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CN110277546B - Positive electrode, lithium ion secondary battery, and coating liquid for positive electrode composite material - Google Patents

Positive electrode, lithium ion secondary battery, and coating liquid for positive electrode composite material Download PDF

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Publication number
CN110277546B
CN110277546B CN201910171117.9A CN201910171117A CN110277546B CN 110277546 B CN110277546 B CN 110277546B CN 201910171117 A CN201910171117 A CN 201910171117A CN 110277546 B CN110277546 B CN 110277546B
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positive electrode
particles
lithium
composite material
ion secondary
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CN110277546A (en
Inventor
柳田英雄
铃木荣子
中岛聪
菅野佑介
座间优
广渡杏奈
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Ricoh Co Ltd
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Ricoh Co Ltd
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Priority claimed from JP2018227390A external-priority patent/JP7302165B2/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/362—Composites
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to a positive electrode, a lithium ion secondary battery, a nonaqueous electric storage element, and a coating liquid for a positive electrode composite material. The invention provides a positive electrode capable of improving the energy density and the output density of a lithium ion secondary battery. The positive electrode (40) includes a positive electrode composite material (42) containing lithium vanadium phosphate particles and lithium nickel composite oxide particles. Median diameter D of primary particles of lithium vanadium phosphate particles 50 The content of carbon is not more than 0.8 μm and not less than 2.5 mass%. The mass ratio of lithium vanadium phosphate particles to lithium nickel composite oxide particles of the positive electrode composite material (42) is 9% or less.

Description

Positive electrode, lithium ion secondary battery, and coating liquid for positive electrode composite material
Technical Field
The present invention relates to a positive electrode, a lithium ion secondary battery, a nonaqueous electric storage element, and a coating liquid for a positive electrode composite material.
Background
While the market of lithium ion secondary batteries is expanding as consumer, vehicle-mounted, and infrastructure applications, lithium ion secondary batteries are used in a variety of environments for a variety of devices, and thus, it is desired to increase energy density and output density.
Patent document 1 discloses a positive electrode provided with a positive electrode composite material layer containing a positive electrode active material. The positive electrode active material is in mass ratioThe range of (2) includes lithium vanadium phosphate and lithium nickel composite oxides. Further, the carbon content of the lithium vanadium phosphate particles is +.>
However, when the positive electrode composite material layer is formed, there are problems in that coating unevenness occurs and the output density of the lithium ion secondary battery is lowered.
Japanese patent application laid-open No. 2012-256591 (patent document 1)
Disclosure of Invention
The present invention has been made in view of the above-described problems, and an object of one embodiment of the present invention is to provide a positive electrode capable of improving the energy density and the output density of a lithium ion secondary battery.
In one embodiment of the present invention, the positive electrode comprises a positive electrode composite material containing lithium vanadium phosphate particles and lithium nickel composite oxide particles, wherein the median diameter D of primary particles of the lithium vanadium phosphate particles 50 The content of carbon is not more than 0.8 μm, and the mass ratio of the lithium vanadium phosphate particles to the lithium nickel composite oxide particles in the positive electrode composite material is not more than 9%.
The effects of the present invention are described below:
according to one aspect of the present invention, a positive electrode capable of improving both the energy density and the output density of a lithium ion secondary battery can be provided.
Drawings
Fig. 1 is a schematic diagram showing the structure of lithium vanadium phosphate particles.
Fig. 2 is a schematic diagram showing an example of the nonaqueous electricity storage element of the present embodiment.
Fig. 3 is a plan view showing a negative electrode of the example.
Fig. 4 is a plan view showing the positive electrode of the embodiment.
Fig. 5 (a) and (b) are diagrams showing electrode elements of the embodiment.
Fig. 6 is a graph showing a relationship between output density and energy density of a lithium ion secondary battery.
Detailed description of the preferred embodiments
The following describes embodiments for carrying out the present invention.
< cathode >
The positive electrode of the present embodiment is not particularly limited as long as it includes a positive electrode composite material containing lithium vanadium phosphate particles and lithium nickel composite oxide particles as a positive electrode active material, and may be appropriately selected according to the purpose, and examples thereof include a positive electrode having a positive electrode composite material provided on a positive electrode substrate.
The shape of the positive electrode is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include a flat plate shape and the like.
Positive electrode composite Material
The positive electrode composite material contains lithium vanadium phosphate particles and lithium nickel composite oxide particles, and may further contain a conductive agent, a binder, a tackifier, and the like as necessary.
