of a silicon-containing alloy is performed.
  • raw materials for the alloy are mixed.
  • the raw material of the alloy is not particularly limited as long as the ratio of elements necessary as the negative electrode active material can be realized.
  • raw materials in a powder state are mixed. Thereby, the mixed powder which consists of a raw material is obtained.
  • the intensity ratio (B / A) of the diffraction peak can be controlled by adjusting the composition ratio between silicon (Si) and titanium (Ti) in the raw material. For example, when the composition ratio of Ti to Si is increased, the strength ratio (B / A) can be increased.
  • Examples of alloying methods include a solid phase method, a liquid phase method, and a gas phase method.
  • a mechanical alloy method for example, a mechanical alloy method, an arc plasma melting method, a casting method, a gas atomizing method, a liquid quenching method, an ion beam sputtering method, a vacuum method, and the like.
  • Examples include vapor deposition, plating, and gas phase chemical reaction.
  • a step of melting the raw material and a step of rapidly cooling and solidifying the molten material may be included.
  • the alloying process described above is performed. Thereby, it can be set as the structure which consists of a mother phase / silicide phase as mentioned above.
  • a negative electrode active material Si-containing alloy
  • the alloying treatment time is preferably 30 hours or more, more preferably 36 hours or more, still more preferably 42 hours or more, and particularly preferably 48 hours or more.
  • the diffraction peak intensity ratio (B / A) can also be increased by increasing the time required for the alloying treatment.
  • the upper limit of the time for alloying process is not set in particular, it may usually be 72 hours or less.
  • the alloying treatment by the method described above is usually performed in a dry atmosphere, but the particle size distribution after the alloying treatment may be very large or small. For this reason, it is preferable to perform the grinding
  • the predetermined alloy included in the negative electrode active material layer has been described, but the negative electrode active material layer may contain other negative electrode active materials.
  • the negative electrode active material other than the predetermined alloy include natural graphite, artificial graphite, carbon black, activated carbon, carbon fiber, coke, soft carbon, carbon such as hard carbon, pure metal such as Si and Sn, and the predetermined composition.
  • Alloy-based active material out of ratio or metal oxide such as TiO, Ti 2 O 3 , TiO 2 , SiO 2 , SiO, SnO 2 , lithium such as Li 4/3 Ti 5/3 O 4 or Li 7 MnN And transition metal complex oxides (composite nitrides), Li—Pb alloys, Li—Al alloys, Li, and the like.
  • the content of the predetermined alloy in the total amount of 100% by mass of the negative electrode active material is preferably It is 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, particularly preferably 95 to 100% by mass, and most preferably 100% by mass.
  • the negative electrode active material layer contains a negative electrode active material represented by the following formula (1).
  • ⁇ represents the weight percent of each component in the negative electrode active material layer, and 40 ⁇ ⁇ 98.
  • the content of the negative electrode active material made of the Si-containing alloy in the negative electrode active material layer is more than 40 mass% and 98 mass% or less.
  • the negative electrode active material layer preferably contains a binder and a conductive additive in addition to the negative electrode active material described above. Further, if necessary, it further contains other additives such as an electrolyte (polymer matrix, ion conductive polymer, electrolytic solution, etc.) and a lithium salt for increasing the ion conductivity.
  • an electrolyte polymer matrix, ion conductive polymer, electrolytic solution, etc.
  • a lithium salt for increasing the ion conductivity.
  • each active material layer (active material layer on one side of the current collector) is not particularly limited, and conventionally known knowledge about the battery can be appropriately referred to.
  • the thickness of each active material layer is usually about 1 to 500 ⁇ m, preferably 2 to 100 ⁇ m, taking into consideration the intended use of the battery (emphasis on output, energy, etc.) and ion conductivity.
  • the current collectors (11, 12) are made of a conductive material.
  • the size of the current collector is determined according to the intended use of the battery. For example, if it is used for a large battery that requires a high energy density, a current collector having a large area is used.
  • the thickness of the current collector is usually about 1 to 100 ⁇ m.
  • the shape of the current collector is not particularly limited.
  • a mesh shape (such as an expanded grid) can be used.
  • the negative electrode active material is formed directly on the negative electrode current collector 12 by sputtering or the like, it is preferable to use a current collector foil.
  • a metal or a resin in which a conductive filler is added to a conductive polymer material or a non-conductive polymer material can be employed.
  • examples of the metal include aluminum, nickel, iron, stainless steel, titanium, and copper.
  • a clad material of nickel and aluminum, a clad material of copper and aluminum, or a plating material of a combination of these metals can be preferably used.
  • covered on the metal surface may be sufficient.
