WO2016152056A1 - 非水電解質二次電池 - Google Patents
非水電解質二次電池 Download PDFInfo
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- WO2016152056A1 WO2016152056A1 PCT/JP2016/001294 JP2016001294W WO2016152056A1 WO 2016152056 A1 WO2016152056 A1 WO 2016152056A1 JP 2016001294 W JP2016001294 W JP 2016001294W WO 2016152056 A1 WO2016152056 A1 WO 2016152056A1
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- This disclosure relates to a non-aqueous electrolyte secondary battery.
- Patent Documents 1 and 2 disclose a nonaqueous electrolyte secondary battery using a polyacrylic acid as a binder for a negative electrode mixture layer in a nonaqueous electrolyte secondary battery including a negative electrode containing a silicon-based active material. ing. Since silicon materials have a larger volume change due to charging / discharging than graphite, it has been proposed to use graphite and silicon-based active materials together in order to maintain good cycle characteristics while increasing battery capacity. ing.
- JP 2000-348730 A Japanese Patent No. 3703667
- non-aqueous electrolyte secondary batteries using a high-capacity negative electrode containing a silicon-based active material further improvement in cycle characteristics is required, and conventional techniques including those disclosed in Patent Documents 1 and 2 are still improved. There is room for. Further, in a non-aqueous electrolyte secondary battery containing a silicon-based active material, a large amount of gas is generated due to decomposition of the non-aqueous electrolyte, and it is also required to suppress the gas generation.
- a nonaqueous electrolyte secondary battery that is one embodiment of the present disclosure includes a positive electrode, a negative electrode, and a nonaqueous electrolyte.
- the negative electrode includes a negative electrode current collector and a negative electrode mixture layer formed on the current collector.
- the negative electrode composite material layer includes a negative electrode active material containing a silicon-based active material and a water-soluble polymer, and the water-soluble polymer has an acrylic acid monomer unit of 0.30 mol / 100 g or more and 0.0.
- the viscosity is 0.05 Pa ⁇ s or more and 0.70 Pa ⁇ s or less.
- a non-aqueous electrolyte secondary battery using a high-capacity negative electrode containing a silicon-based active material is excellent in cycle characteristics and has a small amount of gas generation during charge storage and the like.
- a secondary battery can be provided.
- the present inventors use the above water-soluble polymer as a binder of a negative electrode mixture layer having a high capacity negative electrode containing a silicon-based active material, thereby improving cycle characteristics and suppressing gas generation during charge storage. It was found that it was done.
- the binding property between the active material particles is greatly improved by the water-soluble polymer mixed in the negative electrode mixture layer, and the charge / discharge cycle is repeated. Even after this, a good contact state between the active material particles is maintained. Therefore, in the nonaqueous electrolyte secondary battery using the negative electrode according to the present disclosure, the active material particles isolated from the conductive path are reduced, and the cycle characteristics are improved. In addition, the amount of gas generation can be reduced by suppressing the formation of a new interface. Note that the reduction in gas generation amount also contributes to the improvement of cycle characteristics.
- the above water-soluble polymer has a polymer strength suitable as a binder for a negative electrode mixture layer using a silicon-based active material, and a good adsorptivity to active material particles. It is thought that it coats widely and uniformly.
- the binding property between the active material particles is greatly improved, the negative electrode mixture layer is hardened, the volume change due to charge / discharge is suppressed, and a good conductive path even after the charge / discharge cycle is repeated. Is maintained. Further, if the particle surface of the active material is widely and uniformly covered with the water-soluble polymer, it is considered that the side reaction between the active material and the non-aqueous electrolyte is also suppressed.
- “including a monomer unit” means “a structural unit derived from a monomer is contained in a polymer obtained using the monomer”.
- “(Meth) acrylate” refers to acrylate and / or methacrylate.
- FIG. 1 is a cross-sectional view of a nonaqueous electrolyte secondary battery 10 which is an example of an embodiment.
- the non-aqueous electrolyte secondary battery 10 includes a positive electrode 11, a negative electrode 12, and a non-aqueous electrolyte.
- a separator 13 is provided between the positive electrode 11 and the negative electrode 12.
- the nonaqueous electrolyte secondary battery 10 has a structure in which, for example, a wound electrode body 14 in which a positive electrode 11 and a negative electrode 12 are wound via a separator 13 and a nonaqueous electrolyte are housed in a battery case.
- a battery case that houses the electrode body 14 and the non-aqueous electrolyte
- examples of the battery case that houses the electrode body 14 and the non-aqueous electrolyte include a metal case such as a cylindrical shape, a square shape, a coin shape, and a button shape, and a resin case (laminated battery) formed by laminating a resin sheet. It can be illustrated.
- a battery case is constituted by a bottomed cylindrical case body 15 and a sealing body 16.
- the nonaqueous electrolyte secondary battery 10 includes insulating plates 17 and 18 disposed above and below the electrode body 14, respectively.
- the positive electrode lead 19 attached to the positive electrode 11 extends to the sealing body 16 side through the through hole of the insulating plate 17, and the negative electrode lead 20 attached to the negative electrode 12 passes through the outside of the insulating plate 18. Extending to the bottom side of the case body 15.
- the positive electrode lead 19 is connected to the lower surface of the filter 22 that is the bottom plate of the sealing body 16 by welding or the like, and the cap 26 that is the top plate of the sealing body 16 electrically connected to the filter 22 serves as the positive electrode terminal.
- the negative electrode lead 20 is connected to the bottom inner surface of the case main body 15 by welding or the like, and the case main body 15 serves as a negative electrode terminal.
- the sealing body 16 is provided with a current interruption mechanism (CID) and a gas discharge mechanism (safety valve). It is preferable to provide a gas discharge valve at the bottom of the case body 15 as well.
- the case body 15 is, for example, a bottomed cylindrical metal container.
- a gasket 27 is provided between the case main body 15 and the sealing body 16 to ensure the airtightness inside the battery case.
- the case body 15 preferably has an overhanging portion 21 that supports the sealing body 16 formed by pressing the side surface portion from the outside, for example.
- the overhang portion 21 is preferably formed in an annular shape along the circumferential direction of the case body 15, and supports the sealing body 16 on the upper surface thereof.
- the sealing body 16 has a filter 22 in which a filter opening 22 a is formed, and a valve body disposed on the filter 22.
- the valve element closes the filter opening 22a of the filter 22, and breaks when the internal pressure of the battery rises due to heat generated by an internal short circuit or the like.
- a lower valve body 23 and an upper valve body 25 are provided as valve bodies, and an insulating member 24 disposed between the lower valve body 23 and the upper valve body 25, and a cap having a cap opening 26a. 26 is further provided.
