WO2023276527A1 - 非水電解質二次電池 - Google Patents

非水電解質二次電池 Download PDF

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Publication number
WO2023276527A1
WO2023276527A1 PCT/JP2022/022083 JP2022022083W WO2023276527A1 WO 2023276527 A1 WO2023276527 A1 WO 2023276527A1 JP 2022022083 W JP2022022083 W JP 2022022083W WO 2023276527 A1 WO2023276527 A1 WO 2023276527A1
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aqueous electrolyte
lithium
composite oxide
secondary battery
positive electrode
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French (fr)
Japanese (ja)
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淵龍 仲
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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 US18/564,871 priority Critical patent/US20240291033A1/en
Priority to JP2023531723A priority patent/JP7814002B2/ja
Priority to EP22832685.6A priority patent/EP4366015A4/en
Priority to CN202280045885.XA priority patent/CN117581406A/zh
Publication of WO2023276527A1 publication Critical patent/WO2023276527A1/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
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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 non-aqueous electrolyte secondary batteries.
  • a non-aqueous electrolyte secondary battery represented by a lithium-ion secondary battery includes a positive electrode, a negative electrode, and a non-aqueous electrolyte.
  • a positive electrode positive electrode
  • a negative electrode negative electrode
  • a non-aqueous electrolyte In order to ensure excellent characteristics of non-aqueous electrolyte secondary batteries, attempts have been made to improve battery components.
  • Patent Document 1 describes a compound (A) having an organic group having 1 to 20 carbon atoms which may have a substituent on the nitrogen atom of isocyanuric acid, a nitrile compound, an isocyanate compound, a difluorophosphoric acid compound, or a fluoro proposed a non-aqueous electrolyte containing sulfonate and the like.
  • Patent Document 2 discloses a lithium-containing composite oxide represented by Formula 1: Li x Ni 1-yz-v-w Co y Al z M1 v M2 w O 2 , wherein element M1 in Formula 1 is at least one selected from the group consisting of Mn, Ti, Y, Nb, Mo and W, element M2 is at least two selected from the group consisting of Mg, Ca, Sr and Ba, and The element M2 contains at least Mg and Ca, and formula 1 satisfies 0.97 ⁇ x ⁇ 1.1, 0.05 ⁇ y ⁇ 0.35, 0.005 ⁇ z ⁇ 0.1, 0.0001 ⁇ Satisfying v ⁇ 0.05 and 0.0001 ⁇ w ⁇ 0.05, the composite oxide has primary particles aggregated to form secondary particles, and the average particle diameter of the primary particles of the composite oxide is , 0.1 ⁇ m or more and 3 ⁇ m or less, and the average particle size of the secondary particles of the composite oxide is 8 ⁇ m or more and 20 ⁇ m or less.
  • Formula 1 Li x Ni 1-yz-v-
  • JP 2014-194930 A Japanese Patent Application Laid-Open No. 2006-310181
  • One aspect of the present disclosure includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, wherein the positive electrode includes a positive electrode active material, the positive electrode active material includes Ni, Mn, and Al.
  • the ratio of Ni, Mn, and Al to the metal elements other than Li contained in the lithium-transition metal composite oxide is Ni: 50 atomic % or more, Mn: 10 atomic % or less, and Al, respectively.
  • the lithium-transition metal composite oxide contains Co
  • the proportion of Co in metal elements other than Li is 1.5 atomic % or less
  • the non-aqueous electrolyte contains an oxalate compound and wherein the oxalate compound relates to a non-aqueous electrolyte secondary battery comprising a lithium cation and an anion of an oxalate complex.
  • FIG. 1 is a schematic perspective view of a partially cutaway non-aqueous electrolyte secondary battery according to an embodiment of the present disclosure
  • any of the illustrated lower limits and any of the illustrated upper limits can be arbitrarily combined as long as the lower limit is not greater than or equal to the upper limit.
  • a plurality of materials are exemplified, one of them may be selected and used alone, or two or more may be used in combination.
  • the present disclosure encompasses a combination of matters described in two or more claims arbitrarily selected from the multiple claims described in the attached claims. In other words, as long as there is no technical contradiction, the matters described in two or more claims arbitrarily selected from the multiple claims described in the attached claims can be combined.
  • Non-aqueous electrolyte secondary batteries include at least lithium ion batteries and lithium metal secondary batteries.
  • a nonaqueous electrolyte secondary battery includes a positive electrode, a negative electrode, and a nonaqueous electrolyte.
  • the positive electrode contains a positive electrode active material.
