WO2022045302A1 - 活物質及びその製造方法、電極合剤並びに電池 - Google Patents

活物質及びその製造方法、電極合剤並びに電池 Download PDF

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WO2022045302A1
WO2022045302A1 PCT/JP2021/031567 JP2021031567W WO2022045302A1 WO 2022045302 A1 WO2022045302 A1 WO 2022045302A1 JP 2021031567 W JP2021031567 W JP 2021031567W WO 2022045302 A1 WO2022045302 A1 WO 2022045302A1
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active material
compound
conductive material
mass
positive electrode
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French (fr)
Japanese (ja)
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徳彦 宮下
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Mitsui Kinzoku Co Ltd
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Mitsui Mining and Smelting Co Ltd
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Priority to JP2022545739A priority Critical patent/JPWO2022045302A1/ja
Priority to US18/017,992 priority patent/US20230278881A1/en
Priority to EP21861723.1A priority patent/EP4206124A4/en
Priority to CN202511316755.7A priority patent/CN121394331A/zh
Priority to KR1020237005173A priority patent/KR20230057346A/ko
Priority to CN202180056936.4A priority patent/CN116057009B/zh
Publication of WO2022045302A1 publication Critical patent/WO2022045302A1/ja
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    • C01B25/14—Sulfur, selenium, or tellurium compounds of phosphorus
    • C—CHEMISTRY; METALLURGY
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    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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    • H01M4/139—Processes of manufacture
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
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    • 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 active substance and a method for producing the same.
  • the present invention also relates to an electrode mixture containing the active material and a battery.
  • Lithium-ion batteries are widely used as power sources for portable electronic devices such as notebook computers and mobile phones because of their high energy density and easy miniaturization and weight reduction. Recently, the development of high-output, high-capacity lithium-ion batteries to be installed in electric vehicles and hybrid electric vehicles has been promoted.
  • Patent Document 1 proposes a positive electrode active material containing a sulfide solid electrolyte material and a conductive material. Further, Non-Patent Document 1 proposes a positive electrode active material in which Li 3 PS 4 glass, which is a sulfide solid electrolyte, and a carbon-based conductive auxiliary agent are combined.
  • the present inventor has repeated research on a sulfide solid electrolyte used in a lithium ion battery, and has a composition formula Li 7-x PS 6-x Ha (in the formula, x is 0.2 or more and 1.8 or less.
  • Ha has proposed a compound represented by Cl) or Br (see Patent Document 2). This compound has high lithium ion conductivity.
  • An object of the present invention is to provide an active material capable of enhancing the performance of a lithium ion battery.
  • Electrolytes and active materials used in batteries play completely different roles.
  • the material used for the sulfide solid electrolyte is diverted to the material of the active material, it is difficult to further improve the battery performance such as capacity and rate characteristics.
  • the present inventor not only exhibits a function as an active material but also exhibits a positive electrode of a lithium ion battery by mixing and complexing the sulfide solid electrolyte proposed in Patent Document 2 described above with a conductive material. It was found that the battery performance such as capacity and rate characteristics can be improved more than before by using it as an active material.
  • the present invention has been made based on the above findings, and lithium (Li) element, sulfur (S) element, and M element (M is phosphorus (P), germanium (Ge), antimony (Sb), silicon (S). Si), tin (Sn), aluminum (Al), titanium (Ti), iron (Fe), nickel (Ni), cobalt (Co) and manganese (Mn)).
  • M is phosphorus (P), germanium (Ge), antimony (Sb), silicon (S). Si), tin (Sn), aluminum (Al), titanium (Ti), iron (Fe), nickel (Ni), cobalt (Co) and manganese (Mn)).
  • a compound containing a crystal phase having an algyrodite type crystal structure, and With a conductive material The above-mentioned problems are solved by providing an active material which is a composite material of the compound and the conductive material.
  • the present invention provides a suitable method for producing the active material.
  • Lithium (Li) element, sulfur (S) element, and M element M is phosphorus (P), germanium (Ge), antimony (Sb), silicon (Si), tin (Sn), aluminum (Al), titanium (Ti), iron (Fe), nickel (Ni), cobalt (Co) and manganese (Mn) are at least one of them), and a compound containing a crystal phase having an algyrodite type crystal structure is prepared.
  • the first step to do and The present invention provides a method for producing an active material, which comprises a second step of mixing and compounding the compound and a conductive material.
  • FIG. 1 is a charge / discharge curve of a battery using the positive electrode active material produced in Example 1.
  • FIG. 2 is a charge / discharge curve of the battery using the positive electrode active material produced in Example 5.
  • FIG. 3 is a charge / discharge curve of a battery using the positive electrode active material produced in Comparative Example 3.
  • FIG. 4 is an SEM-EDS image of the positive electrode active material produced in Example 5.
  • FIG. 5 is an SEM-EDS image of the positive electrode active material produced in Comparative Example 4.
