WO2023120032A1 - 二次電池用セパレータおよびその製造方法、ならびに二次電池 - Google Patents

二次電池用セパレータおよびその製造方法、ならびに二次電池 Download PDF

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WO2023120032A1
WO2023120032A1 PCT/JP2022/043545 JP2022043545W WO2023120032A1 WO 2023120032 A1 WO2023120032 A1 WO 2023120032A1 JP 2022043545 W JP2022043545 W JP 2022043545W WO 2023120032 A1 WO2023120032 A1 WO 2023120032A1
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Prior art keywords
secondary battery
polysaccharide
porous substrate
positive electrode
battery separator
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English (en)
French (fr)
Japanese (ja)
Inventor
千咲希 長谷川
雪尋 沖
充朗 白髪
和子 浅野
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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 US18/722,065 priority Critical patent/US20250055128A1/en
Priority to JP2023569200A priority patent/JPWO2023120032A1/ja
Priority to EP22910750.3A priority patent/EP4456305A4/en
Priority to CN202280083443.4A priority patent/CN118402128A/zh
Publication of WO2023120032A1 publication Critical patent/WO2023120032A1/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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • 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 mainly relates to separators for secondary batteries.
  • a secondary battery containing a lithium ion conductive non-aqueous electrolyte tends to increase the amount of metal ions eluted from the positive electrode as the end-of-charge voltage increases.
  • the eluted metal ions reach the negative electrode by electrophoresis, they are deposited as metal on the negative electrode, which causes deterioration of the safety and load characteristics of the battery.
  • Patent Document 1 discloses a binder that connects electrode materials of an electrochemical device, which is a pH-adjusting functional agent that neutralizes a base in an aqueous system, and a metal ion derived from an electrode active material that crosslinks in an aqueous system to form a hydrophobic gel. and a metal cross-linked thickener that forms Patent document 1 provides a binder that can be prepared using water as a solvent and without alkalinizing an electrode slurry even when using an electrode active material that is very easily hydrolyzed. It is an object.
  • Patent Document 2 discloses a nanoobject or submicron object made of at least one first electron-conducting material and at least one second material different from the first material. from a three-dimensional network of nano-objects each made of at least one first electronically conducting material bound to and supported by a polysaccharide
  • the nano- or sub-micron objects comprising nanostructures of the form and made of at least one second material different from the first material are self-assembled around said network and are bound by said polysaccharide to at least one are combined with nano-objects made of a first electron-conducting material of , wherein said nanostructures are uniformly distributed throughout the material.
  • Patent Document 3 describes a negative electrode active material for a non-aqueous secondary battery in which graphite particles for a negative electrode of a non-aqueous secondary battery using a group of massive graphite particles are adsorbed and coated with first and second organic components.
  • the particle group has an apparent density of 0.70 g/cm 3 or more by the tapping method, an ash content of 0.5% by mass or less, and a total of Fe, Cu, and Zn of 100 ppm or less by acid extraction ICP analysis.
  • Patent Document 4 discloses a metal oxide or metal hydroxide as an active material, and one or more of glucose, glucuronic acid, rhamnose, mannose, galactose, or a salt thereof, at least a part of which contains a 2-substituted product, a 3-position Characterized by using a mixture containing a saccharide copolymer containing a substituted or 5-substituted saccharide and a copolymer of maleic acid or its anhydride or its salt and at least one unsaturated monomer
  • a metal oxide or metal hydroxide as an active material, and one or more of glucose, glucuronic acid, rhamnose, mannose, galactose, or a salt thereof, at least a part of which contains a 2-substituted product, a 3-position Characterized by using a mixture containing a saccharide copolymer containing a substituted or 5-substituted saccharide and a copolymer of maleic acid or its
  • the separator By coating the separator with an organic polymer that has an anionic functional group capable of trapping metal ions, it is expected to suppress metal deposition on the negative electrode. However, it is difficult to uniformly apply an organic polymer having a highly polar anionic functional group on the surface of a separator having a low polarity. Even if it can be applied, the organic polymer tends to aggregate and the pores of the separator are clogged with the organic polymer, which tends to lower the load characteristics of the battery.
  • One aspect of the present disclosure includes a porous substrate having a first surface and a second surface opposite the first surface, and a polysaccharide attached to the porous substrate, the polysaccharide comprising:
  • the present invention relates to a secondary battery separator having a sulfo group.
  • Another aspect of the present disclosure includes a positive electrode, a negative electrode, a lithium ion conductive non-aqueous electrolyte, and a separator interposed between the positive electrode and the negative electrode, wherein the separator is the above secondary battery separator. , relating to secondary batteries.
  • Yet another aspect of the present disclosure is providing a porous substrate having a first surface and a second surface opposite said first surface; providing a solution of a polysaccharide having sulfo groups;
  • the present invention relates to a method for manufacturing a secondary battery separator, comprising the steps of: applying the solution to the first surface of the porous substrate; and drying the porous substrate to which the solution has been applied.
  • the polysaccharide having a sulfo group attached to the porous substrate has a high effect of trapping metal ions, does not easily clog the pores of the porous substrate, and improves the wettability of the separator with respect to the non-aqueous electrolyte. , metal deposition on the negative electrode is suppressed and the load characteristics of the secondary battery are improved.
