WO2015008626A1 - Binder composition for storage device, slurry for storage device, electrode for storage device, separator, and storage device - Google Patents
Binder composition for storage device, slurry for storage device, electrode for storage device, separator, and storage device Download PDFInfo
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- WO2015008626A1 WO2015008626A1 PCT/JP2014/067681 JP2014067681W WO2015008626A1 WO 2015008626 A1 WO2015008626 A1 WO 2015008626A1 JP 2014067681 W JP2014067681 W JP 2014067681W WO 2015008626 A1 WO2015008626 A1 WO 2015008626A1
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- storage device
- slurry
- electricity storage
- binder composition
- active material
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- 0 *C(C(*N(*)*)=O)=C Chemical compound *C(C(*N(*)*)=O)=C 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a binder composition for an electricity storage device, a slurry for an electricity storage device containing the binder composition, an electricity storage device electrode comprising a layer prepared by applying and drying the slurry, and applying and drying the slurry.
- the present invention relates to a separator provided on the surface with an applied layer, and an electricity storage device provided with at least one of the electrode and the separator.
- a positive electrode and a negative electrode (hereinafter, also referred to as “electrode”) used in an electricity storage device are formed by applying a mixture of an active material and a binder to a surface of a current collector and drying the active material layer on the surface of the current collector.
- electrode a negative electrode
- a technique has also been proposed in which a mixture of a filler and a binder is applied to the separator surface and dried to form a protective film that can withstand dendrites on the separator surface.
- it is common to provide a layer containing an active material or filler on the surface of an electrode or a separator see, for example, Patent Document 2.
- composition layer for an electrode containing active material particles (hereinafter also referred to as “active material layer”) and a current collector.
- active material layer a composition layer for an electrode containing active material particles
- Patent Document 3 and Patent Document 4 disclose a technique for achieving both oxidation resistance and adhesion of an electrode binder by using a rubber polymer and another polymer in combination.
- Patent Document 5 discloses a technique for improving adhesion by dissolving polyvinylidene fluoride in a specific organic solvent, applying it onto the current collector surface, and then removing the solvent at a low temperature. Has been proposed.
- Patent Document 6 examines a technique for improving battery characteristics by forming a porous layer containing a resin binder containing polyamide, polyimide, and polyamideimide on a porous separator substrate.
- Patent Document 7 discusses a technique for improving battery characteristics by forming a porous protective film containing a binder containing a fluorine resin and a rubber resin on at least one surface of a positive electrode and a negative electrode. ing.
- Patent Document 3 and Patent Document 4 in which a rubber-based polymer and another polymer are used in combination, although the adhesion is improved, the oxidation resistance of the organic polymer is greatly impaired.
- An electricity storage device manufactured using this has a problem that charge and discharge characteristics are irreversibly deteriorated by repeated charge and discharge.
- the binder component since the acrylic copolymer dispersed in water is used as a binder component, the binder component is not uniform in the coating film depending on the dispersion state of the acrylic copolymer. In some cases, the adhesion is improved but locally insufficient.
- Patent Document 5 that uses only a fluorine-containing organic polymer as a binder component, the adhesion is still insufficient.
- Emulsion-type binders in which polymer particles are dispersed in water as in the prior art, always have an issue of improving the dispersion stability of polymer particles, and ensuring storage stability is particularly important for practical use. It becomes.
- some embodiments according to the present invention can form a layer having excellent adhesion to a current collector or a separator by solving at least a part of the above-described problem, and also have an electric storage device having excellent charge / discharge characteristics.
- the binder composition for electrical storage devices which can manufacture is provided.
- some embodiments according to the present invention provide a binder composition for an electricity storage device that further improves storage stability.
- the present invention has been made to solve at least a part of the above-described problems, and can be realized as the following aspects or application examples.
- the water-soluble polymer (A) may have a weight average molecular weight (Mw) / number average molecular weight (Mn) of 3 to 30.
- binder composition for an electricity storage device of Application Example 1 or Application Example 2 It can further contain at least one compound (B) selected from the group consisting of unsaturated carboxylic acids, unsaturated amides, and salts thereof.
- the proportion of the repeating unit derived from the (meth) acrylamide contained in 100 parts by mass of the water-soluble polymer (A) may be 40 to 100 parts by mass.
- the compound (B) can be contained in an amount of 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the water-soluble polymer (A).
- the water-soluble polymer (A) is a repeating unit derived from at least one selected from the group consisting of an acid having a polymerizable unsaturated double bond, an unsaturated carboxylic acid ester, and an ⁇ , ⁇ -unsaturated nitrile compound. Can further be included.
- the acid having a polymerizable unsaturated double bond may be at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, vinyl sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid.
- One aspect of the slurry for an electricity storage device according to the present invention is: It contains the binder composition for electrical storage devices of any one of the application examples 1 to 8, and an active material.
- a slurry for an electricity storage device for producing an electricity storage device negative electrode, wherein an average particle diameter of the active material may be 3 ⁇ m or more and 10 ⁇ m or less.
- the active material may include at least one of a carbon material and a silicon material.
- a slurry for an electricity storage device for producing an electricity storage device positive electrode, wherein an average particle size of the active material may be 0.4 ⁇ m or more and 7 ⁇ m or less.
- One aspect of the slurry for an electricity storage device according to the present invention is: It contains the binder composition for electrical storage devices of any one of the application examples 1 to 8, and a filler.
- the filler may be at least one particle selected from the group consisting of silica, titanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide.
- One aspect of the electricity storage device electrode according to the present invention is: It is characterized by comprising: a current collector; and a layer formed by applying and drying the electricity storage device slurry of any one of application examples 9 to 12 on the surface of the current collector.
- One aspect of the electricity storage device electrode according to the present invention is: A current collector, and an active material layer formed on the surface of the current collector, It is further characterized by further comprising a layer formed by applying and drying the electricity storage device slurry of Application Example 13 or Application Example 14 on the surface of the active material layer.
- One aspect of the separator according to the present invention is: A layer formed by applying and drying the slurry for an electricity storage device of Application Example 13 or Application Example 14 is provided on the surface.
- One aspect of the electricity storage device according to the present invention is: At least one of the electricity storage device electrode of Application Example 15 or Application Example 16 and the separator of Application Example 17 is provided.
- an electricity storage device electrode excellent in binding ability between active material particles, binding ability between active material particles and a current collector, and powder fall resistance, so-called adhesion is manufactured. can do.
- the electrical storage device provided with the electrical storage device electrode manufactured using the binder composition for electrical storage devices which concerns on this invention the charge / discharge rate characteristic which is one of the electrical characteristics becomes very favorable.
- the binder composition for an electricity storage device according to the present invention the storage stability is extremely good.
- the electricity storage device including the protective film produced using the binder composition for an electricity storage device according to the present invention it is excellent in electrolyte permeability and liquid retention and can suppress an increase in internal resistance. That is, the power storage device according to the present invention has excellent charge / discharge characteristics because the degree of increase in the internal resistance of the power storage device is small even after repeated charge / discharge or overcharge.
- the said protective film can also suppress the short circuit resulting from the dendrite generate
- (meth) acrylic acid is a concept encompassing both “acrylic acid” and “methacrylic acid”.
- Binder composition for electricity storage device contains a repeating unit derived from (meth) acrylamide and has a weight average molecular weight (Mw) of 3 ⁇ 10 5 to 6 ⁇ 10. 6.
- Mw weight average molecular weight
- a water-soluble polymer (A) 6 and a liquid medium (C) are contained.
- the water-soluble polymer (A) contained in the binder composition for an electricity storage device according to the present embodiment has not only a function as a thickener typified by conventional carboxymethyl cellulose but also a binding ability between active material particles. In addition, it also has a function as a binder for improving the binding ability between the active material particles and the current collector and the resistance to powder falling. Therefore, in the binder composition for an electricity storage device according to the present embodiment, it is not necessary to use a water-insoluble polymer (organic particles) having a function as a binder as described in JP2012-151108A. Excellent in terms.
- the “water-soluble polymer” in the present invention refers to a polymer having a solubility in 1 g of water at 1 atm and 23 ° C. of 0.01 g or more.
- the “water-insoluble polymer” in the present invention refers to a polymer having a solubility in 1 g of water at 1 atm and 23 ° C. of less than 0.01 g.
- the binder composition for an electricity storage device can be roughly divided into two applications.
- As the first application there is an application for producing an electricity storage device electrode. Specifically, it can be used as a binder for producing an active material layer formed on the surface of a current collector.
- As a second application there is an application for producing a protective film on the surface of an electrode or a separator for suppressing a short circuit caused by a dendrite generated along with charge and discharge.
- each component contained in the binder composition for electrical storage devices which concerns on this Embodiment is demonstrated in detail.
- the binder composition for an electricity storage device includes a water-soluble polymer (A) containing a repeating unit derived from (meth) acrylamide.
- the water-soluble polymer (A) may contain a repeating unit derived from another monomer copolymerizable therewith.
- the other monomer include an acid having a polymerizable unsaturated double bond, an unsaturated carboxylic acid ester, an ⁇ , ⁇ -unsaturated nitrile compound, a cationic monomer, a conjugated diene compound, and an aromatic vinyl compound.
- Repeating units derived from (meth) acrylamide The proportion of repeating units derived from (meth) acrylamide contained in 100 parts by weight of the water-soluble polymer (A) is preferably 40 to 100 parts by weight, and 45 to 95. The amount is more preferably part by mass, and particularly preferably 50 to 85 parts by mass.
- the oxidation resistance of the polymer becomes good, and therefore, deterioration at high voltage is suppressed, and good charge / discharge durability characteristics are exhibited.
- (Meth) acrylamide in the present invention is a generic name for compounds having a (meth) acrylamide skeleton represented by the following general formula (1).
- R 1 represents a hydrogen atom or a methyl group.
- Examples of such (meth) acrylamide include acrylamide, methacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, and N, N-diethylmethacrylate.
- Examples include amide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylamide, N-methylol methacrylamide, N-methylol acrylamide, diacetone acrylamide, maleic acid amide, acrylamide t-butyl sulfonic acid and the like. .
- These (meth) acrylamides may be used alone or in combination of two or more.
- the water-soluble polymer (A) is an acid having a polymerizable unsaturated double bond (excluding those corresponding to the above (meth) acrylamide). It may have repeating units derived from it.
- the water-soluble polymer (A) has a repeating unit derived from an acid having a polymerizable unsaturated double bond, the polymerizable unsaturated double bond contained in 100 parts by mass of the water-soluble polymer (A)
- the ratio of the repeating unit derived from the acid is preferably 0 to 30 parts by mass, and more preferably 5 to 25 parts by mass.
- the water-soluble polymer (A) was prepared using the binder composition for an electricity storage device according to the present embodiment by containing a repeating unit derived from an acid having a polymerizable unsaturated double bond in the above range. The stability of the slurry for the electricity storage device is improved.
- an unsaturated carboxylic acid or an unsaturated sulfonic acid can be preferably used as the acid having a polymerizable unsaturated double bond.
- Specific examples of the acid having a polymerizable unsaturated double bond include, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and other unsaturated carboxylic acids; vinyl sulfonic acid, allyl sulfonic acid, An unsaturated sulfonic acid such as methallylsulfonic acid can be mentioned, and one or more selected from these can be used. Among these, at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, vinyl sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid is preferable.
- the water-soluble polymer (A) may further have a repeating unit derived from an unsaturated carboxylic acid ester.
- the ratio of the repeating unit derived from the unsaturated carboxylic acid ester contained in 100 parts by mass of the water-soluble polymer (A) is The content is preferably 0 to 30 parts by mass, more preferably 1 to 10 parts by mass.
- the water-soluble polymer (A) has a more favorable affinity with the electrolytic solution, and the binder in the electricity storage device is an electrical resistance component. It is possible to prevent an increase in internal resistance due to the above and to prevent a decrease in adhesion due to excessive absorption of the electrolytic solution.
- the unsaturated carboxylic acid ester is preferably a (meth) acrylic acid ester.
- (meth) acrylic acid esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth ) N-butyl acrylate, i-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth ) Monofunctional (meth) acrylate esters such as 2-ethylhexyl acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate; glycidyl (meth)
- a polyfunctional (meth) acrylic acid ester a compound represented by the following general formula (2): (meth) acrylic acid 3 [4 [1-trifluoromethyl-2,2-bis [bis (trifluoromethyl) fluoro Fluorine-containing (meth) acrylic acid esters such as methyl] ethynyloxy] benzooxy] 2-hydroxypropyl can be mentioned, and one or more selected from these can be used.
- R 2 is a hydrogen atom or a methyl group
- R 3 is a C 1-18 hydrocarbon group containing a fluorine atom.
- polyfunctional (meth) acrylic acid ester in the present invention means other polymerizable double bond, epoxy group, in addition to one polymerizable double bond possessed by (meth) acrylic acid ester, It means having at least one functional group selected from the group consisting of hydroxy groups.
- monofunctional (meth) acrylates selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate Is preferably at least one selected from the group consisting of methyl (meth) acrylate.
- polyfunctional (meth) acrylic acid esters it is at least one selected from the group consisting of glycidyl (meth) acrylate, hydroxymethyl (meth) acrylate and hydroxyethyl (meth) acrylate. Of these, glycidyl (meth) acrylate is particularly preferable.
- the water-soluble polymer (A) may further have a repeating unit derived from an ⁇ , ⁇ -unsaturated nitrile compound.
- the repeating derived from the ⁇ , ⁇ -unsaturated nitrile compound contained in 100 parts by mass of the water-soluble polymer (A)
- the unit ratio is preferably 0 to 30 parts by mass, and more preferably 1 to 10 parts by mass.
- the affinity of the water-soluble polymer (A) for the electrolytic solution is improved, so that the electrolytic solution absorption ability is improved. That is, the presence of the nitrile group makes it easy for the solvent to uniformly diffuse into the network structure formed of polymer chains formed in the electrode, so that the solvated lithium ions can easily move through the network structure. Thereby, it is thought that the diffusibility of lithium ion improves, As a result, electrode resistance falls and it is thought that a more favorable charge / discharge characteristic can be implement
- ⁇ , ⁇ -unsaturated nitrile compound examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile, vinylidene cyanide, and the like. Can be. Among these, at least one selected from acrylonitrile and methacrylonitrile is preferable, and acrylonitrile is particularly preferable.
- the “cationic monomer” in the present invention refers to a cationic monomer other than the above-mentioned (meth) acrylamide.
- the ratio of the repeating unit derived from the cationic monomer contained in 100 parts by mass of the water-soluble polymer (A) is preferably 10 to 30 parts by mass, more preferably 13 to 28 parts by mass.
- the amount is preferably 15 to 25 parts by mass.
- the oxidation resistance of a polymer becomes favorable by containing the repeating unit derived from a cationic monomer in the said range, the deterioration at the time of a high voltage is suppressed and a favorable charge / discharge durability characteristic is shown.
- the ratio of the repeating unit derived from the cationic monomer is less than the above range, the leveling property is insufficient when the slurry is applied, and thus the uniformity of the thickness of the coating film may be impaired.
- an electrode having a non-uniform thickness is used, an in-plane distribution of charge / discharge reaction occurs, making it difficult to achieve stable battery performance.
- the ratio of the repeating unit derived from the cationic monomer exceeds the above range, the charge / discharge rate characteristics of the electricity storage device may be deteriorated.
