WO2023026642A1 - 負極活物質、及びリチウムイオン電池 - Google Patents

負極活物質、及びリチウムイオン電池 Download PDF

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WO2023026642A1
WO2023026642A1 PCT/JP2022/023708 JP2022023708W WO2023026642A1 WO 2023026642 A1 WO2023026642 A1 WO 2023026642A1 JP 2022023708 W JP2022023708 W JP 2022023708W WO 2023026642 A1 WO2023026642 A1 WO 2023026642A1
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Prior art keywords
negative electrode
active material
electrode active
lithium ion
ion battery
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English (en)
French (fr)
Japanese (ja)
Inventor
和子 浅野
雪尋 沖
菜々美 竹田
光宏 日比野
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to US18/681,158 priority Critical patent/US20240282946A1/en
Priority to EP22860936.8A priority patent/EP4394935A4/en
Priority to JP2023543711A priority patent/JPWO2023026642A1/ja
Priority to CN202280056876.0A priority patent/CN117836980A/zh
Publication of WO2023026642A1 publication Critical patent/WO2023026642A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si 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
    • H01M4/38—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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 disclosure relates to negative electrode active materials and lithium ion batteries.
  • Lithium-ion batteries which are charged and discharged by moving lithium ions (Li ions) between the positive and negative electrodes, are widely used.
  • Si which has a higher capacity than graphite, has been used as a negative electrode active material contained in the negative electrode of this lithium ion battery.
  • Si has a problem that its volume changes greatly during charging and discharging, and the battery capacity tends to decrease due to repeated charging and discharging.
  • Non-Patent Document 1 the alloy having the La 3 Ni 2 Sn 7 -type crystal structure described in Non-Patent Document 1 has a higher volume energy density but a lower weight energy density than graphite.
  • An object of the present disclosure is to provide a negative electrode active material having a La 3 Ni 2 Sn 7 -type crystal structure and high weight energy density, and a lithium ion battery using the same.
  • a negative electrode active material that is one aspect of the present disclosure is a negative electrode active material contained in a negative electrode of a lithium ion battery, and has the general formula M 3 Me 2 X 7 (wherein M is at least one of La and Ca, Me contains at least one element selected from the group consisting of Mn, Ni, Fe, and Co, and X contains at least one element selected from the group consisting of Ge, Si, Sn, and Al
  • M is at least one of La and Ca
  • Me contains at least one element selected from the group consisting of Mn, Ni, Fe, and Co
  • X contains at least one element selected from the group consisting of Ge, Si, Sn, and Al
  • the half width of the diffraction peak of the (1 17 1) plane of the negative electrode active material is 0.4713 ° or more. characterized by
  • a lithium ion battery includes a negative electrode containing the negative electrode active material, a positive electrode, and a non-aqueous electrolyte.
  • weight energy density can be increased.
  • FIG. 1 is a vertical cross-sectional view of a cylindrical lithium-ion battery that is an example of an embodiment
  • FIG. 4 shows XRD patterns of negative electrode active materials contained in test cells of Examples and Comparative Examples.
  • Patent Document 1 discloses an alloy having a La 3 Ni 2 Sn 7 -type crystal structure as a negative electrode active material for high-capacity lithium-ion batteries.
  • the alloy disclosed in Patent Document 1 has a higher volume energy density but a lower weight energy density than graphite.
  • the present inventors found that in the XRD pattern obtained by XRD measurement using Cu as the anticathode, the half width of the diffraction peak of the (1 17 1) plane of the negative electrode active material is 0.4713 ° or more. By doing so, it was found that the weight energy density can be increased.
  • a lithium ion battery is charged and discharged by movement of lithium ions between a positive electrode and a negative electrode.
  • a cylindrical battery in which a wound electrode assembly is housed in a bottomed cylindrical outer can be exemplified.
  • it may be an exterior body composed of a laminate sheet including a metal layer and a resin layer.