  • the positive electrode active material contains a lithium transition metal composite oxide containing Ni, Mn and Al.
  • the Co content of the lithium-transition metal composite oxide can be reduced and the Ni content can be increased, it is advantageous in terms of cost and can ensure a high capacity. Therefore, in the non-aqueous electrolyte secondary battery according to the present disclosure, the Ni content of the lithium-transition metal composite oxide is increased.
  • the lithium-transition metal composite oxide does not contain Co, or the ratio of Co to metal elements other than Li is limited to 1.5 atomic % or less. .
  • the lithium-transition metal composite oxide in the non-aqueous electrolyte secondary battery according to the present disclosure is also referred to as “composite oxide NMA”.
  • the proportions of Ni, Mn, and Al in the metal elements other than Li contained in the composite oxide NMA are Ni: 50 atomic % or more, Mn: 10 atomic % or less, and Al: 10 atomic % or less, and The composite oxide NMA does not contain Co, or the ratio of Co to metal elements other than Li is 1.5 atomic % or less.
  • Mn and Al contribute to stabilization of the crystal structure of the composite oxide NMA with a reduced Co content.
  • the composite oxide NMA has a Co content limited to 1.5 atomic % or less and a high Ni content, the crystal structure is likely to be unstable, and the composite oxide NMA has Al, Ni and other metals can be eluted.
  • the positive electrode capacity is lowered, and the cycle characteristics (or capacity retention rate) are lowered.
  • eluted Ni forms an oxide film having a structure that prevents the absorption and release of Li ions on the particle surface of the composite oxide NMA, which may lead to an increase in internal resistance. .
  • the eluted metal is deposited on the negative electrode, which may affect the durability of the secondary battery.
  • the non-aqueous electrolyte secondary battery uses the composite oxide NMA and also uses a non-aqueous electrolyte containing an oxalate compound.
  • the oxalate compound contains the lithium cation and the anion of the oxalate complex.
  • the anion of the oxalate complex produced by the oxalate compound has a high degree of dissociation, increases the ion conductivity of the entire non-aqueous electrolyte, forms a film on the particle surface of the composite oxide NMA, and has the effect of suppressing metal elution. It is considered to be a thing. Therefore, excellent cycle characteristics can be ensured, and since the film derived from the oxalate compound has excellent ion conductivity, it is presumed that the effect of inhibiting the electrode reaction is slight.
  • the non-aqueous electrolyte may further contain an organosilicon compound represented by general formula (2) described below.
  • the organosilicon compound forms a strong film that suppresses side reactions on the particle surfaces of the composite oxide NMA. As a result, more excellent cycle characteristics can be ensured, and an increase in internal resistance is further suppressed. If the organosilicon compound is used alone, the coating tends to be excessively thick, and resistance to ionic conduction may increase.
  • a film derived from a combination of an oxalate compound and an organosilicon compound has excellent ion conductivity. That is, the oxalate compound also has the effect of improving the ionic conductivity of the film derived from the organosilicon compound.
  • the effect of improving the cycle characteristics and the effect of suppressing the increase in internal resistance cannot be significantly obtained.
  • the above effect can be remarkably obtained by combining the oxalate compound with the composite oxide NMA.
  • the effect of the composite oxide NMA is remarkable because the composite oxide NMA has a large resistance of the composite oxide itself and relatively brittle particles compared to the lithium transition metal composite oxide having a higher Co content. It is considered to be for Particles of the composite oxide NMA are prone to cracking, elution of metal is likely to be significant, and resistance is likely to increase during charging and discharging.
  • the range of improvement in properties due to the film derived from the oxalate compound is large.
  • lithium-transition metal composite oxides with a high Co content are superior from this point of view, so it can be said that the need for using oxalate compounds is low.
  • the non-aqueous electrolyte secondary battery of the present embodiment will be specifically described below for each constituent element.
  • the positive electrode contains a positive electrode active material.
  • a positive electrode generally includes a positive electrode current collector and a layered positive electrode mixture (hereinafter referred to as a positive electrode mixture layer) held by the positive electrode current collector.
  • the positive electrode mixture layer can be formed by coating the surface of the positive electrode current collector with a positive electrode slurry in which the components of the positive electrode mixture are dispersed in a dispersion medium, and drying the slurry. The dried coating film may be rolled if necessary.
  • the positive electrode mixture contains a positive electrode active material as an essential component, and may contain a binder, a thickener, a conductive agent, etc. as optional components.
  • the positive electrode active material contains composite oxide NMA.