- the members constituting the sealing body 16 have, for example, a disk shape or a ring shape, and the members other than the insulating member 24 are electrically connected to each other.
- the filter 22 and the lower valve body 23 are joined to each other at the peripheral portion, and the upper valve body 25 and the cap 26 are also joined to each other at the peripheral portion.
- the lower valve body 23 and the upper valve body 25 are connected to each other at the center, and an insulating member 24 is interposed between the peripheral edges.
- the positive electrode includes a positive electrode current collector and a positive electrode mixture layer formed on the current collector.
- a positive electrode current collector a metal foil that is stable in the potential range of the positive electrode such as aluminum, a film in which the metal is disposed on the surface layer, or the like can be used.
- the positive electrode mixture layer preferably contains a conductive material and a binder (positive electrode binder) in addition to the positive electrode active material.
- a positive electrode mixture slurry containing a positive electrode active material, a conductive material, a positive electrode binder, and the like is applied onto a positive electrode current collector, the coating film is dried, and then rolled to form a positive electrode mixture layer. It can produce by forming on both surfaces.
- the positive electrode active material a lithium composite oxide containing Li and the metal element M can be exemplified.
- the metal element M is, for example, a transition metal element such as Co, Ni, or Mn, and the positive electrode active material is preferably a lithium-containing transition metal oxide.
- the lithium-containing transition metal oxide may contain a metal element M other than the transition metal.
- the metal element M include Mg, Sc, Y, Fe, Cu, Zn, Al, Cr, Pb, Sb, and B in addition to Co, Ni, and Mn. These may be used individually by 1 type, and may mix and use multiple types.
- the particle surface of the positive electrode active material may be covered with fine particles of an oxide such as aluminum oxide (Al 2 O 3 ), an inorganic compound such as a phosphoric acid compound, or a boric acid compound.
- the lithium-containing transition metal oxide may be a composite oxide in which the ratio of nickel (Ni) to the total number of moles of metal elements excluding lithium (Li) is greater than 30 mol%.
- the ratio (content) of Ni in the lithium-containing transition metal oxide is, for example, 80 mol% or more.
- the general formula Li a Co x Ni y M 1-xy O 2 (0.9 ⁇ a ⁇ 1.2, 0.01 ⁇ x ⁇ 0.2,. 8 ⁇ y ⁇ 1.0, 0 ⁇ x + y ⁇ 1, M is a metal element containing at least one selected from Mn and Al), and a composite of Ni—Co—Mn and Ni—Co—Al It is an oxide.
- the conductive material increases the electrical conductivity of the positive electrode mixture layer.
- Examples of the conductive material include carbon materials such as carbon black, acetylene black, ketjen black, and graphite. These may be used alone or in combination of two or more.
- the positive electrode binder maintains a good contact state between the positive electrode active material and the conductive material, and enhances the binding property of the active material particles and the like to the surface of the positive electrode current collector.
- the positive electrode binder include fluorine resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide resin, acrylic resin, and polyolefin resin.
- these resins and cellulose derivatives such as carboxymethyl cellulose (CMC) or a salt thereof (CMC-Na, CMC-K, CMC-NH 4 or the like, or a partially neutralized salt), polyethylene oxide (PEO) or the like may be used in combination. These may be used alone or in combination of two or more.
- FIG. 2 is a cross-sectional view of the negative electrode 12 which is an example of the embodiment.
- the negative electrode 12 includes a negative electrode current collector 33 and a negative electrode mixture layer 34 formed on the current collector.
- a metal foil that is stable in the potential range of the negative electrode 12, such as copper, a film in which the metal is disposed on the surface layer, or the like can be used.
- 2 includes a carbon-based active material 35, a silicon-based active material 36, and a specific water-soluble polymer (hereinafter referred to as “water-soluble polymer A”).
- the water-soluble polymer A is an acrylic acid monomer unit that is a repeating unit derived from an acrylic acid monomer, and a tetrafunctional (meth) that is a repeating unit derived from a tetrafunctional (meth) acrylate monomer. Each acrylate monomer unit is included in a predetermined amount (mol) per 100 g of the polymer.
- the negative electrode 12 includes, for example, a carbon-based active material 35, a silicon-based active material 36, a water-soluble polymer A (an aqueous solution of a water-soluble polymer A that is a binder composition described later), and the like on a negative electrode current collector 33. The mixture slurry can be applied and dried, and then rolled to form the anode mixture layer 34 on both sides of the current collector.
- the form in which the carbon-based active material 35 and the silicon-based active material 36 are used together as the negative electrode active material is shown, but only the silicon-based active material may be used as the negative electrode active material, or in addition, a silicon-based active material, a carbon-based active material, a metal or alloy material alloyed with lithium, a metal composite oxide, or the like may be used in combination.
- the silicon-based active material is used in combination with the carbon-based active material, the volume change of the negative electrode mixture layer 34 due to charge / discharge is easily relaxed.
- the mass ratio of the carbon-based active material 35 and the silicon-based active material 36 is preferably 95: 5 to 70:30, More preferably, it is 95: 5 to 80:20.
- the mass ratio of the carbon-based active material 35 and the silicon-based active material 36 is within the range, it is easy to achieve both higher capacity and improved cycle characteristics.
- graphite, hard carbon and the like conventionally used as a negative electrode active material can be used.
- graphite include natural graphite such as flaky graphite, massive graphite, and earthy graphite, and artificial graphite such as massive artificial graphite (MAG) and graphitized mesophase carbon microbeads (MCMB). These may be used singly or in combination of two or more for the carbon-based active material 35.
- the average particle diameter of the graphite particles is, for example, 1 to 30 ⁇ m.
- the average particle diameter of the graphite particles means a volume average particle diameter (Dv50) at which the volume integrated value is 50% in the particle size distribution measured by the laser diffraction scattering method.
- the average particle diameter of the graphite particles can be measured using, for example, LA-750 manufactured by HORIBA (the same applies to the silicon-based active material 36).
- the silicon-based active material 36 contains at least one of silicon (Si) and a silicon compound.
- the silicon-based active material 36 may be composed of only Si, but is preferably composed of silicon oxide represented by SiO x (0.5 ⁇ x ⁇ 1.5).
- As the silicon-based active material 36 one kind of silicon compound or the like may be used alone, or two or more kinds may be used in combination.
- a conductive film made of a material having higher conductivity than SiO x is preferably formed on the surface of the SiO x particles.
- the average particle diameter (Dv50) of SiO x is, for example, 1 to 15 ⁇ m, and is smaller than Dv50 of graphite particles.