  • the electrode body may be a laminated electrode body in which a plurality of positive electrodes and a plurality of negative electrodes are alternately laminated with separators interposed therebetween.
  • a liquid non-aqueous electrolyte is exemplified below, the non-aqueous electrolyte is not limited to a liquid and may be solid.
  • FIG. 1 is a vertical cross-sectional view of a cylindrical lithium-ion battery 10 that is an example of an embodiment.
  • an electrode body 14 and a non-aqueous electrolyte (not shown) are housed in an exterior body 15 .
  • the electrode body 14 has a wound structure in which the positive electrode 11 and the negative electrode 12 are wound with the separator 13 interposed therebetween.
  • the solvent organic solvent
  • carbonates, lactones, ethers, ketones, esters and the like can be used, and two or more of these solvents can be mixed and used.
  • a mixed solvent containing a cyclic carbonate and a chain carbonate For example, cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC) can be used, and chain carbonates such as dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), and diethyl carbonate ( DEC) or the like can be used.
  • cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC)
  • chain carbonates such as dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), and diethyl carbonate ( DEC) or the like can be used.
  • the electrolyte salt of the non-aqueous electrolyte LiPF 6 , LiBF 4 , LiCF 3 SO 3 and mixtures thereof can be used.
  • the amount of electrolyte salt dissolved in the solvent can be, for example, 0.5 to 2.0 mol/L.
  • the inside of the lithium ion battery 10 is hermetically sealed by closing the opening end of the exterior body 15 with the sealing body 16 .
  • Insulating plates 17 and 18 are provided above and below the electrode body 14, respectively.
  • the positive electrode lead 19 extends upward through the through hole of the insulating plate 17 and is welded to the lower surface of the filter 22 which is the bottom plate of the sealing member 16 .
  • the cap 26, which is the top plate of the sealing member 16 electrically connected to the filter 22, serves as a positive electrode terminal.
  • the negative electrode lead 20 passes through the through hole of the insulating plate 18 , extends to the bottom side of the exterior body 15 , and is welded to the bottom inner surface of the exterior body 15 .
  • the exterior body 15 becomes a negative electrode terminal.
  • the negative electrode lead 20 When the negative electrode lead 20 is installed at the terminal end, the negative electrode lead 20 extends through the outside of the insulating plate 18 toward the bottom of the package 15 and is welded to the inner surface of the bottom of the package 15 .
  • the exterior body 15 is, for example, a bottomed cylindrical metal exterior can.
  • a gasket 27 is provided between the exterior body 15 and the sealing body 16 to ensure hermetic sealing of the inside of the lithium ion battery 10 .
  • the exterior body 15 has a grooved portion 21 that supports the sealing body 16 and is formed, for example, by pressing the side portion from the outside.
  • the grooved portion 21 is preferably annularly formed along the circumferential direction of the exterior body 15 and supports the sealing body 16 via a gasket 27 on its upper surface.
  • the sealing body 16 has a filter 22, a lower valve body 23, an insulating member 24, an upper valve body 25, and a cap 26 which are stacked in order from the electrode body 14 side.
  • Each member constituting the sealing member 16 has, for example, a disk shape or a ring shape, and each member other than the insulating member 24 is electrically connected to each other.
  • the lower valve body 23 and the upper valve body 25 are connected to each other at their central portions, and an insulating member 24 is interposed between their peripheral edge portions.
  • the positive electrode 11, the negative electrode 12, and the separator 13 that make up the electrode body 14 will be described in detail below, particularly the negative electrode active material that makes up the negative electrode 12.
  • the positive electrode 11 has, for example, a positive electrode core and a positive electrode mixture layer provided on the surface of the positive electrode core.
  • a foil of a metal such as aluminum that is stable in the potential range of the positive electrode 11, a film having the metal on the surface layer, or the like can be used.
  • the thickness of the positive electrode core is, for example, 10 ⁇ m to 30 ⁇ m.