The mass ratio of the lithium vanadium phosphate particles to the lithium nickel composite oxide particles in the positive electrode composite material is 9% or less, preferably 7% or less. If the mass ratio of the lithium vanadium phosphate particles to the lithium nickel composite oxide particles in the positive electrode composite material exceeds 9%, uneven coating occurs when the positive electrode composite material is formed, and the output density of the lithium ion secondary battery is reduced. The mass ratio of the lithium vanadium phosphate particles to the lithium nickel composite oxide particles in the positive electrode composite material is usually 1% or more.
Lithium vanadium phosphate particles
Fig. 1 shows the structure of lithium vanadium phosphate particles.
The lithium vanadium phosphate particles 10 are an aggregate of primary particles 11, i.e., secondary particles 12. The primary particles 11 are an aggregate of crystallites 13, and have a conductive carbon coating layer 14 on the surface thereof.
Median diameter D of primary particles 11 50 Is 0.8 μm or less, preferably 0.5 μm or less. If the median diameter D of the primary particles 11 50 If the average particle size exceeds 0.5. Mu.m, the output density of the lithium ion secondary battery decreases. Median diameter D of primary particles 11 50 Typically 0.05 μm or more.
The content of carbon in the lithium vanadium phosphate particles 10 is 2.5 mass% or more, preferably 3 mass% or more. If the content of carbon in the lithium vanadium phosphate particles 10 is less than 2.5 mass%, the output density of the lithium ion secondary battery decreases. The content of carbon in the lithium vanadium phosphate particles 10 is generally 10 mass% or less.
Median diameter D of secondary particles 12 50 Preferably 5 μm or less, more preferably 3.5 μm or less. If the median diameter D of the secondary particles 12 50 When the particle size is 5 μm or less, the output density of the lithium ion secondary battery increases. Median diameter D of secondary particles 12 50 Typically 0.5 μm or more.
In this embodiment, the lithium vanadium phosphate is NASICON-type lithium vanadium phosphate, and for example, a compound represented by the following general formula is used as a basic skeleton: li (Li) x V 2-y M y (PO 4 ) z
( Wherein M is at least one selected from the group consisting of Fe, co, mn, cu, zn, al, sn, B, ga, cr, V, ti, mg, ca, sr, zr, satisfying the following formula: x-y+6=3z )
From the standpoint of the output density of the lithium ion secondary battery, the lithium vanadium phosphate will preferably be represented by the formula Li 3 V 2 (PO 4 ) 3 Or by the general formula Li 3 V 2-x M x (PO 4 ) 3 Represented compounds as radicalsThe skeleton (in the general formula, M is at least one selected from the group consisting of Fe, co, mn, cu, zn, al, sn, B, ga, cr, ti, mg, ca, sr).
As the lithium vanadium phosphate, a similar compound doped with a heterogeneous element in the basic skeleton can be used.
As a method for synthesizing lithium vanadium phosphate, a known synthesis method can be used (for example, refer to patent document 1).
Lithium nickel composite oxide particles
In this embodiment, for example, a compound represented by the following general formula is used as a basic skeleton of the lithium nickel composite oxide: liNi x M y O 2
( Wherein M is at least one selected from the group consisting of Fe, co, mn, cu, zn, al, sn, B, ga, cr, V, ti, mg, ca, sr, satisfying the following formula: x+y=1 )
The lithium nickel composite oxide is preferably represented by the general formula LiNi from the viewpoint of energy density of the lithium ion secondary battery x Co y M z O 2 The compound represented by the formula (in the above formula, M is at least one selected from the group consisting of Fe, mn, cu, zn, al, sn, B, ga, cr, V, ti, mg, ca, sr, satisfying the formula: x+y+z=1) as a basic skeleton.
As the lithium nickel composite oxide, a similar compound doped with a heterogeneous element in the basic skeleton can be used.
As a method for synthesizing the lithium nickel composite oxide, a known synthesis method can be used (for example, refer to patent document 1).
Median diameter D of lithium nickel composite oxide particles 50 Preferably 30 μm or less, more preferably 22 μm or less. If the median diameter D of the lithium nickel composite oxide particles 50 When the output density of the lithium ion secondary battery is 30 or less, the output density of the lithium ion secondary battery is increased. In addition, coating unevenness is less likely to occur when forming a positive electrode composite material, and long-term life characteristics are improved. Median diameter D of lithium nickel composite oxide particles 50 Typically 0.5 μm or more.
Adhesive agent
The binder is not particularly limited as long as it is a material that stabilizes the applied potential, a solvent or dispersion medium contained in a coating liquid used in the production of the positive electrode, a nonaqueous electrolyte, and the like, and may be appropriately selected according to the purpose, and examples thereof include a fluorine-based binder such as polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), isoprene rubber, and polyacrylate.
The binder may be used alone, or two or more kinds may be used in combination.