  • FIG. 6 is a cross-sectional SEM-EDS image of the battery using the positive electrode active material produced in Example 5.
  • FIG. 7 is a cross-sectional SEM-EDS image of the battery using the positive electrode active material produced in Comparative Example 4.
  • FIG. 1 is a charge / discharge curve of a battery using the positive electrode active material produced in Example 1.
  • FIG. 2 is a charge / discharge curve of the battery using the positive electrode active material produced in Example 5.
  • FIG. 3 is a charge
  • FIG. 8 is an X-ray diffraction pattern of the positive electrode active material produced in Examples 1, 3 and 4.
  • FIG. 9 is an X-ray diffraction pattern of the positive electrode active material produced in Comparative Examples 3 and 4.
  • FIG. 10 is a charge / discharge curve of a battery using the positive electrode active material produced in Comparative Example 4.
  • the present invention relates to an active material of a battery.
  • the mainstream of secondary batteries is lithium-ion batteries, but lithium-ion batteries are required to have a higher energy density.
  • solid-state batteries that use sulfide, which is a substance that has few restrictions on active materials and can achieve high energy density, as a solid electrolyte.
  • an active material having a high capacity is required.
  • the active material of the present invention meets these requirements.
  • the active material of the present invention has particles of a specific compound and a conductive material composited with the particles. That is, the active material of the present invention is composed of a main portion containing particles of a specific compound and a conductive portion containing a conductive material dispersed in the surface and / or inside of the main portion and imparting electronic conductivity. Contains particles.
  • these main parts and conductive parts will be described.
  • the main part is composed of a compound containing a specific element.
  • the main part is preferably composed of a compound containing a lithium (Li) element, a sulfur (S) element, and an M element.
  • the M element is, for example, phosphorus (P) element, germanium (Ge) element, antimony (Sb) element, silicon (Si) element, tin (Sn) element, aluminum (Al) element, titanium (Ti) element, iron (Fe). ) Element, nickel (Ni) element, cobalt (Co) element and manganese (Mn) element at least one.
  • Examples of the compound containing Li element, S element and M element include Li 7 PS 6 , Li 7 + 3x (P 5 + 1-x Fe 2+ x ) S 6 , Li which is a compound containing only Li element, S element and M element. 7 + x (P 5 + 1-x Si 4 + x ) S 6 and the like can be mentioned (in the formula, x represents a number of 0.1 or more and 1.0 or less).
  • a compound containing the Li element, the S element and the M element a compound containing other elements in addition to these three types of elements can also be used.
  • Examples of the other element include a halogen (X) element. It is preferable to use a compound containing an element X in addition to the elements Li, S and M because the active material of the present invention has higher properties.
  • the element X at least one selected from F, Cl, Br and I can be used.
  • the compound containing the Li element, the S element, the M element and the X element has a composition formula (1) Li a MS b X c (in the formula, M is phosphorus (P), germanium (Ge), antimon (Sb), It is at least one element of silicon (Si), tin (Sn), aluminum (Al), titanium (Ti), iron (Fe), nickel (Ni), cobalt (Co) and manganese (Mn).
  • X is represented by at least one element selected from fluorine (F), chlorine (Cl), bromine (Br) and iodine (I)), which is activated by improving ionic conductivity. It is preferable because it has higher properties as a substance.
  • a is preferably 3.0 or more and 9.0 or less, more preferably 3.5 or more and 8.0 or less, and even more preferably 4.0 or more and 7.5 or less. ..
  • b is preferably 3.5 or more and 6.0 or less, more preferably 4.0 or more and 5.8 or less, and even more preferably 4.2 or more and 5.5 or less.
  • c is preferably 0.10 or more and 3.0 or less, more preferably 0.50 or more and 2.5 or less, and further preferably 1.0 or more and 1.8 or less.
  • the M element in the above composition formula is preferably at least one of phosphorus (P) element, germanium (Ge) element, antimony (Sb) element, tin (Sn) element and silicon (Si) element, and in particular. It is preferable that the element phosphorus (P) is contained because the characteristics as an active material are further enhanced.
  • the compound constituting the main part is particularly preferably represented by the composition formula (2) Li 7-d MS 6-d X d from the viewpoint of further enhancing the characteristics as an active material.
  • d is preferably 0.40 or more and 2.2 or less, more preferably 0.80 or more and 2.0 or less, and even more preferably 1.2 or more and 1.8 or less.
  • a part of the M element is silicon (Si) element, germanium (Ge) element, tin (Sn) element, lead (Pb) element, boron (B) element, aluminum ( It may be substituted with one or more elements selected from Al) element, gallium (Ga) element, arsenic (As) element, antimony (Sb) element and bismuth (Bi) element.
  • the formula (1) is Li a (M1 1-y M2 y ) S b X c
  • the formula (2) is Li 7-d (M1 1-y M2 y ) S 6-d X d .