  • the positive electrode material mixture layer contains a positive electrode active material, a binder, and a conductive agent, and is preferably provided on both sides of the positive electrode core excluding the portion where the positive electrode lead 19 is connected.
  • a positive electrode mixture slurry containing a positive electrode active material, a binder, a conductive agent, and the like is applied to the surface of a positive electrode core, the coating film is dried, and then compressed to convert the positive electrode mixture layer into a positive electrode. It can be produced by forming on both sides of the core.
  • the positive electrode active material contains lithium transition metal oxide as its main component.
  • the positive electrode active material may be substantially composed only of the lithium transition metal oxide, and inorganic compound particles such as aluminum oxide and lanthanoid-containing compounds are adhered to the surfaces of the lithium transition metal oxide particles. good too.
  • One type of lithium transition metal oxide may be used, or two or more types may be used in combination.
  • Metal elements contained in the lithium transition metal oxide include nickel (Ni), cobalt (Co), manganese (Mn), aluminum (Al), boron (B), magnesium (Mg), titanium (Ti), vanadium. (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), gallium (Ga), strontium (Sr), zirconium (Zr), niobium (Nb), indium (In), tin (Sn), tantalum (Ta), tungsten (W), and the like.
  • An example of a suitable lithium transition metal oxide has the general formula: Li ⁇ Ni x M (1 ⁇ x) O 2 (0.1 ⁇ 1.2, 0.3 ⁇ x ⁇ 1, M is Co, Mn , including at least one of Al).
  • Examples of the conductive agent contained in the positive electrode mixture layer include carbon materials such as carbon black, acetylene black, ketjen black, carbon nanotubes, carbon nanofibers, and graphite.
  • Examples of the binder contained in the positive electrode mixture layer include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide resins, acrylic resins, and polyolefin resins. . These resins may be used in combination with cellulose derivatives such as carboxymethyl cellulose (CMC) or salts thereof, polyethylene oxide (PEO), and the like.
  • the negative electrode 12 has, for example, a negative electrode core and a negative electrode mixture layer provided on the surface of the negative electrode core.
  • a foil of a metal such as copper that is stable in the potential range of the negative electrode 12, a film having the metal on the surface layer, or the like can be used.
  • the thickness of the negative electrode core is, for example, 5 ⁇ m to 15 ⁇ m.
  • the negative electrode mixture layer contains a negative electrode active material and a binder, and is preferably provided on both sides of the negative electrode substrate except for the portion where the negative electrode lead 20 is connected, for example.
  • a negative electrode mixture slurry containing a negative electrode active material, a binder, a conductive agent, and the like is applied to the surface of a negative electrode core, the coating film is dried, and then compressed to turn the negative electrode mixture layer into a negative electrode. It can be produced by forming on both sides of the core.
  • the negative electrode 12 may be formed by mixing a negative electrode active material and copper powder, and then compressing the mixture into pellets.
  • the negative electrode active material contained in the negative electrode 12 has the general formula M 3 Me 2 X 7 (wherein M contains at least one of La and Ca, and Me is selected from the group consisting of Mn, Ni, Fe, and Co). and X contains at least one element selected from the group consisting of Ge, Si, Sn, and Al) (hereinafter referred to as M 3 Me 2 X (sometimes referred to as type 7 alloys).
  • M 3 Me 2 X 7 type alloy is, for example, La 3 Ni 2 Sn 7 .
  • the negative electrode 12 may contain a negative electrode active material other than the M 3 Me 2 X 7 type alloy.
  • the negative electrode active material other than the M 3 Me 2 X 7 type alloy is not particularly limited as long as it can reversibly absorb and release lithium ions.
  • Examples include graphite (natural graphite, artificial graphite), silicon (Si), A metal alloying with lithium such as tin (Sn), or an oxide containing a metal element such as Si or Sn can be used.
  • the half width of the diffraction peak of the (1 17 1) plane of the M 3 Me 2 X 7 type alloy is, for example, 0.4713° or more. This can increase the gravimetric energy density of the M 3 Me 2 X 7 type alloy.