Tackifier(s)
Examples of the thickener include carboxymethyl cellulose (CMC), methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorus oxidized starch, casein, and the like.
The tackifier may be used alone, or two or more kinds may be used in combination.
Conductive agent-
Examples of the conductive agent include carbonaceous materials such as carbon black and acetylene black.
The conductive agent may be used alone, or two or more kinds may be used in combination.
Method for forming positive electrode composite material
The positive electrode composite material may be formed by adding a binder, a thickener, a conductive agent, a dispersion medium, and the like to lithium vanadium phosphate particles and lithium nickel composite oxide particles as necessary to form a slurry-like coating liquid, coating the slurry-like coating liquid on a positive electrode substrate, and drying the slurry-like coating liquid.
The dispersion medium is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include an aqueous solvent and an organic solvent.
Examples of the water-based solvent include water and alcohol.
Examples of the organic solvent include N-methyl-2-pyrrolidone (NMP), toluene, and the like.
Positive electrode base (collector)
The material constituting the positive electrode base is not particularly limited as long as it is formed of a conductive material and is stable with respect to the applied potential, and may be appropriately selected according to the purpose, and examples thereof include aluminum, titanium, tantalum, and the like. Among them, aluminum is particularly suitable because of its light weight, low cost, and high oxidation resistance.
The shape of the positive electrode substrate is not particularly limited, and may be appropriately selected according to the purpose.
The size of the positive electrode substrate is not particularly limited as long as it can be used for the nonaqueous electric storage element, and may be appropriately selected according to the purpose.
Use of Positive electrode
The positive electrode according to the present embodiment is applicable to, for example, a nonaqueous secondary battery, a nonaqueous capacitor, and other nonaqueous electric storage elements.
< nonaqueous electric storage element >
The nonaqueous electric storage element according to the present embodiment can be assembled into a predetermined shape by using the positive electrode, the negative electrode, and the nonaqueous electrolyte according to the present embodiment, and using a separator as necessary.
The nonaqueous electricity storage element of the present embodiment preferably satisfies the following formula:
y＞-47.115x+11310
(in the above formula, x is the energy density [ Wh/kg ], and y is the output density at 50% depth of charge [ W/kg ])
The nonaqueous electric storage element of the present embodiment may further include components such as a case and an electrode lead wire, if necessary.
The method for assembling the positive electrode, the negative electrode, the nonaqueous electrolyte, and the separator to be used as needed is not particularly limited, and may be appropriately selected from known methods.
The shape of the nonaqueous electricity storage element of the present embodiment is not particularly limited, and may be generally selected as appropriate from various shapes to be used according to the application. For example, a cylindrical shape in which the sheet electrode and the separator are spirally formed, a cylindrical shape in which the granular electrode and the separator are combined and having an inner and outer structure, a coin shape in which the granular electrode and the separator are laminated, a case shape using a laminated film in which the sheet electrode and the separator are laminated, and the like can be cited.
< cathode >
The negative electrode is not particularly limited as long as it contains a negative electrode active material, and may be appropriately selected according to the purpose, and examples thereof include a negative electrode in which a negative electrode composite material containing a negative electrode active material is provided on a negative electrode base.
The shape of the negative electrode is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include a flat plate shape and the like.
Negative electrode composite Material
The negative electrode composite material contains a negative electrode active material, and may further contain a binder, a conductive agent, and the like as necessary.
Negative electrode active material
Examples of the negative electrode active material include lithium, lithium alloy, graphite (artificial graphite, natural graphite), graphitizable carbon, thermal decomposition products of organic substances under various thermal decomposition conditions, and lithium titanate.
Adhesive agent
The binder is not particularly limited as long as it is a solvent or dispersion medium, a nonaqueous electrolyte, or a material having a stable potential applied thereto, which are used in the production of the negative electrode, and may be appropriately selected according to the purpose, and examples thereof include a fluorine-based binder such as polyvinylidene fluoride (PVDF) or Polytetrafluoroethylene (PTFE), ethylene-propylene-butadiene rubber (EPBR), styrene-butadiene rubber (SBR), isoprene rubber, and carboxymethyl cellulose (CMC).
The binder may be used alone, or two or more kinds may be used in combination.
Conductive agent-
Examples of the conductive agent include carbonaceous materials such as carbon black and acetylene black.
The conductive agent may be used alone, or two or more kinds may be used in combination.
Method for forming anode composite material
The negative electrode composite material may be formed by adding a binder, a conductive agent, a dispersion medium, and the like to a negative electrode active material as necessary to form a slurry-like coating liquid, coating the slurry-like coating liquid on a negative electrode substrate, and drying the coating liquid.
As the dispersion medium, the same dispersion medium as in the case of forming the positive electrode composite material can be used.