- SiO x has a structure in which Si is dispersed in an amorphous SiO 2 matrix.
- TEM transmission electron microscope
- SiO x may contain lithium silicate (for example, lithium silicate represented by Li 2z SiO (2 + z) (0 ⁇ z ⁇ 2)) in the particles, and Si is dispersed in the lithium silicate phase. You may have a structure.
- the material constituting the conductive film is preferably an electrochemically stable material, and is preferably at least one selected from a carbon material, a metal, and a metal compound. Among these, it is particularly preferable to use a carbon material.
- the carbon film is formed, for example, at 0.5 to 10% by mass with respect to the mass of the SiO x particles. Examples of the method for forming the carbon film include a method in which coal tar or the like is mixed with SiO x particles and heat-treated, and a chemical vapor deposition method (CVD method) using a hydrocarbon gas or the like. Alternatively, the carbon coating may be formed by fixing carbon black, ketjen black, or the like to the surface of the SiO x particles using a binder.
- the water-soluble polymer A is attached to the surface of the negative electrode active material, maintains a good contact state between the active material particles, and enhances the binding property of the negative electrode active material and the like to the surface of the negative electrode current collector 33. It has a function. That is, the water-soluble polymer A functions as a binder (negative electrode binder).
- the water-soluble polymer A is preferably a main component of the binder, and is contained, for example, by 50% by mass or more with respect to the total mass of the binder component.
- the negative electrode binder may be composed only of the water-soluble polymer A.
- the water-soluble polymer A has an acrylic acid monomer unit of 0.30 mol / 100 g or more and 0.40 mol / 100 g or less, and a tetrafunctional (meth) acrylate monomer unit of 10 ⁇ 4 mol / 100 g or more and 10 ⁇
- the viscosity of the aqueous solution containing 3 mol / 100 g or less and the solid content concentration of the polymer is 1% by mass is 0.05 Pa ⁇ s or more and 0.70 Pa ⁇ s or less.
- water-soluble of the water-soluble polymer A means that a mixture obtained by adding 0.5 parts by mass (corresponding to a solid content) of 100 parts by mass of ion-exchanged water and stirring is used at a temperature of 23. 250 ° C. or higher and 27 ° C. or lower, and pH 7.5 or higher and 8.5 or lower (in order to adjust pH, NaOH aqueous solution and / or HCl aqueous solution is used).
- pH 7.5 or higher and 8.5 or lower in order to adjust pH, NaOH aqueous solution and / or HCl aqueous solution is used.
- Acrylic acid and its salt are mentioned as an acrylic acid monomer which comprises an acrylic acid monomer unit. One of these may be used alone, or two or more of these may be used in combination at any ratio.
- the content of the acrylic acid monomer unit in the water-soluble polymer A is 0.30 mol / 100 g or more and 0.40 mol / 100 g or less, preferably 0.32 mol / 100 g or more and 0.35 mol / 100 g or less.
- the content of the acrylic acid monomer unit in the water-soluble polymer A is less than 0.30 mol / 100 g, good cycle characteristics cannot be obtained, and when it exceeds 0.40 mol / 100 g, the storage stability is lowered. .
- the tetrafunctional (meth) acrylate monomer constituting the tetrafunctional (meth) acrylate monomer unit is a (meth) acrylate having an ethylenically unsaturated bond number (functional number) of 4, for example,
- n1, n2, n3 and n4 are integers of 2 or more and may be the same or different from each other, and ethoxylated pentaerythritol tetraacrylate represented by the formula: One of these may be used alone, or two or more of these may be used in combination at any ratio.
- the content of the tetrafunctional (meth) acrylate monomer unit in the water-soluble polymer A is 10 ⁇ 4 mol / 100 g or more and 10 ⁇ 3 mol / 100 g or less, preferably 2.0 ⁇ 10 ⁇ 4 mol / It is 100 g or more and 9.0 ⁇ 10 ⁇ 4 mol / 100 g or less.
- the content of the tetrafunctional (meth) acrylate monomer unit in the water-soluble polymer A is less than 10 ⁇ 4 mol / 100 g, good cycle characteristics cannot be obtained, and it exceeds 10 ⁇ 3 mol / 100 g. And storage stability decreases.
- the water-soluble polymer A may contain other monomer units other than the acrylic acid monomer unit and the tetrafunctional (meth) acrylate monomer unit.
- the monomer constituting the other monomer unit is not particularly limited as long as it does not inhibit the effect of the present disclosure.
- acrylate, methacrylate, 2-hydroxyethyl acrylate, styrene, vinyl acetate, glycidyl Examples include methacrylate, 2-pyridylpyridine, acrylamide, methacrylamide, dimethylacrylamide, dimethylmethacrylamide, isopropylacrylamide, acrylonitrile, methacrylonitrile, 2-acrylamide-2-methylpropanesulfonic acid, and the like. One of these may be used alone, or two or more of these may be used in combination at any ratio.
- Water-soluble polymer A has an aqueous solution viscosity of 0.05 Pa ⁇ s or more and 0.70 Pa ⁇ s or less with a solid content concentration of the polymer of 1% by mass.
- the viscosity of the aqueous solution is measured by a method described in Examples below using a rotary rheometer (Anton-Pearl, MCR30).
- the viscosity of the aqueous solution in which the solid content concentration of the water-soluble polymer A is 1% by mass is preferably 0.10 Pa ⁇ s or more and 0.65 Pa ⁇ s or less, and is 0.10 Pa ⁇ s or more and 0.60 Pa ⁇ s. The following is more preferable.
- the viscosity is less than 0.05 Pa ⁇ s, good cycle characteristics cannot be obtained, and when it exceeds 0.70 Pa ⁇ s, the water-soluble polymer A can be uniformly coated on the particle surface of the negative electrode active material. It becomes difficult, especially storage stability decreases.
- the viscosity of the aqueous solution in which the solid content concentration of the water-soluble polymer A is 1% by mass can be adjusted by a known method, for example, by changing the weight average molecular weight of the water-soluble polymer A. Specifically, the viscosity can be increased by increasing the weight average molecular weight of the water-soluble polymer, and the viscosity can be decreased by decreasing the weight average molecular weight of the water-soluble polymer.
- the water-soluble polymer A is prepared by polymerizing the monomer composition containing the monomer mentioned above in an aqueous solvent, for example.
- the content (mol / 100 g) of each monomer in all monomers in the monomer composition is usually the content (mol / 100 g) of each monomer unit in the desired water-soluble polymer.
- the polymerization mode is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be used.
- any reaction such as ionic polymerization, radical polymerization, and living radical polymerization can be used.