  • the diffraction peak of the (1 17 1) plane of the M 3 Me 2 X 7 type alloy is detected near 64°.
  • the upper limit of the half-value width of the diffraction peak of the (1 17 1) plane of the M 3 Me 2 X 7 type alloy is, for example, 5°.
  • the half width of the diffraction peak of the (1 17 1) plane of the general M 3 Me 2 X 7 type alloy is about 0.11 °, and the dislocation of the M 3 Me 2 X 7 type alloy according to the present disclosure
  • the half width of the diffraction peak of the dense (1 17 1) plane is larger than that of the (1 17 1) plane of the general M 3 Me 2 X 7 type alloy.
  • XRD measurement can be performed under the following conditions using a powder X-ray diffractometer (radiation source Cu-K ⁇ ). Measurement range: 10° to 70° Scanning speed: 10°/min
  • the volume-based median diameter (D50) of the M 3 Me 2 X 7 type alloy may be, for example, 0.1 ⁇ m to 50 ⁇ m, or may be 1 ⁇ m to 10 ⁇ m.
  • the D50 of the M 3 Me 2 X 7 type alloy can be reduced by, for example, ball milling, and can be adjusted by the ball milling conditions.
  • D50 means a particle size at which the cumulative frequency is 50% from the smaller particle size in the volume-based particle size distribution, and is also called median diameter.
  • the particle size distribution of the M 3 Me 2 X 7 type alloy can be measured using a laser diffraction particle size distribution analyzer (eg MT3000II manufactured by Microtrack Bell Co., Ltd.) using water as a dispersion medium.
  • the M 3 Me 2 X 7 type alloy according to the present disclosure can be produced, for example, as follows.
  • M metal, Me metal, and X metal are prepared as raw materials, and these raw materials are mixed in a predetermined ratio and then arc-melted to produce an M 3 Me 2 X 7 type alloy ingot.
  • the annealing conditions are, for example, an annealing temperature of 400° C. to 1000° C. and a holding time of 10 hours to 720 hours.
  • the lump of M 3 Me 2 X 7 type alloy after annealing is pulverized, for example, by a mortar or a planetary ball mill.
  • Ball mill processing conditions are, for example, a rotation speed of 100 rpm to 500 rpm and a processing time of 1 hour to 720 hours.
  • the ball-milled M 3 Me 2 X 7 type alloy is classified, for example, with a mesh to remove coarse particles.
  • the half width of the diffraction peak of the (1 17 1) plane is 0.4713° in the XRD pattern obtained by XRD measurement using Cu as the anticathode. That's it.
  • the ball mill process pulverizes the particles and reduces the particle size, and the ball mill process causes distortion (defects, etc.) in the crystal structure on the surface of the particles crushed and sheared by the planetary ball mill, destroying the periodicity of the atomic arrangement.
  • the half-value width is considered to be larger than before the ball mill treatment. It is presumed that Li ions are inserted into these defects and voids.
  • fluorine resin, PAN, polyimide resin, acrylic resin, polyolefin resin, or the like can be used as the binder contained in the negative electrode mixture layer.
  • fluorine resin, PAN, polyimide resin, acrylic resin, polyolefin resin, or the like can be used as the binder contained in the negative electrode mixture layer.
  • CMC styrene-butadiene rubber
  • PAA polyacrylic acid
  • the negative electrode mixture layer may contain a conductive agent.
  • the conductive agent can make the conductive paths uniform.
  • Carbon black (CB), acetylene black (AB), ketjen black, carbon nanotubes (CNT), graphene, graphite, and other carbon-based particles can be exemplified as the conductive agent contained in the negative electrode mixture layer. These may be used alone or in combination of two or more.
  • the conductive agent preferably contains CNTs.