- the cationic monomer is preferably at least one monomer selected from the group consisting of a secondary amine (salt), a tertiary amine (salt), and a quaternary ammonium salt. It is more preferable that it is at least one monomer selected from the group consisting of compounds represented by the general formula (3) and the following general formula (4).
- R 4 represents a hydrogen atom or a methyl group.
- R 5 represents —O—, —COO—, —NH—, an alkylene group having 1 to 9 carbon atoms, or an oxyalkylene group having 1 to 9 carbon atoms (—OC q H 2q — (q is an arbitrary one of 1 to 9). Integer))) or a combination thereof.
- a plurality of R 6 each independently represents a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms and may be bonded to each other to form a ring.
- a cationic monomer examples include, for example, 2- (dimethylamino) ethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate methyl chloride quaternary salt, (meth) acrylic acid 2- ( Diethylamino) ethyl, 3- (dimethylamino) propyl (meth) acrylate, 3- (diethylamino) propyl (meth) acrylate, 4- (dimethylamino) phenyl (meth) acrylate, 2- [meth) acrylic acid 2- [ (3,5-dimethylpyrazolyl) carbonylamino] ethyl, 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl (meth) acrylate, 2- (1-aziridinyl) ethyl (meth) acrylate , Methacryloylcholine chloride, tris (2-acrylacryl
- the water-soluble polymer (A) may further contain a repeating unit derived from a conjugated diene compound or an aromatic vinyl compound.
- conjugated diene compound examples include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene and the like. , One or more selected from these.
- aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene, and the like, and one or more selected from these can be given. be able to.
- the repeating unit derived from the conjugated diene compound and the repeating unit derived from the aromatic vinyl compound are substantially included. It is preferably not included.
- the environment exposed to high voltage include positive electrodes such as lithium ion batteries, lithium ion capacitors, and electric double layer capacitors, and protective films formed between the positive electrode surface and the separator.
- the polymer when the molecular weight of the polymer is less than 300,000, the polymer is highly likely to elute into the electrolyte. In this case, not only the adhesiveness is lowered, but also there is a risk that the low molecular weight polymer component eluted in the electrolytic solution is adversely affected on the charge / discharge characteristics such as being electrolyzed during the charge / discharge. On the other hand, when the molecular weight exceeds 6 million, there is a risk that the binder does not swell sufficiently depending on the electrolyte.
- the water-soluble polymer (A) according to the present embodiment is considered to have further improved charge / discharge characteristics by having a sufficiently large molecular weight as described above.
- the water-soluble polymer (A) has a weight average molecular weight (Mw) / number average molecular weight (Mn), a so-called dispersion ratio of preferably 3 to 30, preferably 7 to 30, and preferably 10 to 30. It is more preferable. Generally, the value of the dispersion ratio is considered to mean the spread of the molecular weight distribution, and the closer this value is to 1, the narrower the molecular weight distribution is.
- the electricity storage device binder composition according to the present embodiment contains the water-soluble polymer (A) having a specific spread in the above-described range, good charge / discharge characteristics are easily exhibited. The reason is not necessarily clear, but is presumed as follows.
- a slurry having good dispersibility and fluidity can be prepared by using a polymer having a specific molecular weight distribution.
- An electrode or a protective film formed from a slurry having good dispersibility and fluidity has characteristics that it is uniform and has few structural defects.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the water-soluble polymer (A) can be obtained, for example, by converting a measured value by a GPC (gel permeation chromatography) method into standard polyethylene oxide. it can.
- degree of neutralization of water-soluble polymer (A) When the water-soluble polymer (A) has an acid group, the degree of neutralization can be appropriately adjusted according to the use.
- the degree of neutralization when the active material or filler is dispersed is not particularly limited, but it is preferably 0.7 to 1.0, and preferably 0.85 to 1.0 after the formation of the electrode or the protective film. Is more preferable.
- the degree of neutralization after electrode preparation within the above range, most of the acid is in a neutralized state and is preferably combined with Li ions or the like in the battery and does not cause a decrease in capacity.
- the neutralized salt include Li salt, Na salt, K salt, ammonium salt, Mg salt, Ca salt, Zn salt, Al salt and the like.
- the method for synthesizing the water-soluble polymer (A) is not particularly limited, but polymerization performed in a solvent containing water as a main component is preferable.
- a particularly preferred polymerization form is aqueous solution polymerization.
- the polymerization initiator used in the synthesis of the water-soluble polymer (A) is preferably a water-soluble radical initiator, and is a persulfate such as lithium persulfate, potassium persulfate, sodium persulfate, ammonium persulfate, or 4,4′-azobis. Water-soluble azo initiators such as (4-cyanovaleric acid) are particularly preferred. From the viewpoint of obtaining a water-soluble polymer (A) having the above-mentioned weight average molecular weight (300,000 to 6,000,000), the amount of the polymerization initiator used is 0. The amount is preferably 1 to 1.0 part by mass.
- the polymerization temperature during the synthesis of the water-soluble polymer (A) is not particularly limited, but the synthesis is carried out in the range of 30 to 95 ° C taking into account the production time and the conversion rate of the monomer to the copolymer (reaction rate). It is preferably 50 to 85 ° C.
- a pH adjuster, EDTA which is a metal ion sealing agent or a salt thereof for the purpose of improving production stability.
- pH may be adjusted with a general neutralizing agent such as ammonia, organic amine, potassium hydroxide, sodium hydroxide, lithium hydroxide before the polymerization or when water-solubilizing the polymer. Is preferably adjusted to a pH in the range of 5 to 11. It is also possible to use EDTA which is a metal ion sealing agent or a salt thereof.
- a general neutralizing agent such as ammonia, organic amine, potassium hydroxide, sodium hydroxide, lithium hydroxide before the polymerization or when water-solubilizing the polymer.
- EDTA which is a metal ion sealing agent or a salt thereof.
- the type and amount of the initiator in order to control the molecular weight and molecular weight distribution of the water-soluble polymer (A), the type and amount of the initiator, the temperature control during the polymerization, the time until the total amount of monomer is added, after the total amount of monomer is added Temperature management and temperature holding time are important. For example, in the synthesis of the polymer described in JP 2012-151108 A, about 2 parts by mass of initiator (ammonium persulfate) is used with respect to 100 parts by mass of the monomer. Generally, when the amount of the initiator increases with respect to the amount of the monomer, the molecular weight decreases, but it is considered that the above-described weight average molecular weight cannot be reached by such a synthesis method.
- initiator ammonium persulfate
- the water-soluble polymer (A) is obtained by radical polymerization in a solvent containing water as a main component, temperature control and reaction time are strictly controlled in order to synthesize a polymer having a desired molecular weight. There is a need to. Such time and temperature management needs to be adjusted in a timely manner according to the type of monomer used. For example, when controlling the molecular weight and molecular weight distribution of a water-soluble polymer (A) containing 40 to 100 parts by mass of repeating units derived from (meth) acrylamide with respect to 100 parts by mass of all repeating units, temperature control during polymerization It is necessary to carry out at about ⁇ 3 ° C.
- the control must be performed at about ⁇ 3 ° C., and must be strictly controlled to the temperature holding time after addition of the entire amount of monomer.
- the binder composition for an electricity storage device according to the present embodiment may contain at least one compound (B) selected from the group consisting of unsaturated carboxylic acids, unsaturated amides, and salts thereof.
- the binder composition for an electricity storage device according to the present embodiment contains the compound (B)
- the charge / discharge characteristics of the electricity storage device are improved.
- the expression mechanism of this effect is not necessarily clear, but is estimated as follows. In general, when a new component is added to a dispersion of active material particles, filler particles, or the like, the new component is a trigger, and aggregation of these particles is likely to occur.
- the slurry for an electricity storage device is prepared by mixing the binder composition for an electricity storage device to which the compound (B) is added and the active material particles or filler particles, non-uniformity is caused by the aggregation of the active material particles and the filler particles. Has been confirmed to be significantly suppressed.
- the reason for this is considered to be that the compound (B) is excellent in affinity with the active material particles and filler particles.
- the homogeneity of the coating film formed on the surface of the current collector, electrode and separator is improved, so that the adhesion between them and the coating film is improved, and the charge / discharge characteristics of the electricity storage device are improved. It is guessed.
- the compound (B) has an unsaturated bond, it is presumed that a solid electrolyte membrane (Solid Electrolyte Interface Film, hereinafter also referred to as “SEI membrane”) is formed on the surface of the active material. It is considered that the compound (B) rapidly undergoes electrolytic crosslinking on the active material surface in the initial charging process, and forms a dense SEI film on the entire surface of the active material. And since the SEI film
- SEI membrane Solid Electrolyte Interface Film
- the electrode material slurry is prepared by mixing the power storage device binder composition according to the present embodiment and the active material, and the slurry is applied to the surface of the current collector to form the active material layer, It is considered that the metal oxide layer formed on the surface of the current collector by the compound (B) contained in the slurry can be removed, and as a result, the electrical characteristics are improved.
- the current collector is an aluminum foil
- a passive aluminum oxide film is formed on the surface of the aluminum foil.
- Such an aluminum oxide film is insulative and tends to increase internal resistance in electrode formation.
- the binder composition for an electricity storage device of the present invention is used, such an insulating aluminum oxide film can be removed by the action of an acid or a base, so that charge / discharge characteristics can be improved.
- the content ratio of the compound (B) in the binder composition for an electricity storage device according to the present embodiment is 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the water-soluble polymer (A). Is preferable, 0.02 to 0.4 parts by mass is more preferable, and 0.03 to 0.3 parts by mass is particularly preferable.
- the content ratio of the compound (B) is in the above range, not only the above-mentioned effects are sufficiently obtained, but also the storage stability of the binder composition for an electricity storage device is improved, which is preferable.
- Such compound (B) include unsaturated carboxylic acids, unsaturated amides, and salts thereof.
- unsaturated carboxylic acid and salt thereof may be referred to as “unsaturated carboxylic acid (salt)”
- unsaturated amide and salt thereof may be referred to as “unsaturated amide (salt)”.
- Unsaturated carboxylic acid (salt) Unsaturated carboxylic acids (salts) are susceptible to decarboxylation when heated, and are easily decomposed into low molecular weight components. For this reason, when the compound (B) is an unsaturated carboxylic acid (salt), the compound (B) remaining in the coating film evaporates when heated for drying the coating film in the electrode manufacturing process or the separator manufacturing process. In addition, it is considered that even if it is gradually decomposed and remains, it can be removed from the coating film to an amount that does not adversely affect the electricity storage device characteristics. As a result, since the corrosion of the current collector with the compound (B) is suppressed over time, it is considered that deterioration of the electricity storage device characteristics can be suppressed and stable charge / discharge characteristics can be expressed.
- the unsaturated carboxylic acid (salt) has an acid dissociation index (pKa) at 25 ° C. in at least one dissociation stage of 5.0 or more. It is preferable that In this specification, the “acid dissociation index (pKa)” refers to the pKa value of the second carboxy group for an organic acid having two carboxy groups, and 3 for an organic acid having three or more carboxy groups. The pKa value of the carboxy group is used as an index.
- the metal oxide layer that can be formed on the surface of the current collector with the above-described addition amount can be easily removed, and the remaining in the active material layer can be suppressed. Therefore, it is preferable.
- the acid dissociation index (pKa) is, for example, (a) The Journal of Physical Chemistry vol. 68, number 6, page 1560 (1964), (b) a method using an automatic potentiometric titrator (COM-980Win, etc.) manufactured by Hiranuma Sangyo Co., Ltd., and (c) The Chemical Society of Japan. It is possible to use the acid dissociation index described in the chemical manual of the edition (revised edition 3, June 25, 1984, published by Maruzen Co., Ltd.), (d) a database such as pKaBASE manufactured by Comprugrug, etc. it can.
- unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, citric acid, acetic acid, and salts thereof. It is done. Among these, acrylic acid, methacrylic acid, itaconic acid, acetic acid, and salts thereof are preferable.
- unsaturated carboxylic acids (salts) can be used alone or in combination of two or more.
- the unsaturated amide (salt) preferably has a polymerizable unsaturated group from the viewpoint of improving adhesion, and more preferably has a (meth) acrylamide group.
- Specific examples of the unsaturated amide (salt) include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol crotonamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide, diacetone acrylamide, diacetone methacrylamide, Aminopropylacrylamide, aminopropylmethacrylamide, monomethylacrylamide, monomethylmethacrylamide, monoethylacrylamide, monoethylmethacrylamide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, N- (2 -Hydroxypropyl) acrylamide, N- (2-hydroxypropyl) methacrylamide, N, N-dimethylacryl
- acrylamide methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N-isopropylacrylamide are preferable.
- unsaturated amides salts can be used alone or in combination of two or more.
- the binder composition for an electricity storage device contains a liquid medium (C).
- the liquid medium (C) is preferably an aqueous medium containing water.
- This aqueous medium can contain a non-aqueous medium other than water.
- the non-aqueous medium include amide compounds, hydrocarbons, alcohols, ketones, esters, amine compounds, lactones, sulfoxides, sulfone compounds, and the like. Use one or more selected from these. Can do.
- the liquid medium (C) is an aqueous medium, 90% by mass or more is preferably water, and more preferably 98% by mass or more is water in the total amount of 100% by mass of the liquid medium (C).
- the binder composition for an electricity storage device decreases the degree of adverse effects on the environment and increases the safety for handling workers.
- the content ratio of the non-aqueous medium contained in the aqueous medium is preferably 10% by mass or less, more preferably 5% by mass or less, particularly not substantially contained in 100% by mass of the aqueous medium. preferable.
- “substantially does not contain” means that a non-aqueous medium is not intentionally added as the liquid medium (C), and is unavoidably mixed when preparing the binder composition for an electricity storage device. Non-aqueous media may be included.
- the power storage device binder composition according to the present embodiment can be broadly divided into two uses, that is, a use for producing a power storage device electrode and a use for producing a protective film.
- the power storage device slurry according to the present embodiment can also be classified into two types depending on the application.
- the slurry for the electricity storage device used for the purpose of producing the electricity storage device electrode is referred to as “slurry for the electricity storage device electrode”
- the slurry for the electricity storage device used for the purpose of producing the protective film is referred to as the “slurry for the protection film”.
- Storage device electrode slurry refers to a dispersion liquid used to form an active material layer on the surface of a current collector after it is applied to the surface of the current collector and then dried. That means.
- the slurry for an electricity storage device electrode according to the present embodiment contains the above-mentioned binder composition for an electricity storage device and an active material.
- the slurry for an electricity storage device electrode according to the present embodiment can be used for an application for producing either a positive electrode or a negative electrode.
- components contained in the slurry for the electricity storage device electrode according to the present embodiment will be described in detail. However, since it is as having mentioned above about the binder composition for electrical storage devices, description is abbreviate
- Active material there is no restriction
- the active material include carbon materials, silicon materials, oxides containing lithium atoms, lead compounds, tin compounds, arsenic compounds, antimony compounds, aluminum compounds, and the like.
- Examples of the carbon material include amorphous carbon, graphite, natural graphite, mesocarbon microbeads (MCMB), and pitch-based carbon fibers.
- Examples of the silicon material include silicon simple substance, silicon oxide, and silicon alloy.
- the silicon oxide is preferably a silicon oxide represented by the composition formula SiO x (0 ⁇ x ⁇ 2, preferably 0.1 ⁇ x ⁇ 1).