The negative electrode active material may be optionally added with a binder, a conductive agent, or the like to form a composition, and the composition may be roll-formed into a sheet electrode, die-cut into a sheet electrode, or compression-formed into a granular electrode.
The thin film of the negative electrode active material may be formed on the negative electrode substrate by vapor deposition, sputtering, plating, or the like.
Negative electrode base (collector)
The material constituting the negative electrode base is not particularly limited as long as it is formed of a conductive material and is stable against the applied potential, and may be appropriately selected according to the purpose, and examples thereof include stainless steel, nickel, aluminum, copper, and the like. Among them, stainless steel, copper, aluminum are particularly suitable.
The shape of the negative electrode substrate is not particularly limited, and may be appropriately selected according to the purpose.
The size of the negative electrode substrate is not particularly limited as long as it can be used for the nonaqueous electric storage element, and may be appropriately selected according to the purpose.
< nonaqueous electrolyte >
As the nonaqueous electrolyte, a solid electrolyte or a nonaqueous electrolyte may be used.
The nonaqueous electrolyte is an electrolyte in which an electrolyte salt (particularly an electrolyte salt containing a halogen atom) is dissolved in a nonaqueous solvent.
Nonaqueous solvent
The nonaqueous solvent is not particularly limited and may be appropriately selected according to the purpose, but an aprotic organic solvent is suitable.
As the aprotic organic solvent, carbonate-based organic solvents such as chain carbonates and epoxy carbonates can be used. Among them, chain carbonates are preferable in view of high solubility of the electrolyte salt.
The aprotic organic solvent is preferably low in viscosity.
Examples of the chain carbonate include dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethylmethyl carbonate (EMC).
The content of the chain carbonate in the nonaqueous solvent is not particularly limited, and may be appropriately selected according to the purpose, but is preferably 50 mass% or more, and if the content of the chain carbonate in the nonaqueous solvent is 50 mass% or more, the content of the cyclic substance becomes small even if the solvent other than the chain carbonate is a cyclic substance (for example, cyclic carbonate, cyclic ester) having a high dielectric constant. Therefore, even when a nonaqueous electrolytic solution having a high concentration of 2M or more is produced, the viscosity of the nonaqueous electrolytic solution is low, and permeation or ion diffusion of the nonaqueous electrolytic solution into the electrode is good.
Examples of the cyclic carbonate include Propylene Carbonate (PC), ethylene Carbonate (EC), butylene Carbonate (BC), and Vinylene Carbonate (VC).
As the nonaqueous solvent other than the carbonate-based organic solvent, ester-based organic solvents such as cyclic esters and chain esters, ether-based organic solvents such as cyclic ethers and chain ethers, and the like can be used as required.
Examples of the cyclic ester include gamma-butyrolactone (γbl), 2-methyl-gamma-butyrolactone, acetyl-gamma-butyrolactone, and gamma-valerolactone.
Examples of the chain ester include alkyl propionate, dialkyl malonate, alkyl acetate (methyl acetate (MA), ethyl acetate, etc.), alkyl formate (methyl formate (MF), ethyl formate, etc.), and the like.
Examples of the cyclic ether include tetrahydrofuran, alkyl tetrahydrofuran, alkoxy tetrahydrofuran, dialkoxy tetrahydrofuran, 1, 3-dioxoglutarate, alkyl-1, 3-dioxolane, and 1, 4-dioxolane.
Examples of the chain ether include 1, 2-Dimethylethane (DME), diethyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, and tetraethylene glycol dialkyl ether.
Electrolyte salt
The electrolyte salt is not particularly limited as long as it is dissolved in a nonaqueous solvent and has high ion conductivity, and preferably contains a halogen atom.
Examples of the anions constituting the electrolyte salt include lithium ions.
Examples of the cations constituting the electrolyte salt include BF 4 - 、PF 6 - 、AsF 6 - 、CF 3 SO 3 - 、(CF 3 SO 2 ) 2 N - 、(C 2 F 5 SO 2 ) 2 N - Etc.
The lithium salt is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include lithium hexafluorophosphate (LiPF 6 ) Lithium fluoride (LiBF) 4 ) Lithium arsenic hexafluoride (LiAsF) 6 ) Lithium triflate (LiCF) 3 SO 3 ) Lithium bis (trifluoromethylsulfonyl) imide (LiN (CF) 3 SO 2 ) 2 ) Lithium bis (perfluoroethylsulfonyl) imide (LiN (C) 2 F 5 SO 2 ) 2 ) Etc. Among them, liPF is preferable from the viewpoint of ion conductivity 6 LiBF is preferred from the viewpoint of stability 4 。
The electrolyte salt may be used alone or in combination of two or more.