- known emulsifiers, polymerization initiators and the like can be used as necessary.
- polymerizing the said monomer composition in an aqueous solvent you may use the aqueous solution containing the water-soluble polymer A obtained as a negative electrode binder composition added to a negative mix slurry as it is. .
- a negative electrode mixture slurry can be prepared by mixing and stirring the negative electrode active material powder and the binder composition.
- the negative electrode binder composition that is an aqueous solution of the water-soluble polymer A contains water as a main component of the solvent.
- the solvent only water may be used, but a mixed solvent containing water and an organic solvent compatible with water can also be used.
- At least a part of the solvent of the binder composition is not particularly limited, and can be a polymerization solvent (for example, water) contained in the monomer composition used in preparing the water-soluble polymer. .
- the pH of the aqueous solution in which the solid content concentration of the water-soluble polymer A is 1% by mass is preferably 7.5 or more and 8.5 or less. When the pH is within this range, the handleability of the binder composition is improved.
- the negative electrode binder composition may contain additive components such as a thickener (excluding those corresponding to the above-mentioned water-soluble polymer A) and a leveling agent in addition to the components described above. These are not particularly limited as long as they do not affect the battery reaction, and known ones can be used. Moreover, these components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- additive components such as a thickener (excluding those corresponding to the above-mentioned water-soluble polymer A) and a leveling agent in addition to the components described above. These are not particularly limited as long as they do not affect the battery reaction, and known ones can be used. Moreover, these components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- a resin (binder component) other than the water-soluble polymer A may be used in combination with the negative electrode binder.
- the main component of the negative electrode binder is preferably the water-soluble polymer A as described above.
- the binder component used in combination with the water-soluble polymer A is not particularly limited as long as it does not inhibit the effect of the present disclosure.
- cellulose such as styrene-butadiene copolymer (SBR), carboxymethylcellulose (CMC), methylcellulose and the like.
- SBR styrene-butadiene copolymer
- CMC carboxymethylcellulose
- examples thereof include resins and polyvinyl alcohol. These may be used alone or in combination of two or more.
- the content of the water-soluble polymer A in the negative electrode mixture layer 34 is preferably 1 to 7% by mass, more preferably 2 to 6% by mass, and more preferably 3 to 5% by mass with respect to the mass of the negative electrode active material. Particularly preferred.
- the content of the water-soluble polymer A is 1 to 7% by mass, it is easy to maintain a good contact state between the active material particles even after charge and discharge, and good cycle characteristics and storage stability are easily obtained.
- the water-soluble polymer A has a good adsorptivity to the particle surface of the negative electrode active material as described above and covers the particle surface of the active material widely and uniformly. Thereby, the adhesive force of negative electrode active materials improves, and the hard negative mix layer 34 is obtained.
- the hardness of the negative electrode mixture layer 34 can be evaluated by a stiffness test of the negative electrode 12.
- the negative electrode composite layer 34 has a yield stress in a stiffness test of 100 mN or more, and preferably 130 mN or more. In consideration of the ability to drop the composite material during bending of the electrode, the yield stress is preferably 300 mN or less. The yield stress in the stiffness test is measured by the method described in Examples described later.
- the separator As the separator, a porous sheet having ion permeability and insulating properties is used. Specific examples of the porous sheet include a microporous thin film, a woven fabric, and a nonwoven fabric.
- the material of the separator polyolefin resin such as polyethylene and polypropylene, cellulose and the like are suitable.
- the separator may be a laminate having a cellulose fiber layer and a thermoplastic resin fiber layer such as a polyolefin resin.
- the multilayer separator containing a polyethylene layer and a polypropylene layer may be sufficient, and what applied the aramid resin etc. to the surface of the separator may be used.
- the thickness of the separator is, for example, 10 to 20 ⁇ m.
- a filler layer containing an inorganic filler may be formed at the interface between the separator and at least one of the positive electrode and the negative electrode.
- the inorganic filler include oxides containing at least one of Ti, Al, Si, and Mg, and phosphoric acid compounds.
- the filler layer can be formed, for example, by applying a slurry containing the filler to the surface of the positive electrode, the negative electrode, or the separator.
- the non-aqueous electrolyte includes a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
- the non-aqueous solvent for example, esters, ethers, nitriles such as acetonitrile, amides such as dimethylformamide, and a mixed solvent of two or more of these can be used.
- the non-aqueous solvent may contain a halogen-substituted product in which at least a part of hydrogen in these solvents is substituted with a halogen atom such as fluorine.
- esters examples include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate, dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC), and methyl propyl carbonate.
- Chain carbonates such as ethyl propyl carbonate and methyl isopropyl carbonate
- cyclic carboxylic acid esters such as ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL), methyl acetate, ethyl acetate, propyl acetate, methyl propionate (MP )
- chain carboxylic acid esters such as ethyl propionate.
- ethers examples include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1,4 -Cyclic ethers such as dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineol, crown ether, 1,2-dimethoxyethane, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether , Dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, benzyl ethyl ether, diphenyl ether, diphen
- a fluorinated cyclic carbonate such as fluoroethylene carbonate (FEC), a fluorinated chain carbonate, a fluorinated chain carboxylate such as methyl fluoropropionate (FMP), or the like.
- FEC fluoroethylene carbonate
- FMP fluorinated chain carboxylate
- FEC fluoroethylene carbonate
- FMP fluorinated chain carboxylate
- the electrolyte salt is preferably a lithium salt.
- the lithium salt LiBF 4, LiClO 4, LiPF 6, LiAsF 6, LiSbF 6, LiAlCl 4, LiSCN, LiCF 3 SO 3, LiCF 3 CO 2, Li (P (C 2 O 4) F 4), LiPF 6-x (C n F 2n + 1 ) x (1 ⁇ x ⁇ 6, n is 1 or 2), LiB 10 Cl 10 , LiCl, LiBr, LiI, chloroborane lithium, lower aliphatic lithium carboxylate, Li Borates such as 2 B 4 O 7 and Li (B (C 2 O 4 ) F 2 ), LiN (SO 2 CF 3 ) 2 , LiN (C 1 F 2l + 1 SO 2 ) (C m F 2m + 1 SO 2 ) and imide salts such as ⁇ 1, m is an integer of 1 or more ⁇ .
- lithium salts may be used alone or in combination of two or more.
- LiPF 6 is preferably used from the viewpoint of ion conductivity, electrochemical stability, and the like.
- concentration of the lithium salt is preferably 0.8 to 1.8 mol per liter of the nonaqueous solvent.