  • FIG. 1 is a vertical cross-sectional view schematically showing the internal structure of a secondary battery according to an embodiment of the present disclosure
  • 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 items described in two or more claims arbitrarily selected from the multiple claims described in the attached claims can be combined.
  • a secondary battery separator includes a porous substrate and a polysaccharide attached to the porous substrate.
  • Polysaccharides have one or more sulfo groups (--SO 3 X or --SO 3 ⁇ ) in the molecule. Since the polysaccharide contains many hydrophilic groups and has a relatively large molecular weight, it hardly dissolves in the non-aqueous electrolyte in the battery and can be fixed on the porous substrate for a long period of time without being peeled off.
  • the sulfo group can be in any of an acid form (--SO 3 X (where X is H)), a salt form (--SO 3 X (where X is a cation)) and an anion form (--SO 3 ⁇ ). There may be.
  • the cation contained in the sulfo group as X may be a metal ion, an organic cation, or an ammonium ion (NH 4 + ).
  • the metal ions can be cations such as alkali metals and alkaline earth metals, and can be cations such as barium, calcium, magnesium, potassium, sodium, and lithium.
  • the multiple sulfo groups that the polysaccharide has in the molecule may be of the same type (type) or of different types.
  • a polysaccharide with sulfo groups in salt form may have two or more sulfo groups with different cations.
  • a plurality of types of polysaccharides having different molecular structures may be used in combination and attached to the porous substrate, or only one type of polysaccharide may be attached to the porous substrate.
  • polysaccharides having sulfo groups are also referred to as “polysaccharides (S)”.
  • the porous substrate has a first surface and a second surface opposite the first surface.
  • the porous substrate may have the form of a membrane, sheet or film.
  • Porous substrates can be stretched films, nonwovens, wovens, and the like.
  • a secondary battery separator containing a porous substrate and a polysaccharide (S) adhering to the porous substrate has the effect of suppressing metal deposition on the negative electrode and improves the load characteristics of the secondary battery. can let for that reason. The following are possible.
  • polysaccharide (S) can serve as a barrier that suppresses the movement of metal ions between electrodes.
  • the sulfo group of the polysaccharide (S) efficiently traps impurities and metal ions eluted from the positive electrode.
  • the ability of the sulfo group to trap metal ions is high.
  • polysaccharide (S) has the property of being easily attached to a porous substrate, it is difficult to clog the pores of the porous substrate. Since the polysaccharide (S) exhibits high solubility in a predetermined hydrophilic solvent, it is easy to thinly and uniformly adhere along the inner walls of the pores of the porous substrate. Therefore, it is possible to easily avoid the phenomenon that the polysaccharide (S) blocks the opening of the pores and the filling of the pores with the polysaccharide (S). It is considered that the highly ionic nature of the sulfo group contributes to the high solubility of the polysaccharide (S).
  • the polysaccharide (S) tends to improve the wettability of the porous substrate (that is, the separator) to the non-aqueous electrolyte.
  • Polysaccharides (S) are almost insoluble in non-aqueous electrolytes, but have a higher affinity with non-aqueous electrolytes than porous substrates generally used as separators in secondary batteries.
  • a separator composed of a porous substrate to which a polysaccharide (S) is adhered has higher wettability to a non-aqueous electrolyte than a separator containing no polysaccharide (S).
  • the effect of suppressing the movement of metal ions by polysaccharide (S) is remarkable, for example, when impurity metals such as copper and iron are present in the secondary battery.
  • impurity metals such as copper and iron are present in the secondary battery.
  • metal ions are eluted from the impurity metal into the non-aqueous electrolyte.
  • metal ions can also be eluted from the active material particles in the positive electrode.
  • the positive electrode potential of a secondary battery whose upper limit voltage exceeds 4.3 V is high and the positive electrode active material particles contain metal components (transition metals in many cases), metal ions can be eluted.
  • Metal ions eluted into the non-aqueous electrolyte move from the positive electrode side to the negative electrode side and are deposited as impurity metals.
  • polysaccharide (S) is included in the separator, the movement of the eluted metal ions between the electrodes is remarkably suppressed.
  • metal ions that can be deposited as impurity metals in the negative electrode are also referred to as impurity metal ions.
  • the impurity metal ions eluted into the non-aqueous electrolyte on the positive electrode side pass through the separator when moving to the negative electrode side. Therefore, the probability of impurity metal ions being trapped by the polysaccharide (S) is increased.
  • the trapped metal ions like polysaccharides (S), settle on the porous substrate and have limited freedom of movement. Therefore, migration of impurity metal ions from the positive electrode side to the negative electrode side is greatly suppressed.
  • the secondary battery separator according to the present disclosure (that is, the separator containing the porous substrate and the polysaccharide (S) attached thereto (hereinafter also referred to as "separator (S)”)) defined in JIS P 8117
  • the air permeability measured by the method may be, for example, 100 seconds/100 mL or more and 500 seconds/100 mL or less, or 400 seconds/100 mL or less. Since the polysaccharide (S) hardly clogs the pores of the porous substrate, such a low air permeability can be easily ensured. In general, the smaller the air permeability, the larger the pore volume of the separator.
