Patent Application
20220119571
The present invention relates to a composition, a slurry for a positive electrode, and a battery.
In recent years, a secondary battery has been used as a power source for electronic devices such as notebook computers, mobile phones. Moreover, the development of hybrid vehicles and electric vehicles using secondary batteries is promoted to reduce the environmental load. Secondary batteries having high energy density, high voltage, and high durability are required for their power sources. Lithium ion secondary batteries are attracting attention as secondary batteries that can achieve high voltage and high energy density.
A lithium ion secondary battery is composed of a positive electrode, a negative electrode, an electrolyte, and a separator. The positive electrode is composed of a positive electrode active material, a conductive auxiliary agent, a metal foil, and a binder (Patent Literatures 1 to 3).
As a binder for positive electrode for a lithium ion secondary battery, a binder (a graft copolymer), having high binding properties and oxidation resistance and mainly composed of polyvinyl alcohol and polyacrylonitrile is disclosed (Patent Literature 4).
However, when a binder (a graft copolymer) mainly containing polyvinyl alcohol and polyacrylonitrile is used, it has been required that the viscosity of the slurry is low and stable in the production of the electrode. Further, it has been required to solve such a problem of viscosity and to improve the characteristics as a secondary battery.
The present invention was made in consideration of such problems and provides a composition for a positive electrode capable of producing a slurry excellent in stability. The present invention also provides a composition for a positive electrode capable of producing a low viscosity slurry. Further, the present invention provides a composition for a positive electrode capable of producing a positive electrode excellent in rate characteristics.
According to the invention, a composition comprising a graft copolymer, wherein
the graft copolymer has a stem polymer and a plurality of branch polymers,
the stem polymer has a polyvinyl alcohol structure,
each of a first monomer unit and a second monomer unit is included in at least one of the plurality of branch polymers,
the first monomer unit is a (meth) acrylonitrile monomer unit and/or a (meth)acrylic acid monomer unit, and
the second monomer unit has an ether structure is provided.
The inventors have made intensive studies and found that when a composition containing a graft copolymer having a structure in which a first monomer unit, which is a (meth) acrylonitrile monomer unit and/or (meth) acrylic acid monomer unit, and a second monomer unit having an ether structure are graft-copolymerized to a stem polymer having a polyvinyl alcohol structure is used as a composition for a positive electrode, the stability of the slurry is improved, completing the present invention.
The following are examples of various embodiments of the present invention. The embodiments shown below can be combined with each other.
Preferably, the composition further comprises a free polymer,
the free polymer does not have a covalent bond with the graft copolymer, and
the free polymer contains at least one of a polymer having the polyvinyl alcohol structure and a polymer having the first monomer unit and/or the second monomer unit.
Preferably, when a content of the polyvinyl alcohol structure in the composition is CPVA% by mass and a total content of the first monomer unit and the second monomer unit in the composition is CM% by mass, a ratio of the content of the polyvinyl alcohol structure to the total content of the first monomer unit and the second monomer unit (CPVA/(CM+CPVA)) is 0.05 to 0.7.
Preferably, when a content of the first monomer unit is PM1 mol %, and a content of the second monomer unit is PM2 mol %, a ratio of the first monomer unit and the second monomer unit contained in the composition (PM1/(PM2+PM1)) is 0.1 to 0.9.
Preferably, at least one of the plurality of branch polymers has a copolymerization structure of the first monomer unit and the second monomer unit.
Preferably, the second monomer unit has a structure derived from at least one monomer selected from the group consisting of a (meth) acrylic acid ester derivative, a styrene derivative, a polysubstituted ethylene, and a vinyl ether derivative.
Preferably, the ether structure has at least one selected from the group consisting of a linear polyether structure, a branched polyether structure, and an annular ether structure.
Preferably, the ether structure has a polyethylene oxide structure, and
when a content of the polyethylene oxide structure in the composition is CPEO% by mass, and a total content of the first monomer unit and the second monomer unit in the composition is CM% by mass, a ratio of the content of the polyethylene oxide structure to the total content of the first monomer unit and the second monomer unit (CPEO/(CM+CPEO)) is 0.05 to 0.4.
Preferably, an average polymerization degree of the polyvinyl alcohol structure in the composition is 300 to 4000.
Preferably, a saponification degree of the polyvinyl alcohol structure in the composition is 60 to 100 mol %.
Preferably, a graft ratio of the graft copolymer is 40 to 3000%.
According to another aspect of the present invention, a slurry for a positive electrode containing the composition, a positive electrode active material, and a conductive auxiliary agent is provided.
Preferably, a solid content of the composition is 0.1 to 20% by mass with respect to a total solid content in the slurry for the positive electrode.
Preferably, the positive electrode active material contains at least one selected from the group consisting of: LiNiXMn(2-X)O4 (0<X<2); Li(CoXNiYMnZ)O2 (0<X<1, 0<Y<1, 0<Z<1, and X+Y+Z=1); and Li(NiXCoYAlZ)O2 (0<X<1, 0<Y<1, 0<Z<1, and X+Y+Z=1).
Preferably, the conductive auxiliary agent is at least one selected from the group consisting of (i) fibrous carbon, (ii) carbon black, and (iii) a carbon composite in which fibrous carbon and carbon black are interconnected.
Preferably, a positive electrode comprising a metal foil and a coating film of the slurry for the positive electrode formed on the metal foil.
A battery comprising the positive electrode.