  • aluminum, stainless steel, copper, and nickel are preferable from the viewpoints of electronic conductivity, battery operating potential, and adhesion of the negative electrode active material by sputtering to the current collector.
  • examples of the conductive polymer material include polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyphenylene vinylene, polyacrylonitrile, and polyoxadiazole. Since such a conductive polymer material has sufficient conductivity without adding a conductive filler, it is advantageous in terms of facilitating the manufacturing process or reducing the weight of the current collector.
  • Non-conductive polymer materials include, for example, polyethylene (PE; high density polyethylene (HDPE), low density polyethylene (LDPE), etc.), polypropylene (PP), polyethylene terephthalate (PET), polyether nitrile (PEN), polyimide (PI), polyamideimide (PAI), polyamide (PA), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyacrylonitrile (PAN), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA) , Polyvinyl chloride (PVC), polyvinylidene fluoride (PVdF), or polystyrene (PS).
  • PE polyethylene
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • PEN polyether nitrile
  • PI polyimide
  • PAI polyamideimide
  • PA polyamide
  • PTFE polytetraflu
  • a conductive filler may be added to the conductive polymer material or the non-conductive polymer material as necessary.
  • a conductive filler is inevitably necessary to impart conductivity to the resin.
  • the conductive filler can be used without particular limitation as long as it has a conductivity.
  • metals, conductive carbon, etc. are mentioned as a material excellent in electroconductivity, electric potential resistance, or lithium ion barrier
  • the metal is not particularly limited, but at least one metal selected from the group consisting of Ni, Ti, Al, Cu, Pt, Fe, Cr, Sn, Zn, In, Sb, and K, or these metals It is preferable to contain an alloy or metal oxide containing.
  • it includes at least one selected from the group consisting of acetylene black, vulcan, black pearl, carbon nanofiber, ketjen black, carbon nanotube, carbon nanohorn, carbon nanoballoon, and fullerene.
  • the amount of the conductive filler added is not particularly limited as long as it is an amount capable of imparting sufficient conductivity to the current collector, and is generally about 5 to 35% by weight.
  • the separator has a function of holding an electrolyte and ensuring lithium ion conductivity between the positive electrode and the negative electrode, and a function as a partition wall between the positive electrode and the negative electrode.
  • separator examples include a separator made of a porous sheet made of a polymer or fiber that absorbs and holds the electrolyte and a nonwoven fabric separator.
  • a microporous (microporous film) can be used as the separator of the porous sheet made of polymer or fiber.
  • the porous sheet made of the polymer or fiber include polyolefins such as polyethylene (PE) and polypropylene (PP); a laminate in which a plurality of these are laminated (for example, three layers of PP / PE / PP) And a microporous (microporous membrane) separator made of a hydrocarbon resin such as polyimide, aramid, polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), glass fiber, and the like.
  • PE polyethylene
  • PP polypropylene
  • a microporous (microporous membrane) separator made of a hydrocarbon resin such as polyimide, aramid, polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), glass fiber, and the like.
  • the thickness of the microporous (microporous membrane) separator cannot be uniquely defined because it varies depending on the intended use. For example, in applications such as secondary batteries for driving motors such as electric vehicles (EV), hybrid electric vehicles (HEV), and fuel cell vehicles (FCV), it is 4 to 60 ⁇ m in a single layer or multiple layers. Is desirable.
  • the fine pore diameter of the microporous (microporous membrane) separator is desirably 1 ⁇ m or less (usually a pore diameter of about several tens of nm).
  • nonwoven fabric separator cotton, rayon, acetate, nylon, polyester; polyolefins such as PP and PE; conventionally known ones such as polyimide and aramid are used alone or in combination.
  • the bulk density of the nonwoven fabric is not particularly limited as long as sufficient battery characteristics can be obtained by the impregnated polymer gel electrolyte.
  • the thickness of the nonwoven fabric separator may be the same as that of the electrolyte layer, and is preferably 5 to 200 ⁇ m, particularly preferably 10 to 100 ⁇ m.
  • the separator includes an electrolyte.
  • the electrolyte is not particularly limited as long as it can exhibit such a function, but a liquid electrolyte or a gel polymer electrolyte is used.
  • a gel polymer electrolyte By using the gel polymer electrolyte, the distance between the electrodes is stabilized, the occurrence of polarization is suppressed, and the durability (cycle characteristics) is improved.
  • the liquid electrolyte functions as a lithium ion carrier.
  • the liquid electrolyte constituting the electrolytic solution layer has a form in which a lithium salt as a supporting salt is dissolved in an organic solvent as a plasticizer.