  • Polysaccharide is a general term for polymers having a structure in which multiple monosaccharide molecules are linked via glycosidic bonds.
  • the polysaccharide is not particularly limited, it preferably has the property of dissolving in a mixed solvent of water and ethanol at a volume ratio of 50:50, for example, from the viewpoint of ensuring ease of manufacturing the separator.
  • polysaccharides examples include aldoses, ketoses, pyranoses and furanoses.
  • Monosaccharide molecules (monomers) constituting polysaccharides include triose, tetrose, pentose, hexose, and heptose. Among them, aldopentose, ketopentose, aldohexose, ketohexose and the like are preferable, and for example, galactose classified as aldohexose can be used.
  • the polysaccharide (S) may have a backbone of galactose polymers.
  • a polysaccharide (S) may be obtained by sulfuric acid esterification of a polymer of these monosaccharides.
  • Polysaccharides originally having a sulfo group may be used, and pectin, alginic acid, pullulan, mannan, xanthan gum, guar gum, starch, glycogen, chitin, dextran, agarose, carrageenan, heparin, hyaluronic acid, glucomannan , gum arabic, gelatin, tremel gum, etc. may be subjected to sulfate esterification to obtain the polysaccharide (S).
  • carrageenan can be preferably used.
  • Carrageenan is classified into types such as kappa, iota, and lambda, and any of them may be used.
  • the content of carrageenan contained in the polysaccharide (S) attached to the porous substrate (that is, contained in the separator) may be, for example, 70% by mass or more, or 100% carrageenan.
  • the separator contains polysaccharide (S) can be easily confirmed by analyzing the infrared absorption spectrum obtained by FT-IR measurement of the separator.
  • the separator contains a sulfo group that binds to the polysaccharide is quantitatively determined by elemental analysis (for example, IPC (inductively coupled plasma emission spectroscopy), SEM-EDX (scanning electron microscope-energy dispersive X-ray analysis), etc.). can be verified.
  • elemental analysis for example, IPC (inductively coupled plasma emission spectroscopy), SEM-EDX (scanning electron microscope-energy dispersive X-ray analysis), etc.
  • the number of moles of sulfo groups contained in the polysaccharide (S) per unit mass is, for example, 1.0 ⁇ 10 ⁇ 6 mol/g or more, and may be 1.0 ⁇ 10 ⁇ 4 mol/g or more. It may be 0 ⁇ 10 ⁇ 3 mol/g or more and 1.0 ⁇ 10 ⁇ 2 mol/g or less.
  • Polysaccharides with a high sulfo group content have the ability to trap more metal ions, are highly soluble in a mixed solvent of water and ethanol, and spread thinly and uniformly along the inner walls of the pores of the porous substrate. Easy to adhere to.
  • the amount of polysaccharide (S) attached to the porous substrate per apparent unit area is, for example, 1.0 ⁇ 10 ⁇ 5 g/m 2 or more and 1.0 ⁇ 10 2 g/m 2 or less, may be 1.0 ⁇ 10 ⁇ 4 g/m 2 or more and 1.0 ⁇ 10 1 g/m 2 or less, or 1.0 ⁇ 10 ⁇ 3 g /m 2 or more and 1.0 g/m 2 or less.
  • the apparent unit area is one unit (1 m 2 ) of the area surrounded by the outline of the projected image of the porous substrate when viewed from the normal direction of the first surface and the second surface of the porous substrate. means.
  • the area density of the polysaccharide (S) To determine the area density of the polysaccharide (S), first, a sample of a predetermined size is cut out from the separator, the sample is dried by heating at 60°C for 1 hour or more, and then the dry mass W1 is determined. Next, the dry sample is immersed in a mixed solvent of water and ethanol at a volume ratio of 50:50 (20° C. to 30° C.) for 1 hour, and then in a mixed solvent of water and ethanol at a volume ratio of 50:50. It is thoroughly washed and dried by heating at 60° C. for 1 hour or more, and then the dry weight W2 is determined. Polysaccharide (S) is virtually completely removed by immersion in mixed solvent and washing with mixed solvent. After that, the areal density of the polysaccharide (S) is determined from the dry weights W1, W2 and the sample size (apparent area).
  • DMC dimethyl carbonate
  • the distribution of the polysaccharide (S) may be changed in the thickness direction of the porous substrate. For example, more polysaccharide (S) may be distributed near the surface facing the positive electrode, which is the elution source of metal ions. This shortens the migration distance of the metal ions eluted from the positive electrode, further reducing the probability of the metal ions reaching the negative electrode.
  • the saccharide content C1 may be greater than the polysaccharide content C2 contained in the second region.
  • the mass ratio of the content C1 to the content C2: C1/C2 may be greater than 1, may be 1.1 or more, may be 1.2 or more, or may be 1.5 or more.
  • the polysaccharide (S) and the existence probability P2 of the polysaccharide (S) existing in the second region from the position of 0.5T (the center in the thickness direction) to the second surface are 1 ⁇ P1/P2.