According to another aspect of the present invention, a positive electrode comprising a metal foil and a coating film of the slurry for the positive electrode formed on the metal foil is provided.
According to another aspect of the present invention, a battery comprising the positive electrode.
The present invention provides a slurry having excellent stability and a composition for a positive electrode capable of producing a battery having excellent rate characteristics.
The following is an explanation of the embodiments of the present invention. The various features shown in the following embodiments can be combined with each other. In addition, the invention is independently established for each property.
A composition according to one embodiment of the present invention is a composition containing a graft copolymer, wherein the graft copolymer is a composition having a stem polymer and a plurality of branch polymers. A polymer is hereinafter also referred to as a copolymer.
The graft copolymer of one embodiment of the invention is synthesized by graft-copolymerizing a first monomer and a second monomer to the stem polymer. The branch polymer produced by the graft-polymerization is grafted to the stem polymer, that is, covalently bonded to the stem polymer. In this process, the ungrafted stem polymer and the polymer containing the first monomer and/or the second monomer which is not grafted to the stem polymer, that is, which is not covalently bound to the graft copolymer, may be simultaneously generated as a free polymer. Thus, the composition of one embodiment of the present invention preferably consists substantially of the graft copolymer and the free polymer. In addition, monomers other than the first monomer and the second monomer may be polymerized as long as the effect of the present invention is not impaired.
The graft ratio of the graft copolymer is preferably 40 to 3000%, and more preferably 300 to 1500%. From the viewpoint of solubility, the graft ratio is preferably within the above range. When the graft ratio is 40% or higher, the solubility in NMP is improved. When the graft ratio is 3000% or lower, the viscosity of the NMP solution is reduced and the fluidity of the NMP solution is improved.
The stem polymer has a polyvinyl alcohol structure. Here, the polyvinyl alcohol structure is derived from polyvinyl alcohol, for example, which is synthesized by polymerizing a vinyl acetate monomer to obtain polyvinyl acetate and saponifying the polyvinyl acetate. Preferably, the stem polymer is composed mainly of the polyvinyl alcohol structure. More preferably, the stem polymer is polyvinyl alcohol.
The average polymerization degree of the polyvinyl alcohol structure in the composition is preferably 300 to 4000, and more preferably 500 to 2000. When the average polymerization degree is in the above range, the stability of the slurry is particularly high. It is also preferable to be in the above range in terms of solubility, binding properties, and viscosity of the binder. When the average polymerization degree is 300 or higher, the bonding between the binder, and the active material and conductive auxiliary agent is improved, and durability is enhanced. When the average polymerization degree is 4000 or less, solubility is improved and viscosity is reduced, making it easier to manufacture the slurry for the positive electrode. The average polymerization degree here is the value measured by the method according to JIS K 6726.
The saponification degree of the polyvinyl alcohol structure in the composition is preferably 60 to 100 mol %, and more preferably 90 to 100 mol %. When the saponification degree is in the above range, the stability of the slurry is particularly high. The saponification degree here is the value measured by the method according to JIS K 6726.
Each of the first monomer unit and the second monomer unit is contained in at least one of the plurality of branch polymers. That is, only one of the first monomer unit and the second monomer unit may be included in one of the plurality of branch polymers, and both of the first monomer unit and the second monomer unit may be included in one of the plurality of branch polymers. Further, a monomer unit other than the first monomer unit and the second monomer unit may be contained as long as the effect of the present invention is not impaired. Here, the first monomer unit and the second monomer unit are monomer units derived from the first monomer and the second monomer used in the synthesis of the graft copolymer, respectively. Preferably, at least one of the plurality of branch polymers has a copolymerization structure of the first monomer unit and the second monomer unit. The branched polymer is preferably a copolymer substantially consisting of the first monomer unit and the second monomer unit, and more preferably a copolymer consisting of the first monomer unit and the second monomer unit.
The composition for the positive electrode according to one embodiment of the present invention may further contain a free polymer. The free polymer is at least one selected from a polymer having a polyvinyl alcohol structure and a polymer having the first monomer unit and/or the second monomer unit. The polymer having a polyvinyl alcohol structure mainly means the stem polymer which was not involved in the graft-copolymerization. The polymer having the first monomer unit and/or the second monomer unit means a homopolymer of the first monomer, a homopolymer of the second monomer, a copolymer containing the first monomer and the second monomer, and the like, which is not copolymerized to the graft copolymer (i.e., the stem polymer). In addition, as long as the effect of the present invention is not impaired, a homopolymer of a monomer other than the first monomer and the second monomer and a copolymer of the monomer other than the first monomer and the second monomer, the first monomer, and the second monomer may be included. The free polymer is preferably a copolymer consisting substantially of the first monomer and the second monomer, and even more preferably a copolymer consisting of the first monomer and the second monomer.
In addition, a weight average molecular weight of the free polymer other than the stem polymer, such as a homopolymer of the first monomer, a homopolymer of the second monomer, and a copolymer containing the first monomer and the second monomer is preferably 30,000 to 300,000, more preferably 40000 to 200,000, and more preferably 50000 to 150000. From the viewpoint of suppressing the increase in viscosity and easily producing the slurry for positive electrodes, the weight average molecular weight of the free polymer other than the stem polymer is preferably 300,000 or less, more preferably 200,000 or less, and still more preferably 1500,00 or less. The weight average molecular weight of the free polymer other than the stem polymer can be determined by GPC (gel permeation chromatography).