- the silicon alloy is preferably an alloy of silicon and at least one transition metal selected from the group consisting of titanium, zirconium, nickel, copper, iron and molybdenum. These transition metal silicon alloys are preferably used because they have high electronic conductivity and high strength. Moreover, since the transition metal existing on the surface of the active material is oxidized and becomes an oxide having a hydroxyl group on the surface when the active material contains these transition metals, the binding force with the binder is also improved. preferable.
- As the silicon alloy it is more preferable to use a silicon-nickel alloy or a silicon-titanium alloy, and it is particularly preferable to use a silicon-titanium alloy.
- the silicon content in the silicon alloy is preferably 10 mol% or more, more preferably 20 to 70 mol%, based on all the metal elements in the alloy. Note that the silicon material may be single crystal, polycrystalline, or amorphous.
- active materials when using a silicon material as an active material, you may use together active materials other than a silicon material.
- active materials include the above carbon materials; conductive polymers such as polyacene; A X B Y O Z (where A is an alkali metal or transition metal, B is cobalt, nickel, aluminum, tin, manganese) At least one selected from transition metals such as O represents an oxygen atom, and X, Y and Z are 1.10>X> 0.05, 4.00>Y> 0.85, 5.00>, respectively. Z> 1.5 is a number in the range.) And other metal oxides.
- it is preferable to use a carbon material in combination because the volume change associated with insertion and extraction of lithium is small.
- oxide containing a lithium atom examples include lithium cobaltate, lithium nickelate, lithium manganate, ternary nickel cobalt lithium manganate, LiFePO 4 , LiCoPO 4 , LiMnPO 4 , Li 0.90 Ti 0.05 Nb. 0.05 Fe 0.30 Co 0.30 Mn 0.30 PO 4 and the like.
- the shape of the active material is preferably granular.
- the average particle size of the active material is preferably 0.1 to 100 ⁇ m, more preferably 0.3 to 20 ⁇ m.
- the slurry for electrical storage devices for producing an electrical storage device negative electrode contains the active material whose average particle diameter is 3 micrometers or more and 10 micrometers or less.
- the active material whose average particle diameter is 3 micrometers or more and 10 micrometers or less.
- the average particle diameter of the active material When the average particle diameter of the active material is less than 3 ⁇ m, the strength of the active material layer tends to decrease, so that cracks tend to occur. In addition, since the active material is further pulverized by the volume change associated with charge / discharge (lithium ion insertion / release), the charge / discharge durability characteristics of the electricity storage device tend to be low. On the other hand, when the average particle diameter of the active material exceeds 15 ⁇ m, the active material layer tends to be brittle, and thus cracks tend to occur. In addition, since the surface area of the active material is relatively small, lithium ion insertion / desorption is difficult to occur, and the output characteristics of the electricity storage device tend to deteriorate.
- a suitable material can be suitably selected according to the kind of target electrical storage device.
- examples of such an active material include the active materials exemplified above, but among the materials exemplified above, it is preferable to include at least one of a carbon material and a silicon material.
- the slurry for an electricity storage device for producing the electricity storage device positive electrode preferably contains an active material having an average particle size of 0.4 ⁇ m or more and 7 ⁇ m or less. .
- an active material having an average particle size of 0.4 ⁇ m or more and 7 ⁇ m or less and the water-soluble polymer (A)
- a slurry excellent in spinnability can be obtained.
- the coatability is improved, so that an electricity storage device positive electrode provided with an active material layer having good adhesion to the current collector can be produced. Discharge durability characteristics are improved.
- the average particle size of the active material When the average particle size of the active material is less than 0.4 ⁇ m, the strength of the active material layer tends to decrease, and thus cracks tend to occur. In addition, since the active material is further pulverized by the volume change associated with charge / discharge (lithium ion insertion / release), the charge / discharge durability characteristics of the electricity storage device tend to be low. On the other hand, when the average particle diameter of the active material exceeds 7 ⁇ m, the active material layer tends to be brittle, and thus cracks tend to occur. In addition, since the surface area of the active material is relatively small, lithium ion insertion / desorption is difficult to occur, and the output characteristics of the electricity storage device tend to deteriorate.
- a suitable material can be suitably selected according to the kind of the electrical storage device made into the objective.
- an active material include the active materials exemplified above, but among these, from the viewpoints of the performance and stability of the assembled battery, ease of assembly process, reliability, and the like, cobalt acid Lithium, lithium nickelate, lithium manganate, ternary nickel manganese lithium cobaltate, LiFePO 4 , LiCoPO 4 , LiMnPO 4 , Li 0.90 Ti 0.05 Nb 0.05 Fe 0.30 Co 0.30 Mn 0 An oxide containing a lithium atom such as .30 PO 4 is preferred.
- the average particle size of the active material is determined by measuring the particle size distribution using a particle size distribution measuring apparatus based on the light scattering method, and the cumulative number of particles when the particles are accumulated from small particles is 50%. This is the value of (D50).
- a particle size distribution measuring apparatus include Coulter LS230, LS100, LS13 320 (above, manufactured by Beckman Coulter. Inc), FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), and the like.
- the average particle diameter of the active material represents the average particle diameter of a mixture obtained by mixing all the active materials when two or more active materials are used.
- the use ratio of the active material is preferably such that the content ratio of the binder (water-soluble polymer (A)) to 100 parts by mass of the active material is 0.1 to 25 parts by mass, More preferably, it is used at a ratio of ⁇ 15 parts by mass. By setting it as such a usage rate, it is possible to produce an electrode that is excellent in adhesiveness and has low electrode resistance and excellent charge / discharge characteristics.
- a conductive additive, a non-aqueous medium, a thickener, a pH adjuster, a corrosion inhibitor, and the like can be added to the electricity storage device electrode slurry according to the present embodiment as necessary.
- Conductive aids include carbon in lithium ion secondary batteries; in nickel metal hydride secondary batteries, cobalt oxide at the positive electrode: nickel powder, cobalt oxide, titanium oxide, carbon at the negative electrode, etc. Are used respectively.
- examples of carbon include graphite, activated carbon, acetylene black, furnace black, graphite, carbon fiber, and fullerene. Among these, acetylene black or furnace black can be preferably used.
- the proportion of the conductive auxiliary agent used is preferably 20 parts by mass or less, more preferably 1 to 15 parts by mass, and particularly preferably 2 to 10 parts by mass with respect to 100 parts by mass of the active material.
- the slurry for an electricity storage device electrode according to the present embodiment can contain a non-aqueous medium having a standard boiling point of 80 to 350 ° C. from the viewpoint of improving its applicability.
- a non-aqueous medium include, for example, amide compounds such as N-methylpyrrolidone, dimethylformamide, and N, N-dimethylacetamide; hydrocarbons such as toluene, xylene, n-dodecane, and tetralin; 2-ethyl Alcohols such as -1-hexanol, 1-nonanol and lauryl alcohol; ketones such as methyl ethyl ketone, cyclohexanone, phorone, acetophenone and isophorone; esters such as benzyl acetate, isopentyl butyrate, methyl lactate, ethyl lactate and butyl lactate; o-toluidine
- the slurry for an electricity storage device electrode according to the present embodiment can contain a thickener from the viewpoint of adjusting its fluidity and stability.
- thickeners include cellulose compounds such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose; ammonium salts or alkali metal salts of the above cellulose compounds; poly (meth) acrylic acid, modified poly (meth) acrylic acid, and the like.
- particularly preferred thickeners include alkali metal salts of carboxymethyl cellulose and alkali metal salts of poly (meth) acrylic acid.
- carboxymethyl cellulose and salts thereof are preferably not included when used in an environment exposed to a high voltage because the oxidation potential is low. By adding carboxymethyl cellulose and its salt, the flexibility of the electrode may be reduced, and the winding property may be impaired, or the adhesion of the active material layer may be insufficient.
- Examples of the environment exposed to high voltage include positive electrodes such as lithium ion batteries, lithium ion capacitors, and electric double layer capacitors, and protective films formed between the positive electrode surface and the separator.
- the use ratio of the thickener is preferably 20% by mass or less with respect to the total solid content of the electricity storage device electrode slurry. More preferably, the content is 0.1 to 15% by mass, and particularly preferably 0.5 to 10% by mass.
- the slurry for the electricity storage device electrode according to the present embodiment is prepared by adding a pH adjusting agent or a corrosion inhibitor for the purpose of suppressing the corrosion of the current collector to be applied according to the type of the active material. Can be contained.
- pH adjuster examples include hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, formic acid, ammonium phosphate, ammonium sulfate, ammonium acetate, ammonium formate, and ammonium chloride, and sulfuric acid and ammonium sulfate are preferable.
- Corrosion inhibitors include ammonium metavanadate, sodium metavanadate, potassium metavanadate, ammonium metatungstate, sodium metatungstate, potassium metatungstate, ammonium paratungstate, sodium paratungstate, potassium paratungstate, and molybdic acid.
- Ammonium, sodium molybdate, potassium molybdate and the like can be mentioned, and ammonium paratungstate, ammonium metavanadate, sodium metavanadate, potassium metavanadate and ammonium molybdate are preferable.
- the power storage device electrode slurry according to the present embodiment is a mixture of the power storage device binder composition described above, an active material, water, and an additive used as necessary. Can be manufactured. These mixing can be performed by stirring by a known method, and for example, a stirrer, a defoamer, a bead mill, a high-pressure homogenizer, or the like can be used.
- a mixer capable of stirring to such an extent that no agglomerates of the active material remain in the slurry, and a sufficient dispersion condition as necessary.
- the degree of dispersion can be measured by a particle gauge, but it is preferable to mix and disperse so that aggregates larger than at least 100 ⁇ m are eliminated.
- the mixer that meets such conditions include a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, and a Hobart mixer.
- the slurry for protective films which concerns on this Embodiment contains the binder composition for electrical storage devices mentioned above and a filler.
- each component contained in the slurry for protective films according to the present embodiment will be described in detail.
- description is abbreviate
- the slurry for a protective film according to the present embodiment can improve the toughness of the formed protective film by containing a filler.
- a filler silica, titanium oxide (titania), aluminum oxide (alumina), zirconium oxide (zirconia), magnesium oxide (magnesia), or the like can be used.
- titanium oxide and aluminum oxide are preferable from the viewpoint of further improving the toughness of the protective film.
- rutile type titanium oxide is more preferable.
- the average particle diameter of the filler is preferably 1 ⁇ m or less, and more preferably in the range of 0.1 to 0.8 ⁇ m.
- the average particle diameter of a filler is larger than the average hole diameter of the separator which is a porous film.
- the protective film slurry according to the present embodiment preferably contains 0.1 to 20 parts by mass of the above-mentioned binder (water-soluble polymer (A)) with respect to 100 parts by mass of filler. More preferably, 10 parts by mass is contained.
- the content ratio of the binder is 0.1 to 10 parts by mass, the balance between the toughness of the formed protective film and the lithium ion permeability is improved, and as a result, the resistance increase rate of the obtained electricity storage device is further increased. Can be lowered.
- the protective film slurry according to the present embodiment may contain the materials and addition amounts described in the above-mentioned “2.1.2. Other Additives” slurry for an electricity storage device electrode as necessary. It can be used as needed.
- the protective film slurry according to the present embodiment is prepared by mixing the above-mentioned binder composition for an electricity storage device, a filler, and an additive used as necessary.
- a known mixing device such as a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, a Hobart mixer can be used.
- a mixer that can stir to such an extent that filler aggregates do not remain in the slurry and, if necessary, sufficient dispersion conditions.
- the degree of dispersion can be measured by a particle gauge, but it is preferable to mix and disperse so that aggregates larger than at least 100 ⁇ m are eliminated.
- the mixer that meets such conditions include a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, and a Hobart mixer.
- the power storage device slurry according to the present embodiment preferably has a spinnability of 30 to 80%, more preferably 33 to 79%, and particularly preferably 35 to 78%. .
- spinnability When the spinnability is less than the above range, the leveling property is insufficient when applying the slurry, and thus the uniformity of the thickness of the coating film may be impaired. If an electrode or a protective film having a non-uniform thickness is used, an in-plane distribution of charge / discharge reaction occurs, making it difficult to achieve stable battery performance.
- the spinnability exceeds the above range, dripping easily occurs when applying the slurry, and it is difficult to obtain a stable quality electrode or protective film. Therefore, if the spinnability is within the above range, the occurrence of these problems can be suppressed, and it becomes easy to manufacture an electricity storage device having both good electrical characteristics and adhesion.
- the “threadability” in the present specification is a physical property measured as follows. First, a Zaan cup (made by Dazai Equipment Co., Ltd., Zaan Bisco City Cup No. 5) having an opening with a diameter of 5.2 mm at the bottom is prepared. With this opening closed, 40 g of slurry is poured into the Zahn cup. Thereafter, when the opening is opened, the slurry flows out from the opening.
- T 0 when opening the opening, the T A when the slurry of the thread is finished, when the outflow of the slurry is completed when the T B, the following equation (5) .
- Spinnability (%) ((T A ⁇ T 0 ) / (T B ⁇ T 0 )) ⁇ 100 (5)
- An electricity storage device electrode includes a current collector and a layer formed by applying and drying the above-mentioned slurry for an electricity storage device electrode on the surface of the current collector. is there.
- Such an electricity storage device electrode is formed by applying the aforementioned slurry for an electricity storage device electrode on the surface of an appropriate current collector such as a metal foil to form a coating film, and then drying the coating film to form an active material layer.
- An electricity storage device electrode thus manufactured is formed by binding an active material layer containing the above-described binder, active material, and optional components added as necessary, on a current collector.
- Such an electricity storage device electrode has excellent adhesion between the current collector and the active material layer, and therefore has good charge / discharge rate characteristics, which is one of the electrical characteristics.
- the current collector is not particularly limited as long as it is made of a conductive material.
- a current collector made of metal such as iron, copper, aluminum, nickel, and stainless steel is used.
- aluminum is used for the positive electrode and copper is used for the negative electrode, the above-mentioned storage device is used.
- the effect of the slurry for an electricity storage device electrode produced using the binder composition is most apparent.
- a punching metal, an expanded metal, a wire mesh, a foam metal, a mesh metal fiber sintered body, a metal plated resin plate, or the like is used.
- the shape and thickness of the current collector are not particularly limited, but it is preferable that the current collector be a sheet having a thickness of about 0.001 to 0.5 mm.
- the coating can be performed by an appropriate method such as a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a dipping method, or a brush coating method.
- the coating amount of the power storage device electrode slurry is not particularly limited, but the thickness of the active material layer formed after removing the liquid medium (which is a concept including both water and a non-aqueous medium that is optionally used). However, the amount is preferably 0.005 to 5 mm, and more preferably 0.01 to 2 mm.
- the active material layer When the thickness of the active material layer is within the above range, the active material layer can be effectively infiltrated with the electrolytic solution. As a result, it is preferable because the metal ions can be easily transferred between the active material and the electrolytic solution in the active material layer, so that the electrode resistance can be further reduced. In addition, since the thickness of the active material layer is within the above range, even when the electrode is folded or wound, the active material layer is not peeled off from the current collector. It is preferable at the point from which the electrical storage device electrode which is favorable and is rich in flexibility is obtained.
- drying method from the coated film after coating (method for removing water and optionally used non-aqueous medium); for example, drying with warm air, hot air, low humidity air; vacuum drying; (far) infrared , Drying by irradiation with an electron beam or the like.
- the drying speed is appropriately set so that the liquid medium can be removed as quickly as possible within a speed range in which the active material layer does not crack due to stress concentration or the active material layer does not peel from the current collector. be able to.
- the pressing method includes a die press and a roll press.