  • organic solvent include carbonates such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • ethyl methyl carbonate ethyl methyl carbonate.
  • Li (CF 3 SO 2) 2 N Li (C 2 F 5 SO 2) 2 N, LiPF 6, LiBF 4, LiClO 4, LiAsF 6, LiTaF such 6, LiCF 3 SO 3
  • a compound that can be added to the active material layer of the electrode can be similarly employed.
  • the liquid electrolyte may further contain additives other than the components described above.
  • additives include, for example, vinylene carbonate, methyl vinylene carbonate, dimethyl vinylene carbonate, phenyl vinylene carbonate, diphenyl vinylene carbonate, ethyl vinylene carbonate, diethyl vinylene carbonate, vinyl ethylene carbonate, 1,2-divinyl ethylene carbonate.
  • vinylene carbonate, methyl vinylene carbonate, and vinyl ethylene carbonate are preferable, and vinylene carbonate and vinyl ethylene carbonate are more preferable.
  • These cyclic carbonates may be used alone or in combination of two or more.
  • the gel polymer electrolyte has a configuration in which the above liquid electrolyte is injected into a matrix polymer (host polymer) made of an ion conductive polymer.
  • a gel polymer electrolyte as the electrolyte is superior in that the fluidity of the electrolyte is lost and the ion conductivity between the layers is easily cut off.
  • ion conductive polymer used as the matrix polymer (host polymer) examples include polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), polyacrylonitrile (PAN), polyvinylidene fluoride-hexafluoropropylene ( PVdF-HEP), poly (methyl methacrylate (PMMA), and copolymers thereof.
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • PEG polyethylene glycol
  • PAN polyacrylonitrile
  • PVdF-HEP polyvinylidene fluoride-hexafluoropropylene
  • PMMA methyl methacrylate
  • the matrix polymer of gel electrolyte can express excellent mechanical strength by forming a crosslinked structure.
  • thermal polymerization, ultraviolet polymerization, radiation polymerization, electron beam polymerization, etc. are performed on a polymerizable polymer (for example, PEO or PPO) for forming a polymer electrolyte using an appropriate polymerization initiator.
  • a polymerization treatment may be performed.
  • the separator is preferably a separator in which a heat-resistant insulating layer is laminated on a porous substrate (a separator with a heat-resistant insulating layer).
  • the heat resistant insulating layer is a ceramic layer containing inorganic particles and a binder.
  • a highly heat-resistant separator having a melting point or a heat softening point of 150 ° C. or higher, preferably 200 ° C. or higher is used.
  • the separator is less likely to curl in the battery manufacturing process due to the effect of suppressing thermal shrinkage and high mechanical strength.
  • the inorganic particles in the heat resistant insulating layer contribute to the mechanical strength and heat shrinkage suppressing effect of the heat resistant insulating layer.
  • the material used as the inorganic particles is not particularly limited. Examples thereof include silicon, aluminum, zirconium, titanium oxides (SiO 2 , Al 2 O 3 , ZrO 2 , TiO 2 ), hydroxides and nitrides, and composites thereof. These inorganic particles may be derived from mineral resources such as boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine and mica, or may be artificially produced. Moreover, only 1 type may be used individually for these inorganic particles, and 2 or more types may be used together. Of these, silica (SiO 2 ) or alumina (Al 2 O 3 ) is preferably used, and alumina (Al 2 O 3 ) is more preferably used from the viewpoint of cost.
  • the basis weight of the heat-resistant particles is not particularly limited, but is preferably 5 to 15 g / m 2 . If it is this range, sufficient ion conductivity will be acquired and it is preferable at the point which maintains heat resistant strength.
  • the binder in the heat-resistant insulating layer has a role of adhering the inorganic particles and the inorganic particles to the resin porous substrate layer.
  • the heat resistant insulating layer is stably formed, and peeling between the porous substrate layer and the heat resistant insulating layer is prevented.
  • the binder used for the heat-resistant insulating layer is not particularly limited.
  • a compound such as butadiene rubber, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), or methyl acrylate can be used as the binder.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PVF polyvinyl fluoride
  • methyl acrylate methyl acrylate
  • PVDF polyvinylidene fluoride
  • these compounds only 1 type may be used independently and 2 or more types may be used together.
  • the binder content in the heat-resistant insulating layer is preferably 2 to 20% by weight with respect to 100% by weight of the heat-resistant insulating layer.
  • the binder content is 2% by weight or more, the peel strength between the heat-resistant insulating layer and the porous substrate layer can be increased, and the vibration resistance of the separator can be improved.
  • the binder content is 20% by weight or less, the gap between the inorganic particles is appropriately maintained, so that sufficient lithium ion conductivity can be ensured.