The first monomer unit is a (meth) acrylonitrile monomer unit and/or a (meth) acrylic acid monomer unit. The first monomer unit is preferably a (meth) acrylonitrile monomer unit and is more preferably an acrylonitrile monomer unit.
That is, the first monomer used to synthesize the graft copolymer is preferably (meth) acrylonitrile and/or (meth) acrylic acid, more preferably (meth) acrylonitrile, and still more preferably acrylonitrile. Thus, the first monomer unit has a structure derived from these.
The second monomer unit has an ether structure. The ether structure preferably has at least one selected from the group consisting of a linear polyether structure, a branched polyether structure, and a cyclic ether structure. More preferably, the ether structure has a polyethylene oxide structure.
Further, the second monomer unit preferably has a structure derived from a monomer which is a (meth) acrylic acid ester derivative, a styrene derivative, a polysubstituted ethylene, or a vinyl ether derivative.
That is, a second monomer used in synthesizing the graft polymer is a monomer having an ether structure, preferably a (meth) acrylic acid ester derivative, a styrene derivative, a polysubstituted ethylene derivative a vinyl ether derivative, or the like, each of which has an ether structure.
Among these, a (meth) acrylic acid ester derivative having an ether structure is preferable. Among the (meth) acrylic acid ester derivatives having an ether structure, the (meth) acrylic acid ester derivative represented by the following general formula A is preferable.
In the general formula (A), Y is preferably -(AO)n-R. AO is an oxyalkylene group. The number of carbon atoms of the oxyalkylene group is preferably 1 to 18, and more preferably 2 to 10. As the oxyalkylene group, one or more of an ethylene oxide group and a propylene oxide group is most preferable, and an ethylene oxide group is more preferable. n is 0 or more. n is preferably 1 or more. n is preferably 30 or less, and more preferably 10 or less.
Further, each of R1, R2, R3, and R is hydrogen (H), an optionally substituted hydrocarbon group, an ether group, or the like. Preferably, an optionally substituted hydrocarbon group and an ether group is a hydrocarbon group or an ether group having 1 to 20 carbon atoms.
As R1, R2, R3, and R, an unsubstituted group is preferable. As R, a hydrocarbon group is preferable. As the hydrocarbon group, one or more of a methyl group and an ethyl group are preferable.
As the (meth) acrylic acid ester derivative, alkoxypolyalkylene glycol (meth) acrylate is preferable. Among the alkoxypolyalkylene glycol (meth) acrylate, one or more of alkoxypolyethylene glycol (meth) acrylate and alkoxypolypropylene glycol (meth) acrylate are preferable. More specifically, one or more of (2-(2-ethoxy) ethoxy) ethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate (poly: n=23), and methoxydipropylene glycol (meth) acrylate are preferable. The second monomer is more preferably one or more of (2-(2-ethoxy) ethoxy) ethyl (meth) acrylate and methoxydipropylene glycol (meth) acrylate, and most preferably (2-(2-ethoxy) ethoxy) ethyl (meth) acrylate. Therefore, the second monomer unit has a structure derived from these.
By containing both the first monomer unit and the second monomer unit, when a slurry is prepared using the composition for the positive electrode according to the present invention, the change in viscosity of the slurry is small and the stability of the slurry is excellent. Further, it is more preferable when the following requirements are satisfied for the content of each component.
The composition contains a polyvinyl alcohol structure. When the content of the polyvinyl alcohol structure in the composition is CPVA% by mass and the total content of the first monomer unit and the second monomer unit in the composition is CM% by mass, the ratio of the content of the polyvinyl alcohol structure to the total content of the first monomer unit and the second monomer unit (CPVA/(CM+CPVA)) is preferably 0.05 to 0.7, and more preferably 0.10 to 0.55. When the ratio (CPVA/(CM+CPVA)) is in the above range, the slurry having low viscosity can be obtained. The ratio (CPVA/(CM+CPVA)) is specifically, for example, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70 and may be within the range between the numerical values exemplified herein.
That is, the composition preferably contains 5 to 70% by mass of the polyvinyl alcohol structure. The composition preferably contains 95 to 30% by mass of the first monomer unit and the second monomer unit.
When the content of the first monomer unit is PM1 mol %, and the content of the second monomer unit is PM2 mol %, the ratio of the first monomer unit and the second monomer unit contained in the composition (PM1/(PM2+PM1)) is preferably 0.1 to 0.9, more preferably 0.2 to 0.9. When the ratio of the first monomer unit and the second monomer unit is in the above range, the stability of the slurry is particularly high. The ratio is specifically, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and may be within the range between the numerical values exemplified herein.
The composition preferably comprises a polyalkylene oxide structure (-AO-). Among the polyalkylene oxide structure, one or more of a polyethylene oxide structure and a polypropylene oxide structure are preferable, and a polyethylene oxide structure is most preferable. The composition containing a polyethylene oxide structure contains a polyethylene oxide structure (—CH2CH2O—). When the content of the polyethylene oxide structure (hereinafter, also referred to as a monomer having a PEO structure) in the composition is CPEO% by mass, and a total content of the first monomer unit and the second monomer unit in the composition is CM% by mass, the ratio of the content of the polyethylene oxide structure to the total content of the first monomer unit and the second monomer unit (CPEO/(CM+CPEO)) is 0.05 to 0.4, more preferably 0.10 to 0.35. When the ratio (CPEO/(CM+CPEO)) is in above range, high-rate discharge capacity retention ratio is excellent. Specifically, the ratio (CPEO/(CM+CPEO)) is, for example, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40% by mass, and may be within the range between the numerical values exemplified herein.