- the press conditions should be set appropriately depending on the type of press equipment used and the desired values of the porosity and density of the active material layer. This condition can be easily set by a few preliminary experiments by those skilled in the art.
- the linear pressure of the roll press machine is 0.1 to 10 (t / cm), preferably 0.
- the current collector feed speed (roll rotation speed) after drying is 1 to 80 m / min, preferably 5 to 50 m / min. It can be performed in min.
- the density of the active material layer after pressing is preferably 1.5 to 5.0 g / cm 3 , more preferably 1.5 to 4.0 g / cm 3, and 1.6 to 3.8 g. / Cm 3 is particularly preferable.
- Protective film A protective film can be formed by applying the above-mentioned slurry for protective film on the surface of the positive electrode, negative electrode or separator and drying it.
- Specific embodiments of the protective film include the following three embodiments.
- a protective film can be formed in the active material layer surface by apply
- a protective film can be formed in the surface of a separator by apply
- the protective film is applied to the surface of the functional layer by applying the above-mentioned slurry for protective film on the surface of the functional layer and drying it. Can be formed.
- the coating can be performed by an appropriate method such as a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a dipping method, or a brush coating method.
- the coating amount of the protective film slurry is not particularly limited, but the thickness of the protective film formed after removing the liquid medium is preferably 0.5 to 4 ⁇ m, and preferably 0.5 to 3 ⁇ m. It is more preferable to use the amount. When the thickness of the protective film is in the above range, the permeability of the electrolytic solution into the electrode and the liquid retaining property are improved, and an increase in the internal resistance of the electrode can be suppressed.
- drying method from the coated film after coating (method for removing water and optionally used non-aqueous medium); for example, drying with warm air, hot air, low humidity air; vacuum drying; (far) infrared , Drying by irradiation with an electron beam or the like.
- the drying speed is appropriately set so that the liquid medium can be removed as quickly as possible within a speed range in which the active material layer does not crack due to stress concentration or the active material layer does not peel from the current collector. be able to.
- the coating film is preferably dried at a temperature of 20 to 250 ° C., more preferably 50 to 150 ° C., preferably for 1 to 120 minutes, more preferably 5 to 60 minutes. be able to.
- the power storage device only needs to include at least one of the above-described power storage device electrode and the separator including the above-described protective film.
- a positive electrode and a negative electrode are laminated with a separator for preventing a short circuit between the electrodes, or a positive electrode, a separator, a negative electrode, and a separator are laminated in this order to form an electrode.
- / Separator laminated body this may be wound or folded according to the shape of the battery, put into a battery container, and an electrolyte solution is injected into the battery container and sealed.
- the shape of the battery can be an appropriate shape such as a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, or a flat shape.
- the electrolytic solution may be liquid or gel, and a material that effectively expresses the function as a battery may be selected from known electrolytic solutions used for the electricity storage device, depending on the type of active material.
- the electrolytic solution can be a solution in which an electrolyte is dissolved in a suitable solvent.
- any conventionally known lithium salt can be used, and specific examples thereof include, for example, LiClO 4 , LiBF 4 , LiPF 6 , LiCF 3 CO 2 , LiAsF. 6 , LiSbF 6 , LiB 10 Cl 10 , LiAlCl 4 , LiCl, LiBr, LiB (C 2 H 5 ) 4 , LiCF 3 SO 3 , LiCH 3 SO 3 , LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 2 N, lithium of lower fatty acid carboxylate etc.
- an aqueous potassium hydroxide solution having a conventionally known concentration of 5 mol / liter or more can be used.
- the solvent for dissolving the electrolyte is not particularly limited, but specific examples thereof include carbonate compounds such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate; Lactone compounds such as butyrolactone; ether compounds such as trimethoxymethane, 1,2-dimethoxyethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran; sulfoxide compounds such as dimethyl sulfoxide, etc. One or more selected from among them can be used.
- the concentration of the electrolyte in the electrolytic solution is preferably 0.5 to 3.0 mol / L, more preferably 0.7 to 2.0 mol / L.
- the power storage device is suitable as a secondary battery or a capacitor mounted on an automobile such as an electric vehicle, a hybrid car, and a truck, and also used as a secondary battery used in AV equipment, OA equipment, communication equipment, and the like. It is also suitable as a battery or a capacitor.
- the reaction was performed at ⁇ 3 ° C. for 2 hours. Then, it cooled and adjusted to pH 7 with 20 wt% sodium hydroxide aqueous solution, and obtained the aqueous solution containing 8 wt% of water-soluble polymers (A).
- An aqueous solution containing 8 wt% of the water-soluble polymer (A) thus obtained was designated as a binder composition S1 for an electricity storage device. It was 3000 mPa * s when the binder composition S1 for electrical storage devices was adjusted to 25 degreeC, and the viscosity was measured using the BM type
- the weight average molecular weight (Mw) of the water-soluble polymer (A) measured under the following conditions is 6 ⁇ 10 6 , and the value of weight average molecular weight (Mw) / number average molecular weight (Mn) ( The dispersion ratio) was 30.
- ⁇ Measuring equipment GPC (model number: HLC-8220) manufactured by Tosoh Corporation
- Calibration curve standard polyethylene oxide Measurement method: Dissolved in the eluent so that the concentration of the water-soluble polymer (A) is 0.3 wt%, and measured after filter filtration.
- Binder Composition for Electricity Storage Device (1) Preparation of Binder Composition for Electricity Storage Device To 100 parts by mass of the water-soluble polymer (A) in the aqueous solution containing the water-soluble polymer (A) obtained above. On the other hand, 0.03 parts by mass of acrylamide as the compound (B) was added and stirred at 150 rpm to prepare a binder composition for an electricity storage device.
- content of the compound (B) in the binder composition for electrical storage devices can also be confirmed by analyzing the binder composition for electrical storage devices by the following procedures. That is, 0.2 g of the obtained binder composition for an electricity storage device was weighed, and 200 ppm maleic acid aqueous solution was added as an internal standard solution to dilute it 50 times. The measurement sample thus prepared was subjected to compound (B) using an ion chromatography apparatus (Tosoh Corporation: IC-2010, UV detector: UV-8320IC) using a TSKgelSCX (H +) column manufactured by Tosoh Corporation. ) Content of acrylamide was quantified. Based on this quantitative result, it was confirmed that the content of acrylamide with respect to 100 parts by mass of the water-soluble polymer (A) contained in the binder composition for an electricity storage device was 0.03 parts by mass.
- a binder composition for an electricity storage device may be stored in large quantities for use in a factory for producing an electricity storage device.
- the properties of the binder composition for an electricity storage device consumed first and the binder composition for an electricity storage device after being stored for a long period of time are more preferable because the polymer does not settle and can be used easily.
- the 100-g polybin was filled with the binder composition for electrical storage devices prepared above, and it stored for one month with the refrigerator set to 2 degreeC.
- the storage device binder composition after storage was visually observed. When sedimentation was not observed, “no” was indicated, and when sedimentation was observed, “present” was also shown in Table 1.
- the storage environment of the binder composition for an electricity storage device cannot be strictly controlled from the viewpoint of cost, and is therefore exposed to an environment near 0 ° C. due to changes in temperature. There is. Therefore, in the following evaluation of the freezing temperature, it is not preferable to freeze at 0 ° C., and it is more preferable that the freezing temperature is ⁇ 0.5 ° C. or lower because it can be stored easily.
- the freezing temperature of the electrical storage device binder composition was measured as follows. 1,000 g of polybin was charged with the binder composition for an electricity storage device prepared above and stored in a freezer at ⁇ 10 ° C., and the temperature at which freezing started (freezing temperature) was measured. The measurement results are also shown in Table 1.
- the slurry for positive electrode was prepared by stirring and mixing at 800 rpm for 5 minutes and further under vacuum (about 5.0 ⁇ 10 3 Pa) at 1,800 rpm for 1.5 minutes.
- a slurry for negative electrode was prepared by stirring and mixing at 1,800 rpm for 1.5 minutes at (about 5.0 ⁇ 10 3 Pa).
- the crack rate is allowed up to 20%.
- the electrode plates are easily cut, making it impossible to manufacture the electrode plate group, and the productivity of the electrode plate group is lowered. From this, it is considered that the crack rate is good within 20%.
- Table 3 The results are also shown in Table 3.
- a lithium ion battery cell (power storage device) was assembled by placing the positive electrode manufactured in the above-described method by punching and molding the positive electrode to a diameter of 16.16 mm, and sealing the outer body of the bipolar coin cell with a screw.
- charging is started at a constant current (3C) for the same cell, and when the voltage reaches 4.2V, charging is continued at a constant voltage (4.2V).
- the charging capacity at 3C was measured with the time point of becoming the completion of charging (cut-off).
- discharge was started at a constant current (3C), and when the voltage reached 2.7 V, the discharge was completed (cut off), and the discharge capacity at 3C was measured.
- the cell after the aging charge / discharge is put in a thermostat at 25 ° C., and charging is started at a constant current (0.2 C).
- a constant current 0.2 C
- the cell is continuously maintained at a constant voltage (4.1 V).
- Charging was continued, and charging was completed (cut off) when the current value reached 0.01C.
- discharge was started at a constant current (0.2 C), and when the voltage reached 2.5 V, the discharge was completed (cut off), and C1 which was the value of the discharge capacity (initial) at 0.2 C was measured. did.
- 5C rate characteristics (%) (C2 / C1) ⁇ 100 (7) It can be determined that the larger the value of the 5C rate characteristic, the better the output characteristic can be obtained even in the high-speed discharge, but it can be determined that the value is particularly good when the value of the 5C rate characteristic is 60% or more.
- EIS measurement (“Electrochemical Impedance Spectroscopy”, “electrochemical impedance measurement”) was performed on the charged cell, and the initial resistance value EISA was measured.
- the charged cell was placed in a constant temperature bath at 25 ° C., the cell temperature was lowered to 25 ° C., and then discharging was started at a constant current (0.2 C), and the voltage became 2.5V. Was completed (cutoff), and C2 as a value of the discharge capacity at 0.2 C (after the test) was measured.
- the cell having the above discharge capacity (after the test) is placed in a constant temperature bath at 25 ° C., and charging is started at a constant current (0.2 C).
- a constant current 0.2 C
- the constant voltage 4.1 V
- the charging was continued at, and the time when the current value reached 0.01 C was regarded as charging completion (cut-off).
- discharging was started at a constant current (0.2 C), and the time when the voltage reached 2.5 V was regarded as completion of discharging (cut-off).
- EIS measurement of this cell was performed, and EISb which is a resistance value after application of thermal stress and overcharge stress was measured.
- “1C” indicates a current value at which discharge is completed in 1 hour after constant-current discharge of a cell having a certain electric capacity.
- “0.1 C” is a current value at which discharge is completed over 10 hours
- “10 C” is a current value at which discharge is completed over 0.1 hours.
- AMM acrylamide MAMMA: methacrylamide NMAM: N-methylol acrylamide
- ATBS acrylamide t-butyl sulfonic acid
- AA acrylic acid
- MAA methacrylic acid
- VS vinyl sulfonic acid
- AS allyl sulfonic acid
- MAS Methallylsulfonic acid
- MMA methyl methacrylate
- MA methyl acrylate
- BA n-butyl acrylate
- EA ethyl acrylate
- HEMA 2-hydroxyethyl methacrylate
- AN acrylonitrile
- MAN methacrylonitrile
- DMAEA dimethylaminoethyl acrylate
- DMAEA-Q dimethylaminoethyl acrylate methyl chloride quaternary salt
- 2VP 2-vinylpyridine
- 1VI 1-vinylimidazole
- NMC (111): manufactured by Umicore, nickel, manganese, lithium cobaltate (nickel (Ni): cobalt (Co): manganese (Mn) is 1: 1: 1), grade name “MX-10” NMC (532): manufactured by Umicore, nickel, manganese, lithium cobalt oxide (nickel (Ni): cobalt (Co): manganese (Mn) is 5: 3: 2), grade name "TX-10” AB: Acetylene black (Denka Black 50% press, manufactured by Denki Kagaku Kogyo Co., Ltd.) ⁇ Graphite: Made by Hitachi Chemical Co., Ltd., trade name “MAG” NaVO 3 : manufactured by Wako Pure Chemical Industries, Ltd., sodium metavanadate (V)
- the slurry for an electricity storage device electrode prepared using the binder composition for an electricity storage device according to the present invention shown in Examples 1 to 24 has excellent spinnability and adhesion. Since the properties (for example, the binding property between the current collector and the active material layer, the binding property between the active materials) are good, an excellent electrode having a low crack rate was provided. Moreover, the electrical storage device (lithium ion battery) provided with these electrodes had favorable charge / discharge rate characteristics.
- Example 25 6.4.1. Preparation of slurry for protective film Titanium oxide (product name “KR380”, manufactured by Titanium Industry Co., Ltd., rutile type, average particle size 0.38 ⁇ m) is 100 parts by mass with respect to 500 parts by mass of water. An amount corresponding to 5 parts by mass of the obtained binder composition S1 for an electricity storage device in terms of a water-soluble polymer (A) with respect to 100 parts by mass of the filler was calculated using T.P. K. Using a Mixmix (R) type 56-50 (manufactured by PRIMIX Co., Ltd.), a mixture dispersion treatment was performed to prepare a slurry for a protective film in which titanium oxide was dispersed. The spinnability of the protective film slurry thus obtained was evaluated in the same manner as in Example 1.
- Titanium oxide product name “KR380”, manufactured by Titanium Industry Co., Ltd., rutile type, average particle size 0.38 ⁇ m
- the slurry for positive electrode was prepared by stirring and mixing for 5 minutes at 1800 rpm for 1 minute at 1800 rpm.
- the obtained positive electrode slurry was uniformly applied to the surface of a current collector made of aluminum foil by a doctor blade method so that the film thickness after drying was 120 ⁇ m, followed by drying treatment at 120 ° C. for 20 minutes.
- the positive electrode was obtained by pressing with a roll press so that the density of an active material layer might be 3.0 g / cm ⁇ 3 >.
- the protective film slurry prepared above was applied to the surface of the active material layer using a die coating method, and then dried at 120 ° C. for 5 minutes to form a protective film on the surface of the active material layer.
- the formed protective film had a thickness of 3 ⁇ m.
- the crack rate of the electrode plate (protective film) was evaluated in the same manner as in Example 1.
- Negative electrode Biaxial planetary mixer product name “TK Hibismix 2P-03” manufactured by PRIMIX Corporation
- PVDF polyvinylidene fluoride
- NMP N-methylpyrrolidone
- the negative electrode slurry prepared above was uniformly applied to the surface of a current collector made of copper foil by a doctor blade method so that the film thickness after drying was 110 ⁇ m, and dried at 120 ° C. for 20 minutes. Then, the negative electrode was obtained by pressing using a roll-press machine so that the density of a film
- a separator made of a polypropylene porous membrane punched into a diameter of 24 mm (trade name “Celguard # 2400” manufactured by Celgard Co., Ltd.) was placed, and after injecting 500 ⁇ L of an electrolyte solution so that air did not enter,
- the positive electrode manufactured in the above is punched and molded to a diameter of 16.16 mm and placed so that the protective film formed on the positive electrode and the separator face each other, and the outer body of the bipolar coin cell is closed with a screw and sealed.
- a lithium ion battery cell (electric storage device) was assembled.