- a negative electrode binder composition a1 an aqueous solution containing the water-soluble polymer A1.
- the prepared negative electrode mixture slurry was applied to the surface of a 15 ⁇ m-thick copper foil as a current collector using a comma coater so that the coating amount was 8.4 to 9.0 mg / cm 2 .
- the copper foil coated with the slurry is conveyed at a rate of 300 mm / min in an oven at a temperature of 80 ° C. for 2 minutes and further in an oven at a temperature of 110 ° C. for 2 minutes, thereby forming a slurry composition on the copper foil.
- the product was dried to obtain a negative electrode raw material.
- the negative electrode raw material is pressed with a roll press so that the density becomes 1.58 to 1.62 g / cm 3, and further, under the vacuum condition, at a temperature of 105 ° C. for the purpose of removing moisture and further promoting crosslinking.
- the negative electrode was obtained by placing in the environment for 4 hours.
- the prepared positive electrode mixture slurry was applied onto a 20 ⁇ m-thick aluminum foil as a current collector using a comma coater so that the amount applied was 17.3 to 17.7 mg / cm 2 . Thereafter, the aluminum foil coated with the slurry composition was dried by conveying it in an oven at a temperature of 60 ° C. at a rate of 0.5 m / min for 2 minutes. Thereafter, heat treatment was performed at 120 ° C. for 2 minutes to obtain a positive electrode raw material.
- the positive electrode fabric is pressed with a roll press machine so that the density becomes 3.40 to 3.50 g / cm 3, and further, in order to remove the dispersion medium, it is placed in an environment with a temperature of 120 ° C. under vacuum conditions. After a while, a positive electrode was obtained.
- Lithium hexafluorophosphate LiPF 6 was added to a mixed solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 3: 7 so as to have a concentration of 1.0 mol / L. Then, 2% by volume (solvent ratio) of vinylene carbonate was further added to prepare a non-aqueous electrolyte.
- EC ethylene carbonate
- EMC ethyl methyl carbonate
- a tab was attached to each of the positive electrode and the negative electrode, and each electrode was spirally wound through a separator so that the tab was positioned on the outermost peripheral portion, thereby producing a wound electrode body.
- a single-layer polypropylene separator was used as the separator.
- the electrode body is inserted into an exterior body made of an aluminum laminate sheet and vacuum-dried at 105 ° C. for 2 hours, and then the nonaqueous electrolyte solution is injected to seal the opening of the exterior body to provide a nonaqueous electrolyte.
- a secondary battery (laminated cell) was produced. The design capacity of the battery is 800 mAh.
- Negative electrode binder compositions a2 to a5 (aqueous solutions containing water-soluble polymers A2 to A5) were prepared in the same manner as in Example 1 except that the monomers shown in Table 1 were used in the proportions shown in the table.
- a negative electrode and a battery were produced in the same manner as in Example 1 except that the negative electrode binder compositions a2 to a5 were used in place of the negative electrode binder composition a1.
- Example 6 In the preparation of the negative electrode mixture slurry, the negative electrode and the battery were treated in the same manner as in Example 3, except that the negative electrode binder composition a3 was mixed so that the amount of the water-soluble polymer A3 added to the negative electrode active material was 1% by mass. Was made.
- Example 7 In the preparation of the negative electrode mixture slurry, the negative electrode and the battery were treated in the same manner as in Example 3 except that the negative electrode binder composition a3 was mixed so that the amount of the water-soluble polymer A3 added to the negative electrode active material was 5% by mass. Was made.
- Example 8 A negative electrode and a battery were produced in the same manner as in Example 3 except that a mixture of artificial graphite and SiO x having a mixing ratio of 95: 5 was used as the negative electrode active material.
- Example 9 A negative electrode and a battery were produced in the same manner as in Example 3 except that a mixture of artificial graphite and SiO x having a mixing ratio of 70:30 was used as the negative electrode active material.
- Example 10 As the positive electrode active material, nickel cobalt lithium aluminate (LiNi 0.89 Co 0.08 Al 0.03 O 2 : NCA) is used instead of LCO, and a styrene butadiene copolymer (SBR) is added in the preparation of the negative electrode mixture slurry.
- SBR styrene butadiene copolymer
- Negative electrode binder compositions b1 and b2 were prepared in the same manner as in Example 1 except that the monomers shown in Table 1 were used in the proportions shown in the table.
- a negative electrode and a battery were produced in the same manner as in Example 1 except that the negative electrode binder compositions b1 and b2 were used instead of the negative electrode binder composition a1.
- polyethylene glycol diacrylate (PEGDA, manufactured by Kyoeisha Chemical Co., Ltd., Light Acrylate 9EG-A), which is a bifunctional (meth) acrylate monomer was used in the preparation of the negative electrode binder composition b2.
- ⁇ Comparative example 4> As the positive electrode active material, nickel cobalt lithium aluminate (LiNi 0.89 Co 0.08 Al 0.03 O 2 : NCA) is used instead of LCO, and a styrene butadiene copolymer (SBR) is added in the preparation of the negative electrode mixture slurry.
- SBR styrene butadiene copolymer
- a negative electrode and a battery were produced in the same manner as in Comparative Example 3, except that a graphite / SiO x mixing ratio changed to 80:20 was used as the negative electrode active material.
- the evaluation results are shown in Tables 1 and 2.
- the batteries of Examples 1 to 5 had a higher capacity retention rate after 40 cycles than the batteries of Comparative Examples 1 and 3, and were excellent in cycle characteristics. Furthermore, all of the batteries of Examples 1 to 5 had a smaller amount of gas generation during charge storage (high temperature storage) than the batteries of Comparative Examples 2 and 3, and were excellent in storage stability.
- the battery of Comparative Example 1 has good storage stability but poor cycle characteristics
- the battery of Comparative Example 2 has good cycle characteristics but poor storage stability.
- the battery of Comparative Example 3 using polyacrylic acid as the negative electrode binder had poor cycle characteristics and storage stability. That is, the batteries of Examples 1 to 5 have both excellent cycle characteristics and storage stability.