  • M2 is a silicon (Si) element, a germanium (Ge) element, a tin (Sn) element, a lead (Pb) element, a boron (B) element, an aluminum (Al) element, a gallium (Ga) element, and an arsenic (As) element.
  • Antimon (Sb) element and bismuth (Bi) element selected from one or more elements.
  • y is preferably 0.010 or more and 0.70 or less, more preferably 0.020 or more and 0.40 or less, and even more preferably 0.050 or more and 0.20 or less.
  • the M1 element is the same as the M element described in the composition formula (1).
  • composition of each element in the compound constituting the main part can be measured by, for example, ICP emission spectroscopy.
  • the compound constituting the main part preferably contains a crystal phase having an argylodite type crystal structure in addition to containing each of the above-mentioned elements.
  • the properties of the active material of the present invention are further improved.
  • the compound constituting the main portion preferably contains a crystal phase having a cubic algyrodite type crystal structure. Whether or not a crystal phase having an algyrodite type crystal structure is contained can be determined by analyzing the active material of the present invention by an X-ray diffraction method.
  • the CuK ⁇ ray for example, CuK ⁇ 1 ray can be used.
  • it is more preferred to have a peak at one or more positions selected from 51.70 ° ⁇ 1.00 ° and 2 ⁇ 25.19 ° ⁇ 1.00 ° and 29.62 ° ⁇ 1.00 °.
  • the above-mentioned peak positions are represented by a median value of ⁇ 1.00 °, the median value is preferably ⁇ 0.500 °, and the median value is more preferably ⁇ 0.300 °.
  • the main part contains the above-mentioned compounds, and may contain other materials and other components as needed. Therefore, the main part may be composed of a single phase composed of a crystal phase having an algyrodite type crystal structure, or may contain another phase in addition to the phase.
  • the core portion may contain a Li 2S phase, a Li 3 PS 4 phase, a Li 4 P 2 S 6 phase, a LiCl or a LiBr phase, etc., in addition to the crystal phase having an algyrodite type crystal structure.
  • the main portion contains a Li 2S phase in addition to the crystal phase having an algyrodite type crystal structure, because the capacity of the active material increases.
  • the main part is a compound containing a Li element, an S element, an M element and an X element and containing a crystal phase having an argylodite type crystal structure as a main material.
  • the main part may contain unavoidable impurities to a degree that does not adversely affect the effect of the present invention, for example, less than 5% by mass, particularly less than 3% by mass.
  • the main portion containing the above-mentioned compound has the form of particles, and the conductive portion containing the above-mentioned conductive material is arranged on the surface or inside of the particles.
  • the conductive material a material having electronic conductivity can be used without particular limitation.
  • the conductive material include various metal materials and conductive non-metal materials.
  • the metallic material and the conductive non-metallic material either one of them may be used, or both may be used in combination.
  • the metal material examples include various noble metal elements such as gold (Au) element, silver (Ag) element, platinum (Pt) element, palladium (Pd) element, rhodium (Rh) element, iridium (Ir) element, and ruthenium ( Examples include Ru) element and osmium (Os) element. Further, various transition metal elements such as copper (Cu) element, iron (Fe) element and tin (Sn) element can be mentioned. These metal elements may be used alone or in combination of two or more. As the conductive non-metal material, for example, a carbon material can be used.
  • Examples thereof include graphite, acetylene black, carbon black, carbon nanofibers, carbon nanotubes, nanographene and fullerene nanowhisca. These carbon materials may be used alone or in combination of two or more. Of these carbon materials, it is preferable to use carbon black from the viewpoint of enhancing the initial capacity and discharge rate characteristics of the battery. From the viewpoint of further enhancing this advantage, it is preferable to use Ketjen black as the carbon black, and it is particularly preferable to use furnace black, and particularly preferably oil furnace black.
  • the conductive part containing the above-mentioned various conductive materials plays the role of an electron conduction path when lithium is occluded from the main part, so it is necessary that the conductive part is uniformly dispersed and adhered to the surface and the inside.
  • the size of the conductive material is preferably smaller than the size of the main portion.
  • the value of D1 / D2 is preferably, for example, 2 or more, more preferably 5 or more, and 10 The above is more preferable.
  • the value of D1 / D2 is, for example, preferably 1000 or less, more preferably 500 or less, and further preferably 10 or more and 100 or less.
  • the particle size D1 of the main portion is, for example, preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and even more preferably 0.5 ⁇ m or more.
  • D1 is preferably, for example, 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
  • the particle size D2 of the conductive portion is, for example, preferably 1 nm or more, more preferably 10 nm or more, and even more preferably 20 nm or more.
  • D2 is preferably, for example, 500 nm or less, more preferably 300 nm or less, and even more preferably 200 nm or less.