- Example 26 to 28, Comparative Examples 5 to 6 In Example 25 above, the protective film was used in the same manner as in Example 25, except that the binder composition for an electricity storage device used was changed to that shown in Table 5 and the filler used was that shown in Table 5. Slurry was prepared and its spinnability was evaluated. Further, a positive electrode was produced in the same manner as in Example 25 except that the protective film slurry used in Example 25 was changed to that shown in Table 5, and the crack rate was evaluated. Furthermore, after producing a negative electrode in the same manner as in Example 25, an electricity storage device was produced, and charge / discharge rate characteristics were similarly evaluated. These evaluation results are also shown in Table 5.
- Example 25 the binder composition for an electricity storage device used was changed to that shown in Table 6, and the same procedure as in Example 25 was applied except that the filler used was that shown in Table 6. A membrane slurry was prepared and evaluated for spinnability. The evaluation results are also shown in Table 6.
- a negative electrode is produced in the same manner as in Example 25, and the obtained slurry for protective film is applied to the surface of the active material layer of the negative electrode using a die coating method, followed by drying at 120 ° C. for 5 minutes.
- a protective film was formed on the surface of the active material layer.
- the crack rate of the electrode plate (protective film) was evaluated in the same manner as in Example 25 above. The evaluation results are also shown in Table 6.
- Example 25 the battery was charged in the same manner as in Example 25 except that the positive electrode before forming the protective film produced in Example 25 was used as the positive electrode and the negative electrode with protective film obtained above was used as the negative electrode.
- a device was manufactured (however, the negative electrode protective film and the separator were placed facing each other), and the charge / discharge rate characteristics, the remaining capacity rate, and the resistance increase rate were similarly evaluated. These evaluation results are also shown in Table 6.
- Example 32 A wire bar was prepared by applying the slurry for the protective film prepared in Example 25 on one side of a separator (trade name “Celguard # 2400” manufactured by Celgard Co., Ltd.) made of a polypropylene porous film so that the thickness after drying was 10 ⁇ m. And then dried at 90 ° C. for 20 minutes to obtain a separator with a protective film. About the separator with a protective film thus obtained, the crack rate of the protective film was evaluated in the same manner as in Example 25. The evaluation results are also shown in Table 7.
- a separator trade name “Celguard # 2400” manufactured by Celgard Co., Ltd.
- Example 25 the positive electrode before the protective film produced in Example 25 was formed as the positive electrode, and the negative electrode produced in Example 25 was used as the negative electrode, and the protective film surface of the separator with protective film obtained above was An electricity storage device was produced in the same manner as in Example 25 so as to be on the positive electrode side, and charge / discharge rate characteristics were similarly evaluated. The results are also shown in Table 7.
- Example 33 to 39 Comparative Examples 9 to 10
- a separator with a protective film was prepared in the same manner as in Example 32 except that the slurry for protective film was prepared by changing the binder composition and filler for the electricity storage device used to those shown in Table 7.
- a positive electrode, a negative electrode, and an electricity storage device were manufactured and evaluated in the same manner. The results are also shown in Table 5.
- Titanium oxide The product name “KR380” (manufactured by Titanium Industry Co., Ltd., rutile type, average particle size 0.38 ⁇ m) is used as it is, or is ground in a mortar with the product name “KR380” and used with a sieve. By classification, titanium oxides having an average particle diameter of 0.08 ⁇ m and 0.12 ⁇ m were prepared and used.
- Aluminum oxide Product name “AKP-3000” (manufactured by Sumitomo Chemical Co., Ltd., average particle size 0.74 ⁇ m), or product name “AL-160SG-3” (manufactured by Showa Denko Co., Ltd., average particle size 0.98 ⁇ m) Was used.
- Zirconium oxide Product name “UEP zirconium oxide” (Daiichi Rare Element Chemical Industries, Ltd., average particle size 0.67 ⁇ m)
- Silica The product name “Seahoster KE-S50” (manufactured by Nippon Shokubai Co., Ltd., average particle size 0.54 ⁇ m) was used.
- Magnesium oxide Product name “PUREMAG® FNM-G” (manufactured by Tateho Chemical Co., Ltd., average particle size 0.50 ⁇ m)
- the protective film slurry prepared using the binder composition for an electricity storage device according to the present invention shown in Examples 25 to 42 has excellent spinnability and a crack rate. A low excellent protective film was given.
- the electrical storage device lithium ion battery
- the electrode with a protective film or the separator with a protective film had favorable charge / discharge rate characteristics.
- the present invention is not limited to the above embodiment, and various modifications can be made.
- the present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same objects and effects).
- the present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration.
- the present invention includes a configuration that achieves the same effects as the configuration described in the above embodiment or a configuration that can achieve the same object.
- the present invention includes a configuration obtained by adding a known technique to the configuration described in the above embodiment.
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Abstract
Description
本発明に係る蓄電デバイス用バインダー組成物の一態様は、
(メタ)アクリルアミドに由来する繰り返し単位を含有し、かつ、重量平均分子量(Mw)が3×105~6×106である水溶性重合体(A)と、
液状媒体(C)と、
を含有することを特徴とする。 [Application Example 1]
One aspect of the binder composition for an electricity storage device according to the present invention is:
A water-soluble polymer (A) containing a repeating unit derived from (meth) acrylamide and having a weight average molecular weight (Mw) of 3 × 10 5 to 6 × 10 6 ;
A liquid medium (C);
It is characterized by containing.
適用例1の蓄電デバイス用バインダー組成物において、
前記水溶性重合体(A)の重量平均分子量(Mw)/数平均分子量(Mn)が3~30であることができる。 [Application Example 2]
In the binder composition for an electricity storage device of Application Example 1,
The water-soluble polymer (A) may have a weight average molecular weight (Mw) / number average molecular weight (Mn) of 3 to 30.
適用例1または適用例2の蓄電デバイス用バインダー組成物において、
不飽和カルボン酸、不飽和アミド、およびこれらの塩よりなる群から選択される少なくとも1種の化合物(B)をさらに含有することができる。 [Application Example 3]
In the binder composition for an electricity storage device of Application Example 1 or Application Example 2,
It can further contain at least one compound (B) selected from the group consisting of unsaturated carboxylic acids, unsaturated amides, and salts thereof.
適用例1ないし適用例3のいずれか一例の蓄電デバイス用バインダー組成物において、
前記水溶性重合体(A)100質量部中に含有される前記(メタ)アクリルアミドに由来する繰り返し単位の割合が40~100質量部であることができる。 [Application Example 4]
In the binder composition for an electricity storage device according to any one of Application Examples 1 to 3,
The proportion of the repeating unit derived from the (meth) acrylamide contained in 100 parts by mass of the water-soluble polymer (A) may be 40 to 100 parts by mass.
適用例1ないし適用例4のいずれか一例の蓄電デバイス用バインダー組成物において、
前記水溶性重合体(A)100質量部中に含有される、前記(メタ)アクリルアミドに由来する繰り返し単位の割合が40~90質量部であり、かつ、カチオン性単量体に由来する繰り返し単位の割合が10~30質量部であることができる。 [Application Example 5]
In the binder composition for an electricity storage device according to any one of Application Examples 1 to 4,
The proportion of the repeating unit derived from (meth) acrylamide contained in 100 parts by mass of the water-soluble polymer (A) is 40 to 90 parts by mass, and the repeating unit derived from a cationic monomer. Can be 10 to 30 parts by mass.
適用例3ないし適用例5のいずれか一例の蓄電デバイス用バインダー組成物において、
前記水溶性重合体(A)100質量部に対して、前記化合物(B)を0.01~0.5質量部含有することができる。 [Application Example 6]
In the binder composition for an electricity storage device according to any one of Application Examples 3 to 5,
The compound (B) can be contained in an amount of 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the water-soluble polymer (A).
適用例1ないし適用例6のいずれか一例の蓄電デバイス用バインダー組成物において、
前記水溶性重合体(A)が、重合性不飽和二重結合を有する酸、不飽和カルボン酸エステルおよびα,β-不飽和ニトリル化合物よりなる群から選択される少なくとも1種に由来する繰り返し単位をさらに含むことができる。 [Application Example 7]
In the binder composition for an electricity storage device according to any one of Application Examples 1 to 6,
The water-soluble polymer (A) is a repeating unit derived from at least one selected from the group consisting of an acid having a polymerizable unsaturated double bond, an unsaturated carboxylic acid ester, and an α, β-unsaturated nitrile compound. Can further be included.
適用例7の蓄電デバイス用バインダー組成物において、
前記重合性不飽和二重結合を有する酸が、アクリル酸、メタクリル酸、イタコン酸、ビニルスルホン酸、アリルスルホン酸およびメタリルスルホン酸よりなる群から選択される少なくとも1種であることができる。 [Application Example 8]
In the binder composition for an electricity storage device of Application Example 7,
The acid having a polymerizable unsaturated double bond may be at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, vinyl sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid.
本発明に掛かる蓄電デバイス用スラリーの一態様は、
適用例1ないし適用例8のいずれか一例の蓄電デバイス用バインダー組成物と、活物質と、を含有することを特徴とする。 [Application Example 9]
One aspect of the slurry for an electricity storage device according to the present invention is:
It contains the binder composition for electrical storage devices of any one of the application examples 1 to 8, and an active material.
適用例9の蓄電デバイス用スラリーにおいて、
蓄電デバイス負極を作製するための蓄電デバイス用スラリーであって、前記活物質の平均粒子径が3μm以上10μm以下であることができる。 [Application Example 10]
In the slurry for the electricity storage device of Application Example 9,
A slurry for an electricity storage device for producing an electricity storage device negative electrode, wherein an average particle diameter of the active material may be 3 μm or more and 10 μm or less.
適用例10の蓄電デバイス用スラリーにおいて、
前記活物質が、炭素材料およびケイ素材料の少なくとも一方を含むことができる。 [Application Example 11]
In the slurry for the electricity storage device of Application Example 10,
The active material may include at least one of a carbon material and a silicon material.
適用例9の蓄電デバイス用スラリーにおいて、
蓄電デバイス正極を作製するための蓄電デバイス用スラリーであって、前記活物質の平均粒子径が0.4μm以上7μm以下であることができる。 [Application Example 12]
In the slurry for the electricity storage device of Application Example 9,
A slurry for an electricity storage device for producing an electricity storage device positive electrode, wherein an average particle size of the active material may be 0.4 μm or more and 7 μm or less.
本発明に係る蓄電デバイス用スラリーの一態様は、
適用例1ないし適用例8のいずれか一例の蓄電デバイス用バインダー組成物と、フィラーと、を含有することを特徴とする。 [Application Example 13]
One aspect of the slurry for an electricity storage device according to the present invention is:
It contains the binder composition for electrical storage devices of any one of the application examples 1 to 8, and a filler.
適用例13の蓄電デバイス用スラリーにおいて、
前記フィラーが、シリカ、酸化チタン、酸化アルミニウム、酸化ジルコニウムおよび酸化マグネシウムよりなる群から選択される少なくとも1種の粒子であることができる。 [Application Example 14]
In the slurry for the electricity storage device of Application Example 13,
The filler may be at least one particle selected from the group consisting of silica, titanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide.
本発明に係る蓄電デバイス電極の一態様は、
集電体と、前記集電体の表面上に適用例9ないし適用例12のいずれか一例の蓄電デバイス用スラリーが塗布および乾燥されて形成された層と、を備えることを特徴とする。 [Application Example 15]
One aspect of the electricity storage device electrode according to the present invention is:
It is characterized by comprising: a current collector; and a layer formed by applying and drying the electricity storage device slurry of any one of application examples 9 to 12 on the surface of the current collector.
本発明に係る蓄電デバイス電極の一態様は、
集電体と、前記集電体の表面に形成された活物質層と、を備え、
前記活物質層の表面に適用例13または適用例14の蓄電デバイス用スラリーを塗布および乾燥させて形成された層をさらに備えることを特徴とする。 [Application Example 16]
One aspect of the electricity storage device electrode according to the present invention is:
A current collector, and an active material layer formed on the surface of the current collector,
It is further characterized by further comprising a layer formed by applying and drying the electricity storage device slurry of Application Example 13 or Application Example 14 on the surface of the active material layer.
本発明に係るセパレーターの一態様は、
適用例13または適用例14の蓄電デバイス用スラリーを塗布および乾燥させて形成された層を表面に備えることを特徴とする。 [Application Example 17]
One aspect of the separator according to the present invention is:
A layer formed by applying and drying the slurry for an electricity storage device of Application Example 13 or Application Example 14 is provided on the surface.
本発明に係る蓄電デバイスの一態様は、
適用例15または適用例16の蓄電デバイス電極および適用例17のセパレーターの少なくとも一方を備えることを特徴とする。 [Application Example 18]
One aspect of the electricity storage device according to the present invention is:
At least one of the electricity storage device electrode of Application Example 15 or Application Example 16 and the separator of Application Example 17 is provided.
本実施の形態に係る蓄電デバイス用バインダー組成物は、(メタ)アクリルアミドに由来する繰り返し単位を含有し、かつ、重量平均分子量(Mw)が3×105~6×106である水溶性重合体(A)と、液状媒体(C)と、を含有することを特徴とする。 1. Binder composition for electricity storage device The binder composition for electricity storage device according to the present embodiment contains a repeating unit derived from (meth) acrylamide and has a weight average molecular weight (Mw) of 3 × 10 5 to 6 × 10. 6. A water-soluble polymer (A) 6 and a liquid medium (C) are contained.
本実施の形態に係る蓄電デバイス用バインダー組成物は、(メタ)アクリルアミドに由来する繰り返し単位を含有する水溶性重合体(A)を含む。また、水溶性重合体(A)は、(メタ)アクリルアミドに由来する繰り返し単位の他に、それと共重合可能な他の単量体に由来する繰り返し単位を含有してもよい。他の単量体としては、例えば、重合性不飽和二重結合を有する酸、不飽和カルボン酸エステル、α,β-不飽和ニトリル化合物、カチオン性単量体、共役ジエン化合物、芳香族ビニル化合物等が挙げられる。 1.1. Water-soluble polymer (A)
The binder composition for an electricity storage device according to the present embodiment includes a water-soluble polymer (A) containing a repeating unit derived from (meth) acrylamide. In addition to the repeating unit derived from (meth) acrylamide, the water-soluble polymer (A) may contain a repeating unit derived from another monomer copolymerizable therewith. Examples of the other monomer include an acid having a polymerizable unsaturated double bond, an unsaturated carboxylic acid ester, an α, β-unsaturated nitrile compound, a cationic monomer, a conjugated diene compound, and an aromatic vinyl compound. Etc.
水溶性重合体(A)100質量部中に含有される(メタ)アクリルアミドに由来する繰り返し単位の割合は40~100質量部であることが好ましく、45~95質量部であることがより好ましく、50~85質量部であることが特に好ましい。(メタ)アクリルアミドに由来する繰り返し単位を前記範囲で含有することにより、活物質やフィラーの分散性が良好となり、均一な活物質層や保護膜の作製が可能となるため構造欠陥がなくなり、良好な充放電特性を示す。さらに(メタ)アクリルアミドに由来する繰り返し単位を前記範囲で含有することにより、ポリマーの耐酸化性が良好となるため、高電圧時の劣化が抑制され良好な充放電耐久特性を示す。 1.1.1. Repeating units derived from (meth) acrylamide The proportion of repeating units derived from (meth) acrylamide contained in 100 parts by weight of the water-soluble polymer (A) is preferably 40 to 100 parts by weight, and 45 to 95. The amount is more preferably part by mass, and particularly preferably 50 to 85 parts by mass. By containing the repeating unit derived from (meth) acrylamide in the above range, the dispersibility of the active material and filler becomes good, and it becomes possible to produce a uniform active material layer and a protective film. Shows excellent charge / discharge characteristics. Furthermore, by containing a repeating unit derived from (meth) acrylamide in the above range, the oxidation resistance of the polymer becomes good, and therefore, deterioration at high voltage is suppressed, and good charge / discharge durability characteristics are exhibited.