  • the CNTs may be single-walled carbon nanotubes (SWCNTs) or multi-walled carbon nanotubes (MWCNTs). Since SWCNTs can form a conductive path in the negative electrode mixture layer in a smaller amount than MWCNTs, the CNTs preferably contain SWCNTs.
  • a porous sheet having ion permeability and insulation is used for the separator 13 .
  • porous sheets include microporous membranes, woven fabrics, and non-woven fabrics.
  • Suitable materials for the separator 13 include olefin resins such as polyethylene and polypropylene, and cellulose.
  • the separator 13 may have either a single layer structure or a laminated structure.
  • a heat-resistant layer containing a heat-resistant material may be formed on the surface of the separator 13 . Examples of heat-resistant materials include polyamide resins such as aliphatic polyamides and aromatic polyamides (aramids), and polyimide resins such as polyamideimides and polyimides.
  • Example 1 [Preparation of negative electrode active material] A metal piece of La, a wire of Ni, and a metal piece of Sn were used as raw materials. A metal piece made of yttrium and having a purity of 3N was arc-melted once, the gas was removed, and then the surface was polished with a metal brush. The Ni wire used was made by Kojundo Chemical Co., Ltd. and had a purity of 3N and a diameter of 3 mm. As the Sn metal piece, a shot-shaped one with a purity of 4N manufactured by Furuuchi Chemical Co., Ltd. was used.
  • the ball mill treatment was performed with a 5-minute pause every time it was performed for 5 minutes.
  • the powder after ball milling was classified with a mesh of 45 ⁇ m to remove coarse particles.
  • the volume-based median diameter (D50) of the produced negative electrode active material (powdered La 3 Ni 2 Sn 7 ) was 6.8 ⁇ m.
  • Li metallic lithium
  • Lithium ion batteries generally use a lithium transition metal oxide such as LiNiO 2 (generally containing a transition metal such as Co, Mn, Ni) as a positive electrode active material.
  • a lithium metal foil cut into ⁇ 17 mm was used as the counter electrode instead of the positive electrode active material generally used for the electrode. Such methods are often used to evaluate active materials.
  • a non-aqueous electrolyte was prepared by dissolving 1.0 mol/L of LiPF 6 as an electrolyte salt in a non-aqueous solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 1:3.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • An electrode body was constructed by arranging the above negative electrode and a positive electrode made of a lithium metal foil so as to face each other with a separator interposed therebetween, and the electrode body was accommodated in a coin-shaped outer can. After injecting the non-aqueous electrolyte into the outer can, the outer can was sealed to obtain a coin-shaped test cell (non-aqueous electrolyte secondary battery).
  • Example 2 to 5 Test cells of Examples 2 to 5 were produced in the same manner as in Example 1, except that the time for ball milling using a planetary ball mill was changed in the production of the negative electrode active material. From Example 2 to Example 5, the ball milling time was lengthened. That is, in Examples 1 to 5, the ball mill treatment time of Example 1 was the shortest, and the ball mill treatment time of Example 5 was the longest.
  • Example 1 A test cell was produced in the same manner as in Example 1, except that the ball mill treatment using a planetary ball mill was not performed in the production of the negative electrode active material.
  • Example 1 For each test cell of Examples 1 to 5 and Comparative Example 1, the battery capacity (charge capacity and discharge capacity) was evaluated by the following method. Table 1 shows the evaluation results. Table 1 also shows the half width of the diffraction peak of the (1171) plane and the charge/discharge efficiency. Further, XRD patterns of the negative electrode active materials of Examples 1, 2, 4 to 7 (Examples 6 and 7 will be described later) and Comparative Example 1 are shown in FIG.
  • Discharge in this evaluation means discharge in a battery in which the negative electrode active materials of Example 1 and Comparative Examples 1 to 5 are combined with a generally used positive electrode such as LiNiO 2 .
  • a generally used positive electrode such as LiNiO 2 .
  • the coin-shaped battery has a negative electrode as a working electrode and metal lithium (Li) as a counter electrode, it should be called charging, but the negative electrode in a battery that combines a positive electrode and a negative electrode generally used.