  • the particle size of the main part is the volume cumulative particle size D 50 at the cumulative volume of 50% by volume measured by the laser diffraction / scattering type particle size distribution measurement method (hereinafter, “D 50 ” means this particle size). do.).
  • D 50 the particle size of the conductive portion is difficult to measure by the laser diffraction / scattering type particle size distribution measurement when the conductive portion is dispersed inside the particles of the main portion. Therefore, using an SEM (scanning electron microscope) or TEM (transmission electron microscope), the average particle size is measured by directly observing the conductive parts dispersed inside the main part.
  • the fiber diameter refers to the diameter in the fiber cross section or the average value of the major axis and the minor axis.
  • the material is a composite of the main part and the conductive part, that is, the composite material of the particles of the compound constituting the main part and the conductive material constituting the conductive part.
  • the conductive portion is inseparably and inseparably dispersed on the surface or inside of the main portion.
  • the particles of the conductive material are inseparably dispersed on the surface and / or inside of the particles of the compound, or the particles of the compound constituting the main part and the conductivity constituting the conductive part are formed.
  • An embodiment in which the particles of the material are chemically reacted and bonded to each other can be mentioned.
  • the particles of the conductive material are inseparably dispersed on the surface or inside of the particles of the compound constituting the main part.
  • scanning the active material of the present invention with an energy-dispersed X-ray spectroscope.
  • the active material is observed with a type electron microscope (SEM-EDS) and the constituent elements of the compound constituting the main part (for example, sulfur element) and the constituent elements of the conductive material constituting the conductive part are mapped, the main component is used. It means that it can be confirmed that the constituent elements of the compound constituting the portion (for example, sulfur element) and the constituent elements of the conductive material constituting the conductive portion are present so as to overlap each other.
  • the constituent elements for example, sulfur element
  • the constituent elements of the compound constituting the main part and the conductive part are observed on the surface or inside of the active material. It means that it can be confirmed that the constituent elements of the constituent conductive materials are present so as to overlap each other.
  • the fact that the main portion and the conductive portion are composite can be confirmed from the presence or absence of CS bonds by, for example, Raman spectroscopy or photoelectron spectroscopy (when the conductive material is a carbon material).
  • the active material of the present invention enables smooth transfer of electrons between the outside of the active material and the main part via the conductive portion, acquires conductivity, and has a lithium ion desorption function. Acquire. Furthermore, the battery having the active material of the present invention exhibits high capacity and high rate characteristics by mainly using a compound having an algyrodite type crystal structure having a high lithium content and high lithium ion conductivity as a main part. Will be. In particular, the active material of the present invention is useful as a positive electrode active material for a lithium ion battery.
  • the amount of the conductive material with respect to 100 parts by mass of the particles of the compound constituting the main part is preferably, for example, 1 part by mass or more, more preferably 2 parts by mass or more, and 5 parts by mass. It is more preferable that the amount is more than one part.
  • the amount of the conductive material with respect to 100 parts by mass of the particles of the compound constituting the main part is preferably, for example, 50 parts by mass or less, more preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. More preferred.
  • the presence of the main portion and the conductive portion in this range makes it possible for the battery provided with the active material of the present invention to remarkably exhibit high capacity and high rate characteristics.
  • the content of the lithium element in the compound is preferably, for example, 10% by mass or more, more preferably 12% by mass or more, and further preferably 15% by mass or more. preferable.
  • the content is preferably, for example, 25% by mass or less, more preferably 23% by mass or less, and further preferably 21% by mass or less.
  • the lithium ion conductivity of the compound constituting the main part in the active material is preferably, for example, 1 ⁇ 10 -5 S / cm or more, and 1 ⁇ 10 -4 S / cm. The above is more preferable, and 1 ⁇ 10 -3 S / cm or more is further preferable.
  • the rate characteristics of the battery having the active material of the present invention can be further improved.
  • This manufacturing method is mainly divided into a first step of preparing particles of a compound constituting a main part and a second step of mixing the particles of the compound and a conductive material to combine the two.
  • a first step of preparing particles of a compound constituting a main part
  • a second step of mixing the particles of the compound and a conductive material to combine the two.
  • each step will be described.
  • particles of a compound containing the above-mentioned element and containing a crystal phase having an algyrodite type crystal structure are prepared.
  • This compound can be produced by a known method.
  • this compound contains, for example, lithium (Li) element, phosphorus (P) element, sulfur ( S) element, chlorine (Cl) element and bromine (Br) element, lithium sulfide (Li 2S) powder and five Dirin sulfide (P2 S 5 ) powder, lithium chloride (LiCl) powder, and lithium bromide (LiBr) powder are mixed and fired to obtain particles of the compound.
  • a method for mixing these powders for example, a ball mill, a bead mill, a homogenizer or the like is preferably used.
  • the mixed powder is dried if necessary, and then the mixed powder is fired in an inert atmosphere or in the flow of hydrogen sulfide gas ( H 2S), crushed and crushed as necessary, and classified.