水溶性重合体(A)は、さらに重合性不飽和二重結合を有する酸(上記(メタ)アクリルアミドに該当するものを除く。)に由来する繰り返し単位を有してもよい。水溶性重合体(A)が重合性不飽和二重結合を有する酸に由来する繰り返し単位を有する場合、水溶性重合体(A)100質量部中に含有される重合性不飽和二重結合を有する酸に由来する繰り返し単位の割合は、0~30質量部であることが好ましく、5~25質量部であることがより好ましい。水溶性重合体(A)が重合性不飽和二重結合を有する酸に由来する繰り返し単位を前記範囲で含有することにより、本実施の形態に係る蓄電デバイス用バインダー組成物を用いて調製された蓄電デバイス用スラリーの安定性が向上する。 1.1.2. Repeating unit derived from an acid having a polymerizable unsaturated double bond The water-soluble polymer (A) is an acid having a polymerizable unsaturated double bond (excluding those corresponding to the above (meth) acrylamide). It may have repeating units derived from it. When the water-soluble polymer (A) has a repeating unit derived from an acid having a polymerizable unsaturated double bond, the polymerizable unsaturated double bond contained in 100 parts by mass of the water-soluble polymer (A) The ratio of the repeating unit derived from the acid is preferably 0 to 30 parts by mass, and more preferably 5 to 25 parts by mass. The water-soluble polymer (A) was prepared using the binder composition for an electricity storage device according to the present embodiment by containing a repeating unit derived from an acid having a polymerizable unsaturated double bond in the above range. The stability of the slurry for the electricity storage device is improved.
水溶性重合体(A)は、さらに不飽和カルボン酸エステルに由来する繰り返し単位を有してもよい。水溶性重合体(A)が不飽和カルボン酸エステルに由来する繰り返し単位を有する場合、水溶性重合体(A)100質量部中に含有される不飽和カルボン酸エステルに由来する繰り返し単位の割合は、0~30質量部であることが好ましく、1~10質量部であることがより好ましい。不飽和カルボン酸エステルに由来する繰り返し単位を前記範囲で含有することにより、水溶性重合体(A)は電解液との親和性がより好適なものとなり、蓄電デバイス中でバインダーが電気抵抗成分となることによる内部抵抗の上昇を抑制すると共に、電解液を過大に吸収することによる密着性の低下を防ぐことができる。 1.1.3. Repeating unit derived from unsaturated carboxylic acid ester The water-soluble polymer (A) may further have a repeating unit derived from an unsaturated carboxylic acid ester. When the water-soluble polymer (A) has a repeating unit derived from an unsaturated carboxylic acid ester, the ratio of the repeating unit derived from the unsaturated carboxylic acid ester contained in 100 parts by mass of the water-soluble polymer (A) is The content is preferably 0 to 30 parts by mass, more preferably 1 to 10 parts by mass. By containing the repeating unit derived from the unsaturated carboxylic acid ester in the above range, the water-soluble polymer (A) has a more favorable affinity with the electrolytic solution, and the binder in the electricity storage device is an electrical resistance component. It is possible to prevent an increase in internal resistance due to the above and to prevent a decrease in adhesion due to excessive absorption of the electrolytic solution.
水溶性重合体(A)は、さらにα,β-不飽和ニトリル化合物に由来する繰り返し単位を有してもよい。重合体(A)がα,β-不飽和ニトリル化合物に由来する繰り返し単位を有する場合、水溶性重合体(A)100質量部中に含有されるα,β-不飽和ニトリル化合物に由来する繰り返し単位の割合は、0~30質量部であることが好ましく、1~10質量部であることがより好ましい。α,β-不飽和ニトリル化合物に由来する繰り返し単位を前記範囲で含有することにより、水溶性重合体(A)の電解液に対する親和性が良好となるため、電解液吸収能が向上する。すなわち、ニトリル基の存在によって電極中に形成された重合体鎖からなる網目構造に溶媒が均一に拡散し易くなるため、溶媒和したリチウムイオンがこの網目構造をすり抜けて移動し易くなる。これにより、リチウムイオンの拡散性が向上すると考えられ、その結果、電極抵抗が低下してより良好な充放電特性を実現することができると考えられる。 1.1.4. Repeating unit derived from α, β-unsaturated nitrile compound The water-soluble polymer (A) may further have a repeating unit derived from an α, β-unsaturated nitrile compound. When the polymer (A) has a repeating unit derived from an α, β-unsaturated nitrile compound, the repeating derived from the α, β-unsaturated nitrile compound contained in 100 parts by mass of the water-soluble polymer (A) The unit ratio is preferably 0 to 30 parts by mass, and more preferably 1 to 10 parts by mass. By containing the repeating unit derived from the α, β-unsaturated nitrile compound within the above range, the affinity of the water-soluble polymer (A) for the electrolytic solution is improved, so that the electrolytic solution absorption ability is improved. That is, the presence of the nitrile group makes it easy for the solvent to uniformly diffuse into the network structure formed of polymer chains formed in the electrode, so that the solvated lithium ions can easily move through the network structure. Thereby, it is thought that the diffusibility of lithium ion improves, As a result, electrode resistance falls and it is thought that a more favorable charge / discharge characteristic can be implement | achieved.
本発明における「カチオン性単量体」とは、上述の(メタ)アクリルアミド以外のカチオン性単量体のことをいう。水溶性重合体(A)100質量部中に含有されるカチオン性単量体に由来する繰り返し単位の割合は、10~30質量部であることが好ましく、13~28質量部であることがより好ましく、15~25質量部であることが特に好ましい。カチオン性単量体に由来する繰り返し単位を前記範囲で含有することにより、活物質やフィラーの分散性が良好となり、均一な活物質層の作製が可能となるため構造欠陥がなくなり、良好な充放電特性を示す。さらにカチオン性単量体に由来する繰り返し単位を前記範囲で含有することにより、ポリマーの耐酸化性が良好となるため、高電圧時の劣化が抑制され良好な充放電耐久特性を示す。カチオン性単量体に由来する繰り返し単位の割合が前記範囲未満であると、スラリーを塗布する際、レベリング性が不足するため、塗膜の厚みの均一性が損なわれる場合がある。厚みが不均一な電極を使用すると、充放電反応の面内分布が発生するため、安定した電池性能の発現が困難となる。一方、カチオン性単量体に由来する繰り返し単位の割合が前記範囲を超えると、蓄電デバイスの充放電レート特性が劣化するおそれがある。 1.1.5. Repeating Unit Derived from Cationic Monomer The “cationic monomer” in the present invention refers to a cationic monomer other than the above-mentioned (meth) acrylamide. The ratio of the repeating unit derived from the cationic monomer contained in 100 parts by mass of the water-soluble polymer (A) is preferably 10 to 30 parts by mass, more preferably 13 to 28 parts by mass. The amount is preferably 15 to 25 parts by mass. By containing the repeating unit derived from the cationic monomer within the above range, the dispersibility of the active material and filler becomes good, and a uniform active material layer can be produced, so that there is no structural defect and good filling is achieved. Shows the discharge characteristics. Furthermore, since the oxidation resistance of a polymer becomes favorable by containing the repeating unit derived from a cationic monomer in the said range, the deterioration at the time of a high voltage is suppressed and a favorable charge / discharge durability characteristic is shown. When the ratio of the repeating unit derived from the cationic monomer is less than the above range, the leveling property is insufficient when the slurry is applied, and thus the uniformity of the thickness of the coating film may be impaired. When an electrode having a non-uniform thickness is used, an in-plane distribution of charge / discharge reaction occurs, making it difficult to achieve stable battery performance. On the other hand, when the ratio of the repeating unit derived from the cationic monomer exceeds the above range, the charge / discharge rate characteristics of the electricity storage device may be deteriorated.
水溶性重合体(A)は、さらに共役ジエン化合物や芳香族ビニル化合物に由来する繰り返し単位を含有してもよい。 1.1.6. Repeating unit derived from other monomer The water-soluble polymer (A) may further contain a repeating unit derived from a conjugated diene compound or an aromatic vinyl compound.
1.1.7.1.水溶性重合体(A)の分子量
水溶性重合体(A)の重量平均分子量(Mw)は、30万~600万の範囲内にあることが必要であり、55万~450万であることが好ましく、60万~300万であることがより好ましい。本実施の形態に係る蓄電デバイス用バインダー組成物が、上述の分子量範囲を有する水溶性重合体(A)を含有することにより、良好な充放電特性が発現しやすくなる。その理由は必ずしも明確ではないが、以下のように推測される。 1.1.7. Characteristics of water-soluble polymer (A) 1.1.7.1. Molecular weight of water-soluble polymer (A) The weight average molecular weight (Mw) of the water-soluble polymer (A) needs to be within the range of 300,000 to 6 million, and should be 550,000 to 4.5 million. Preferably, it is 600,000-3 million. When the binder composition for an electricity storage device according to the present embodiment contains the water-soluble polymer (A) having the above-described molecular weight range, good charge / discharge characteristics are easily developed. The reason is not necessarily clear, but is presumed as follows.
水溶性重合体(A)が酸基を有する場合には、用途に応じて適宜中和度を調整して使用できる。活物質やフィラーを分散させるときの中和度は特に限定されないが、電極または保護膜などの形成後には0.7~1.0であることが好ましく、0.85~1.0であることがより好ましい。電極作製後の中和度を上記範囲とすることで、酸の大半が中和された状態となり、電池内でLiイオンなどと結合して、容量低下を引き起こすことがなくなるため好ましい。中和塩としては、Li塩、Na塩、K塩、アンモニウム塩、Mg塩、Ca塩、Zn塩、Al塩などが挙げられる。 1.1.7.2. Degree of neutralization of water-soluble polymer (A) When the water-soluble polymer (A) has an acid group, the degree of neutralization can be appropriately adjusted according to the use. The degree of neutralization when the active material or filler is dispersed is not particularly limited, but it is preferably 0.7 to 1.0, and preferably 0.85 to 1.0 after the formation of the electrode or the protective film. Is more preferable. By setting the degree of neutralization after electrode preparation within the above range, most of the acid is in a neutralized state and is preferably combined with Li ions or the like in the battery and does not cause a decrease in capacity. Examples of the neutralized salt include Li salt, Na salt, K salt, ammonium salt, Mg salt, Ca salt, Zn salt, Al salt and the like.
水溶性重合体(A)の合成方法は特に制限されないが、水を主成分とした溶媒中で行う重合が好ましい。特に好ましい重合形態は水溶液重合である。水溶性重合体(A)の合成時に用いる重合開始剤は、水溶性ラジカル開始剤が好ましく、過硫酸リチウム、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の過硫酸塩や4,4’-アゾビス(4-シアノ吉草酸)等の水溶性アゾ系開始剤が特に好ましい。重合開始剤の使用量は上述の重量平均分子量(30万~600万)を有する水溶性重合体(A)を得る観点から、重合させる単量体の全質量100質量部に対して、0.1~1.0質量部であることが好ましい。 1.1.8. Production Method of Water-Soluble Polymer (A) The method for synthesizing the water-soluble polymer (A) is not particularly limited, but polymerization performed in a solvent containing water as a main component is preferable. A particularly preferred polymerization form is aqueous solution polymerization. The polymerization initiator used in the synthesis of the water-soluble polymer (A) is preferably a water-soluble radical initiator, and is a persulfate such as lithium persulfate, potassium persulfate, sodium persulfate, ammonium persulfate, or 4,4′-azobis. Water-soluble azo initiators such as (4-cyanovaleric acid) are particularly preferred. From the viewpoint of obtaining a water-soluble polymer (A) having the above-mentioned weight average molecular weight (300,000 to 6,000,000), the amount of the polymerization initiator used is 0. The amount is preferably 1 to 1.0 part by mass.
本実施の形態に係る蓄電デバイス用バインダー組成物は、不飽和カルボン酸、不飽和アミド、およびこれらの塩よりなる群から選択される少なくとも1種の化合物(B)を含有してもよい。本実施の形態に係る蓄電デバイス用バインダー組成物が化合物(B)を含有することにより、蓄電デバイスの充放電特性が良好となる。この効果の発現機構については必ずしも明らかではないが、以下のように推測される。一般的に活物質粒子やフィラー粒子等の分散液へ新たな成分を添加すると、その新たな成分がトリガーとなり、これらの粒子の凝集が発生しやすい。それにもかかわらず、化合物(B)を添加した蓄電デバイス用バインダー組成物と活物質粒子またはフィラー粒子とを混合して蓄電デバイス用スラリーを作製すると、活物質粒子やフィラー粒子の凝集による不均一化が大幅に抑制されることが確認されている。この理由としては、化合物(B)が活物質粒子やフィラー粒子との親和性に優れていることに起因するものと考えられる。これにより、集電体や電極、セパレーターの表面に形成される塗膜の均質性が良好となるため、これらと塗膜との密着性が向上し、蓄電デバイスの充放電特性が良好になるものと推測される。 1.2. Compound (B)
The binder composition for an electricity storage device according to the present embodiment may contain at least one compound (B) selected from the group consisting of unsaturated carboxylic acids, unsaturated amides, and salts thereof. When the binder composition for an electricity storage device according to the present embodiment contains the compound (B), the charge / discharge characteristics of the electricity storage device are improved. The expression mechanism of this effect is not necessarily clear, but is estimated as follows. In general, when a new component is added to a dispersion of active material particles, filler particles, or the like, the new component is a trigger, and aggregation of these particles is likely to occur. Nevertheless, when the slurry for an electricity storage device is prepared by mixing the binder composition for an electricity storage device to which the compound (B) is added and the active material particles or filler particles, non-uniformity is caused by the aggregation of the active material particles and the filler particles. Has been confirmed to be significantly suppressed. The reason for this is considered to be that the compound (B) is excellent in affinity with the active material particles and filler particles. As a result, the homogeneity of the coating film formed on the surface of the current collector, electrode and separator is improved, so that the adhesion between them and the coating film is improved, and the charge / discharge characteristics of the electricity storage device are improved. It is guessed.
不飽和カルボン酸(塩)は加熱されることにより脱炭酸反応が発生しやすく、低分子量成分に分解されやすい。このため、化合物(B)が不飽和カルボン酸(塩)である場合、電極作製工程やセパレーター作製工程において塗膜の乾燥のために加熱すると、塗膜中に残留した化合物(B)が蒸発する他、徐々に分解して、たとえ残留したとしても蓄電デバイス特性に悪影響を与えない量まで塗膜中から除去することができると考えられる。その結果、化合物(B)による集電体の経時的な腐食が抑制されるので、蓄電デバイス特性の劣化を抑制でき、安定した充放電特性を発現できると考えられる。 1.2.1. Unsaturated carboxylic acid (salt)
Unsaturated carboxylic acids (salts) are susceptible to decarboxylation when heated, and are easily decomposed into low molecular weight components. For this reason, when the compound (B) is an unsaturated carboxylic acid (salt), the compound (B) remaining in the coating film evaporates when heated for drying the coating film in the electrode manufacturing process or the separator manufacturing process. In addition, it is considered that even if it is gradually decomposed and remains, it can be removed from the coating film to an amount that does not adversely affect the electricity storage device characteristics. As a result, since the corrosion of the current collector with the compound (B) is suppressed over time, it is considered that deterioration of the electricity storage device characteristics can be suppressed and stable charge / discharge characteristics can be expressed.