  • the opposite charging/discharging direction is expressed.
  • charging means passing current so as to lower the potential of the negative electrode, which is the working electrode
  • the test cell of Example in which the half-value width of the diffraction peak of the (1171) plane is 0.4713° or more is the test cell of Comparative Example 1 in which the half-value width is 0.1114°. battery capacity was higher. In addition, the battery of Example had higher charge-discharge efficiency than the battery of Comparative Example 1.
  • Example 6> [Preparation of negative electrode active material] A metal piece of La, a wire of Ni, and a metal piece of Sn were used as raw materials. A metal piece made of yttrium and having a purity of 3N was arc-melted once, the gas was removed, and then the surface was polished with a metal brush. The Ni wire used was made by Kojundo Chemical Co., Ltd. and had a purity of 3N and a diameter of 3 mm. As the Sn metal piece, a shot-shaped one with a purity of 4N manufactured by Furuuchi Chemical Co., Ltd. was used.
  • the annealed alloy mass was manually pulverized in a mortar for 1 hour, put into a zirconia container together with zirconia balls, and ball milled for a predetermined time at a predetermined rotational speed using a planetary ball mill.
  • the ball mill treatment was performed with a 5-minute pause every time it was performed for 5 minutes.
  • the powder after ball milling was classified with a mesh of 45 ⁇ m to remove coarse particles.
  • the volume-based median diameter (D50) of the produced negative electrode active material (powdered La 3 Ni 2 Sn 7 ) was 6.8 ⁇ m.
  • a counter electrode and a non-aqueous electrolyte were prepared in the same manner as in Example 1.
  • a test cell was fabricated in the same manner as in Example 1 using a counter electrode, a non-aqueous electrolyte, and the above negative electrode.
  • Example 7 A test cell was produced in the same manner as in Example 6, except that the rotation speed of the planetary ball mill was increased in the preparation of the negative electrode active material.
  • Example 8 A test cell was produced in the same manner as in Example 6, except that in producing the negative electrode active material, the rotation speed of the planetary ball mill was increased and the ball milling time was lengthened.
  • Example 2 A test cell was produced in the same manner as in Example 6, except that the ball mill treatment using a planetary ball mill was not performed in the production of the negative electrode active material.
  • the battery capacity (charge capacity and discharge capacity) was evaluated by the following method. Table 2 shows the evaluation results. Table 2 also shows the half width of the diffraction peak of the (1171) plane and the charge/discharge efficiency.
  • test cell of Example had higher battery capacity and charge/discharge efficiency than the test cell of Comparative Example 2.

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JP2000311681A (ja) * 1998-09-18 2000-11-07 Canon Inc 二次電池用負極電極材、電極構造体、二次電池、及びこれらの製造方法
JP2006351516A (ja) * 2005-05-16 2006-12-28 Toshiba Corp 負極活物質及び非水電解質二次電池
JP2009283370A (ja) * 2008-05-23 2009-12-03 Denso Corp 非水電解質二次電池用負極材料，非水電解質二次電池用負極および非水電解質二次電池
WO2021153401A1 (ja) * 2020-01-30 2021-08-05 パナソニックＩｐマネジメント株式会社 リチウムイオン電池

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JP2006351516A (ja) * 2005-05-16 2006-12-28 Toshiba Corp 負極活物質及び非水電解質二次電池
JP2009283370A (ja) * 2008-05-23 2009-12-03 Denso Corp 非水電解質二次電池用負極材料，非水電解質二次電池用負極および非水電解質二次電池
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Title
See also references of EP4394935A4
SHINSUKE MATSUNO ET AL.: "La3Ni2Sn7 Ternary Intermetallic Phase for Lithium Insertion and Deinsertion", ELECTROCHEMICAL AND SOLID-STATE LETTERS, vol. 8, no. 4, 2005, pages A234 - A236, XP055850603, DOI: 10.1149/1.1870692

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