  • H 2S hydrogen sulfide gas
  • the firing temperature is preferably, for example, 350 ° C. or higher, and more preferably 450 ° C. or higher.
  • the firing temperature is preferably, for example, 650 ° C or lower, more preferably 600 ° C or lower, and even more preferably 500 ° C or lower.
  • the firing temperature is preferably 350 ° C. or higher, for example.
  • the firing temperature is preferably, for example, 550 ° C or lower, more preferably 500 ° C or lower, and even more preferably 450 ° C or lower.
  • the particles of the compound constituting the main part can also be produced by amorphizing the raw material powder by a mechanical milling method and heat-treating the amorphized raw material powder as necessary to crystallize it.
  • the treatment apparatus and treatment conditions are not particularly limited as long as the raw material powder can be sufficiently mixed and amorphized.
  • the container filled with the raw material powder revolves at high speed, so high impact energy is generated between the container and the ball, which is the crushing medium to be put into the container together with the raw material powder, and is efficient and uniform. It is possible to amorphize the raw material powder.
  • the mechanical milling method may be either dry or wet.
  • the processing conditions by the mechanical milling method can be appropriately set according to the processing apparatus to be used. For example, by processing in a time of 0.1 hours or more and 100 hours or less, the raw material powder can be amorphized more efficiently and uniformly. ..
  • the ball as the crushing medium is preferably made of ZrO 2 , Al 2 O 3 , Si 3 N 4 (silicon nitride) or WC (tungsten carbide), and the ball diameter is preferably about 0.2 mm or more and 10 mm or less.
  • the compound can be obtained by heat-treating and crystallizing the raw material powder amorphized by the mechanical milling treatment under the same firing conditions as described above. Since the raw material powder subjected to the mechanical milling treatment is in a state of being mixed more uniformly than the raw material powder obtained by ordinary pulverization and mixing, the heat treatment temperature can be further lowered.
  • the particles of the compound constituting the main part can also be produced by the liquid phase method using an organic solvent.
  • it can be obtained by dissolving a sulfide or a halide which is a raw material of a compound constituting a main part in a solvent such as tetrahydrofuran or ethanol, and precipitating the compound using the solvent as a reaction field.
  • the compound can also be obtained by synthesizing a compound constituting the main part by another method in advance, dissolving it in a solvent such as ethanol, and then reprecipitating it.
  • Such a liquid phase method can produce particles of a compound constituting the main part in a shorter time and with less energy than other methods, and it is relatively easy to reduce the particle size of the particles. be.
  • the main part composed of compound particles is obtained in this way, it is preferable to arrange the main part to an appropriate particle size. Since the preferable particle size of the main part can be the same as the above-mentioned contents, the description here is omitted.
  • the main part and the conductive material are mixed and composited. Since the conductive material to be used can be the same as the above-mentioned contents, the description here is omitted.
  • the compounding of the main part and the conductive material is achieved, for example, by applying mechanical energy to the particles of the compound and the particles of the conductive material constituting the main part.
  • the powder is mainly stirred, mixed, kneaded, and manufactured. It is preferable to employ an apparatus used for granulation, pulverization, dispersion, and / or surface modification.
  • an apparatus used for granulation, pulverization, dispersion, and / or surface modification For example, a planetary ball mill, a ball mill, a jet mill, a bead mill, a stirring type crusher, a vibration mill, a hammer mill, a roller mill, an atomizer and the like can be used.
  • the types of main mechanical energy that can be applied using these devices differ depending on each device.
  • the centrifugal acceleration obtained when the device is rotated is not particularly limited as long as the main part and the conductive part can be combined, but for example, it is preferably 10 G or more, more preferably 15 G or more, and 18 G or more. It is more preferable to have.
  • the centrifugal acceleration is, for example, preferably 40 G or less, more preferably 30 G or less, and even more preferably 25 G or less. When the centrifugal acceleration is within the above range, the effect of the present invention can be further enhanced.
  • the conductive material is dispersed in an organic solvent in advance, and then the raw material of the particles of the compound constituting the main part and the compound constituting the main part are put into the organic solvent, whereby the conductive material is formed on the surface or inside of the conductive material. It can be compounded by precipitating particles. In the compounding by such a method, it is possible to further reduce the particle size of the compounded particles.
  • the active material of the present invention can be made into an electrode mixture by mixing it with an electrolyte, a conductive material, a binder, or the like.
  • the electrode mixture becomes a positive electrode mixture constituting the positive electrode layer.
  • the electrolyte can be, for example, a solid electrolyte.
  • the solid electrolyte preferably has ionic conductivity such as lithium ion conductivity.
  • Specific examples thereof include inorganic solid electrolytes such as sulfide solid electrolytes, oxide solid electrolytes, nitride solid electrolytes and halide solid electrolytes, and organic polymer electrolytes such as polymer electrolytes.