  • Composite oxide NMA contains Ni, Mn, and Al, and may contain a trace amount of Co, or may contain no Co. From the viewpoint of manufacturing cost reduction, it is desirable that the Co content is as small as possible. The following are more preferable, and Co-free is the most preferable.
  • the proportions of Ni, Mn and Al in the metal elements other than Li are Ni: 50 atomic % or more, Mn: 10 atomic % or less, and Al: 10 atomic %. atomic % or less.
  • the Ni content in the metal elements other than Li is desirably 80 atomic % or more, more desirably 90 atomic % or more, and may be 92 atomic % or more.
  • the Mn content may be 7 atomic % or less, 5 atomic % or less, or 3 atomic % or less.
  • the Al content may be 9 atomic % or less, 7 atomic % or less, or 5 atomic % or less.
  • Composite oxide NMA has, for example, a layered crystal structure (for example, rock salt type crystal structure).
  • the composite oxide NMA is represented, for example, by the formula: Li ⁇ Ni (1-x1-x2-yz) Co x1 Mn x2 Al y Me z O 2+ ⁇ .
  • Element Me is an element other than Li, Ni, Mn, Al, Co and oxygen.
  • ⁇ indicating the atomic ratio of lithium is, for example, 0.95 ⁇ 1.05. ⁇ increases and decreases due to charging and discharging. In (2+ ⁇ ) representing the atomic ratio of oxygen, ⁇ satisfies ⁇ 0.05 ⁇ 0.05.
  • the valence of Ni in the composite oxide NMA with increased capacity tends to increase.
  • the atomic ratio of Ni increases, the atomic ratio of other elements relatively decreases. In this case, the crystal structure tends to become unstable particularly in a fully charged state, and the crystal structure changes to a crystal structure that makes reversible absorption and release of lithium ions difficult due to repeated charging and discharging, and is easily deactivated. As a result, cycle characteristics tend to deteriorate.
  • non-aqueous electrolyte secondary battery although the composite oxide NMA having a high Ni content is used as described above, excellent cycle characteristics are ensured by using a non-aqueous electrolyte containing an oxalate compound. be able to.
  • x1 which indicates the atomic ratio of Co, is, for example, 0.015 or less (0 ⁇ x1 ⁇ 0.015), may be 0.01 or less, or may be 0.005 or less.
  • x1 0, the case where Co is below the detection limit is included.
  • x2 which indicates the atomic ratio of Mn, is, for example, 0.1 or less (0 ⁇ x2 ⁇ 0.1), may be 0.07 or less, may be 0.05 or less, or may be 0.03 It may be below. x2 may be 0.01 or more, or may be 0.02 or more. Mn contributes to stabilization of the crystal structure of the composite oxide NMA, and the composite oxide NMA contains inexpensive Mn, which is advantageous for cost reduction.
  • y which indicates the atomic ratio of Al, is, for example, 0.1 or less (0 ⁇ y ⁇ 0.1), may be 0.09 or less, may be 0.07 or less, or may be 0.05 It may be below. y may be 0.01 or more, or 0.02 or more. Al contributes to stabilization of the crystal structure of the composite oxide NMA. Moreover, it is preferable to satisfy 0.05 ⁇ x2+y ⁇ 0.1. In this case, the effect of the oxalate compound and the effect of suppressing an increase in internal resistance after repeated charging and discharging are further enhanced.
  • z which indicates the atomic ratio of the element Me, is, for example, 0 ⁇ z ⁇ 0.10, may be 0 ⁇ z ⁇ 0.05, or may be 0.001 ⁇ z ⁇ 0.005.
  • the element Me may be at least one selected from the group consisting of Ti, Zr, Nb, Mo, W, Fe, Zn, B, Si, Mg, Ca, Sr, Sc and Y. Among them, when at least one selected from the group consisting of Nb, Sr and Ca is contained in the composite oxide MNA, the surface structure of the composite oxide NMA is stabilized, the resistance is reduced, and the metal is further eluted. considered to be suppressed. The element Me is more effective when it is unevenly distributed near the particle surfaces of the composite oxide NMA.
  • the content of the elements constituting the composite oxide NMA can be measured using an inductively coupled plasma atomic emission spectroscopy (ICP-AES), an electron probe microanalyzer (EPMA), or an energy dispersive type It can be measured by an X-ray analyzer (Energy dispersive X-ray spectroscopy: EDX) or the like.
  • ICP-AES inductively coupled plasma atomic emission spectroscopy
  • EPMA electron probe microanalyzer
  • EDX X-ray analyzer
  • Composite oxide NMA is, for example, secondary particles in which multiple primary particles are aggregated.