  • P1/P2 may be 1.2 or more, or may be 1.5 or more.
  • the existence probabilities P1 and P2 of the polysaccharide (S) may be measured by a cross section obtained by cutting the separator along the thickness direction. At that time, the separator may be filled with a thermosetting resin and cured. For example, a cross-sectional sample of the separator is obtained by a CP (cross-section polisher) method, an FIB (focused ion beam) method, or the like.
  • the P1/P2 ratio of the polysaccharide (S) existence probabilities P1 and P2 can be determined by analyzing a cross-sectional sample of the separator with SEM and EDX.
  • the sulfur element amount contained in the first region and the sulfur element amount contained in the second region are quantified, and the ratio of the obtained values is P1/ It may be the P2 ratio.
  • P1 and P2 are measured in an observation field of 20 ⁇ m or more along the planar direction of the separator.
  • P1 and P2 may be average values of P1 and P2 obtained from a plurality of (for example, 3 or more) observation fields.
  • the production method includes a step (I) of preparing a porous substrate having a first surface and a second surface opposite to the first surface; solution”), a coating step (III) of coating the polysaccharide solution on the porous substrate, and a drying step of drying the porous substrate coated with the polysaccharide solution ( IV) (that is, the step of obtaining a separator).
  • porous substrates include stretched films (or microporous thin films), nonwoven fabrics, and woven fabrics, which are generally used as separators for secondary batteries (especially lithium ion batteries).
  • the porous sheet used can be used.
  • the porous sheet has moderate mechanical strength and insulating properties.
  • the porous substrate may have a heat-resistant insulating layer on at least one of the first surface and the second surface.
  • the heat-resistant insulating layer may contain an inorganic oxide filler as a main component (for example, 80% by mass or more), or may contain a heat-resistant resin as a main component (for example, 40% by mass or more).
  • a polyamide resin such as an aromatic polyamide (aramid), a polyimide resin, a polyamideimide resin, or the like may be used as the heat-resistant resin.
  • the thickness of the porous substrate is not particularly limited, it is, for example, 1 to 50 ⁇ m, and may be 5 to 30 ⁇ m.
  • the polysaccharide solution is prepared by mixing the polysaccharide (S) with a solvent to dissolve the polysaccharide (S) in the solvent.
  • the polysaccharide solution may further contain additives other than solvents, such as alcohols, phosphorus compounds, boron compounds, and sulfur compounds.
  • Polysaccharide solutions include, but are not limited to, for example, a mixed solvent of water and ethanol, and polysaccharide (S) dissolved in such a mixed solvent.
  • the solvent is preferably water, alcohol (eg, ethanol), or a mixed solvent of water and alcohol, but is not particularly limited as long as it can dissolve the polysaccharide (S).
  • ethers such as tetrahydrofuran, amides such as dimethylformamide, ketones such as cyclohexanone, N-methyl-2-pyrrolidone (NMP), mixed solvents thereof, and the like may be used.
  • NMP N-methyl-2-pyrrolidone
  • mixed solvents thereof and the like
  • the method of applying the polysaccharide solution to the porous substrate is not particularly limited.
  • a coating method using various coaters, an immersion method, a spray method, and the like are applied.
  • the coater for example, a bar coater, gravure coater, blade coater, roll coater, comma coater, die coater, lip coater and the like are used.
  • the polysaccharide solution may be applied only to the first surface of the porous substrate.
  • the polysaccharide solution may be applied only to the first surface side of the porous substrate using various coaters, or the polysaccharide solution may be sprayed only to the first surface side of the porous substrate.
  • the content C1 of the polysaccharide (S) contained in the first region on the first surface side of the porous substrate is contained in the second region on the second surface side of the porous substrate.
  • the ratio of the content C1 to the content C2: C1/C2 may be controlled to 1.1 or more by controlling the coating amount of the applied polysaccharide solution and/or controlling the drying conditions described later.
  • (IV) Drying Step In the drying step, the porous substrate coated with the polysaccharide solution is dried to complete the separator.
  • the C1/C2 ratio is controlled as described above, the polysaccharide (S) may migrate to the first surface side together with the solvent by appropriately controlling the drying conditions. As a result, the polysaccharide (S) is unevenly distributed on the first surface side.
  • the separator may be rolled.
  • a separator with high flatness can be obtained by rolling.
  • the porous substrate coated with the polysaccharide solution may be rolled while being heated by hot rolls having a temperature lower than the melting point of the material of the porous substrate, and drying and rolling may be performed at the same time.
  • a secondary battery according to an embodiment of the present disclosure is a lithium ion secondary battery that uses a material that reversibly absorbs and releases lithium ions as a negative electrode active material.
  • Non-aqueous electrolyte secondary batteries such as lithium secondary batteries in which lithium metal is dissolved and solid batteries containing gel electrolytes or solid electrolytes are included. These secondary batteries comprise a positive electrode, a negative electrode, a lithium ion conductive non-aqueous electrolyte, and the above secondary battery separator (separator (S)) interposed between the positive electrode and the negative electrode.
  • the separator is positioned with the first surface facing the positive electrode.