  • the thermal contraction rate of the separator with a heat-resistant insulating layer is preferably 10% or less for both MD and TD after holding for 1 hour at 150 ° C. and 2 gf / cm 2 .
  • a current collector plate (tab) electrically connected to a current collector is taken out of a laminate film as an exterior material for the purpose of taking out current outside the battery.
  • the material constituting the current collector plate is not particularly limited, and a known highly conductive material conventionally used as a current collector plate for a lithium ion secondary battery can be used.
  • a constituent material of the current collector plate for example, metal materials such as aluminum, copper, titanium, nickel, stainless steel (SUS), and alloys thereof are preferable. From the viewpoint of light weight, corrosion resistance, and high conductivity, aluminum and copper are more preferable, and aluminum is particularly preferable. Note that the same material may be used for the positive electrode current collector plate (positive electrode tab) and the negative electrode current collector plate (negative electrode tab), or different materials may be used.
  • the tabs 58 and 59 shown in FIG. 2 are not particularly limited.
  • the positive electrode tab 58 and the negative electrode tab 59 may be drawn out from the same side, or the positive electrode tab 58 and the negative electrode tab 59 may be divided into a plurality of parts and taken out from each side, as shown in FIG. It is not limited to.
  • a terminal may be formed using a cylindrical can (metal can).
  • the seal portion is a member unique to the serially stacked battery and has a function of preventing leakage of the electrolyte layer. In addition to this, it is possible to prevent current collectors adjacent in the battery from coming into contact with each other and a short circuit due to a slight unevenness at the end of the laminated electrode.
  • the constituent material of the seal part is not particularly limited, but polyolefin resin such as polyethylene and polypropylene, epoxy resin, rubber, polyimide and the like can be used. Among these, it is preferable to use a polyolefin resin from the viewpoints of corrosion resistance, chemical resistance, film-forming property, economy, and the like.
  • ⁇ Positive terminal lead and negative terminal lead> As a material for the negative electrode and the positive electrode terminal lead, a lead used in a known laminated secondary battery can be used.
  • the parts removed from the battery exterior material should be heat-insulating so that they do not affect products (for example, automobile parts, especially electronic devices) by touching peripheral devices or wiring and causing leakage. It is preferable to coat with a heat shrinkable tube or the like.
  • Laminate film A conventionally known metal can case can be used as the exterior material.
  • the power generation element 17 may be packed using a laminate film 22 as shown in FIG.
  • the laminate film can be configured as a three-layer structure in which, for example, polypropylene, aluminum, and nylon are laminated in this order.
  • the manufacturing method in particular of a lithium ion secondary battery is not restrict
  • a lithium ion secondary battery is not limited to this.
  • the electrode (positive electrode and negative electrode) is prepared, for example, by preparing an active material slurry (positive electrode active material slurry or negative electrode active material slurry) and applying the active material slurry onto a current collector. It can be made by drying, then pressing.
  • the active material slurry includes the above-described active material (positive electrode active material or negative electrode active material), a binder, a conductive additive, and a solvent.
  • the solvent is not particularly limited, and N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylformamide, cyclohexane, hexane, water and the like can be used.
  • NMP N-methyl-2-pyrrolidone
  • the method for applying the active material slurry to the current collector is not particularly limited, and examples thereof include a screen printing method, a spray coating method, an electrostatic spray coating method, an ink jet method, and a doctor blade method.
  • the method for drying the coating film formed on the surface of the current collector is not particularly limited as long as at least a part of the solvent in the coating film is removed.
  • An example of the drying method is heating. Drying conditions (drying time, drying temperature, etc.) can be appropriately set according to the volatilization rate of the solvent contained in the applied active material slurry, the coating amount of the active material slurry, and the like. A part of the solvent may remain. The remaining solvent can be removed by a press process described later.
  • the pressing means is not particularly limited, and for example, a calendar roll, a flat plate press, or the like can be used.
  • the single cell layer can be produced by laminating the electrodes (positive electrode and negative electrode) produced in (1) via an electrolyte layer.
  • the power generation element can be produced by laminating the single cell layers in consideration of the output and capacity of the single cell layer, the output and capacity required for the battery, and the like.
  • the structure of the battery various shapes such as a rectangular shape, a paper shape, a laminated shape, a cylindrical shape, and a coin shape can be adopted.
  • the current collector and insulating plate of the component parts are not particularly limited, and may be selected according to the above shape.
  • a stacked battery is preferable.
  • a lead is joined to the current collector of the power generation element obtained above, and the positive electrode lead or the negative electrode lead is joined to the positive electrode tab or the negative electrode tab.