  • the particle size of the primary particles is generally 0.05 ⁇ m or more and 1 ⁇ m or less.
  • the average particle size of the secondary particles of the composite oxide is, for example, 3 ⁇ m or more and 30 ⁇ m or less, and may be 5 ⁇ m or more and 25 ⁇ m or less.
  • the average particle size of secondary particles means the particle size (volume average particle size) at which the volume integrated value is 50% in the particle size distribution measured by the laser diffraction scattering method.
  • particle size is sometimes referred to as D50.
  • LA-750 manufactured by HORIBA, Ltd. can be used as the measuring device.
  • Composite oxide NMA can be obtained, for example, by the following procedure. First, a solution containing an alkali such as sodium hydroxide is added dropwise to a solution of a salt containing a metal element constituting the composite oxide NMA under stirring, and the pH is adjusted to the alkali side (eg, 8.5 to 12.5). , a composite hydroxide containing metal elements (Ni, Mn, Al, optionally Co, and optionally element M) is precipitated. Subsequently, by calcining the composite hydroxide, a composite oxide containing a metal element (hereinafter also referred to as "raw material composite oxide”) is obtained. The firing temperature at this time is not particularly limited, but is, for example, 300°C to 600°C.
  • the firing temperature at this time is not particularly limited, but is, for example, 300°C to 600°C.
  • the composite oxide NMA can be obtained by mixing the raw material composite oxide, the lithium compound, and, if necessary, a compound containing the element M, and firing the mixture in an oxygen stream.
  • the firing temperature at this time is not particularly limited, but is, for example, 450° C. or higher and 800° C. or lower. Each firing may be performed in one step, in multiple steps, or while raising the temperature.
  • the element M By mixing a compound containing the element M when mixing the raw material composite oxide and the lithium compound, the element M can be unevenly distributed near the particle surface of the composite oxide NMA.
  • lithium compound lithium oxide, lithium hydroxide, lithium carbonate, lithium halide, etc. may be used.
  • the positive electrode active material can contain a lithium transition metal composite oxide other than the composite oxide NMA, but it is preferable that the ratio of the composite oxide NMA is large.
  • the ratio of the composite oxide NMA in the positive electrode active material is, for example, 90% by mass or more, and may be 95% by mass or more.
  • the ratio of the composite oxide in the positive electrode active material is 100% by mass or less.
  • a resin material is used as the binder.
  • binders include fluororesins, polyolefin resins, polyamide resins, polyimide resins, acrylic resins, vinyl resins, and rubber-like materials (eg, styrene-butadiene copolymer (SBR)).
  • SBR styrene-butadiene copolymer
  • thickeners examples include cellulose derivatives such as cellulose ethers. Examples of cellulose derivatives include carboxymethyl cellulose (CMC) and modified products thereof, methyl cellulose, and the like. A thickener may be used individually by 1 type, and may be used in combination of 2 or more type.
  • CMC carboxymethyl cellulose
  • Examples of conductive agents include conductive fibers and conductive particles.
  • Examples of conductive fibers include carbon fibers, carbon nanotubes, and metal fibers.
  • Conductive particles include conductive carbon (carbon black, graphite, etc.), metal powder, and the like. Conductive agents may be used singly or in combination of two or more.
  • the dispersion medium used for the positive electrode slurry is not particularly limited, but examples include water, alcohol, N-methyl-2-pyrrolidone (NMP), mixed solvents thereof, and the like.
  • a metal foil can be used as the positive electrode current collector.
  • the positive electrode current collector may be porous. Examples of porous current collectors include nets, punched sheets, expanded metals, and the like. Examples of materials for the positive electrode current collector include stainless steel, aluminum, aluminum alloys, and titanium.
  • the thickness of the positive electrode current collector is not particularly limited, but is, for example, 1 to 50 ⁇ m, and may be 5 to 30 ⁇ m.
  • the negative electrode includes at least a negative electrode current collector and may include a negative electrode active material.
  • a negative electrode generally includes a negative electrode current collector and a layered negative electrode mixture (hereinafter referred to as a negative electrode mixture layer) held by the negative electrode current collector.
  • the negative electrode mixture layer can be formed by coating the surface of the negative electrode current collector with a negative electrode slurry in which the components of the negative electrode mixture are dispersed in a dispersion medium, and drying the slurry. The dried coating film may be rolled if necessary.
  • the negative electrode mixture contains a negative electrode active material as an essential component, and may contain a binder, a thickener, a conductive agent, etc. as optional components.