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Abstract
Description
実施形態の説明で参照する図面は、模式的に記載されたものであり、図面に描画された構成要素の寸法比率などは、現物と異なる場合がある。具体的な寸法比率等は、以下の説明を参酌して判断されるべきである。
非水電解質二次電池10は、正極11と、負極12と、非水電解質とを備える。正極11と負極12との間には、セパレータ13が設けられる。非水電解質二次電池10は、例えば正極11及び負極12がセパレータ13を介して巻回されてなる巻回型の電極体14と、非水電解質とが電池ケースに収容された構造を有する。巻回型の電極体14の代わりに、正極及び負極がセパレータを介して交互に積層されてなる積層型電極体など、他の形態の電極体が適用されてもよい。電極体14及び非水電解質を収容する電池ケースとしては、円筒形、角形、コイン形、ボタン形等の金属製ケース、樹脂シートをラミネートして形成された樹脂製ケース(ラミネート型電池)などが例示できる。図1に示す例では、有底円筒形状のケース本体15と封口体16とにより電池ケースが構成されている。
正極は、正極集電体と、当該集電体上に形成された正極合材層とを備える。正極集電体には、アルミニウムなどの正極の電位範囲で安定な金属の箔、当該金属を表層に配置したフィルム等を用いることができる。正極合材層は、正極活物質の他に、導電材及びバインダー(正極バインダー)を含むことが好適である。正極は、例えば正極集電体上に正極活物質、導電材、及び正極バインダー等を含む正極合材スラリーを塗布し、塗膜を乾燥させた後、圧延して正極合材層を集電体の両面に形成することにより作製できる。
図2は、実施形態の一例である負極12の断面図である。
負極12は、負極集電体33と、当該集電体上に形成された負極合材層34とを備える。負極集電体33には、銅などの負極12の電位範囲で安定な金属の箔、当該金属を表層に配置したフィルム等を用いることができる。図2に例示する負極合材層34は、炭素系活物質35と、シリコン系活物質36と、特定の水溶性重合体(以下、「水溶性重合体A」という)とを含む。水溶性重合体Aは、アクリル酸単量体に由来する繰り返し単位であるアクリル酸単量体単位、及び4官能性(メタ)アクリレート単量体に由来する繰り返し単位である4官能性(メタ)アクリレート単量体単位を、それぞれ当該重合体100g当たり所定の物質量(mol)で含む。負極12は、例えば負極集電体33上に炭素系活物質35、シリコン系活物質36、及び水溶性重合体A(後述のバインダー組成物である水溶性重合体Aの水溶液)等を含む負極合材スラリーを塗布し、塗膜を乾燥させた後、圧延して負極合材層34を集電体の両面に形成することにより作製できる。
水溶性重合体Aは、負極活物質の表面に付着しており、活物質粒子同士の良好な接触状態を維持し、且つ負極集電体33の表面に対する負極活物質等の結着性を高める機能を有する。即ち、水溶性重合体Aはバインダー(負極バインダー)として機能する。水溶性重合体Aは、バインダーの主成分であることが好ましく、例えばバインダー成分の総質量に対して50質量%以上含まれる。負極バインダーは、水溶性重合体Aのみで構成されていてもよい。
アクリル酸単量体単位を構成するアクリル酸単量体としては、アクリル酸及びその塩が挙げられる。これらは1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。水溶性重合体Aにおけるアクリル酸単量体単位の含有量は、0.30mol/100g以上0.40mol/100g以下であり、好ましくは0.32mol/100g以上0.35mol/100g以下である。水溶性重合体A中のアクリル酸単量体単位の含有量が0.30mol/100g未満であると、良好なサイクル特性が得られず、0.40mol/100gを超えると保存安定性が低下する。
4官能性(メタ)アクリレート単量体単位を構成する4官能性(メタ)アクリレート単量体は、エチレン性不飽和結合の数(官能数)が4である(メタ)アクリレートであり、例えば、下記一般式(I):
水溶性重合体Aは、アクリル酸単量体単位及び4官能性(メタ)アクリレート単量体単位以外の他の単量体単位を含有していてもよい。当該他の単量体単位を構成する単量体としては、本開示の効果を阻害するものでなければ特に限定されず、例えばアクリレート、メタクリレート、アクリル酸2-ヒドロキシエチル、スチレン、酢酸ビニル、グリシジルメタクリレート、2-ピリジルピリジン、並びにアクリルアミド 、メタアクリルアミド、ジメチルアクリルアミド、ジメチルメタクリルアミド、イソプロピルアクリルアミド、アクリロニトリル、メタアクリロニトリル、2-アクリルアミドー2-2メチルプロパンスルホン酸等が挙げられる。これらは1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
水溶性重合体Aの調製方法は特に限定されないが、水溶性重合体Aは、例えば上述した単量体を含む単量体組成物を水系溶媒中で重合することにより調製される。なお、単量体組成物における全単量体中の各単量体の含有量(mol/100g)は、通常、所望の水溶性重合体における各単量体単位の含有量(mol/100g)と同様にする。重合様式は、特に制限なく、溶液重合法、懸濁重合法、塊状重合法、乳化重合法などのいずれの方法も用いることができる。重合反応としては、イオン重合、ラジカル重合、リビングラジカル重合などいずれの反応も用いることができる。重合に際しては、必要に応じて既知の乳化剤、重合開始剤等を使用することができる。なお、上記単量体組成物の重合を水系溶媒中で行う場合は、得られる水溶性重合体Aを含む水溶液を、そのまま負極合材スラリーに添加される負極バインダー組成物として使用してもよい。負極活物質粉末及び当該バインダー組成物を混合、攪拌して負極合材スラリーを調製することができる。
セパレータには、イオン透過性及び絶縁性を有する多孔性シートが用いられる。多孔性シートの具体例としては、微多孔薄膜、織布、不織布等が挙げられる。セパレータの材質としては、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂、セルロースなどが好適である。セパレータは、セルロース繊維層及びポリオレフィン樹脂等の熱可塑性樹脂繊維層を有する積層体であってもよい。また、ポリエチレン層及びポリプロピレン層を含む多層セパレータであってもよく、セパレータの表面にアラミド系樹脂等が塗布されたものを用いてもよい。セパレータの厚みは、例えば10~20μmである。
非水電解質は、非水溶媒と、非水溶媒に溶解した電解質塩とを含む。非水溶媒には、例えばエステル類、エーテル類、アセトニトリル等のニトリル類、ジメチルホルムアミド等のアミド類、及びこれらの2種以上の混合溶媒等を用いることができる。非水溶媒は、これら溶媒の水素の少なくとも一部をフッ素等のハロゲン原子で置換したハロゲン置換体を含有していてもよい。