  • the non-aqueous electrolyte may be liquid as a whole (that is, an electrolytic solution), or may be used as a solid electrolyte or a gel electrolyte by holding the electrolytic solution in a matrix material.
  • the end-of-charge voltage may be set to 4.3 V or higher, further 4.4 V or higher, and further 4.5 V or higher.
  • a secondary battery having such a charge termination voltage that is, an upper limit voltage
  • the amount of metal ions eluted from the positive electrode generally tends to increase.
  • the secondary battery according to the present disclosure includes a separator (S) containing a polysaccharide having a sulfo group, the probability that eluted metal ions reach the negative electrode is low, and metal deposition at the negative electrode is significantly suppressed. be done.
  • the configuration of the secondary battery will be specifically described below, taking a lithium-ion secondary battery as an example.
  • the positive electrode includes, for example, a positive electrode current collector and a positive electrode active material layer.
  • the positive electrode active material layer is carried on one or both surfaces of the positive electrode current collector.
  • the positive electrode active material layer is, for example, a positive electrode mixture layer made of a positive electrode mixture.
  • the positive electrode mixture contains a positive electrode active material as an essential component and may contain optional components.
  • Optional components may include binders, conductive materials, thickeners, and the like.
  • the positive electrode active material layer can be formed, for example, by applying a positive electrode slurry in which a positive electrode mixture is dispersed in a dispersion medium to the surface of the positive electrode current collector and drying it.
  • the dried coating film may be rolled if necessary.
  • a sheet-like conductive material (metal foil, mesh, net, punching sheet, etc.) is used as the positive electrode current collector.
  • metal foil is preferred.
  • 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 thickness of the positive electrode active material layer is not particularly limited.
  • a plurality of layers having different shapes may form one positive electrode active material layer.
  • two or more layers containing active material particles having different average particle sizes may be laminated, or two or more layers having different types or compositions of positive electrode active materials may be laminated.
  • the average particle size of the particles of the positive electrode active material 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 diameter is the median diameter (D 50 ) at which the cumulative volume is 50% in the volume-based particle size distribution obtained by a laser diffraction particle size distribution analyzer.
  • the active material particles may be separated and recovered from the positive electrode.
  • "LA-750" manufactured by HORIBA, Ltd. can be used as the measuring device.
  • the positive electrode active material may contain a lithium-containing transition metal oxide. From the viewpoint of increasing the capacity, it is desirable that the lithium-containing transition metal oxide contains lithium and Ni and contains a lithium nickel oxide (composite oxide N) having a layered rock salt crystal structure.
  • the ratio of the composite oxide N in the positive electrode active material is, for example, 70% by mass or more, may be 90% by mass or more, or may be 95% by mass or more.
  • the ratio of Ni to the metal elements other than Li contained in the composite oxide N may be 50 atomic % or more.
  • the composite oxide N is represented, for example, by formula (1): Li ⁇ Ni x1 M1 x2 M2 (1 ⁇ x1 ⁇ x2) O 2+ ⁇ .
  • the element M1 is at least one selected from the group consisting of V, Co and Mn.
  • Element M2 is at least one selected from the group consisting of Mg, Al, Ca, Ti, Cu, Zn and Nb.
  • formula (1) is 0.9 ⁇ ⁇ ⁇ 1.1, -0.05 ⁇ ⁇ ⁇ 0.05, 0.5 ⁇ x1 ⁇ 1, 0 ⁇ x2 ⁇ 0.5, 0 ⁇ 1-x1- satisfies x2 ⁇ 0.5.
  • ⁇ increases and decreases due to charging and discharging.
  • the composite oxide N contains Ni and may contain at least one selected from the group consisting of Co, Mn and Al as the element M1 and the element M2. Co, Mn and Al contribute to stabilization of the crystal structure of the composite oxide N.
  • the ratio of Co in the metal elements other than Li contained in the composite oxide N is preferably 0 atomic % or more and 20 atomic % or less, and 0 atomic % or more and 15 atoms. % or less is more desirable.
  • the proportion of Mn in metal elements other than Li may be 30 atomic % or less, or may be 20 atomic % or less.
  • the ratio of Mn to the metal elements other than Li may be 1 atomic % or more, 3 atomic % or more, or 5 atomic % or more.
  • the ratio of Al to the metal elements other than Li may be 10 atomic % or less, or 5 atomic % or less.
  • the ratio of Al to the metal elements other than Li may be 1 atomic % or more, 3 atomic % or more, or 5 atomic % or more.
  • the composite oxide N can be represented, for example, by formula (2): Li ⁇ Ni (1-y1-y2-y3-z) Co y1 Mn y2 Al y3 M z O 2+ ⁇ .
  • Mn and/or Al contribute to stabilization of the crystal structure of the composite oxide N with a reduced Co content.
  • Element M is an element other than Li, Ni, Co, Mn, Al and oxygen, and consists of Ti, Zr, Nb, Mo, W, Fe, Zn, B, Si, Mg, Ca, Sr, Sc and Y. At least one selected from the group may be used.