  • a power generation element is placed in a laminate sheet so that the positive electrode tab and the negative electrode tab are exposed to the outside of the battery, and an electrolytic solution is injected with a liquid injector and then sealed in a vacuum to produce a stacked battery. sell.
  • the initial charge treatment, gas removal treatment and activation treatment are further performed under the following conditions.
  • it is done (see Example 1).
  • the three sides of the laminate sheet (exterior material) are completely sealed in a rectangular shape by thermocompression when sealing in the production of the laminated battery of (4) so that the gas removal treatment can be performed. Stop (main sealing), and the remaining one side is temporarily sealed by thermocompression bonding.
  • the remaining one side may be freely opened and closed by, for example, clip fastening, but from the viewpoint of mass production (production efficiency), it is preferable to temporarily seal the side by thermocompression bonding.
  • thermocompression it is only necessary to adjust the temperature and pressure for pressure bonding.
  • it can be opened by lightly applying force, and after degassing, it may be sealed again by thermocompression, or finally completely sealed by thermocompression ( Main sealing).
  • the battery aging treatment is preferably performed as follows. At 25 ° C., a constant current charging method is used for 0.05 C for 4 hours (SOC approximately 20%). Next, after charging to 4.45 V at a 0.1 C rate at 25 ° C., the charging is stopped, and the state (SOC is about 70%) is maintained for about 2 days (48 hours).
  • thermocompression bonding Next, the following process is performed as the first (first) gas removal process. First, one side temporarily sealed by thermocompression bonding is opened, gas is removed at 10 ⁇ 3 hPa for 5 minutes, and then thermocompression bonding is performed again to perform temporary sealing. Further, pressurization with a roller (surface pressure 0.5 ⁇ 0.1 MPa) is performed, and the electrode and the separator are sufficiently adhered.
  • the battery is charged at 25 ° C. by a constant current charging method until the voltage reaches 4.45 V at 0.1 C, and then discharged twice to 2.0 V at 0.1 C.
  • a cycle of discharging to 2.0 V at 0.1 C once is 4.65 V at 0.1 C.
  • the battery is charged until it reaches 0, and then discharged once at 0.1 C to 2.0 V.
  • a cycle of charging at 0.1 C to 4.75 V by a constant current charging method at 25 ° C. and then discharging to 0.1 V at 0.1 C may be performed once.
  • the constant current charging method is used as the activation processing method, and the electrochemical pretreatment method when the voltage is set as the termination condition is described as an example, but the charging method is a constant current constant voltage charging method. You may use. Further, as the termination condition, a charge amount or time may be used in addition to the voltage.
  • thermocompression bonding Next, the following process is performed as the first (first) gas removal process. First, one side temporarily sealed by thermocompression bonding is opened, gas is removed at 10 ⁇ 3 hPa for 5 minutes, and then thermocompression bonding is performed again to perform main sealing. Further, pressurization with a roller (surface pressure 0.5 ⁇ 0.1 MPa) is performed, and the electrode and the separator are sufficiently adhered.
  • the performance and durability of the obtained battery can be improved by performing the initial charging process, the gas removal process, and the activation process described above.
  • the assembled battery is configured by connecting a plurality of batteries. Specifically, at least two or more are used, and are configured by serialization, parallelization, or both. Capacitance and voltage can be freely adjusted by paralleling in series.
  • a small assembled battery that can be attached and detached by connecting a plurality of batteries in series or in parallel. Then, a plurality of small assembled batteries that can be attached and detached are connected in series or in parallel to provide a large capacity and large capacity suitable for vehicle drive power supplies and auxiliary power supplies that require high volume energy density and high volume output density.
  • An assembled battery having an output can also be formed. How many batteries are connected to make an assembled battery, and how many small assembled batteries are stacked to make a large-capacity assembled battery depends on the battery capacity of the mounted vehicle (electric vehicle) It may be determined according to the output.
  • the electric device of the present invention including the lithium ion secondary battery according to the present embodiment maintains a discharge capacity even when used for a long time, and has good cycle characteristics. Furthermore, the volume energy density is high. Vehicle applications such as electric vehicles, hybrid electric vehicles, fuel cell vehicles, and hybrid fuel cell vehicles require higher capacity, larger size, and longer life than electric and portable electronic devices. . Therefore, the lithium ion secondary battery (electric device) can be suitably used as a vehicle power source, for example, as a vehicle driving power source or an auxiliary power source.
  • a battery or an assembled battery formed by combining a plurality of these batteries can be mounted on the vehicle.