[負極バインダー組成物a1の調製]
セプタム付き1Lフラスコに、イオン交換水1500gを投入して、温度40℃に加熱し、流量100mL/分の窒素ガスでフラスコ内を置換した。次に、イオン交換水10gと、アクリル酸23.51g(全単量体100部当たり25部、0.326mol/100g)と、エトキシ化ペンタエリスリトールテトラアクリレート(EPETA、新中村化学(株)製、ATM-35E、n1+n2+n3+n4=35の化合物(I)に相当、官能数=4)1.69g(全単量体100部当たり1.69部、8.92×10-4mol/100g)と、アクリルアミド70.1g(全単量体100部当たり70.1部)と、メチルアクリレート 4.7g(全単量体100部当たり4.7部)とを混合して、シリンジでフラスコ内に注入した。その後、重合開始剤として過硫酸カリウムの2.5%水溶液8.0gをシリンジでフラスコ内に追加した。その15分後、重合促進剤としてテトラメチルエチレンジアミンの2.0%水溶液40gをシリンジで追加した。最初の過硫酸カリウムを添加してから4時間後に、再び過硫酸カリウムの2.5%水溶液4.0gをフラスコ内に追加し、さらにテトラメチルエチレンジアミンの2.0%水溶液20gを追加して、温度を80℃に昇温し、重合反応を進めた。3時間後、フラスコを空気中に開放して重合反応を停止させ、生成物を温度80℃で脱臭し、残留モノマーを除去した。その後、水酸化リチウムの10%水溶液を用いて生成物のpHを8に調整して、負極バインダー組成物a1(水溶性重合体A1を含む水溶液)を得た。
プラネタリーミキサーに、人造黒鉛(理論容量:360mAh/g)90質量部と、炭素被膜を有するSiOx(x=0.97、理論容量:2300mAh/g)10質量部と、負極バインダー組成物a1(固形分濃度:4.5%)を固形分相当で3.0質量部とを投入し、さらにイオン交換水にて固形分濃度が60%となるように希釈した。その後、回転速度40rpmで60分混練して、ペースト状のスラリーを得た。さらに、粘度が1100±100mPa・s(B型粘度計、測定条件は後述の「固形分1質量%粘度」と同様)となるようにイオン交換水80質量部を加え、負極合材スラリー(固形分濃度は45質量%)を調製した。
調製した負極合材スラリーをコンマコーターを用いて、集電体である厚さ15μmの銅箔の表面に、塗付量が8.4~9.0mg/cm2となるように塗布した。当該スラリーが塗布された銅箔を、300mm/分の速度で、温度80℃のオーブン内を2分間、さらに温度110℃のオーブン内を2分間かけて搬送することにより、銅箔上のスラリー組成物を乾燥させ、負極原反を得た。当該負極原反をロールプレス機にて密度が1.58~1.62g/cm3となるようプレスし、さらに、水分の除去及び架橋のさらなる促進を目
的として、真空条件下、温度105℃の環境に4時間置き、負極を得た。
プラネタリーミキサーに、コバルト酸リチウム(LiCoO2:LCO)100質量部、アセチレンブラック2質量部(電気化学工業社製、HS-100)、ポリフッ化ビニリデン(PVDF、クレハ化学社製、KF-1100)2質量部を添加し、さらに、分散媒として2-メチルピリロドンを全固形分濃度が67%となるように加えて混合し、正極合材スラリーを調製した。調製した正極合材スラリーをコンマコーターを用いて、集電体である厚さ20μmのアルミニウム箔の上に、塗布量が17.3~17.7mg/cm2となるように塗布した。その後、当該スラリー組成物が塗布されたアルミ箔を、0.5m/分の速度で温度60℃のオーブン内を2分間かけて搬送することにより、乾燥させた。その後、温度120℃にて2分間加熱処理して、正極原反を得た。当該正極原反をロールプレス機にて密度が3.40~3.50g/cm3となるようにプレスし、さらに、分散媒の除去を目的として、真空条件下、温度120℃の環境に3時間置き、正極を得た。
エチレンカーボネート(EC)とエチルメチルカーボネート(EMC)とを、3:7の体積比で混合した混合溶媒に、1.0mol/Lの濃度となるように六フッ化リン酸リチウム(LiPF6)を添加し、さらに2体積%(溶媒比)のビニレンカーボネートを添加して非水電解液を調製した。
上記正極及び上記負極にタブをそれぞれ取り付け、タブが最外周部に位置するようにセパレータを介して各電極を渦巻き状に巻回して巻回型の電極体を作製した。セパレータには、単層のポリプロピレン製セパレータを用いた。当該電極体をアルミニウムラミネートシートで構成される外装体に挿入して、105℃で2時間真空乾燥した後、上記非水電解液を注入し、外装体の開口部を封止して非水電解質二次電池(ラミネートセル)を作製した。電池の設計容量は800mAhである。
表1に示す単量体を当該表に示す割合で使用した以外は、実施例1と同様にして負極バインダー組成物a2~a5(水溶性重合体A2~A5を含む水溶液)を調製した。負極バインダー組成物a1の代わりに、負極バインダー組成物a2~a5をそれぞれ用いたこと以外は、実施例1と同様にして負極及び電池を作製した。
負極合材スラリーの調製において、負極活物質に対する水溶性重合体A3の添加量が1質量%となるように負極バインダー組成物a3を混合したこと以外は、実施例3と同様にして負極及び電池を作製した。
負極合材スラリーの調製において、負極活物質に対する水溶性重合体A3の添加量が5質量%となるように負極バインダー組成物a3を混合したこと以外は、実施例3と同様にして負極及び電池を作製した。
人造黒鉛とSiOxとの混合比を95:5に変更したものを負極活物質として用いたこと以外は、実施例3と同様にして負極及び電池を作製した。
人造黒鉛とSiOxとの混合比を70:30に変更したものを負極活物質として用いたこと以外は、実施例3と同様にして負極及び電池を作製した。
正極活物質として、LCOの代わりにニッケルコバルトアルミン酸リチウム(LiNi0.89Co0.08Al0.03O2:NCA)を用い、負極合材スラリーの調製において、スチレンブタジエン共重合体(SBR)を添加し、人造黒鉛とSiOxとの混合比を80:20に変更したものを負極活物質として用いたこと以外は、実施例3と同様にして負極及び電池を作製した。
表1に示す単量体を当該表に示す割合で使用した以外は、実施例1と同様にして負極バインダー組成物b1,b2を調製した。負極バインダー組成物a1の代わりに、負極バインダー組成物b1,b2をそれぞれ用いたこと以外は、実施例1と同様にして負極及び電池を作製した。なお、比較例2では、負極バインダー組成物b2の調製において、2官能性(メタ)アクリレート単量体であるポリエチレングリコールジアクリレート(PEGDA、共栄社化学社製、ライトアクリレート9EG-A)を使用した。
負極バインダー組成物として、ポリアクリル酸の水溶液(アルドリッチ社製、重量平均分子量=45万、1質量%水溶液をNaOH(和光純薬、特級試薬)でpH=8に調整したもの)を使用したこと以外は、実施例1と同様にして負極及び電池を作製した。