  • the negative electrode active material metallic lithium, a lithium alloy, or the like may be used, but a material capable of electrochemically intercalating and deintercalating lithium ions is preferably used. Examples of such materials include carbonaceous materials and Si-containing materials.
  • the negative electrode may contain one type of negative electrode active material, or may contain two or more types in combination.
  • carbonaceous materials examples include graphite, graphitizable carbon (soft carbon), and non-graphitizable carbon (hard carbon).
  • soft carbon graphitizable carbon
  • hard carbon non-graphitizable carbon
  • graphite is preferable as the carbonaceous material because of its excellent charge-discharge stability and low irreversible capacity.
  • examples of graphite include natural graphite, artificial graphite, and graphitized mesophase carbon particles.
  • Si-containing materials include simple Si, silicon alloys, silicon compounds (such as silicon oxides), and composite materials in which a silicon phase is dispersed in a lithium ion conductive phase (matrix).
  • Silicon oxides include SiO x particles. x is, for example, 0.5 ⁇ x ⁇ 2, and may be 0.8 ⁇ x ⁇ 1.6. At least one selected from the group consisting of SiO 2 phase, silicate phase and carbon phase can be used as the lithium ion conductive phase.
  • binder thickener, conductive agent, and dispersion medium used in the negative electrode slurry
  • the materials exemplified for the positive electrode can be used.
  • a metal foil can be used as the negative electrode current collector.
  • the negative electrode current collector may be porous.
  • materials for the negative electrode current collector include stainless steel, nickel, nickel alloys, copper, and copper alloys.
  • the thickness of the negative electrode current collector is not particularly limited, but is, for example, 1 to 50 ⁇ m, and may be 5 to 30 ⁇ m.
  • Non-aqueous electrolyte usually contains a non-aqueous solvent, a lithium salt (a lithium salt other than the oxalate compound), and an additive.
  • the non-aqueous electrolyte contains an oxalate compound as an additive.
  • the oxalate compound contains the lithium cation and the anion of the oxalate complex.
  • the oxalate compound can form an anion of the oxalate complex in the non-aqueous electrolyte. Therefore, the anion of the oxalate complex is counted as an oxalate compound.
  • the oxalate compound preferably contains a compound represented by the following general formula (1).
  • M is P or B.
  • the oxalate compounds include lithium difluorobisoxalate phosphate: LiPF 2 (C 2 O 4 ) 2 , lithium tetrafluorooxalate phosphate: LiPF 4 (C 2 O 4 ), lithium trisoxalate phosphate: LiP(C 2 O 4 ). 3 , lithium bisoxalate borate: LiB( C2O4 ) 2 , and lithium difluorooxalate borate: LiBF2 ( C2O4 ). Among them, lithium difluorobisoxalate phosphate is more preferable.
  • the content of the oxalate compound in the non-aqueous electrolyte may be 3% by mass or less, 1.5% by mass or less, 1% by mass or less, or 0.5% by mass or less.
  • the content of the oxalate compound is within this range, excessive film formation on the surface of the positive electrode is suppressed, and the effect of suppressing an increase in internal resistance when charging and discharging are repeated can be enhanced.
  • the content of the oxalate compound in the non-aqueous electrolyte changes during storage or charge/discharge.
  • the oxalate compound remains in the non-aqueous electrolyte collected from the non-aqueous electrolyte secondary battery at a concentration equal to or higher than the detection limit.
  • the content of the oxalate compound in the non-aqueous electrolyte may be 0.01% by mass or more.
  • the content of the oxalate compound in the non-aqueous electrolyte used for manufacturing the non-aqueous electrolyte secondary battery may be 0.01% by mass or more, 0.1% by mass or more, or 0.3% by mass or more. may
  • the content of the oxalate compound in the non-aqueous electrolyte used for manufacturing the non-aqueous electrolyte secondary battery is, for example, 1.5% by mass or less, and may be 1% by mass or less or 0.5% by mass or less. . These lower and upper limits can be combined arbitrarily.
  • the non-aqueous electrolyte may further contain an organosilicon compound represented by the following general formula (2) as an additive.
  • R 1 to R 4 are each independently an alkyl group, alkenyl group, alkynyl group, or alkoxy group, and at least one of R 1 to R 4 is an alkenyl group or It is an alkynyl group.
  • An alkyl group, an alkenyl group, an alkynyl group, or an alkyl group of an alkoxy group may be linear or branched.
  • the number of carbon atoms in the alkyl group, alkenyl group, alkynyl group or alkoxy group may be, for example, 1-10, 1-6 or 1-4.
  • Alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, decyl group, tetradecyl group and stearyl group. etc. Among them, a methyl group and an ethyl group are preferable.
  • the alkenyl group includes vinyl group, allyl group, prop-2-en-1-yl group, 4-hexenyl group, 5-hexenyl group and the like. Among them, a vinyl group and an allyl group are preferred.
  • alkynyl groups examples include ethynyl groups and propargyl groups.
  • the alkoxy group includes methoxy group, ethoxy group, n-propoxy group, isopropoxy group and the like.
  • At least one hydrogen atom of an alkyl group, alkenyl group, alkynyl group or alkoxy group may be substituted with a halogen atom or the like.
  • the organosilicon compound preferably contains at least one selected from the group consisting of tetravinylsilane, tetraallylsilane, and dimethyldivinylsilane. Among them, tetravinylsilane is more preferable.
  • the organosilicon compound may have a polymerizable unsaturated bond to form a strong coating containing an oligomeric or polymeric component derived from the compound for positive electrode activity. It can form on the surface of a substance.
  • the coating has an excellent protective function, and further enhances the effect of suppressing elution of metal from the positive electrode active material.
  • the content of the organosilicon compound in the non-aqueous electrolyte is preferably 1.5% by mass or less, and may be 1% by mass or less or 0.5% by mass or less.
  • the content of the organosilicon compound is within this range, excessive film formation on the surface of the positive electrode is suppressed, and the effect of suppressing an increase in internal resistance when charging and discharging are repeated can be enhanced.
  • the content of the organosilicon compound in the non-aqueous electrolyte changes during storage or charge/discharge.
  • the organosilicon compound remains in the non-aqueous electrolyte collected from the non-aqueous electrolyte secondary battery at a concentration equal to or higher than the detection limit.
  • the content of the organosilicon compound in the non-aqueous electrolyte may be 0.01% by mass or more.
  • the content of the organosilicon compound in the non-aqueous electrolyte used for manufacturing the non-aqueous electrolyte secondary battery may be 0.01% by mass or more, 0.1% by mass or more, or 0.3% by mass or more. There may be.
  • the content of the organosilicon compound in the non-aqueous electrolyte used in the production of the non-aqueous electrolyte secondary battery is, for example, 1.5% by mass or less, even if it is 1% by mass or less or 0.5% by mass or less. good.
  • the content of the oxalate compound and the organosilicon compound in the non-aqueous electrolyte can be obtained, for example, using gas chromatography under the following conditions.
  • the mass ratio of the organosilicon compound to the oxalate compound may be, for example, 0.5 to 1.5, or 0.8 to 1.2. good too.
  • the mass ratio of both components is within such a range, the composition of the coating formed on the particle surface of the composite oxide NMA is well balanced. That is, a coating film is formed which has excellent ion conductivity and has a large effect of suppressing the elution of metals and an effect of suppressing an increase in internal resistance when charging and discharging are repeated.
  • Non-aqueous solvent examples include cyclic carbonates, chain carbonates, cyclic carboxylates, and chain carboxylates.
  • Cyclic carbonates include propylene carbonate (PC), ethylene carbonate (EC), and the like.
  • Chain carbonates include diethyl carbonate (DEC), ethylmethyl carbonate (EMC), dimethyl carbonate (DMC) and the like.
  • Cyclic carboxylic acid esters include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
  • Chain carboxylic acid esters include methyl formate, ethyl formate, propyl formate, methyl acetate (MA), ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and propyl propionate.
  • the non-aqueous electrolyte may contain one type of non-aqueous solvent, or may contain two or more types in combination.
  • Lithium salts include, for example, LiClO 4 , LiBF 4 , LiPF 6 , LiAlCl 4 , LiSbF 6 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiB 10 Cl 10 , lithium lower aliphatic carboxylate, LiCl , LiBr, LiI, borates, and imide salts.
  • borates include bis(1,2-benzenediolate(2-)-O,O')lithium borate and bis(2,3-naphthalenediolate(2-)-O,O')boric acid.
  • Lithium bis(2,2'-biphenyldiolate(2-)-O,O') lithium borate, bis(5-fluoro-2-olate-1-benzenesulfonic acid-O,O') lithium borate etc.
  • the imide salt examples include lithium bisfluorosulfonylimide (LiN(FSO 2 ) 2 ), lithium bistrifluoromethanesulfonimide (LiN(CF 3 SO 2 ) 2 ), lithium trifluoromethanesulfonate nonafluorobutanesulfonate (LiN (CF 3 SO 2 )(C 4 F 9 SO 2 )), lithium bispentafluoroethanesulfonic acid imide (LiN(C 2 F 5 SO 2 ) 2 ), and the like.