不飽和アミド(塩)としては、密着性向上の観点から重合性不飽和基を有することが好ましく、(メタ)アクリルアミド基を有することがより好ましい。不飽和アミド(塩)の具体例としては、アクリルアミド、メタクリルアミド、N-メチロールアクリルアミド、N-メチロールクロトンアミド、N-ブトキシメチルアクリルアミド、N-ブトキシメチルメタクリルアミド、ジアセトンアクリルアミド、ジアセトンメタクリルアミド、アミノプロピルアクリルアミド、アミノプロピルメタクリルアミド、モノメチルアクリルアミド、モノメチルメタクリルアミド、モノエチルアクリルアミド、モノエチルメタクリルアミド、N-(2-ヒドロキシエチル)アクリルアミド、N-(2-ヒドロキシエチル)メタクリルアミド、N-(2-ヒドロキシプロピル)アクリルアミド、N-(2-ヒドロキシプロピル)メタクリルアミド、N,N-ジメチルアクリルアミド、N,N-ジメチルメタクリルアミド、N,N-ジエチルアクリルアミド、N,N-ジエチルメタクリルアミド、N-イソプロピルアクリルアミド、N-アクリロイルモルホリン等が挙げられる。これらのうちから選択される1種以上であることができる。これらの中でも、アクリルアミド、メタクリルアミド、N,N-ジメチルアクリルアミド、N,N-ジエチルアクリルアミド、N-イソプロピルアクリルアミドであることが好ましい。これらの不飽和アミド(塩)は、1種単独で用いることもできるし、2種以上組み合わせて用いることもできる。 1.2.2. Unsaturated amide (salt)
The unsaturated amide (salt) preferably has a polymerizable unsaturated group from the viewpoint of improving adhesion, and more preferably has a (meth) acrylamide group. Specific examples of the unsaturated amide (salt) include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol crotonamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide, diacetone acrylamide, diacetone methacrylamide, Aminopropylacrylamide, aminopropylmethacrylamide, monomethylacrylamide, monomethylmethacrylamide, monoethylacrylamide, monoethylmethacrylamide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, N- (2 -Hydroxypropyl) acrylamide, N- (2-hydroxypropyl) methacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacryl Bromide, N, N- diethyl acrylamide, N, N- diethyl methacrylamide, N- isopropylacrylamide, N- acryloyl morpholine, and the like. It can be one or more selected from these. Among these, acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N-isopropylacrylamide are preferable. These unsaturated amides (salts) can be used alone or in combination of two or more.
本実施の形態に係る蓄電デバイス用バインダー組成物は、液状媒体(C)を含有する。液状媒体(C)としては、水を含有する水系媒体であることが好ましい。この水系媒体には、水以外の非水系媒体を含有させることができる。この非水系媒体としては、例えばアミド化合物、炭化水素、アルコール、ケトン、エステル、アミン化合物、ラクトン、スルホキシド、スルホン化合物などを挙げることができ、これらのうちから選択される1種以上を使用することができる。液状媒体(C)が水系媒体である場合、液状媒体(C)の全量100質量%中、90質量%以上が水であることが好ましく、98質量%以上が水であることがより好ましい。本実施の形態に係る蓄電デバイス用バインダー組成物は、液状媒体(C)として水系媒体を使用することにより、環境に対して悪影響を及ぼす程度が低くなり、取扱作業者に対する安全性も高くなる。 1.3. Liquid medium (C)
The binder composition for an electricity storage device according to the present embodiment contains a liquid medium (C). The liquid medium (C) is preferably an aqueous medium containing water. This aqueous medium can contain a non-aqueous medium other than water. Examples of the non-aqueous medium include amide compounds, hydrocarbons, alcohols, ketones, esters, amine compounds, lactones, sulfoxides, sulfone compounds, and the like. Use one or more selected from these. Can do. When the liquid medium (C) is an aqueous medium, 90% by mass or more is preferably water, and more preferably 98% by mass or more is water in the total amount of 100% by mass of the liquid medium (C). By using an aqueous medium as the liquid medium (C), the binder composition for an electricity storage device according to the present embodiment decreases the degree of adverse effects on the environment and increases the safety for handling workers.
上述したように、本実施の形態に係る蓄電デバイス用バインダー組成物は、蓄電デバイス電極を作製する用途および保護膜を作製する用途の二つの用途に大別することができる。本実施の形態に係る蓄電デバイス用スラリーについても、その用途に応じて二種類に分類することができる。以下、蓄電デバイス電極を作製する用途に用いられる蓄電デバイス用スラリーを「蓄電デバイス電極用スラリー」と、保護膜を作製する用途に用いられる蓄電デバイス用スラリーを「保護膜用スラリー」と呼称するものとする。 2. Power Storage Device Slurry As described above, the power storage device binder composition according to the present embodiment can be broadly divided into two uses, that is, a use for producing a power storage device electrode and a use for producing a protective film. The power storage device slurry according to the present embodiment can also be classified into two types depending on the application. Hereinafter, the slurry for the electricity storage device used for the purpose of producing the electricity storage device electrode is referred to as “slurry for the electricity storage device electrode”, and the slurry for the electricity storage device used for the purpose of producing the protective film is referred to as the “slurry for the protection film”. And
「蓄電デバイス電極用スラリー」とは、これを集電体の表面に塗布した後、乾燥して、集電体表面上に活物質層を形成するために用いられる分散液のことをいう。本実施の形態に係る蓄電デバイス電極用スラリーは、上述の蓄電デバイス用バインダー組成物と、活物質と、を含有する。本実施の形態に係る蓄電デバイス電極用スラリーは、正極および負極のいずれの電極を作製する用途にも用いることができる。以下、本実施の形態に係る蓄電デバイス電極用スラリーに含まれる成分について詳細に説明する。但し、蓄電デバイス用バインダー組成物については、上述した通りであるから説明を省略する。 2.1. Storage device electrode slurry "Storage device electrode slurry" refers to a dispersion liquid used to form an active material layer on the surface of a current collector after it is applied to the surface of the current collector and then dried. That means. The slurry for an electricity storage device electrode according to the present embodiment contains the above-mentioned binder composition for an electricity storage device and an active material. The slurry for an electricity storage device electrode according to the present embodiment can be used for an application for producing either a positive electrode or a negative electrode. Hereinafter, components contained in the slurry for the electricity storage device electrode according to the present embodiment will be described in detail. However, since it is as having mentioned above about the binder composition for electrical storage devices, description is abbreviate | omitted.
本実施の形態に係る蓄電デバイス電極用スラリーに含まれる活物質を構成する材料としては特に制限はなく、目的とする蓄電デバイスの種類により適宜適当な材料を選択することができる。活物質としては、例えば炭素材料、ケイ素材料、リチウム原子を含む酸化物、鉛化合物、錫化合物、砒素化合物、アンチモン化合物、アルミニウム化合物等を挙げることができる。 2.1.1. Active material There is no restriction | limiting in particular as a material which comprises the active material contained in the slurry for electrical storage device electrodes which concerns on this Embodiment, According to the kind of target electrical storage device, a suitable material can be selected suitably. Examples of the active material include carbon materials, silicon materials, oxides containing lithium atoms, lead compounds, tin compounds, arsenic compounds, antimony compounds, aluminum compounds, and the like.
本実施の形態に係る蓄電デバイス電極用スラリーには、必要に応じて導電助剤、非水系媒体、増粘剤、pH調整剤、腐食防止剤等を添加することができる。 2.1.2. Other Additives A conductive additive, a non-aqueous medium, a thickener, a pH adjuster, a corrosion inhibitor, and the like can be added to the electricity storage device electrode slurry according to the present embodiment as necessary.
導電助剤の具体例としては、リチウムイオン二次電池においてはカーボンなどが;ニッケル水素二次電池においては、正極では酸化コバルトが:負極ではニッケル粉末、酸化コバルト、酸化チタン、カーボンなどが、それぞれ用いられる。上記両電池において、カーボンとしては、グラファイト、活性炭、アセチレンブラック、ファーネスブラック、黒鉛、炭素繊維、フラーレンなどを挙げることができる。これらの中でも、アセチレンブラックまたはファーネスブラックを好ましく使用することができる。導電助剤の使用割合は、活物質100質量部に対して、好ましくは20質量部以下であり、より好ましくは1~15質量部であり、特に好ましくは2~10質量部である。 2.1.2.1. Conductive aids Specific examples of conductive aids include carbon in lithium ion secondary batteries; in nickel metal hydride secondary batteries, cobalt oxide at the positive electrode: nickel powder, cobalt oxide, titanium oxide, carbon at the negative electrode, etc. Are used respectively. In both the batteries, examples of carbon include graphite, activated carbon, acetylene black, furnace black, graphite, carbon fiber, and fullerene. Among these, acetylene black or furnace black can be preferably used. The proportion of the conductive auxiliary agent used is preferably 20 parts by mass or less, more preferably 1 to 15 parts by mass, and particularly preferably 2 to 10 parts by mass with respect to 100 parts by mass of the active material.
本実施の形態に係る蓄電デバイス電極用スラリーは、その塗布性を改善する観点から、80~350℃の標準沸点を有する非水系媒体を含有することができる。このような非水系媒体の具体例としては、例えば、N-メチルピロリドン、ジメチルホルムアミド、N,N-ジメチルアセトアミドなどのアミド化合物;トルエン、キシレン、n-ドデカン、テトラリンなどの炭化水素;2-エチル-1-ヘキサノール、1-ノナノール、ラウリルアルコールなどのアルコール;メチルエチルケトン、シクロヘキサノン、ホロン、アセトフェノン、イソホロンなどのケトン;酢酸ベンジル、酪酸イソペンチル、乳酸メチル、乳酸エチル、乳酸ブチルなどのエステル;o-トルイジン、m-トルイジン、p-トルイジンなどのアミン化合物;γ-ブチロラクトン、δ-ブチロラクトンなどのラクトン;ジメチルスルホキシド、スルホランなどのスルホキシド・スルホン化合物などを挙げることができ、これらのうちから選択される1種以上を使用することができる。これらの中でも、蓄電デバイス電極用スラリーを塗布する際の作業性などの点から、N-メチルピロリドンを使用することが好ましい。 2.1.2.2. Non-Aqueous Medium The slurry for an electricity storage device electrode according to the present embodiment can contain a non-aqueous medium having a standard boiling point of 80 to 350 ° C. from the viewpoint of improving its applicability. Specific examples of such a non-aqueous medium include, for example, amide compounds such as N-methylpyrrolidone, dimethylformamide, and N, N-dimethylacetamide; hydrocarbons such as toluene, xylene, n-dodecane, and tetralin; 2-ethyl Alcohols such as -1-hexanol, 1-nonanol and lauryl alcohol; ketones such as methyl ethyl ketone, cyclohexanone, phorone, acetophenone and isophorone; esters such as benzyl acetate, isopentyl butyrate, methyl lactate, ethyl lactate and butyl lactate; o-toluidine, Examples include amine compounds such as m-toluidine and p-toluidine; lactones such as γ-butyrolactone and δ-butyrolactone; sulfoxide and sulfone compounds such as dimethyl sulfoxide and sulfolane. One or more selected from the above can be used. Among these, it is preferable to use N-methylpyrrolidone from the viewpoint of workability when applying the slurry for the electricity storage device electrode.
本実施の形態に係る蓄電デバイス電極用スラリーは、その流動性や安定性を調整する観点から、増粘剤を含有することができる。このような増粘剤としては、例えば、カルボキシメチルセルロース、メチルセルロース、ヒドロキシプロピルセルロースなどのセルロース化合物;上記セルロース化合物のアンモニウム塩またはアルカリ金属塩;ポリ(メタ)アクリル酸、変性ポリ(メタ)アクリル酸などのポリカルボン酸;上記ポリカルボン酸のアルカリ金属塩;ポリビニルアルコール、変性ポリビニルアルコール、エチレン-ビニルアルコール共重合体などのポリビニルアルコール系(共)重合体;(メタ)アクリル酸、マレイン酸およびフマル酸などの不飽和カルボン酸とビニルエステルとの共重合体の鹸化物などの水溶性ポリマーなどを挙げることができる。これらの中でも特に好ましい増粘剤としては、カルボキシメチルセルロースのアルカリ金属塩、ポリ(メタ)アクリル酸のアルカリ金属塩などである。 2.1.2.3. Thickener The slurry for an electricity storage device electrode according to the present embodiment can contain a thickener from the viewpoint of adjusting its fluidity and stability. Examples of such thickeners include cellulose compounds such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose; ammonium salts or alkali metal salts of the above cellulose compounds; poly (meth) acrylic acid, modified poly (meth) acrylic acid, and the like. Polycarboxylic acids of the above; alkali metal salts of the above polycarboxylic acids; polyvinyl alcohol (co) polymers such as polyvinyl alcohol, modified polyvinyl alcohol, ethylene-vinyl alcohol copolymers; (meth) acrylic acid, maleic acid and fumaric acid And water-soluble polymers such as saponified products of copolymers of unsaturated carboxylic acids and vinyl esters. Among these, particularly preferred thickeners include alkali metal salts of carboxymethyl cellulose and alkali metal salts of poly (meth) acrylic acid.
本実施の形態に係る蓄電デバイス電極用スラリーは、活物質の種類に応じて塗布する集電体の腐食を抑制することを目的として、pH調整剤や腐食防止剤を含有することができる。 2.1.2.4. pH adjusting agent, corrosion inhibitor The slurry for the electricity storage device electrode according to the present embodiment is prepared by adding a pH adjusting agent or a corrosion inhibitor for the purpose of suppressing the corrosion of the current collector to be applied according to the type of the active material. Can be contained.
本実施の形態に係る蓄電デバイス電極用スラリーは、上述の蓄電デバイス用バインダー組成物と、活物質と、水と、必要に応じて用いられる添加剤と、を混合することにより製造することができる。これらの混合は公知の手法による攪拌によって行うことができ、例えば攪拌機、脱泡機、ビーズミル、高圧ホモジナイザーなどを利用することができる。 2.1.3. Method for producing power storage device electrode slurry The power storage device electrode slurry according to the present embodiment is a mixture of the power storage device binder composition described above, an active material, water, and an additive used as necessary. Can be manufactured. These mixing can be performed by stirring by a known method, and for example, a stirrer, a defoamer, a bead mill, a high-pressure homogenizer, or the like can be used.
「保護膜用スラリー」とは、これを電極またはセパレーターの表面もしくはその両方に塗布した後、乾燥させて、電極またはセパレーターの表面もしくはその両方に保護膜を形成するために用いられる分散液のことをいう。本実施の形態に係る保護膜用スラリーは、上述した蓄電デバイス用バインダー組成物と、フィラーと、を含有する。以下、本実施の形態に係る保護膜用スラリーに含まれる各成分について詳細に説明する。なお、蓄電デバイス用バインダー組成物については、上述した通りであるから説明を省略する。 2.2. "Slurry for protective film""Slurry for protective film" is applied to the surface of the electrode and / or separator and then dried to form a protective film on the surface of the electrode and / or separator. Refers to the dispersion. The slurry for protective films which concerns on this Embodiment contains the binder composition for electrical storage devices mentioned above and a filler. Hereinafter, each component contained in the slurry for protective films according to the present embodiment will be described in detail. In addition, since it is as having mentioned above about the binder composition for electrical storage devices, description is abbreviate | omitted.