  • formula (2) is 0.9 ⁇ 1.1, ⁇ 0.05 ⁇ 0.05, 0 ⁇ y1 ⁇ 0.1, 0 ⁇ y2 ⁇ 0.6, 0 ⁇ y3 ⁇ 0.
  • the ratio of Co to the metal elements other than Li may be 1.5 atomic % or less. If the Co content of the composite oxide N can be reduced and the Ni content can be increased, it is advantageous in terms of cost and can ensure a high capacity. On the other hand, such Co-free or Co-containing composite oxide N generally tends to easily elute metal ions.
  • the secondary battery according to the present disclosure includes a separator (S) containing a polysaccharide having a sulfo group, the probability that eluted metal ions reach the negative electrode is low, and metal deposition at the negative electrode is significant. suppressed by
  • Examples of conductive materials that can be included as optional components in the positive electrode active material layer include carbon nanotubes (CNT), carbon fibers other than CNT, and conductive particles (eg, carbon black and graphite).
  • CNT carbon nanotubes
  • carbon fibers other than CNT carbon fibers other than CNT
  • conductive particles eg, carbon black and graphite
  • the negative electrode includes at least a negative electrode current collector, for example, a negative electrode current collector and a negative electrode active material layer.
  • the negative electrode active material layer is supported on one or both surfaces of the negative electrode current collector.
  • the negative electrode active material layer may be a negative electrode mixture layer composed of a negative electrode mixture.
  • the negative electrode mixture layer is membranous or film-like.
  • the negative electrode mixture contains particles of a negative electrode active material as an essential component, and may contain a binder, a conductive agent, a thickener, and the like as optional components. Also, a lithium metal foil or a lithium alloy foil may be attached to the negative electrode current collector as the negative electrode active material layer.
  • the negative electrode mixture layer can be formed, for example, by applying a negative electrode slurry in which a negative electrode mixture containing particles of a negative electrode active material, a binder, etc. is dispersed in a dispersion medium on the surface of the negative electrode current collector and drying the slurry. .
  • the dried coating film may be rolled if necessary.
  • a sheet-shaped conductive material (metal foil, mesh, net, punching sheet, etc.) is used as the negative electrode current collector.
  • metal foil is preferred.
  • 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.
  • Negative electrode active materials include materials that electrochemically absorb and release lithium ions, lithium metal, and lithium alloys. Carbon materials, alloy materials, and the like are used as materials that electrochemically occlude and release lithium ions. Examples of carbon materials include graphite, graphitizable carbon (soft carbon), and non-graphitizable carbon (hard carbon). Among them, graphite is preferable because it has excellent charging/discharging stability and low irreversible capacity. Examples of alloy-based materials include those containing at least one metal capable of forming an alloy with lithium, and specific examples include silicon, tin, silicon alloys, tin alloys, and silicon compounds. Silicon oxide, tin oxide, etc. may also be used.
  • a lithium ion conductive phase and a composite material in which silicon particles are dispersed in the lithium ion conductive phase can be used.
  • the lithium ion conductive phase for example, a silicon oxide phase, a silicate phase, a carbon phase, or the like can be used.
  • a major component (eg, 95-100% by weight) of the silicon oxide phase can be silicon dioxide.
  • a composite material composed of a silicate phase and silicon particles dispersed in the silicate phase is preferable in terms of high capacity and low irreversible capacity.
  • a lithium silicate phase (a silicate phase containing lithium) having a small irreversible capacity and a high initial charge-discharge efficiency is preferable.
  • the lithium silicate phase may be an oxide phase containing lithium (Li), silicon (Si), and oxygen (O), and may contain other elements.
  • the atomic ratio of O to Si: O/Si in the lithium silicate phase is greater than 2 and less than 4, for example.
  • O/Si is greater than 2 and less than 3.
  • the atomic ratio of Li to Si in the lithium silicate phase: Li/Si is greater than 0 and less than 4, for example.
  • Elements other than Li, Si and O that can be contained in the lithium silicate phase include, for example, iron (Fe), chromium (Cr), nickel (Ni), manganese (Mn), copper (Cu), molybdenum (Mo), Examples include zinc (Zn) and aluminum (Al).
  • the carbon phase can be composed of, for example, amorphous carbon with low crystallinity (that is, amorphous carbon).
  • Amorphous carbon may be, for example, hard carbon, soft carbon, or otherwise.
  • a resin material is used as the binder.
  • binders include polyacrylic acid, polyacrylic acid salts and derivatives thereof, fluororesins, polyolefin resins, polyamide resins, polyimide resins, acrylic resins, vinyl resins, rubber particles and the like.
  • the binder may be used alone or in combination of two or more.
  • Examples of conductive materials include carbon nanotubes (CNT), carbon fibers other than CNT, and conductive particles (eg, carbon black, graphite).
  • CNT carbon nanotubes
  • carbon fibers other than CNT carbon fibers other than CNT
  • conductive particles eg, carbon black, graphite
  • thickeners examples include carboxymethyl cellulose (CMC) and modified products thereof (including salts such as Na salts), cellulose derivatives such as methyl cellulose (cellulose ethers, etc.); polymer cellulose having a vinyl acetate unit such as polyvinyl alcohol; compound; polyether (polyalkylene oxide such as polyethylene oxide, etc.), and the like.