The concentration of the electrolyte salt in the nonaqueous solvent may be appropriately selected depending on the purpose, and in the case of a suspended power storage element, it is preferably 1mol/L to 2mol/L, and in the case of a standby power storage element, it is preferably 2mol/L to 4mol/L.
< spacer >
In order to prevent a short circuit between the negative electrode and the positive electrode, a separator may be provided between the negative electrode and the positive electrode, as needed.
Examples of the separator include kraft paper, vinylon mixed paper, synthetic pulp mixed paper, etc., cellophane, polyethylene grafted film, polyolefin nonwoven fabric such as polypropylene melt-flow nonwoven fabric, polyamide nonwoven fabric, glass fiber nonwoven fabric, microporous film, etc.
The size of the separator is not particularly limited as long as it can be used for the nonaqueous electric storage element, and may be appropriately selected according to the purpose.
The separator may have a single-layer structure or a laminated structure.
When a solid electrolyte is used as the nonaqueous electrolyte, a separator is not required.
Fig. 2 shows an example of the nonaqueous electricity storage element of the present embodiment.
The nonaqueous electric storage element 20 includes a positive electrode 21, a negative electrode 22, a separator 23 holding a nonaqueous electrolyte, a case can 24, a lead-out wire 25 of the positive electrode 21, and a lead-out wire 26 of the negative electrode 22.
Use of non-aqueous electric storage element
The application of the nonaqueous electricity storage element of the present embodiment is not particularly limited, and examples thereof include various applications such as a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a mobile phone, a mobile facsimile machine, a portable copying machine, a portable printer, an earphone stereo, a video camera, a liquid crystal television, a portable cleaner, a portable CD, a mini disk, a transceiver, an electronic notepad, a calculator, a memory card, a portable tape recorder, a radio, a standby power supply, a motor, a lighting device, a toy, a game device, a clock, a flash lamp, a camera, and the like.
[ example ]
The following describes examples of the present invention, but the present invention is not limited to these examples.
The thixotropy index (abbreviated as "TI") and coating unevenness of the coating liquid for the positive electrode composite material were evaluated by the following methods using the coating liquid for the positive electrode composite material and the lithium ion secondary battery, and the charge/discharge test of the lithium ion secondary battery was performed.
[ TI of coating liquid for Positive electrode composite Material ]
The rotor of No.4 was mounted on a B-type viscometer, and the viscosity of the coating liquid for the positive electrode composite material at 6rpm and the viscosity at 60rpm were measured at 25 ℃. Next, TI of the coating liquid for the positive electrode composite material was calculated by the following formula (viscosity at 6 rpm)/(viscosity at 60 rpm).
[ coating unevenness of coating liquid for Positive electrode composite Material ]
As described below, when the coating liquid for the positive electrode composite material was coated on the current collecting foil of aluminum, the coating unevenness was evaluated with naked eyes. The criteria for uneven coating were as follows:
o: the uneven coating cannot be confirmed by naked eyes.
X: the uneven coating can be confirmed by naked eyes.
[ charge/discharge test of lithium ion Secondary Battery ]
A charge/discharge test of the lithium ion secondary battery was performed using a charge/discharge measurement device TOSCAT3001 (manufactured by eastern systems). Specifically, after 3 hours of constant current and constant voltage charging at a maximum voltage of 4.2V and a current ratio of 0.7C at room temperature (25 ℃) and a constant current discharge at a current ratio of 1C, the charging/discharging cycle was repeated 1000 times with 10 minutes of rest interposed between them until 2.5V.
The energy density was calculated by the formula:
(capacity at initial discharge) × (discharge average voltage)/(quality of battery)
The capacity retention rate was calculated by:
(capacity at 100 th discharge)/(capacity at initial discharge) ×100
In a state where the depth (degree) of charge of the lithium ion secondary battery is 50%, the electric power up to the 2.5V cut-off voltage is calculated from the straight line of the voltage and the current after 10 seconds of pulse discharge at the current ratio of 1C to 10C, and the output density is calculated from the ratio to the mass of the lithium ion secondary battery.
[ Synthesis of lithium vanadium phosphate particles ]
And (3) adding phosphoric acid, a carbon source, vanadium pentoxide and lithium hydroxide into a beaker, and heating to obtain a reaction precursor. The amount of carbon source added was adjusted so that the carbon content became the set carbon content. Pulverizing the obtained reaction precursor by a bead mill until the reaction precursor becomes the set median diameter D of primary particles 50 A dispersion was obtained. The obtained dispersion is spray-dried to obtain secondary particles in which primary particles are aggregated. The obtained secondary particles are sintered at 800-1100 ℃ under inert gas atmosphere and then crushed by a jet crusher until the median diameter D of the secondary particles is set 50 To obtain lithium vanadium phosphate (Li) 3 V 2 (PO 4 ) 3 ) Particles (hereinafter, referred to as LVP particles).