That is, the ether structure preferably has a polyethylene oxide structure, and the composition preferably contains 5 to 40% by mass of the polyethylene oxide structure.
The composition containing a polyethylene oxide structure may be paraphrased as a composition containing a polyalkylene oxide structure. In other words, the content of the polyalkylene oxide structure in the composition may be referred to as CPEO.
The composition comprises the PVA component and the first monomer component, and the second monomer component and the composition ratio (PVA/PM1/PM2) in the composition is determined by the charged amount (g) in the polymerization and the polymerization rate of the first and the second monomer. The polymerization rate (%) can be determined by NMR.
The total content (% by mass) of the first monomer unit and the second monomer unit in the composition is calculated by the following formula (2). The amount of PVA charged is calculated based on “the total content of the first monomer unit and the second monomer unit”, and this amount of PVA charged can be regarded as “the content of the polyvinyl alcohol structure”.
[(A×B/100+C×D/100)/(A×B/100+C×D/100+E)]×100(%) (2)
A: Mass of the first monomer used for copolymerization (charged amount)
B: Polymerization rate (%) of the first monomer after the reaction
C: Mass of the second monomer used for copolymerization (charged amount)
D: Polymerization rate (%) of the second monomer after the reaction
E: Mass of PVA used for polymerization (charged amount)
The total content of the first monomer unit and the second monomer unit can also be calculated from the integration ratio by NMR. When the integral value per proton of polyvinyl alcohol is SPVA and each of the integral values per proton of the first monomer and the second monomer is S1 and S2, the total content of the first monomer unit and the second monomer unit can be calculated by the following formula (2-2).
(S1+S2)×100/(SPVA+S1+S2) (2-2)
The content ratio (% by mass) of the first monomer unit to the total amount of the first monomer unit and the second monomer unit in the composition can be obtained from the following formula (3).
[(A×B/100)/(A×B/100+C×D/100)]×100(%) (3)
The content ratio (% by mass) of the first monomer unit to the total amount of the first monomer unit and the second monomer unit in the composition can also be determined from the following formula (3-2).
S×100/(S1+S2) (3-2)
When a graft copolymer is produced (during graft copolymerization), a homopolymer of the first monomer and a homopolymer of the second monomer may be produced. Therefore, the calculation of the graft ratio requires a step of separating the homopolymers from the graft copolymer.
The homopolymers dissolve in dimethylformamide (hereinafter, it may be abbreviated as DMF), but PVA and the graft copolymer are not dissolved in DME. Using the difference in solubility, the homopolymers can be separated by an operation such as centrifugation.
The graft ratio is calculated by the following formula (4).
[(G−F)/(G×(100−H)/100)]×100 (4)
F: Mass (g) of the component dissolved in DMF
G: Mass (g) of the composition used in the test
H: Total content (% by mass) of the first monomer unit and the second monomer unit in the composition
The method for producing the graft copolymer according to one embodiment of the present invention is not particularly limited. The method of polymerizing to obtain polyvinyl acetate, then saponifying the polyvinyl acetate to obtain polyvinyl alcohol, and graft-copolymerizing the first monomer, the second monomer, and other monomers to polyvinyl alcohol is preferable.
As a method for polymerizing to obtain polyvinyl acetate, any known method such as bulk polymerization or solution polymerization can be used.
Examples of an initiator used for the polymerization of polyvinyl acetate include azo initiators such as azobisisobutyronitrile and organic peroxides such as benzoyl peroxide and bis (4-t-butylcyclohexyl) peroxydicarbonate.
The saponification reaction of polyvinyl acetate can be performed, for example, by a method of saponifying in an organic solvent in the presence of a saponification catalyst.
Examples of the organic solvent include methanol, ethanol, propanol, ethylene glycol, methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, benzene, toluene, and the like. One or more of these may be used alone or in combination. Among these, methanol is preferred.
Examples of the saponification catalyst include basic catalysts such as sodium hydroxide, potassium hydroxide, and sodium alkoxide, and acidic catalysts such as sulfuric acid and hydrochloric acid. Among these, sodium hydroxide is preferable from the viewpoint of the saponification rate.
Examples of a method for graft-copolymerizing a monomer with polyvinyl alcohol include a solution polymerization method. Examples of the solvent used for the method include dimethyl sulfoxide, N-methylpyrrolidone, and the like.
Examples of an initiator used for graft copolymerization include organic peroxides such as benzoyl peroxide, azo compounds such as azobisisobutyronitrile, potassium peroxodisulfate, ammonium peroxodisulfate, and the like.
The graft copolymer of one embodiment of the present invention can be used by dissolving in a solvent. Examples of the solvent include dimethyl sulfoxide, N-methylpyrrolidone, and the like. The composition for the positive electrode and the slurry for the positive electrode described later may contain the solvent.
The composition for the positive electrode according to one embodiment of the present invention may contain other components such as a resin or the like as long as the effects of the present invention are not impaired.
Examples of the resin include a fluorine-based resin such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene, a styrene-butadiene copolymer (styrene butadiene rubber and the like), and an acrylic copolymer. Among these, a fluorine-based resin, particularly polyvinylidene fluoride, is preferable from the viewpoint of stability.