正極活物質として、LCOの代わりにニッケルコバルトアルミン酸リチウム(LiNi0.89Co0.08Al0.03O2:NCA)を用い、負極合材スラリーの調製において、スチレンブタジエン共重合体(SBR)を添加し、人造黒鉛とSiOxとの混合比を80:20に変更したものを負極活物質として用いたこと以外は、比較例3と同様にして負極及び電池を作製した。
各負極バインダー組成物に水を添加して固形分濃度を1質量%に調整し、測定用試料を得た。この測定用試料の粘度を、回転型レオメーターMCR30(アントンパール社製)を用いて、温度25℃、せん断速度40(1/s)の条件で測定した。
(1)負極の負極合材層が形成された部分を5cmの長さに切断して試験用極板片を作製し、この両端を2cm幅のガラス板の側面に張り合わせて直径2cmのアーチ体とする。(2)上下方向に移動する上板と、固定具を有する下板の間に上記試験用極板片のアーチ体を配置する。(3)上板を20mm/分の速度で下方に移動させて上記アーチ体の外周面を押圧する。このとき、上記アーチ体に発生する応力を測定し、その応力が急峻に低下する変曲点を求める。この変曲点が確認された時点における応力を計測する。当該応力が降伏応力である。
電解液注液後、温度25℃で5時間静置した電池を用いて、温度25℃、0.2Cの定電流法にて、電池電圧3.65Vまで充電し、その後、温度60℃で12時間エージング処理を行った。そして、温度25℃、0.2Cの定電流法にて、電池電圧2.75Vまで放電した。その後、0.2Cの定電流法にて、CC-CV充電(上限電池電圧4.30V)を行い、0.2Cの定電流法にて電池電圧3.00VまでCC放電を行なった。次に、電池の体積(V0)をアルキメデス法によって算出した。その後、温度25℃、0.2Cの定電流法にて電池電圧4.40Vまで充電し、温度80±2℃の条件下で3日間放置したのち、温度25℃、0.2Cの定電流法にて電池電圧3.00Vまで放電した。その後、電池の体積(V1)を測定し、ガス発生量ΔV(mL)=V1(mL)-V0(mL)で示されるガス発生量を求めた。ガス発生量が少ないほど、保存安定性(充電・高温保存時における安定性)に優れていることを示す。
電解液注液後、温度25℃で5時間静置した電池を用いて、温度25℃、0.2Cの定電流法にて、電池電圧3.65Vまで充電し、その後、温度60℃で12時間エージング処理を行った。そして、温度25℃、0.2Cの定電流法にて、電池電圧3.00Vまで放電した。その後、0.2Cの定電流法にて、CC-CV充電(上限電池電圧4.30V)を行い、0.2Cの定電流法にて3.00VまでCC放電を行なった。その後、温度25℃の環境下、電池電圧4.30-3.00V、1.0Cの充放電レートにて充放電の操作を40サイクル行った。そして、1サイクル目の容量、即ち初期放電容量X1、及び40サイクル目の放電容量X2を測定し、ΔC´=(X2/X1)×100(%)で示される容量維持率を求めた。
Claims (7)
- 正極と、負極と、非水電解質とを備える非水電解質二次電池であって、
前記負極は、負極集電体と、当該集電体上に形成された負極合材層とを備え、
前記負極合材層は、シリコン系活物質を含む負極活物質と、水溶性重合体とを含み、
前記水溶性重合体は、アクリル酸単量体単位を0.30mol/100g以上0.40mol/100g以下、及び4官能性(メタ)アクリレート単量体単位を10-4mol/100g以上10-3mol/100g以下含み、且つ当該重合体の固形分濃度を1質量%とした水溶液の粘度が0.05Pa・s以上0.70Pa・s以下である、非水電解質二次電池。 - 前記負極活物質は、炭素系活物質をさらに含む、請求項1に記載の非水電解質二次電池。
- 前記炭素系活物質と前記シリコン系活物質との質量比は、95:5~70:30である、請求項2に記載の非水電解質二次電池。
- 前記水溶性重合体は、前記4官能性(メタ)アクリレート単量体単位を2.0×10-4mol/100g以上9.0×10-4mol/100g以下含む、請求項1~3のいずれか1項に記載の非水電解質二次電池。
- 前記水溶性重合体は、前記アクリル酸単量体単位を0.32mol/100g以上0.35mol/100g以下含む、請求項1~4のいずれか1項に記載の非水電解質二次電池。
- 前記水溶性重合体の固形分濃度を1質量%とした水溶液の粘度が、0.10Pa・s以上0.65Pa・s以下である、請求項1~5のいずれか1項に記載の非水電解質二次電池。
- 前記水溶性重合体の含有量は、前記負極活物質の質量に対して1~7質量%である、請求項1~6のいずれか1項に記載の非水電解質二次電池。
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CN110114913A (zh) * | 2016-12-20 | 2019-08-09 | 日产自动车株式会社 | 锂离子电池用负极 |
CN110114913B (zh) * | 2016-12-20 | 2021-02-26 | 日产自动车株式会社 | 锂离子电池用负极 |
CN110506350A (zh) * | 2017-04-06 | 2019-11-26 | 株式会社Lg化学 | 二次电池用负极及其制造方法 |
CN110506350B (zh) * | 2017-04-06 | 2023-02-21 | 株式会社Lg新能源 | 二次电池用负极及其制造方法 |
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WO2019167730A1 (ja) * | 2018-02-27 | 2019-09-06 | 日本ゼオン株式会社 | リチウムイオン二次電池用スラリー組成物およびリチウムイオン二次電池用電極 |
JPWO2019167730A1 (ja) * | 2018-02-27 | 2021-02-04 | 日本ゼオン株式会社 | リチウムイオン二次電池用スラリー組成物およびリチウムイオン二次電池用電極 |
JP7298592B2 (ja) | 2018-02-27 | 2023-06-27 | 日本ゼオン株式会社 | リチウムイオン二次電池用スラリー組成物およびリチウムイオン二次電池用電極 |
WO2022107633A1 (ja) * | 2020-11-20 | 2022-05-27 | 日本スピンドル製造株式会社 | 負極用スラリーの製造方法及び負極用スラリー |
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US10483525B2 (en) | 2019-11-19 |
CN107431183B (zh) | 2021-04-20 |
CN107431183A (zh) | 2017-12-01 |
JP6746561B2 (ja) | 2020-08-26 |
US20180062160A1 (en) | 2018-03-01 |
JPWO2016152056A1 (ja) | 2018-01-11 |
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