Median diameter D of primary particles of LVP particles (1) 50 Median diameter D of the secondary particles of 0.53 μm 50 3.2 μm and a carbon content of 5.3 mass%.
Median diameter D of primary particles of LVP particles (2) 50 Median diameter D of the secondary particles of 0.76 μm 50 3.2 μm and a carbon content of 5.3 mass%.
Median diameter D of primary particles of LVP particles (3) 50 Median diameter D of the secondary particles of 0.41 μm 50 3.0 μm and a carbon content of 5.3 mass%.
Median diameter D of primary particles of LVP particles (4) 50 Median diameter D of the secondary particles of 0.53 μm 50 3.2 μm and a carbon content of 3.5 mass%.
Median diameter D of primary particles of LVP particles (5) 50 Median diameter D of the secondary particles of 0.53 μm 50 3.3 μm and a carbon content of 7.2 mass%.
Table 1 shows the characteristics of LVP particles.
TABLE 1
[ median diameter D of primary particles of LVP particles 50 ]
LVP particles were observed by Scanning Electron Microscopy (SEM), randomly selected for particle count, and median diameter D of primary particles of LVP particles was determined 50 。
[ median diameter D of secondary particles of LVP particles 50 ]
Determination of LVP particles by particle size distribution Meter (Malvarn Co., ltd.) and determination of median diameter D of secondary particles of LVP particles 50 。
[ carbon content of LVP particles ]
The carbon content of the LVP particles was measured by TOC-5000A (manufactured by Shimadzu corporation) using a TOC total organic carbon meter.
[ lithium Nickel composite oxide particles ]
As the lithium nickel composite oxide particles, NCA particles (manufactured by JFE minerals) were used.
Example 1
97 parts by mass of graphite as a negative electrode active material, 1 part by mass of carboxymethyl cellulose (CMC) and 2 parts by mass of styrene-butadiene rubber (SBR) as a binder, and 100 parts by mass of water were added to prepare a coating liquid for a negative electrode composite material.
The negative electrode composite material was formed by applying a coating liquid to both surfaces of a copper current collector foil and then drying the same. At this time, the coating liquid for the negative electrode composite material was applied so that the mass per unit area (area density) of the negative electrode composite material in the region (one side) where the negative electrode composite material was formed became 5mg/cm 2 . Next, the negative electrode 30 is produced by punching and cutting to a predetermined size (see fig. 3). At this time, the region on the anode substrate 31 where the anode composite 32 was formed was 30mm×50mm, and the region on the anode substrate 31 where the anode composite 32 was not formed was 10mm×11mm.
7.5 parts by mass of LVP particles (1) and 85 parts by mass of NCA particles as positive electrode active materials, 1 part by mass of Ketjen black (Lion Co.) as a conductive agent, 2 parts by mass of carbon fiber (Showa electric Co.), 4 parts by mass of polyvinylidene fluoride (PVDF) as a binder, and 100 parts by mass of N-methyl-2-pyrrolidone (NMP) were added to prepare a coating liquid for a positive electrode composite material.
The coating liquid for the positive electrode composite had a viscosity of 27900 mPas at 6rpm, a viscosity of 6500 mPas at 60rpm and a TI of 4.5.
The coating liquid for the positive electrode composite material was applied to both surfaces of an aluminum current collecting foil, and then dried to form a positive electrode composite material 42. At this time, the coating liquid for the positive electrode composite material was applied so that the area density of the positive electrode composite material in the region (one side) where the positive electrode composite material was formed became 8.3mg/cm 2 . Next, the positive electrode 40 (see fig. 4) is produced by punching and cutting the positive electrode into a predetermined size. At this time, the region of the positive electrode substrate 41 where the positive electrode composite material 42 was formed was 28mm×48mm, and the region of the positive electrode substrate 41 where the positive electrode composite material 42 was not formed was 10mm×13mm
An electrode element 50 (see fig. 5) having a thickness of about 10mm was produced by laminating a negative electrode 30 and a positive electrode 40 via a polypropylene (PP) film as a separator 51. At this time, a nickel tab 52 is welded to a part of the negative electrode substrate 31 where the negative electrode composite material 32 is not formed, and an aluminum tab 53 is welded to a part of the positive electrode substrate 41 where the positive electrode composite material 42 is not formed. Fig. 5 (a) is a plan view thereof, and fig. 5 (b) is a sectional view thereof.