  • the solid electrolyte is preferably a sulfide solid electrolyte.
  • the sulfide solid electrolyte can be the same as the sulfide solid electrolyte used in a general solid-state battery.
  • the sulfide solid electrolyte may contain, for example, Li and S and have lithium ion conductivity.
  • the sulfide solid electrolyte may be any of a crystalline material, glass ceramics, and glass.
  • the sulfide solid electrolyte may have an algyrodite type crystal structure. Examples of such sulfide solid electrolytes include Li 2 SP 2 S 5 , Li 2 SP 2 S 5 - LiX (“X” indicates one or more halogen elements), Li 2S-.
  • X indicates one or more halogen elements; a is 3.0. It represents a number of 9.0 or less. B represents a number of 3.5 or more and 6.0 or less. C represents a number of 0.1 or more and 3.0 or less.) Examples thereof include compounds represented by. .. In addition to this, for example, the sulfide solid electrolyte described in International Publication No. 2013/099834 Pamphlet and International Publication No. 2015/001818 pamphlet can be mentioned.
  • the active material contained in the electrode mixture may be only the active material of the present invention, or may be used in combination with other active materials.
  • Examples of other active substances include known sulfur simple substances and active substances containing sulfur.
  • the ratio of the active material of the present invention in the electrode mixture may be, for example, 20% by mass or more, 30% by mass or more, or 40% by mass or more. On the other hand, the ratio may be, for example, 70% by mass or less, or 60% by mass or less.
  • the battery of the present invention includes a positive electrode layer containing a positive electrode active material, a negative electrode layer containing a negative electrode active material, and a solid electrolyte layer containing a solid electrolyte, and the positive electrode active material is preferably the above-mentioned active material.
  • the battery can be manufactured, for example, by stacking three layers of the positive electrode layer, the solid electrolyte layer, and the negative electrode layer prepared as described above and press-molding them.
  • the battery of the present invention preferably has an interface in which the positive electrode active material and the solid electrolyte are in contact with each other in order to make the desired effect more remarkable.
  • contact between the positive electrode active material and the solid electrolyte means that the positive electrode active material contained in the positive electrode layer and the solid electrolyte are in contact with each other, and that the positive electrode active material and the solid electrolyte layer contained in the positive electrode layer are in contact with each other. Includes any contact with the contained solid electrolyte.
  • the battery having the active material of the present invention is preferably a lithium ion battery, and more preferably a lithium sulfur battery.
  • the battery here include a solid-state battery having a solid electrolyte layer, particularly an all-solid-state battery.
  • the battery in the present invention may be a primary battery or a secondary battery, but it is particularly preferable to use it as a secondary battery, and particularly preferably to use it as a lithium secondary battery.
  • the term "lithium secondary battery” is intended to broadly include a secondary battery in which lithium ions move between a positive electrode and a negative electrode to charge and discharge.
  • the solid-state battery has a positive electrode layer, a negative electrode layer, and a solid electrolyte layer between the positive electrode layer and the negative electrode layer.
  • the active material of the present invention is preferably contained in the positive electrode layer.
  • the "solid-state battery” includes, for example, 50% by mass or less, 30% by mass or less, 10% by mass or less of a liquid substance or a gel-like substance as an electrolyte, in addition to a solid-state battery containing no liquid substance or a gel-like substance as an electrolyte. Also includes aspects.
  • Lithium sulfide (Li 2 S) powder, diphosphorus pentasulfide (P 2 S 5 ) powder, and lithium chloride (Lithium chloride) have the composition of Li 5.8 PS 4.8 Cl 1.2 shown in Table 1.
  • LiCl Lithium sulfide
  • This mixed powder is filled in a carbon container, and hydrogen sulfide gas ( H2S , purity 100%) is circulated at 1.0 L / min in a tubular electric furnace at an elevating temperature rate of 200 ° C./h.
  • Example 2 to 4 Compositions of Li 6.8 PS 5.8 Cl 0.2 , Li 5.4 PS 4.4 Cl 0.8 Br 0.8 , and Li 5.8 PS 4.8 Cl 1.2 shown in Table 1.
  • a compound powder was obtained in the same manner as in Example 1 except that the raw material powder was mixed.
  • As a result of XRD measurement it was confirmed that the obtained compound had a crystal phase having an algyrodite type crystal structure.
  • As the conductive material carbon nanotubes (manufactured by Showa Denko, VGCF (registered trademark) -H) or Ketjen black was used as in Example 1.
  • the carbon nanotubes had a fiber diameter of 150 nm and a fiber length of 6 ⁇ m.
  • particles of the active substance were obtained in the same manner as in Example 1 except that 10 parts of Ketjen Black was used for 100 parts of the compound.