A slurry for a positive electrode according to one embodiment of the present invention comprises the above composition for the positive electrode and is excellent in stability. In addition, the slurry for the positive electrode according to one embodiment of the present invention contains the above-mentioned composition for the positive electrode and is low viscosity. In addition, the slurry for the positive electrode according to one embodiment of the present invention includes the above-mentioned composition for the positive electrode, and a positive electrode having excellent rate characteristics can be produced by the slurry. The slurry for the positive electrode may contain a composition for a positive electrode and a conductive auxiliary agent or may contain a composition for a positive electrode, positive electrode active materials, and a conductive auxiliary agent.
2-1. Slurry viscosity
The viscosity of the slurry for the positive electrode according to one embodiment of the present invention is preferably 350 mPa·S or less, and more preferably 300 mPa·S or less. The viscosity of the slurry is measured by a method according to JIS Z 8803: 2011 by a cone-and-plate rotary viscometer (Measuring instrument: MCR302 manufactured by Kitahama Seisakujo Corporation, measurement temperature: 25° C., rotational speed: 1s−1).
The amount of change in viscosity (viscosity change amount) of the slurry for the positive electrode according to one embodiment of the present invention is preferably −20% to 10%, more preferably −15% to 5%, wherein the amount of change in viscosity means the amount of change in viscosity before and after allowing the slurry to stand for 5 hours. It can be said that the slurry is stable when the amount of change in viscosity is small. The viscosity change amount ΔV is represented by the following formula.
ΔV(%)=[(V1−V0)N0]×100
V0: The viscosity of the slurry before being allowed to stand for 5 hours
V1: The viscosity of the slurry after being allowed to stand for 5 hours
The slurry for the positive electrode according to one embodiment of the present invention preferably has the solid content of the composition for the positive electrode (binder) of 0.1 to 20% by mass with respect to the total solid content in the slurry for the positive electrode, and it is more preferably 1 to 10% by mass.
The battery comprising the positive electrode according to one embodiment of the present invention is preferably a secondary battery. The secondary battery is preferably one or more selected from a lithium ion secondary battery, a sodium ion secondary battery, a magnesium ion secondary battery, and a potassium ion secondary battery. It is more preferably a lithium ion secondary battery.
The positive electrode and the lithium ion secondary battery comprising the positive electrode according to one embodiment of the present invention can be produced using the slurry for the positive electrode including the above-mentioned composition for the positive electrode. Preferably, the lithium ion secondary battery comprises the above-mentioned positive electrode, negative electrode, separator, and electrolyte solution (hereinafter it may be referred to as electrolytes and electrolyte solution).
The positive electrode according to one embodiment of the present invention is produced by applying the slurry for the positive electrode containing the composition for the positive electrode, the conductive auxiliary agent, and the positive electrode active material, which is used as needed, onto a current collector such as an aluminum foil, then heating to remove the solvent contained in the slurry, and further pressurizing the current collector and the electrode mixture layer with a roll press or the like to bring them into close contact with each other. That is, a positive electrode having a metal foil and a coating film of a slurry for a positive electrode formed on the metal foil can be obtained.
The conductive auxiliary agent is preferably at least one selected from the group consisting of (i) fibrous carbon, (ii) carbon black, and (iii) a carbon composite in which fibrous carbon and carbon black are interconnected.
Examples of the fibrous carbon include vapor growth carbon fibers, carbon nanotubes, carbon nanofibers, and the like. Examples of the carbon black include acetylene black, furnace black, Ketjenblack (registered trademark), and the like. These conductive auxiliary agents may be used alone or in combination of two or more. Among these, at least one selected from acetylene black, carbon nanotube, and carbon nanofiber is preferable from the viewpoint of high effect of improving the dispersibility of the conductive auxiliary agent.
The slurry for the positive electrode according to one embodiment of the present invention preferably has a solid content of the conductive auxiliary agent of 0.01 to 20% by mass with respect to the total solid content in the slurry for the positive electrode, and it is more preferably 0.1 to 10% by mass.
The battery including the positive electrode according to one embodiment of the present invention is preferably a secondary battery. As the secondary battery, one or more selected from a lithium ion secondary battery, a sodium ion secondary battery, a magnesium ion secondary battery, and a potassium ion secondary battery are preferable, and a lithium ion secondary battery is more preferable.
A positive electrode active material may be used as needed. The positive electrode active material is preferably a positive electrode active material capable of reversibly absorbing and releasing cations. The positive electrode active material is preferably a lithium-containing composite oxide containing Mn or lithium-containing polyanionic compound having a volume resistivity of 1×104 Ω·cm or more. Examples include LiCoO2, LiMn2O4, LiNiO2, LiMPO4, Li2MSiO4, LiNiXMn(2-X)O4, Li(CoXNiYMnZ)O2, Li(NiXCoYAlZ)O2, XLi2MnO3-(1-X)LiMO2, and the like. Preferably, X in LiNiXMn(2-X)O4 satisfies 0<X<2. Preferably, X, Y, and Z in Li(CoXNiyMnz)O2 and Li(NiXCoyAlz)O2 satisfy X+Y+Z=1 and 0<X<1, 0<y<1, 0<z<1. Preferably, X in XLi2MnO3-(1-X)LiMO2 satisfies 0<X<1. Preferably, M in LiMPO4, Li2MSiO4, and XLi2MnO3-(1-X)LiMO2 are preferably one or more of the elements selected from Fe, Co, Ni, and Mn.