  • a plug-in hybrid electric vehicle having a long EV mileage or an electric vehicle having a long charge mileage can be formed by mounting such a battery.
  • a car a hybrid car, a fuel cell car, an electric car (four-wheeled vehicles (passenger cars, trucks, buses, commercial vehicles, light cars, etc.) This is because it can be used for motorcycles (including motorcycles) and tricycles) to provide a long-life and highly reliable automobile.
  • the application is not limited to automobiles.
  • it can be applied to various power sources for moving vehicles such as other vehicles, for example, trains, and power sources for mounting such as uninterruptible power supplies. It is also possible to use as.
  • Example 1 Solid solution positive electrode active material C1 (Preparation of aqueous solution of titanium citrate complex) 60 g (0.3 mol) of anhydrous citric acid (molecular weight 192.12 g / mol) was added to 400 ml of acetone and heated to 60 ° C. to dissolve. Next, 56 g (0.2 mol) of titanium tetraisopropoxide (molecular weight 284.22 g / mol) was added to form a precipitate. This liquid was subjected to suction filtration to obtain a precipitate (light yellow).
  • Ti concentration was 5.0% by weight as TiO 2 (molecular weight 79.87 g / mol).
  • the obtained melted solution (slurry) was sprayed by heating at 200 ° C. to 400 ° C. and dried.
  • the obtained dry powder was vacuum-dried at 140 ° C. to 250 ° C. for 12 hours and then calcined at 450 ° C. for 12 hours. Thereafter, the main baking was performed at 900 ° C. for 12 hours.
  • Cu-K ⁇ rays were used as the X-ray source, and the measurement conditions were a tube voltage of 40 KV, a tube current of 20 mA, a scanning speed of 2 ° / min, a divergence slit width of 0.5 °, and a light receiving slit width of 0.15 °.
  • FIG. 3 shows a positive electrode active material C0 having the following composition that does not contain Ti for comparison.
  • the X-ray diffraction pattern of is shown.
  • FIG. 4 shows an X-ray diffraction pattern of the solid solution positive electrode active material C1.
  • 3 and 4 show a peak attributed to the superlattice structure characteristic of the solid solution system at 20-23 °. Furthermore, in FIG. 4, the peaks at 36.5-37.5 (101) and 44-45 ° (104) and 64-65 ° (108) / 65-66 (110) are slightly shifted to the lower angle side. It was observed. Further, no diffraction peak attributed to the spinel phase was observed in any sample.
  • composition of slurry for positive electrode had the following composition.
  • Cathode active material Ti-substituted solid solution cathode active material C1 obtained above 9.4 parts by weight
  • Conductive aid flake graphite 0.15 parts by weight
  • Acetylene black 0.15 parts by weight
  • Binder Polyvinylidene fluoride (PVDF) 0 .3 parts by weight
  • Solvent 8.2 parts by weight of N-methyl-2-pyrrolidone (NMP).
  • a positive electrode slurry having the above composition was prepared as follows. First, 4.0 parts by weight of a solvent (NMP) is added to 2.0 parts by weight of a 20% binder solution obtained by dissolving a binder in a solvent (NMP) into a 50 ml disposable cup, and a stirring defoaming machine (spinning revolving mixer: Awatori) A binder diluted solution was prepared by stirring for 1 minute with Rentaro AR-100).
  • NMP solvent
  • NMP spinning revolving mixer
  • the positive electrode slurry was applied to one side of an aluminum current collector with a thickness of 20 ⁇ m using an automatic coating apparatus (Doctor blade manufactured by Tester Sangyo: PI-1210 automatic coating apparatus). Subsequently, the current collector coated with the positive electrode slurry was dried on a hot plate (100 ° C. to 110 ° C., drying time 30 minutes), and the amount of NMP remaining in the positive electrode active material layer was 0.02 wt%.
  • a sheet-like positive electrode was formed as follows.
  • the sheet-like positive electrode was compression-molded with a roller press and cut to produce a positive electrode. At this time, the coating amount was adjusted in consideration of the discharge capacity of the positive electrode active material and the positive electrode slurry composition so that the discharge capacity of the positive electrode C1 was 5.55 mAh / cm 2 (the same applies to the following negative electrodes C2 to C12). .
  • Si-containing alloy Si 80 Sn 10 Ti 10 (unit: mass%, hereinafter the same) was used as the Si-containing alloy as the negative electrode active material.
  • the Si-containing alloy was produced by a mechanical alloy method. Specifically, using a planetary ball mill device P-6 manufactured by Fricht, Germany, zirconia pulverized balls and alloy raw material powders were put into a zirconia pulverized pot and alloyed at 600 rpm for 24 hours (alloying treatment). ), And then pulverization was performed at 400 rpm for 1 hour. The average particle size of the obtained Si-containing alloy (negative electrode active material) powder was 0.3 ⁇ m.