  • the non-aqueous electrolyte may contain one type of lithium salt, or may contain two or more types in combination.
  • the concentration of the lithium salt (lithium salt other than the oxalate compound) in the non-aqueous electrolyte is, for example, 0.5 mol/L or more and 2 mol/L or less.
  • the non-aqueous electrolyte may further contain other additives.
  • Other additives include, for example, at least one selected from the group consisting of vinylene carbonate, fluoroethylene carbonate, and vinylethylene carbonate.
  • Separator It is desirable to interpose a separator between the positive electrode and the negative electrode.
  • the separator has high ion permeability and moderate mechanical strength and insulation.
  • a microporous thin film, a woven fabric, a nonwoven fabric, or the like can be used as the separator.
  • Polyolefins such as polypropylene and polyethylene are preferable as the material of the separator.
  • An example of the structure of a non-aqueous electrolyte secondary battery is a structure in which an electrode group, in which a positive electrode and a negative electrode are wound with a separator interposed therebetween, is accommodated in an exterior body together with a non-aqueous electrolyte.
  • an electrode group in which a positive electrode and a negative electrode are wound with a separator interposed therebetween
  • a laminated electrode group in which a positive electrode and a negative electrode are laminated with a separator interposed therebetween may be used.
  • the shape of the nonaqueous electrolyte secondary battery is not limited, either, and may be, for example, cylindrical, square, coin, button, laminate, or the like.
  • the battery includes a prismatic battery case 4 with a bottom, and an electrode group 1 and a non-aqueous electrolyte (not shown) housed in the battery case 4 .
  • the electrode group 1 has a long strip-shaped negative electrode, a long strip-shaped positive electrode, and a separator interposed therebetween.
  • the negative electrode current collector of the negative electrode is electrically connected to a negative electrode terminal 6 provided on a sealing plate 5 via a negative electrode lead 3 .
  • the negative electrode terminal 6 is insulated from the sealing plate 5 by a resin gasket 7 .
  • the positive current collector of the positive electrode is electrically connected to the rear surface of the sealing plate 5 via the positive lead 2 . That is, the positive electrode is electrically connected to the battery case 4 which also serves as a positive electrode terminal.
  • the peripheral edge of the sealing plate 5 is fitted into the open end of the battery case 4, and the fitted portion is laser-welded.
  • the sealing plate 5 has an injection hole for a non-aqueous electrolyte, which is closed by
  • a non-aqueous electrolyte secondary battery was produced and evaluated by the following procedure.
  • (1) Fabrication of Positive Electrode To 95 parts by mass of positive electrode active material particles, 2.5 parts by mass of acetylene black, 2.5 parts by mass of polyvinylidene fluoride, and an appropriate amount of NMP were added and mixed to obtain a positive electrode slurry. Next, the positive electrode slurry was applied to the surface of the aluminum foil, the coating film was dried, and then rolled to form a positive electrode mixture layer (thickness: 95 ⁇ m, density: 3.6 g/cm 3 ) on both sides of the aluminum foil. , to obtain the positive electrode.
  • the positive electrode active material particles were produced by the following procedure.
  • An aqueous solution was prepared by dissolving nickel sulfate, aluminum sulfate, and, if necessary, cobalt sulfate or manganese sulfate.
  • the concentration of nickel sulfate in the aqueous solution was set to 1 mol/L, and the concentrations of other sulfates were adjusted so that the relationship between the ratios of Ni and each metal element was the value shown in Table 1.
  • an aqueous solution containing sodium hydroxide at a concentration of 30% by mass was added dropwise until the pH of the mixture reached 12 to precipitate hydroxide.
  • the hydroxide was recovered by filtration, washed with water and dried.
  • a composite oxide was obtained by baking the dried product at 500° C. for 8 hours in a nitrogen atmosphere.
  • the obtained composite oxide and lithium hydroxide were mixed so that the total atomic ratio of Li and Ni, Co, Mn and Al was 1:1.
  • the mixture was fired by heating from room temperature to 650° C. in an oxygen atmosphere at a heating rate of 2.0° C./min using an electric furnace. After that, it was fired by heating from 650° C. to 750° C. at a heating rate of 0.5° C./min.
  • Composite oxide NMA positive electrode active material particles
  • Negative Electrode A silicon composite material and graphite were mixed at a mass ratio of 5:95 and used as a negative electrode active material.