The positive electrode active material is preferably at least one selected from the group consisting of: LiNiXMn(2-X)O4 (0<X<2); Li(CoXNiYMnZ)O2 (0<X<1, 0<Y<1, 0<Z<1, and X+Y+Z=1); and Li(NiXCoYAlZ)O2 (0<X<1, 0<Y<1, 0<Z<1, and X+Y+Z=1), and more preferably one selected from the group consisting of: LiNiXMn(2-X)O4 (0<X<2); Li(CoXNiYMnZ)O2 (0<X<1, 0<Y<1, 0<Z<1, and X+Y+Z=1).
Preferably, the slurry for the positive electrode according to one embodiment of the present invention preferably has the solid content of the positive electrode active material of 50 to 99.8% by mass with respect to the total solid content of in the slurry for the positive electrode, more preferably 80 to 99.5% by mass, and most preferably 95 to 99.0% by mass.
The negative electrode used in the lithium ion secondary battery according to one embodiment of the present invention is not particularly limited, and it can be manufactured using a slurry for a negative electrode containing a negative electrode active material. This negative electrode can be manufactured using, for example, a negative electrode metal foil and the slurry for a negative electrode provided on the metal foil. The slurry for a negative electrode preferably includes a negative electrode binder (a composition for a negative electrode), a negative electrode active material, and the above-described conductive auxiliary agent. The negative electrode binder is not particularly limited. Examples of the negative electrode binder include polyvinylidene fluoride, polytetrafluoroethylene, a styrene-butadiene copolymer (a styrene-butadiene rubber and the like), an acrylic copolymer, and the like may be used. The negative electrode binder is preferably a fluorine-based resin. As the fluorine-based resin, one or more of the group consisting of polyvinylidene fluoride and polytetrafluoroethylene is more preferable, and polyvinylidene fluoride is most preferable.
Examples of the negative electrode active material used for the negative electrode include carbon materials such as graphite, polyacene, carbon nanotubes, and carbon nanofibers, alloy materials such as tin and silicon, and oxidation such as tin oxide, silicon oxide, lithium titanate, and the like. These can be used alone, or two or more of these can be used in combination.
The metal foil for the negative electrode is preferably foil-like copper, and the thickness of the foil is preferably 5 to 30 μm from the viewpoint of workability. The negative electrode can be manufactured using the slurry for the negative electrode and the metal foil for the negative electrode by the method according to the above-mentioned manufacturing method for the positive electrode.
The separator is not particularly limited as long as it has sufficient strength. The examples of the separator include an electrical insulating porous membrane, a mesh, a nonwoven fabric, and the like. In particular, it is preferable to use a material that has low resistance to ion migration of the electrolytic solution and excellent in solution holding. The material is not particularly limited, and examples thereof include inorganic fibers such as glass fibers or organic fibers, a synthetic resin such as polyethylene, polypropylene, polyester, polytetrafluoroethylene, and polyflon and layered composites thereof. From the viewpoints of binding properties and stability, polyethylene, polypropylene, or layered composites thereof is preferable.
[Electrolyte]
As the electrolyte, any known lithium salt can be used. Examples of the electrolyte include LiClO4, LiBF4, LiBF6, LiPF6, LiCF3SO3, LiCF3CO2, LiAsF6, LiSbF6, LiB10Cl10, LiAlCl4, LiCl, LiBr, LiI, LiB(C2H5)4, LiCF3SO3, LiCH3SO3, LiCF3SO3, LiC4F9SO3, LiN(CF3SO2)2, LiN(C2F5SO2)2, LiC(CF3SO2)3, lithium fatty acid carboxylate, and the like.
The electrolyte solution dissolving the electrolyte is not particularly limited. Examples of the electrolyte solution include: carbonates such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate; lactones such as γ-butyrolactone; ethers such as trimethoxymethane, 1,2-dimethoxyethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran and 2-methyltetrahydrofuran; sulfoxides such as dimethyl sulfoxide; oxolanes such as 1,3-dioxolane and 4-methyl-1,3-dioxolane; nitrogen-containing compounds such as acetonitrile, nitromethane and N-methyl-2-pyrrolidone; esters such as methyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate and phosphoric acid triester; inorganic acid esters such as sulfuric acid ester, nitric acid ester and hydrochloric acid ester; amides such as dimethylformamide and dimethylacetamide; glymes such as diglyme, triglyme and tetraglyme; ketones such as acetone, diethyl ketone, methyl ethyl ketone and methyl isobutyl ketone; sulfolanes such as sulfolane; oxazolidinones such as 3-methyl-2-oxazolidinone; sultone such as 1,3-propane sultone, 4-butane sultone and naphtha sultone; and the like. One or more selected from these electrolytic solutions can be used alone or in combination.
Among the above electrolytes and electrolyte solutions, a solution in which LiPF6 is dissolved in carbonates is preferable. The concentration of the electrolyte in the solution varies depending on the electrode and electrolyte used and is preferably 0.5 to 3 mol/L.
The application of the lithium ion secondary battery according to one embodiment of the present invention is not particularly limited. It may be used in a wide range of fields and examples of the application include a digital camera, a video camera, a portable audio player, a portable AV device such as a portable LCD TV, a mobile information terminal such as a notebook computer, a smartphone, or a mobile PC, a portable game device, an electric tool, an electric bicycle, a hybrid vehicle, an electric vehicle, and a power storage system.
The present invention will be described in more detail with reference to examples below. These are exemplary and do not limit the present invention. Data are shown in Tables 1 to 3.