  • composition of slurry for negative electrode The negative electrode slurry had the following composition.
  • Negative electrode active material Si-containing alloy (Si 80 Sn 10 Ti 10 ) 80 parts by weight
  • Conductive auxiliary agent SuperP 5 parts by weight
  • Binder Polyimide 15 parts by weight
  • Solvent N-methyl-2-pyrrolidone (NMP) Appropriate amount.
  • a negative electrode slurry having the above composition was prepared as follows. First, a binder solution in which a binder was dissolved was added to a solvent (NMP), and the mixture was stirred for 1 minute with a stirring deaerator to prepare a binder diluted solution. A conductive additive, negative electrode active material powder, and a solvent (NMP) were added to the binder dilution, and the mixture was stirred for 3 minutes with a stirring deaerator to obtain a negative electrode slurry.
  • NMP solvent
  • the negative electrode slurry was applied to one side of a 10 ⁇ m thick electrolytic copper current collector using an automatic coating apparatus. Subsequently, the current collector coated with the negative electrode slurry was dried on a hot plate (100 ° C. to 110 ° C., drying time 30 minutes), and the amount of NMP remaining in the negative electrode active material layer was 0.02 wt% or less. A sheet-like negative electrode was formed.
  • ethylene carbonate (EC) and diethyl carbonate (DEC) 1 in a mixed nonaqueous solvent were mixed at a volume ratio, the concentration of LiPF 6 a (lithium hexafluorophosphate) 1M What was dissolved so that it might become was used.
  • LiPF 6 a lithium hexafluorophosphate
  • the positive electrode C1 obtained above was cut out so as to have an active material layer area of 2.5 cm in length and 2.0 cm in width, and the two current collectors faced each other, so that the uncoated surface (aluminum current collector)
  • the current collector portion was spot welded together with the surface not coated with the foil slurry.
  • an aluminum positive electrode tab positive electrode current collector plate
  • the negative electrode A1 obtained above was cut out so as to have an active material layer area of 2.7 cm in length and 2.2 cm in width, and then a negative electrode tab of electrolytic copper was further welded to the current collector portion to form a negative electrode A11.
  • the negative electrode A11 has a structure in which a negative electrode active material layer is formed on one surface of a current collector.
  • a porous polypropylene separator (S) (length 3.0 cm ⁇ width 2.5 cm, thickness 25 ⁇ m, porosity 55%) is sandwiched between the negative electrode A11 to which these tabs are welded and the positive electrode C11.
  • a laminated power generation element was produced.
  • the structure of the stacked type power generation element is the structure of negative electrode (single side) / separator / positive electrode (both sides) / separator / negative electrode (single side), that is, A11- (S) -C11- (S) -A11. The configuration.
  • both sides of the power generation element were sandwiched with an aluminum laminate film exterior material (length 3.5 cm ⁇ width 3.5 cm), and the above power generation element was accommodated by thermocompression sealing at three sides.
  • LiPF 6 electrolyzed ethylene carbonate
  • DEC diethyl carbonate
  • lithium lithium fluorophosphate LiPO 2 F 2
  • MMDS methylenemethane disulfonic acid
  • Example 1 a positive electrode and a negative electrode were produced according to Example 1. That is, a positive electrode and a negative electrode were produced in the same manner as in Example 1 described above except as otherwise noted below.
  • positive electrodes C2 to C12 were prepared in the same manner as the positive electrode C1, except that the composition of the solid solution positive electrode active material was changed as shown in Table 1 below.
  • Ni-containing electrode A2 A negative electrode active material and a negative electrode were produced in the same manner as the negative electrode A1 described above, except that the composition of the Si-containing alloy (negative electrode active material) was changed to Si 70 Sn 15 Ti 15 .
  • the average particle size of the obtained Si-containing alloy (negative electrode active material) powder was 0.3 ⁇ m.
  • a negative electrode active material and a negative electrode were prepared in the same manner as described above.
  • the average particle size of the obtained Si-containing alloy (negative electrode active material) powder was 0.3 ⁇ m.
  • Ni-containing electrode A4 A negative electrode active material and a negative electrode were prepared by the same method as that of the negative electrode A3 described above, except that the time of alloying treatment for preparing the Si-containing alloy (negative electrode active material) was changed to 50 hours.
  • the average particle size of the obtained Si-containing alloy (negative electrode active material) powder was 0.3 ⁇ m.