  • Examples 5 and 6 Weigh each of the raw material powders so that the total amount of the raw material powder is 2 g so that the composition of Li 7 PS 6 and Li 7.3 P 0.9 Fe 0.1 S 6 shown in Table 1 is obtained, and the planetary ball mill. (Made by Fritsch, P-7) was subjected to mechanical milling treatment at 500 rpm for 20 hours to prepare an amorphous mixed powder. After that, the amorphized mixed powder is filled in a carbon container, and the inert gas (Ar, 100% purity) is circulated in a tubular electric furnace at 1.0 L / min while raising and lowering the temperature. It was heated at 200 ° C./h and baked at 400 ° C. for 4 hours.
  • the inert gas Ar, 100% purity
  • Example 2 the sample was crushed in a mortar and sized with a sieve having an opening of 53 ⁇ m to obtain a powdery compound having the particle size shown in Table 1. As a result of XRD measurement, it was confirmed that this compound has a crystal phase having an algyrodite type crystal structure. Except for this, particles of the active material were obtained in the same manner as in Example 2.
  • This comparative example is an example in which particles of an active material are produced by compounding a conductive material made of Ketjen black on the surface or inside of elemental sulfur particles.
  • a conductive material made of Ketjen black For 100 parts of sulfur particles having a particle size D 50 of 35.6 ⁇ m, 20 parts of Ketjen black having a particle size D 50 of 0.04 ⁇ m were used, and both were used as a planetary ball mill (Fritsch) in the same manner as in Example 1.
  • Manufactured, P-7) was used, and the mixture was mixed and compounded at 500 rpm for 10 hours. In this way, particles of the active material having a particle size D 50 of 28.4 ⁇ m were obtained.
  • This comparative example is an example in which particles of an active material are produced by compounding a conductive material made of carbon nanotubes on the surface or inside of lithium sulfide particles.
  • a conductive material made of carbon nanotubes for 100 parts, lithium sulfide particles having a particle size D 50 of 20 ⁇ m, 20 parts of carbon nanotubes having a particle size D 50 of 0.15 ⁇ m were used, and both were used in the same manner as in Example 1 of a planetary ball mill (manufactured by Fritsch, Co., Ltd.). Using P-7), the mixture was mixed and compounded at 500 rpm for 10 hours. In this way, particles of the active material having a particle size D 50 of 17.4 ⁇ m were obtained.
  • This comparative example is an example in which particles of an active material are produced without compounding a conductive material made of Ketjen black on the surface or inside of the particles of Li 5.8 PS 4.8 Cl 1.2 used in Example 1. Is. For 100 parts of Li 5.8 PS 4.8 Cl 1.2 particles having a particle size D 50 of 3.8 ⁇ m, 20 parts of Ketjen Black were used, and both were used in a planetary ball mill as in Example 1. Using P-7) manufactured by Fritsch, mixing was performed at 200 rpm for 10 hours. In this way, particles of the active material having a particle size D 50 of 3.6 ⁇ m were obtained.
  • Comparative Example 4 In this comparative example, as in Comparative Example 3, the conductive material made of Ketjen black is active on the surface and inside of the particles of Li 5.8 PS 4.8 Cl 1.2 used in Example 1 without being composited. This is an example of manufacturing particles of a substance. For 100 parts of Li 5.8 PS 4.8 Cl 1.2 particles having a particle size D 50 of 3.8 ⁇ m, 20 parts of Ketjen Black were used, and both were used in a planetary ball mill as in Example 1. Using P-7) manufactured by Fritsch, mixing was performed at 300 rpm for 1 hour. In this way, particles of the active material having a particle size D 50 of 3.3 ⁇ m were obtained.
  • This comparative example is an example in which only the particles of Li 7 PS 6 used in Example 5 are used, and the active material is not combined with the conductive material.
  • the ionic conductivity (S / cm) was measured at room temperature (25 ° C.) by the AC impedance method under the condition of a measurement frequency of 0.1 Hz to 1 MHz using Solartron 1255B, which is a device manufactured by Toyo Corporation.
  • the positive electrode active material powder is not composited with the conductive material, the positive electrode active material powder, the solid electrolyte powder, and the carbon nanotubes are mass-produced as the conductive material for imparting conductivity to the positive electrode layer. It was prepared by mixing in a dairy pot at a ratio of 50:40:10.
  • An all-solid-state battery cell in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer were laminated was produced by sandwiching the battery with the load of. The thickness of each layer is about 40 ⁇ m for the positive electrode layer, about 600 ⁇ m for the solid electrolyte layer, and about 400 ⁇ m for the negative electrode layer.
  • the all-solid-state battery cell was prepared in a glove box substituted with argon gas having a dew point temperature of ⁇ 60 ° C.
  • the produced all-solid-state battery was connected to a charge / discharge measuring device in an environmental tester kept at 25 ° C. to evaluate the battery characteristics. The current of 2.0 mA during charging and discharging was set to 1 C rate.