The electrode member 50 was immersed in a nonaqueous electrolyte solution and sealed in an aluminum laminate film to produce a lithium ion secondary battery. At this time, as the electrolyte, liPF in which 1.5M was used 6 A solution dissolved in a nonaqueous solvent. As the nonaqueous solvent, a mixed solvent in which Ethylene Carbonate (EC), dimethyl carbonate (DMC), and Ethyl Methyl Carbonate (EMC) are mixed in a volume ratio of 1:1:1 was used.
The energy density of the lithium ion secondary battery was 160.5Wh/kg, the capacity retention rate was 90%, and the output density was 4200W/kg.
Example 2
A lithium ion secondary battery was produced in the same manner as in example 1, except that the amounts of LVP particles (1) and NCA particles added were changed to 4 parts by mass and 90 parts by mass, respectively, when producing a coating liquid for a positive electrode composite material.
The viscosity of the coating liquid for the positive electrode composite material at 6rpm was 14200 mPas, the viscosity at 60rpm was 4300 mPas, and the TI was 3.3.
The energy density of the lithium ion secondary battery was 160.9Wh/kg, the capacity retention rate was 88%, and the output density was 3900W/kg.
Example 3
A lithium ion secondary battery was produced in the same manner as in example 1, except that the amounts of LVP particles (1) and NCA particles added were changed to 2 parts by mass and 92 parts by mass, respectively, when producing a coating liquid for a positive electrode composite material.
The coating liquid for the positive electrode composite had a viscosity of 9200 mPas at 6rpm, 3400 mPas at 60rpm and TI of 2.7.
The energy density of the lithium ion secondary battery was 160.9Wh/kg, the capacity retention rate was 88%, and the output density was 3720W/kg.
Example 4
The area density of the negative electrode composite material in the region (one side) where the negative electrode composite material was formed was changed to 9mg/cm 2 The area density of the positive electrode composite material in the region (single surface) where the positive electrode composite material was formed was changed to 15.5mg/cm 2 Except for this, a lithium ion secondary battery was fabricated in the same manner as in example 1.
The energy density of the lithium ion secondary battery was 191.2Wh/kg, the capacity retention rate was 89%, and the output density was 2850W/kg.
Example 5
The area density of the negative electrode composite material in the region (one side) where the negative electrode composite material was formed was changed to 9mg/cm 2 The area density of the positive electrode composite material in the region (single surface) where the positive electrode composite material was formed was changed to 15.5mg/cm 2 Except for this, a lithium ion secondary battery was fabricated in the same manner as in example 2.
The energy density of the lithium ion secondary battery was 192.0Wh/kg, the capacity retention rate was 90%, and the output density was 2650W/kg.
Example 6
The area density of the negative electrode composite material in the region (one side) where the negative electrode composite material was formed was changed to 9mg/cm 2 The area density of the positive electrode composite material in the region (single surface) where the positive electrode composite material was formed was changed to 15.5mg/cm 2 Except for this, a lithium ion secondary battery was fabricated in the same manner as in example 3.
The energy density of the lithium ion secondary battery was 192.3Wh/kg, the capacity retention rate was 88%, and the output density was 2250W/kg.
Example 7
A lithium ion secondary battery was fabricated in the same manner as in example 6, except that LVP particles (2) were used instead of LVP particles (1).
The energy density of the lithium ion secondary battery was 190.9Wh/kg, the capacity retention rate was 86%, and the output density was 2180W/kg.
Example 8
A lithium ion secondary battery was produced in the same manner as in example 6, except that the LVP particles (3) were used instead of the LVP particles (1).
The energy density of the lithium ion secondary battery was 191.8Wh/kg, the capacity retention rate was 87%, and the output density was 2232W/kg.
Example 9
A lithium ion secondary battery was produced in the same manner as in example 6, except that the LVP particles (4) were used instead of the LVP particles (1).
The energy density of the lithium ion secondary battery was 194.1Wh/kg, the capacity retention rate was 88%, and the output density was 2229W/kg.
Example 10
A lithium ion secondary battery was produced in the same manner as in example 6, except that the LVP particles (5) were used instead of the LVP particles (1).
The energy density of the lithium ion secondary battery was 189.7Wh/kg, the capacity retention rate was 86%, and the output density was 2276W/kg.
Comparative example 1
A lithium ion secondary battery was produced in the same manner as in example 1, except that the amounts of LVP particles (1) and NCA particles added were changed to 0 parts by mass and 94 parts by mass, respectively, when producing a coating liquid for a positive electrode composite material.
The viscosity of the coating liquid for the positive electrode composite material at 6rpm was 5200 mPas, the viscosity at 60rpm was 1700 mPas, and TI was 3.1.
The energy density of the lithium ion secondary battery was 161.3Wh/kg, the capacity retention rate was 86%, and the output density was 2600W/kg.