  • a negative electrode active material and a negative electrode were prepared in the same manner as the negative electrode A1 described above, except that the composition of the Si-containing alloy was changed to Si 90 Ti 10 .
  • the average particle diameter of the obtained silicon-containing alloy (negative electrode active material) powder was 0.3 ⁇ m.
  • each of the negative electrode active materials (Si-containing alloys) used for the production of the negative electrodes A1 to A5 described above was analyzed by an X-ray diffraction measurement method.
  • the apparatus and conditions used for the X-ray diffraction measurement method are as follows.
  • X-ray diffractometer SmartLab9kW manufactured by Rigaku Corporation Voltage / Current: 45kV / 200mA
  • X-ray wavelength CuK ⁇ 1
  • X-ray diffraction spectra obtained for the respective negative electrode active materials (Si-containing alloys) are shown in FIGS. 5A to 5E.
  • the ratio values (B / A) are shown in Tables 2 to 6 below.
  • This X-ray diffraction analysis also confirmed that all Ti contained in the silicon-containing alloy was present as a silicide (TiSi 2 ) phase.
  • the power generation element of each battery obtained above was set on an evaluation cell mounting jig, and a positive electrode lead and a negative electrode lead were attached to each tab end of the power generation element, and a test was performed.
  • the battery aging treatment was performed as follows. At 25 ° C., the battery was charged at a constant current charging method of 0.05 C for 4 hours (SOC approximately 20%). Next, after charging to 4.45 V at a 0.1 C rate at 25 ° C., the charging was stopped and the state (SOC about 70%) was maintained for about 2 days (48 hours).
  • thermocompression bonding One side temporarily sealed by thermocompression bonding was opened, gas was removed at 10 ⁇ 3 hPa for 5 minutes, and then thermocompression bonding was performed again to perform temporary sealing. Further, pressurization with a roller (surface pressure 0.5 ⁇ 0.1 MPa) was performed, and the electrode and the separator were sufficiently adhered.
  • thermocompression bonding One side temporarily sealed by thermocompression bonding was opened, gas was removed at 10 ⁇ 3 hPa for 5 minutes, and then thermocompression bonding was performed again to perform main sealing. Further, pressurization with a roller (surface pressure 0.5 ⁇ 0.1 MPa) was performed, and the electrode and the separator were sufficiently adhered.
  • the evaluation cell is set to the constant current / constant voltage mode in the charging process (referring to the Li insertion process to the evaluation electrode) in the thermostat set to the above evaluation temperature using a charge / discharge tester.
  • the battery was charged from 2 V to 10 mV at 0.1 mA.
  • a discharge process referring to a Li desorption process from the electrode for evaluation
  • a constant current mode was set and discharge was performed from 0.3 C, 10 mV to 2 V.
  • the charge / discharge test was conducted from the initial cycle (1 cycle) to 100 cycles under the same charge / discharge conditions with the above charge / discharge cycle as one cycle.
  • the results of determining the ratio of the discharge capacity at the 100th cycle to the discharge capacity at the first cycle are shown in Tables 2 to 6 below.
  • the lithium ion secondary batteries of Examples 1 to 48 which are electrical devices according to the present invention, have excellent cycle characteristics (100 cycles) compared to Comparative Examples 1 to 12. It can be seen that the eye capacity retention ratio has been achieved.

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Abstract

Le problème décrit par la présente invention est de pourvoir à un moyen qui permette d'atteindre une durabilité cyclique suffisante, tout en tirant suffisamment profit des propriétés de haute capacité caractéristiques de matériaux d'électrode positive en solution solide, dans un dispositif électrique tel qu'une batterie rechargeable au lithium-ion comprenant une électrode positive utilisant un matériau actif d'électrode positive en solution solide. La solution de la présente invention consiste à utiliser, comme alliage contenant du silicium destiné à être contenu dans la couche de matériau actif d'électrode négative, un alliage qui a une composition prescrite et une structure obtenue par dispersion d'une phase de siliciure contenant un siliciure de métal de transition dans une phase parente dont le constituant principal est du silicium amorphe ou faiblement cristallin, et présente également des caractéristiques d'intensité de pic prescrites lorsqu'on le mesure au moyen de la diffraction des rayons X. Comme matériau actif d'électrode positive en solution solide à inclure dans la couche de matériau actif d'électrode positive, la présente invention utilise un matériau actif d'électrode positive en solution solide contenant un élément substituant tel que le titane.
PCT/JP2014/083481 2014-12-17 2014-12-17 Dispositif électrique WO2016098215A1 (fr)

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JP2019003814A (ja) * 2017-06-14 2019-01-10 日産自動車株式会社 電気デバイス

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