  • CMC carboxymethyl cellulose
  • modified products thereof including salts such as Na salts
  • cellulose derivatives such as methyl cellulose (cellulose ethers, etc.)
  • polymer cellulose having a vinyl acetate unit such as polyvinyl alcohol
  • compound compound
  • polyether polyalkylene oxide such as polyethylene oxide, etc.
  • the nonaqueous electrolyte may be a liquid electrolyte (electrolytic solution), a gel electrolyte, or a solid electrolyte.
  • the liquid electrolyte (electrolytic solution) is, for example, an electrolytic solution containing a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
  • the lithium salt concentration in the electrolytic solution is, for example, 0.5 mol/L or more and 2 mol/L or less.
  • the electrolytic solution may contain known additives.
  • the gel electrolyte contains a lithium salt and a matrix polymer, or contains a lithium salt, a non-aqueous solvent and a matrix polymer.
  • a matrix polymer for example, a polymer material that gels by absorbing a non-aqueous solvent is used.
  • polymer materials include fluorine resins, acrylic resins, polyether resins, polyethylene oxide, and the like.
  • the solid electrolyte may be an inorganic solid electrolyte.
  • the inorganic solid electrolyte for example, a known material (for example, an oxide-based solid electrolyte, a sulfide-based solid electrolyte, a halide-based solid electrolyte, etc.) is used for all-solid-state lithium ion secondary batteries and the like.
  • non-aqueous solvent for example, cyclic carbonate, chain carbonate, cyclic carboxylate, and the like are used.
  • Cyclic carbonates include propylene carbonate (PC) and ethylene carbonate (EC).
  • Chain carbonates include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC) and the like.
  • Cyclic carboxylic acid esters include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
  • the non-aqueous solvent may be used singly or in combination of two or more.
  • Lithium salts include, for example, lithium salts of chlorine-containing acids ( LiClO4 , LiAlCl4 , LiB10Cl10 , etc.), lithium salts of fluorine-containing acids ( LiPF6 , LiBF4 , LiSbF6 , LiAsF6 , LiCF3SO3 ) . , LiCF3CO2 , etc.
  • LiN( SO2F ) 2 lithium salts of fluorine - containing acid imides (LiN( SO2F ) 2 , LiN ( CF3SO2 ) 2 , LiN( CF3SO2 ) ( C4F9SO2 ) , LiN ( C2F5SO2 ) 2 , etc.), lithium halides (LiCl, LiBr, LiI, etc.).
  • Lithium salts may be used singly or in combination of two or more.
  • a secondary battery there 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 housed in an outer package together with an electrolytic solution.
  • an electrode group in which a positive electrode and a negative electrode are wound with a separator interposed therebetween
  • an electrolytic solution e.g., aqueous solution
  • a laminated electrode group in which a positive electrode and a negative electrode are laminated with a separator interposed therebetween may be used.
  • the form of the secondary battery is also not limited, and may be, for example, cylindrical, square, coin, button, laminate, or the like.
  • FIG. 1 is a vertical cross-sectional view of a cylindrical non-aqueous secondary battery 10 that is an example of the present embodiment.
  • the present disclosure is not limited to the following configurations.
  • the secondary battery 10 includes an electrode group 18, an electrolytic solution (not shown), and a bottomed cylindrical battery can 22 that accommodates them.
  • a sealing member 11 is crimped and fixed to the opening of the battery can 22 via a gasket 21 . The inside of the battery is thereby sealed.
  • the sealing body 11 includes a valve body 12 , a metal plate 13 , and an annular insulating member 14 interposed between the valve body 12 and the metal plate 13 .
  • the valve body 12 and the metal plate 13 are connected to each other at their respective centers.
  • a positive electrode lead 15 a led out from the positive electrode plate 15 is connected to the metal plate 13 . Therefore, the valve body 12 functions as a positive external terminal.
  • a negative lead 16 a led out from the negative plate 16 is connected to the inner surface of the bottom of the battery can 22 .
  • An annular groove 22 a is formed near the open end of the battery can 22 .
  • a first insulating plate 23 is arranged between one end face of the electrode group 18 and the annular groove portion 22a.
  • a second insulating plate 24 is arranged between the other end face of the electrode group 18 and the bottom of the battery can 22 .
  • the electrode group 18 is formed by winding the positive electrode plate 15 and the negative electrode plate 16 with the separator 17 interposed therebetween.
  • the positive electrode was cut into a predetermined shape, and the positive electrode active material layer was partially peeled off to obtain a positive electrode for evaluation.
  • the positive electrode was shaped to have a power generation region of 60 mm ⁇ 40 mm with a positive electrode active material layer and a connection region of 10 mm ⁇ 10 mm without a positive electrode active material layer.
  • a positive tab lead was connected to the connection area.
  • a negative electrode was produced by attaching a lithium metal foil to one side of an electrolytic copper foil (collector). The negative electrode was cut into the same shape as the positive electrode, the lithium metal foil on the connection area was peeled off, and the negative electrode tab lead was connected to the connection area.