Comparative example 2
The area density of the negative electrode composite material in the region (one side) where the negative electrode composite material was formed was changed to 9mg/cm 2 The area density of the positive electrode composite material in the region (single surface) where the positive electrode composite material was formed was changed to 15.5mg/cm 2 Except for this, a lithium ion secondary battery was produced in the same manner as in comparative example 1.
The energy density of the lithium ion secondary battery was 192.6Wh/kg, the capacity retention rate was 84%, and the output density was 1750W/kg.
Comparative example 3
A lithium ion secondary battery was produced in the same manner as in example 1, except that the amounts of LVP particles (1) and NCA particles added were changed to 30 parts by mass and 64 parts by mass, respectively, when the coating liquid for the positive electrode composite material was produced.
The coating liquid for the positive electrode composite had a viscosity of 77200 mPas at 6rpm, a viscosity of 13200 mPas at 60rpm and a TI of 5.8.
The energy density of the lithium ion secondary battery was 186.5Wh/kg, the capacity retention rate was 91%, and the output density was 3080W/kg.
Comparative example 4
A lithium ion secondary battery was produced in the same manner as in example 1, except that the amounts of LVP particles (1) and NCA particles added were changed to 15 parts by mass and 79 parts by mass, respectively, when producing a coating liquid for a positive electrode composite material.
The coating liquid for the positive electrode composite had a viscosity of 43700 mPas at 6rpm, a viscosity of 8600 mPas at 60rpm and a TI of 5.1.
The energy density of the lithium ion secondary battery was 189.1Wh/kg, the capacity retention rate was 89%, and the output density was 2980W/kg.
Table 2 shows the results of evaluation of Thixotropic Index (TI) and coating unevenness of the coating liquid for the positive electrode composite material, and the results of charge/discharge test of the lithium ion secondary battery.
TABLE 2
As is clear from table 2, the lithium ion secondary batteries of examples 1 to 10 have high energy density and output density.
In contrast, the positive electrode composite materials of the lithium ion secondary batteries of comparative examples 1 and 2 do not contain LVP particles, and thus have low output density.
In the positive electrode composite materials of the lithium ion secondary batteries of comparative examples 3 and 4,
the mass ratio of LVP particles to NCA particles was 46.9 and 19.0, respectively, and TI of the coating liquid for the positive electrode composite material was increased, and coating unevenness occurred. As a result, the output densities of the lithium ion secondary batteries of comparative examples 3 and 4 were low.
Fig. 6 is a graph showing a relationship between output density and energy density of a lithium ion secondary battery.
While the preferred embodiments and the like have been described in detail, the present invention is not limited to the above embodiments, and various modifications and substitutions can be made to the above embodiments without departing from the scope of the claims.

Claims (6)

1. A positive electrode, characterized in that:
the positive electrode comprises a positive electrode composite material containing lithium vanadium phosphate particles and lithium nickel composite oxide particles;
median diameter D of primary particles of the above lithium vanadium phosphate particles 50 A carbon content of 0.8 μm or less and 3 mass% or more and 10 mass% or less;
the mass ratio of the lithium vanadium phosphate particles of the positive electrode composite material to the lithium nickel composite oxide particles is 1% to 9%.
2. The positive electrode according to claim 1, wherein the lithium vanadium phosphate is represented by the formula Li 3 V 2 (PO 4 ) 3 The compounds being represented by or by the general formula Li 3 V 2-x M x (PO 4 ) 3 The compound represented by the above general formula wherein M is at least one selected from the group consisting of Fe, co, mn, cu, zn, al, sn, B, ga, cr, ti, mg, ca, sr.
3. The positive electrode according to claim 1 or 2, wherein the lithium nickel composite oxide has the general formula LiNi x Co y M z O 2 The compound represented by the above general formula wherein M is at least one selected from the group consisting of Fe, mn, cu, zn, al, sn, B, ga, cr, V, ti, mg, ca, sr, and satisfies the formula: x+y+z=1.
4. A lithium ion secondary battery comprising the positive electrode according to any one of claims 1 to 3.
5. The lithium ion secondary battery according to claim 4, wherein the following formula is satisfied:
y＞-47.115x+11310
in the above formula, x is the energy density [ Wh/kg ], and y is the output density [ W/kg ] at a depth of charge of 50%.
6. A coating liquid for a positive electrode composite material is characterized in that:
comprising lithium vanadium phosphate particles and lithium nickel composite oxide particles;
median diameter D of primary particles of the above lithium vanadium phosphate particles 50 A carbon content of 0.8 μm or less and 3 mass% or more and 10 mass% or less;
the mass ratio of the lithium vanadium phosphate particles to the lithium nickel composite oxide particles is 1% or more and 9% or less.
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