  • the lithium ion In the first charge / discharge (1st cycle), for the purpose of efficiently desorption of lithium ions contained in the positive electrode active material, the lithium ion is charged to 3.0V at 0.03C by the CC-CV method, and 0.03C is 0. It was discharged by the CC method up to 38V.
  • the battery In the second cycle, the battery was charged to 3.0 V at 0.1 C by the CC-CV method and discharged to 0.38 V at 0.1 C by the CC method.
  • the charge / discharge capacity in the second cycle is defined as the initial charge / discharge capacity.
  • the active material in which elemental sulfur and the conductive material were combined in Comparative Example 1 since the active material did not contain a lithium element, the first cycle was started from electric discharge.
  • the charge / discharge rates are 0.1 C and 0.
  • the charge / discharge curves when changed to 2C, 0.5C, 1C, 2C and 5C are shown.
  • the all-solid-state battery using the positive electrode active material prepared in Examples 1 and 5 shows a high discharge capacity even if the charge / discharge rate is increased, but the positive electrode active material prepared in Comparative Examples 3 and 4 is used. In all solid-state batteries, the discharge capacity is greatly reduced when the charge / discharge rate is increased.
  • Comparative Examples 3 and 4 although the powder of the compound having the same composition as that of Example 1 is used in the main part, the initial capacity and the discharge rate characteristics are significantly inferior to those of Example 1.
  • the reason for this is that the particle size of the compound powder used in Comparative Example 3 is large and the rotation speed, which is a condition of the planetary ball mill used when performing the compounding treatment, is low, so that the conductive material is present on the surface and inside of the compound particles.
  • the present inventor presumes that the particles were not uniformly dispersed and could not exhibit the performance as a positive electrode active material.
  • FIGS. 4 and 5 are SEM images obtained by observing the appearance of the positive electrode active material powder produced in Example 5 and Comparative Example 4, and mapping the existence states of carbon elements and sulfur elements by EDS.
  • the composition of the compounds used in Example 5 and Comparative Example 4 is the same. Since the carbon element, which is a component of the conductive material of the positive electrode active material powder produced in Example 5, and the sulfur element, which is a component of the compound, exist so as to overlap each other, the particles of the compound and the conductive material are uniformly composited. I was able to confirm that it was there.
  • the carbon element which is a conductive material component exists at a position different from the sulfur element of the compound, so that the positive electrode active material prepared in Comparative Example 4 is a compound. It was confirmed that the particles and the conductive material were not compounded and were simply mixed.
  • an all-solid-state battery using the positive electrode active material powder prepared in Example 5 and Comparative Example 4 is processed with a cross section polisher (CP) to obtain a cross section, and carbon elements are obtained by SEM observation and EDS. , The existence state of sulfur element and bromine element is mapped.
  • the carbon element, which is a conductive material component is in a place where the bromine element, which is a component of the solid electrolyte, does not exist, and the abundance of the sulfur element is large. Since it is located in place, it was confirmed that the conductive material was uniformly composited on the surface and inside of the compound particles.
  • the carbon element which is a conductive material component is a place where the bromine element which is a component of the compound is present and the abundance of the sulfur element is large. Since it exists around the place, it was confirmed that the conductive material was not composited with the particles of the compound, and the powder of the compound and the powder of the conductive material were simply mixed.
  • FIG. 8 is an XRD pattern of the positive electrode active material powder produced in Examples 1, 3 and 4.
  • Examples 1, 3 and 4 when the main part and the conductive part in the mixed state are combined by the planetary ball mill, the condition of high rotation speed is adopted to give high centrifugal acceleration. Therefore, high mechanical energy is applied to the main part and the conductive part, and both are combined.
  • the half-value width of each diffraction peak attributed to the argylodite-type crystal phase is widened by appropriately lowering the crystallization of the argilodite-type crystal phase while maintaining the argilodite-type crystal phase. It was confirmed from the XRD diffraction pattern shown in FIG. 8 and the half-price range shown in Table 3 below.
  • FIG. 9 is an XRD pattern of the positive electrode active material powder produced in Comparative Examples 3 and 4.
  • the centrifugal acceleration applied is not sufficient due to the adoption of the condition of low rotation speed when the main part and the conductive part in the mixed state are combined by the planetary ball mill. Therefore, high mechanical energy was not applied to the main part and the conductive part, and both were not sufficiently combined. Further, it was confirmed from the XRD diffraction pattern shown in FIG. 9 and the full width at half maximum shown in Table 3 below that the crystallinity of the algyrodite type crystal phase contained in the main portion was maintained in a high state.
  • the performance of the lithium ion battery can be enhanced.

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CN117638056A (zh) * 2022-08-25 2024-03-01 南京大学 一种硫化物层状正极材料、制备方法以及在超长循环全固态锂电池中的应用
WO2024166908A1 (ja) 2023-02-07 2024-08-15 三井金属鉱業株式会社 活物質、固体電解質、電極合剤並びに電池

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