  • Porous Substrate As the porous substrate, a 12 ⁇ m-thick polyethylene microporous thin film (air permeability: 108 seconds/100 mL) was prepared.
  • the microporous thin film is a biaxially stretched film generally used as a separator for lithium ion secondary batteries as it is.
  • (IV) Drying step In the drying step, the porous substrate coated with the polysaccharide solution is placed on a mounting substrate with the first surface side facing upward, and the second surface side is placed on a mounting substrate, and dried at 60°C for 3 hours. It was dried for a period of time to complete a separator to which polysaccharide (S) was adhered.
  • the obtained separator had an air permeability of 128 seconds/100 mL, and its IR spectrum was measured by FT-IR. was observed. Elemental analysis by IPC detected elemental sulfur, confirming the presence of a sulfo group.
  • PC propylene carbonate
  • Electrolyte Solution An electrolyte solution was prepared by dissolving LiPF 6 at a concentration of 1 mol/L in a mixed solvent of fluoroethylene carbonate (FEC) and dimethyl carbonate (DMC) at a volume ratio of 20:80.
  • FEC fluoroethylene carbonate
  • DMC dimethyl carbonate
  • a battery having a design capacity of 114 mAh was produced using the positive electrode, the negative electrode, and the above separator for evaluation.
  • An electrode plate group was obtained by stacking the positive electrode and the negative electrode with a separator for evaluation interposed between the positive electrode active material layer and the lithium metal foil. At this time, the first surface was made to face the positive electrode active material layer.
  • the electrode plate group was housed in an envelope-like case made of a laminate film with both ends opened, together with 1.2 cm 3 of an electrolytic solution. After that, the positive electrode active material layer and the separator were impregnated with the electrolytic solution by allowing to stand under a reduced pressure of 0.02 MPa for 3 minutes and then returning to atmospheric pressure twice. Finally, the other opening was sealed to obtain an evaluation battery A1 of Example 1. Evaluation batteries were produced in a dry air atmosphere with a dew point of ⁇ 60° C. or lower.
  • a constant current charge of 0.3C (1C is a current value for discharging the design capacity in one hour) is performed until the battery voltage reaches 4.5V, and then a constant voltage charge of 4.5V is performed. was carried out for 3 days.
  • the battery was discharged at a constant current of 0.3 C until the battery voltage reached 2.5 V at room temperature, and then charged at a constant current of 0.3 C until the battery voltage reached 4.5 V.
  • Constant voltage charging was carried out until the temperature became less than 05C. After that, discharge was performed at a constant current of 0.3C until reaching 2.5V. It was left in open circuit for 20 minutes between charging and discharging.
  • the battery was disassembled and the amount of metal deposited on the surface of the negative electrode was analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES).
  • ICP-AES inductively coupled plasma atomic emission spectrometry
  • the battery was charged at a constant current of 0.3C until the battery voltage reached 4.5V, and then charged at a constant voltage of 4.5V until the current value was less than 0.05C. Then, the battery was discharged at a constant current of 0.1C until the battery voltage reached 2.5V. Subsequently, the battery was charged at a constant current of 0.3C until the battery voltage reached 4.5V, and then charged at a constant voltage of 4.5V until the current value was less than 0.05C. Then, the battery was discharged at a constant current of 1C until the battery voltage reached 2.5V. It was left in open circuit for 20 minutes between charging and discharging.
  • Table 1 shows the amount of deposited metal and load characteristics. Both the amount of deposited metal and the load characteristics are relative values (%) when the value in B1 is 100%.
  • a secondary battery separator according to the present disclosure and a secondary battery including the same are useful as main power sources for mobile communication devices, portable electronic devices, electric vehicles, and the like.

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PCT/JP2022/043545 2021-12-24 2022-11-25 二次電池用セパレータおよびその製造方法、ならびに二次電池 Ceased WO2023120032A1 (ja)

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JP2011134572A (ja) 2009-12-24 2011-07-07 Hitachi Powdered Metals Co Ltd 非水二次電池用負極活物質およびこれを用いた非水二次電池
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WO2020095466A1 (ja) 2018-11-07 2020-05-14 Ｔｐｒ株式会社 バインダ
JP2021501456A (ja) * 2018-05-10 2021-01-14 エルジー・ケム・リミテッド 安全性が向上したリチウム金属二次電池及びそれを含む電池モジュール

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CN108807819B (zh) * 2018-06-15 2021-06-29 珠海冠宇电池股份有限公司 隔膜及其制备方法和锂硫电池

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JP2003308840A (ja) 2001-12-21 2003-10-31 Hitachi Maxell Ltd 電極およびそれを用いた電池
JP2011134572A (ja) 2009-12-24 2011-07-07 Hitachi Powdered Metals Co Ltd 非水二次電池用負極活物質およびこれを用いた非水二次電池
JP2011150866A (ja) * 2010-01-21 2011-08-04 Hitachi Maxell Energy Ltd リチウムイオン二次電池
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JP2021501456A (ja) * 2018-05-10 2021-01-14 エルジー・ケム・リミテッド 安全性が向上したリチウム金属二次電池及びそれを含む電池モジュール
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