  • the negative electrode slurry was applied to the surface of a copper foil as a negative electrode current collector, the coating film was dried, and then rolled to form negative electrode mixture layers on both sides of the copper foil.
  • Nonaqueous Electrolyte Secondary Battery An Al positive electrode lead was attached to the positive electrode obtained above, and a Ni negative electrode lead was attached to the negative electrode obtained above. In an inert gas atmosphere, the positive electrode and the negative electrode were spirally wound via a polyethylene thin film (separator) to prepare a wound electrode group.
  • the electrode group was housed in a bag-shaped exterior body formed of a laminate sheet having an Al layer, and after the non-aqueous electrolyte was injected, the exterior body was sealed to produce a non-aqueous electrolyte secondary battery. When the electrode group was housed in the package, part of the positive electrode lead and the negative electrode lead were each exposed to the outside from the package.
  • the voltage value was measured when the battery with an SOC of 50% was discharged for 10 seconds at current values of 0A, 0.1A, 0.5A and 1.0A.
  • DCIR initial DCIR was calculated from the absolute value of the slope when the relationship between the discharge current value and the voltage value after 10 seconds was linearly approximated by the method of least squares.
  • DCIR increase rate ( ⁇ DCIR) DCIR (DCIR at the 200th cycle) was calculated in the same manner as in (a) above, except that the battery after 200 cycles of charging and discharging in the charge-discharge cycle test (b) above was used. The ratio of the DCIR after 200 cycles to the initial DCIR was calculated as the DCIR increase rate using the following formula.
  • DCIR increase rate (%) ⁇ (DCIR at 200th cycle-initial DCIR) / initial DCIR ⁇ x 100
  • Table 1 shows the evaluation results.
  • E1-E7 are Examples 1-7
  • C1-C6 are Comparative Examples 1-6.
  • A1 is lithium difluorobisoxalate phosphate
  • A2 is lithium tetrafluorobisoxalate phosphate
  • A3 is lithium bisoxalate borate.
  • B1 is tetravinylsilane
  • B2 is tetraallylsilane
  • B3 is dimethyldivinylsilane
  • B4 is tetramethylsilane
  • B5 is tetraethylsilane.
  • Silane. B4 and B5 are not compounds represented by general formula (2).
  • E1 and C4 a composite oxide NMA containing no Co was used as the positive electrode active material, respectively, A1 was added to the non-aqueous electrolyte in E1, and A1 was not added to the non-aqueous electrolyte in C4.
  • E1 MR was significantly increased by 3.8% (84.5% ⁇ 88.3%) and ⁇ DCIR was significantly reduced by 5.0% (19.2% ⁇ 24%) compared to C4. .2%).
  • C1 and C2 a composite oxide containing a relatively large amount of Co was used as the positive electrode active material.
  • A1 was added to the non-aqueous electrolyte, and in C1, A1 was not added to the non-aqueous electrolyte.
  • C2 increased MR by only 0.8% (86.5% ⁇ 87.3%) and reduced ⁇ DCIR by only 2.2% (22.4% ⁇ 20.2%) relative to C1. %).
  • E1 and E2 composite oxide NMA containing no Co was used as the positive electrode active material, respectively, A1 was added to the non-aqueous electrolyte in E1, and A1 and B1 were added to the non-aqueous electrolyte in E2.
  • E2 Compared to E1, E2 further increased the MR by 1.5% (88.3% ⁇ 89.8%) and further reduced the ⁇ DCIR (19.2% ⁇ 17.2%).
  • C4 and C5 a composite oxide NMA containing no Co was used as the positive electrode active material, in C4 neither A1 nor B1 was added to the non-aqueous electrolyte, and in C5 B1 was added to the non-aqueous electrolyte. , A1 were not added.
  • C5 only increased MR by 0.4% (84.5% ⁇ 84.9%) relative to C4.
  • E4 and E6 a composite oxide NMA containing no Co was used as the positive electrode active material, respectively, A2 was added to the non-aqueous electrolyte in E4, and A3 was added to the non-aqueous electrolyte in E6.
  • MR was greatly increased and ⁇ DCIR was greatly reduced.
  • a non-aqueous electrolyte secondary battery according to the present disclosure is useful as a main power source for mobile communication devices, portable electronic devices, and the like.
  • non-aqueous electrolyte secondary batteries are suitable for in-vehicle use because they have high capacity and excellent cycle characteristics.
  • the uses of the non-aqueous electrolyte secondary battery are not limited to these.

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