600 parts by mass of vinyl acetate and 400 parts by mass of methanol are prepared and degassed by bubbling nitrogen gas. Then, 0.3 parts by mass of bis (4-tert-butylcyclohexyl) peroxydicarbonate were added thereto as a polymerization initiator, and polymerization was carried out at 60° C. for 4 hours. When the polymerization was stopped, the solid content concentration of the polymerization solution was 48% by mass, and the polymerization rate of vinyl acetate determined on the basis of the solid content was 80%. Methanol vapor was blown into the obtained polymerization solution to remove unreacted vinyl acetate, and then the polymerization solution was diluted with methanol so that the concentration of polyvinyl acetate was 40% by mass.
20 parts by mass of a methanol solution of sodium hydroxide of 10% by mass of sodium hydroxide were added to 1,200 parts by mass of the diluted polyvinyl acetate solution, and a saponification reaction was performed at 30° C. for 2 hours.
The saponified solution was neutralized with acetic acid, filtered and dried at 100° C. for 2 hours to obtain PVA. The average degree of polymerization and saponification of the obtained PVA are shown in Table 1. The average degree of polymerization and saponification of PVA were measured by a method according to JIS K 6726.
1.65 parts by mass of the obtained PVA was added to 78.63 parts by mass of dimethyl sulfoxide and dissolved by stirring at 60° C. for 2 hours. In addition, 3.56 parts by mass of acrylonitrile, 3.39 parts by mass of (2-(2-ethoxy)ethoxy) ethyl acrylate, and 0.45 parts by mass of ammonium peroxodisulfate dissolved in 1.43 parts by mass of dimethyl sulfoxide were added at 60° C., and graft-copolymerization was carried out with stirring at 60° C. After 4 hours from the start of the polymerization, the mixture was cooled to room temperature to stop the polymerization.
100 parts by mass of the obtained reaction solution were dropped to 300 parts by mass of methanol to precipitate the composition. The polymer was separated by filtration and vacuum-dried at room temperature for 2 hours, and further vacuum-dried at 80° C. for 2 hours. The solid content was 9.76% by mass. The polymerization rate of acrylonitrile (the first monomer) and (2-(2-ethoxy) ethoxy) ethyl acrylate (the second monomer) was calculated to be 95% based on 1H-NMR.
In the obtained composition, the content ratio by mass of the polyvinyl alcohol structure is 20% by mass, the total content by mass of the first monomer unit and the second monomer unit is 80% by mass, and the graft ratio is 382%. The weight average molecular weight of the free polymer other than the stem polymer among the free polymer was 76200. These measuring methods will be described later in (Total content of first monomer unit and second monomer unit), (Graft ratio) and (Weight average molecular weight).
Table 1 shows the component and the like of the composition containing the obtained graft copolymer.
The total content by mass of the first monomer unit and the second monomer unit in the composition was calculated by the following formula (2).
[(A×B/100+C×D/100)/(A×B/100+C×D/100+E)]×100(%) (2)
A: Mass of the first monomer used for copolymerization (charged amount)
B: Polymerization rate (%) of the first monomer after the reaction
C: Mass of the second monomer used for copolymerization (charged amount)
D: Polymerization rate (%) of the second monomer after the reaction
E: Mass of PVA used for polymerization (charged amount)
The total content of the first monomer unit and the second monomer unit can also be calculated from the integration ratio by NMR. When the integral value per proton of polyvinyl alcohol is SPVA and each of the integral values per proton of the first monomer and the second monomer is S1 and S2, the total content of the first monomer unit and the second monomer unit can be calculated by the following formula (2-2).
(S1+S2)×100/(SPVA+S1+S2) (2-2)
The content ratio (% by mass) of the first monomer unit to the total amount of the first monomer unit and the second monomer unit in the composition was obtained from the following formula (3).
[(A×B/100)/(A×B/100+C×D/100)]×100(%) (3)
The content ratio (% by mass) of the first monomer unit to the total amount of the first monomer unit and the second monomer in the composition can also be determined from the following equation---(3-2).
S1×100/(S1+S2) (3-2)
1.00 g of the binder was weighed and added to 50 cc of special grade DMF (manufactured by Kokusan Chemical Co., Ltd.) and stirred at 80° C. for 24 hours at 1000 rpm. Next, the mixture was centrifuged for 30 minutes at a rotational speed of 10,000 rpm with a centrifuge (model: H2000B, rotor: H) manufactured by Kokusan Co., Ltd. After carefully separating the filtrate (DMF soluble component), the DMF insoluble component was vacuum-dried at 100° C. for 24 hours, and the graft ratio was calculated according to the above formula (4).
The obtained filtrate at the time of centrifugation (DMF soluble component) was put into 1000 ml of methanol to obtain a precipitate. The precipitate was vacuum-dried at 80° C. for 24 hours, and the weight average molecular weight in terms of standard polystyrene was measured by GPC. GPC was measured under the following conditions.
Column: two of GPC LF-804, 98.0×300 mm (manufactured by Showa Denko KK) were connected in series
Column Temperature: 40° C.
Solvent: 20 mM LiBr/DMF
5 parts by mass of the obtained binder were dissolved in 95 parts by mass of N-methyl-2-pyrrolidone (hereinafter, abbreviated as NMP) to obtain a binder solution. Further, 1 part by mass of acetylene black (Denka Black (registered trademark) “HS-100” manufactured by Denka Company Limited) and 1 part by mass of the binder solution in solid content were added and the mixture was stirred. After mixing, 98 parts by mass of LiNi0.5Mn1.5O4 were added and the mixture was stirred to obtain a slurry for a positive electrode.
The viscosity of the slurry was measured by a cone-and-plate rotary viscometer. The viscosity referred to here is a value measured by a method according to JIS Z 8803: 2011. The viscosity measurement was performed under the following conditions.
Measuring equipment: MCR302 manufactured by Kitahama Seisakujo Corporation
Measurement temperature: 25° C.
Rotational speed: 1 s−1
The prepared slurry for positive electrode was applied to an aluminum foil having a thickness of 20 μm by an automatic coating machine so that the coating film has 140 mg/cm2 and was preliminarily dried at 105° C. for 30 minutes. Next, it was pressed with a roll press machine at a linear pressure of 0.1 to 3.0 ton/cm so that the positive electrode plate has an average thickness of 75 μm. Furthermore, the positive electrode plate was cut into a width of 54 mm to produce a strip-shaped positive electrode plate. After ultrasonically welding a current collecting tab made of aluminum to the end of the positive electrode plate, in order to completely remove volatile components such as residual solvent and adsorbed moisture, it was dried at 105° C. for 1 hour to obtain a positive electrode.
96.6 parts by mass of graphite (“Carbotron (registered trademark) P” manufactured by Kureha Corporation) as a negative electrode active material, 3.4 parts by mass in the solid content of polyvinylidene fluoride (“KF polymer (registered trademark) #1120” manufactured by Kureha Corporation) as a binder, and an appropriate amount of NMP was added and mixed with stirring so that the total solid content is 50% by mass, to obtain a slurry of the negative electrode.
The prepared slurry for negative electrode was applied to both sides of a cupper foil having a thickness of 10 μm by an automatic coating machine so that each coating film has 70 mg/cm2 and was preliminarily dried at 105° C. for 30 minutes. Next, it was pressed with a roll press machine at a linear pressure of 0.1 to 3.0 ton/cm so that the negative electrode plate has an average thickness of 90 μm as the total thickness including the coating films of both sides. Furthermore, the negative electrode plate was cut into a width of 54 mm to produce a strip-shaped positive electrode plate. After ultrasonically welding a current collecting tab made of nickel to the end of the negative electrode plate, in order to completely remove volatile components such as residual solvent and adsorbed moisture, it was dried at 105° C. for 1 hour to obtain a negative electrode.
The obtained positive electrode and negative electrode were combined and wound with a polyethylene microporous membrane separator having a thickness of 25 μm and a width of 60 mm to produce a spiral wound group, which was then inserted into a battery can. Next, 5 ml of a non-aqueous electrolyte solution (ethylene carbonate/methylethyl carbonate=30/70 (mass ratio) mixed solution) in which LiPF6 was dissolved at a concentration of 1 mol/L as an electrolyte was injected into the battery container. Thereafter, the inlet was caulked and sealed to produce a cylindrical lithium secondary battery having a diameter of 18 mm and a height of 65 mm. The battery performance of the prepared lithium ion secondary battery was evaluated with the following method.
The manufactured lithium ion battery was charged at a constant current and a constant voltage limitation of 5.00±0.02 V and 0.2 ItA at 25° C., and then discharged to 3.00±0.02 V at a constant current of 0.2 ItA. Next, the discharge current was changed to 0.2 ItA, 1 ItA, and the discharge capacity for each discharge current was measured. In the recovery charge in each measurement, constant current and constant voltage charge of limitation of 5.00±0.02V (1 ItA cut) were performed. Then, the high-rate discharge capacity retention ratio at 1 ItA discharge with respect to the second time of 0.2 ItA discharge was calculated.
At an environmental temperature of 25° C., a constant current and constant voltage charge of 5.00±0.02 V of a charging voltage and 1 ItA was performed and a constant current discharge of 3.00±0.02 V of a discharge end voltage and 1 ItA was performed. The charge and discharge cycles were repeated, and the ratio of the discharge capacity at the 500th cycle to the discharge capacity at the first cycle was obtained and used as the cycle capacity retention rate.
The compositions having the composition and physical properties shown in Tables 1 and 2 were obtained in the same manner as in Example 1 except that PVA having an average degree of polymerization and saponification as shown in Tables 1 and 2 is used, and the first monomer unit and the second monomer unit of the types as shown in Tables 1 and 2 were used at the contents shown in Tables 1 and 2. The results are shown in Tables 1 and 2. In Tables 1 and 2, the content of the polyalkylene oxide structure in the composition is represented as CPEO.
Polyvinylidene fluoride resin (HSV900: manufactured by Arkema Co., Ltd.) was used as the composition. The results are shown in Table 3.
The compositions having the composition and physical properties shown in Table 3 were obtained in the same manner as in Example 2 except that the contents of PVA, the first monomer unit, and the second monomer unit are set as shown in Table 3. The results are shown in Table 3.
The abbreviations used in the following tables and the like represent the following compounds. The monomer unit represents a monomer from which the monomer unit is derived.
AN: acrylonitrile
AA: acrylic acid
EEA: 2-(2-ethoxyethoxy) ethyl acrylate
MDA: methoxydipropylene glycol acrylate
MPM: methoxypolyethylene glycol methacrylate (poly: n=23)
PHD: 3,6,9,12,15-pentaoxa-1-heptadecene
PVDF: polyvinylidene fluoride
| Number | Date | Country | Kind |
|---|---|---|---|
| 2019-019786 | Feb 2019 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2020/004408 | 2/5/2020 | WO | 00 |