本実施の形態に係る保護膜用スラリーは、フィラーを含有することにより、形成される保護膜のタフネスを向上させることができる。フィラーとしては、シリカ、酸化チタン(チタニア)、酸化アルミニウム(アルミナ)、酸化ジルコニウム(ジルコニア)、酸化マグネシウム(マグネシア)等を用いることができる。これらの中でも、保護膜のタフネスをより向上させる観点から、酸化チタン、酸化アルミニウムが好ましい。また、酸化チタンとしてはルチル型の酸化チタンがより好ましい。 2.2.1. Filler The slurry for a protective film according to the present embodiment can improve the toughness of the formed protective film by containing a filler. As the filler, silica, titanium oxide (titania), aluminum oxide (alumina), zirconium oxide (zirconia), magnesium oxide (magnesia), or the like can be used. Among these, titanium oxide and aluminum oxide are preferable from the viewpoint of further improving the toughness of the protective film. Further, as the titanium oxide, rutile type titanium oxide is more preferable.
本実施の形態に係る保護膜用スラリーは、必要に応じて、前述の蓄電デバイス電極用スラリー「2.1.2.その他の添加剤」に記載されている材料、添加量を必要に応じて用いることができる。 2.2.2. Other Additives The protective film slurry according to the present embodiment may contain the materials and addition amounts described in the above-mentioned “2.1.2. Other Additives” slurry for an electricity storage device electrode as necessary. It can be used as needed.
本実施の形態に係る保護膜用スラリーは、前述の蓄電デバイス用バインダー組成物と、フィラーと、必要に応じて用いられる添加剤と、を混合することにより調製される。これらを混合するための手段としては、例えばボールミル、サンドミル、顔料分散機、擂潰機、超音波分散機、ホモジナイザー、プラネタリーミキサー、ホバートミキサー等の公知の混合装置を利用することができる。 2.2.3. Production Method of Protective Film Slurry The protective film slurry according to the present embodiment is prepared by mixing the above-mentioned binder composition for an electricity storage device, a filler, and an additive used as necessary. . As a means for mixing them, for example, a known mixing device such as a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, a Hobart mixer can be used.
本実施の形態に係る蓄電デバイス用スラリーは、その曳糸性が30~80%であることが好ましく、33~79%であることがより好ましく、35~78%であることが特に好ましい。曳糸性が前記範囲未満であると、スラリーを塗布する際、レベリング性が不足するため、塗膜の厚みの均一性が損なわれる場合がある。厚みが不均一な電極や保護膜を使用すると、充放電反応の面内分布が発生するため、安定した電池性能の発現が困難となる。一方、曳糸性が前記範囲を超えると、スラリーを塗布する際、液ダレが起き易くなり、安定した品質の電極や保護膜が得られにくい。そこで、曳糸性が前記範囲にあれば、これらの問題の発生を抑制することができ、良好な電気的特性と密着性とを両立させた蓄電デバイスを製造することが容易となるのである。 2.3. Slurry Characteristics The power storage device slurry according to the present embodiment preferably has a spinnability of 30 to 80%, more preferably 33 to 79%, and particularly preferably 35 to 78%. . When the spinnability is less than the above range, the leveling property is insufficient when applying the slurry, and thus the uniformity of the thickness of the coating film may be impaired. If an electrode or a protective film having a non-uniform thickness is used, an in-plane distribution of charge / discharge reaction occurs, making it difficult to achieve stable battery performance. On the other hand, if the spinnability exceeds the above range, dripping easily occurs when applying the slurry, and it is difficult to obtain a stable quality electrode or protective film. Therefore, if the spinnability is within the above range, the occurrence of these problems can be suppressed, and it becomes easy to manufacture an electricity storage device having both good electrical characteristics and adhesion.
曳糸性(%)=((TA-T0)/(TB-T0))×100 ・・・・・(5) The “threadability” in the present specification is a physical property measured as follows. First, a Zaan cup (made by Dazai Equipment Co., Ltd., Zaan Bisco City Cup No. 5) having an opening with a diameter of 5.2 mm at the bottom is prepared. With this opening closed, 40 g of slurry is poured into the Zahn cup. Thereafter, when the opening is opened, the slurry flows out from the opening. Here, it is possible to obtain T 0 when opening the opening, the T A when the slurry of the thread is finished, when the outflow of the slurry is completed when the T B, the following equation (5) .
Spinnability (%) = ((T A −T 0 ) / (T B −T 0 )) × 100 (5)
本実施の形態に係る蓄電デバイス電極は、集電体と、前記集電体の表面上に上述の蓄電デバイス電極用スラリーが塗布および乾燥されて形成された層と、を備えるものである。かかる蓄電デバイス電極は、金属箔などの適宜の集電体の表面に、前述の蓄電デバイス電極用スラリーを塗布して塗膜を形成し、次いで該塗膜を乾燥して活物質層を形成することにより製造することができる。このようにして製造された蓄電デバイス電極は、集電体上に、前述のバインダー、活物質、さらに必要に応じて添加した任意成分を含有する活物質層が結着されてなるものである。かかる蓄電デバイス電極は、集電体と活物質層との密着性に優れるため、電気的特性の一つである充放電レート特性が良好となる。 3. An electricity storage device electrode according to the present embodiment includes a current collector and a layer formed by applying and drying the above-mentioned slurry for an electricity storage device electrode on the surface of the current collector. is there. Such an electricity storage device electrode is formed by applying the aforementioned slurry for an electricity storage device electrode on the surface of an appropriate current collector such as a metal foil to form a coating film, and then drying the coating film to form an active material layer. Can be manufactured. The electricity storage device electrode thus manufactured is formed by binding an active material layer containing the above-described binder, active material, and optional components added as necessary, on a current collector. Such an electricity storage device electrode has excellent adhesion between the current collector and the active material layer, and therefore has good charge / discharge rate characteristics, which is one of the electrical characteristics.
正極、負極またはセパレーターの表面に、前述した保護膜用スラリーを塗布して乾燥させることにより保護膜を形成することができる。保護膜の具体的態様としては、以下に示す3態様が挙げられる。 4). Protective film A protective film can be formed by applying the above-mentioned slurry for protective film on the surface of the positive electrode, negative electrode or separator and drying it. Specific embodiments of the protective film include the following three embodiments.
(2)第2の態様としては、セパレーター表面に、前述の保護膜用スラリーを直接塗布して乾燥させることにより、セパレーターの表面に保護膜を形成することができる。
(3)第3の態様としては、セパレーター表面に機能層が形成されている場合には、該機能層表面に前述の保護膜用スラリーを塗布して乾燥させることにより、機能層表面に保護膜を形成することができる。 (1) As a 1st aspect, a protective film can be formed in the active material layer surface by apply | coating and drying the above-mentioned slurry for protective films on the active material layer surface of a positive electrode and / or a negative electrode.
(2) As a 2nd aspect, a protective film can be formed in the surface of a separator by apply | coating and drying the above-mentioned slurry for protective films directly on the separator surface.
(3) As a third aspect, when a functional layer is formed on the separator surface, the protective film is applied to the surface of the functional layer by applying the above-mentioned slurry for protective film on the surface of the functional layer and drying it. Can be formed.
本実施の形態に係る蓄電デバイスは、上述の蓄電デバイス電極および上述の保護膜を備えるセパレーターの少なくとも一方を備えていればよい。蓄電デバイスの具体的製造方法としては、正極と負極との間にこれら電極間の短絡を防止するためのセパレーターを挟んで積層し、または正極、セパレーター、負極およびセパレーターをこの順序に積層して電極/セパレーター積層体とし、これを電池形状に応じて巻く、折るなどして電池容器に入れ、この電池容器に電解液を注入して封口する方法が挙げられる。なお、電池の形状は、コイン型、ボタン型、シート型、円筒型、角型、扁平型など、適宜の形状であることができる。 5. Power Storage Device The power storage device according to the present embodiment only needs to include at least one of the above-described power storage device electrode and the separator including the above-described protective film. As a specific method for manufacturing an electricity storage device, a positive electrode and a negative electrode are laminated with a separator for preventing a short circuit between the electrodes, or a positive electrode, a separator, a negative electrode, and a separator are laminated in this order to form an electrode. / Separator laminated body, this may be wound or folded according to the shape of the battery, put into a battery container, and an electrolyte solution is injected into the battery container and sealed. In addition, the shape of the battery can be an appropriate shape such as a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, or a flat shape.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。実施例、比較例中の「部」および「%」は、特に断らない限り質量基準である。 6). EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. “Part” and “%” in Examples and Comparative Examples are based on mass unless otherwise specified.
6.1.1.水溶性重合体(A)の合成および評価
(1)水溶性重合体(A)を含む水溶液の調製
容量7Lのセパラブルフラスコの内部を十分に窒素置換した後、水1050質量部を仕込み、内温70℃に昇温し、次いで過硫酸ナトリウム0.3質量部を投入した。次いで、水110質量部、アクリルアミド80質量部、アクリル酸10質量部、アクリル酸エチル10質量部の混合液を1時間かけて滴下し、70℃±3℃で2時間反応を行い、さらに90℃±3℃で2時間反応を行った。その後、冷却し、20wt%水酸化ナトリウム水溶液でpH7に調節することにより、水溶性重合体(A)を8wt%含有する水溶液を得た。このようにして得られた水溶性重合体(A)を8wt%含有する水溶液を蓄電デバイス用バインダー組成物S1とした。蓄電デバイス用バインダー組成物S1を25℃に調整し、BM型粘度計を用いて粘度を測定したところ3000mPa・sであった。 6.1. Example 1
6.1.1. Synthesis and Evaluation of Water-Soluble Polymer (A) (1) Preparation of Aqueous Solution Containing Water-Soluble Polymer (A) The interior of a 7-L separable flask was sufficiently purged with nitrogen, and charged with 1050 parts by weight of water. The temperature was raised to 70 ° C., and then 0.3 part by mass of sodium persulfate was added. Next, a mixed solution of 110 parts by mass of water, 80 parts by mass of acrylamide, 10 parts by mass of acrylic acid, and 10 parts by mass of ethyl acrylate was added dropwise over 1 hour, reacted at 70 ° C ± 3 ° C for 2 hours, and further 90 ° C. The reaction was performed at ± 3 ° C. for 2 hours. Then, it cooled and adjusted to pH 7 with 20 wt% sodium hydroxide aqueous solution, and obtained the aqueous solution containing 8 wt% of water-soluble polymers (A). An aqueous solution containing 8 wt% of the water-soluble polymer (A) thus obtained was designated as a binder composition S1 for an electricity storage device. It was 3000 mPa * s when the binder composition S1 for electrical storage devices was adjusted to 25 degreeC, and the viscosity was measured using the BM type | mold viscosity meter.
以下の条件により測定した水溶性重合体(A)の重量平均分子量(Mw)は6×106であり、重量平均分子量(Mw)/数平均分子量(Mn)の値(分散比)は30であった。
・測定機器:東ソー株式会社製、GPC(型番:HLC-8220)
・カラム:TSKgel guardcolum PWXL (東ソー株式会社製)、TSK-GEL G2500PWXL(東ソー株式会社製)、TSK-GEL GMPWXL(東ソー株式会社製)
・溶離液:0.1M NaNO3水溶液
・検量線:標準ポリエチレンオキシド
・測定方法:水溶性重合体(A)の濃度が0.3wt%となるように溶離液に溶解し、フィルターろ過後に測定。 (2) Measurement of molecular weight The weight average molecular weight (Mw) of the water-soluble polymer (A) measured under the following conditions is 6 × 10 6 , and the value of weight average molecular weight (Mw) / number average molecular weight (Mn) ( The dispersion ratio) was 30.
・ Measuring equipment: GPC (model number: HLC-8220) manufactured by Tosoh Corporation
Column: TSKgel guardcolumn PW XL (manufactured by Tosoh Corporation), TSK-GEL G2500PW XL (manufactured by Tosoh Corporation), TSK-GEL GMPW XL (manufactured by Tosoh Corporation)
Eluent: 0.1M NaNO 3 aqueous solution Calibration curve: standard polyethylene oxide Measurement method: Dissolved in the eluent so that the concentration of the water-soluble polymer (A) is 0.3 wt%, and measured after filter filtration.
(1)蓄電デバイス用バインダー組成物の調製
上記で得られた水溶性重合体(A)を含有する水溶液に、水溶性重合体(A)100質量部に対して化合物(B)としてのアクリルアミドを0.03質量部添加し、150rpmで撹拌することにより蓄電デバイス用バインダー組成物を調製した。 6.1.2. Preparation and Evaluation of Binder Composition for Electricity Storage Device (1) Preparation of Binder Composition for Electricity Storage Device To 100 parts by mass of the water-soluble polymer (A) in the aqueous solution containing the water-soluble polymer (A) obtained above. On the other hand, 0.03 parts by mass of acrylamide as the compound (B) was added and stirred at 150 rpm to prepare a binder composition for an electricity storage device.
一般的に蓄電デバイス用バインダー組成物は、蓄電デバイスを作製する工場において、使用に備えて大量に貯蔵される場合がある。このような場合、最初に消費した蓄電デバイス用バインダー組成物の特性と長期間にわたり貯蔵した後の蓄電デバイス用バインダー組成物について、重合体が沈降しないことが簡便に使用できるためより好ましい。 (2) Sedimentation evaluation In general, a binder composition for an electricity storage device may be stored in large quantities for use in a factory for producing an electricity storage device. In such a case, the properties of the binder composition for an electricity storage device consumed first and the binder composition for an electricity storage device after being stored for a long period of time are more preferable because the polymer does not settle and can be used easily.
また、蓄電デバイス用バインダー組成物の貯蔵環境は、コストの観点から温度管理を厳密に行うことができず、このため気温の変化により0℃近くの環境に晒される場合がある。このため、下記の凍結温度の評価において、0℃で凍結することは好ましくなく、凍結温度が-0.5℃以下であると簡便に保管できるためより好ましい。 (3) Evaluation of freezing temperature In addition, the storage environment of the binder composition for an electricity storage device cannot be strictly controlled from the viewpoint of cost, and is therefore exposed to an environment near 0 ° C. due to changes in temperature. There is. Therefore, in the following evaluation of the freezing temperature, it is not preferable to freeze at 0 ° C., and it is more preferable that the freezing temperature is −0.5 ° C. or lower because it can be stored easily.
(1)正極用スラリーの調製
二軸型プラネタリーミキサー(プライミクス株式会社製、商品名「TKハイビスミックス 2P-03」)に上記で得られた蓄電デバイス用バインダー組成物S1を水溶性重合体(A)換算で1.5質量部に相当する量を投入し、さらに粒子径(D50値)が10μmの市販のニッケル・マンガン・コバルト酸リチウム(ニッケル(Ni)、コバルト(Co)、マンガン(Mn)の比率1:1:1)活物質粒子100質量部、アセチレンブラック3質量部、バナジン酸ナトリウム0.5質量部および水4質量部を投入し、90rpmで1時間攪拌を行った。得られたペーストに水を加えて固形分濃度を70%に調整した後、攪拌脱泡機(株式会社シンキー製、商品名「あわとり練太郎」)を使用して、200rpmで2分間、1,800rpmで5分間、さらに真空下(約5.0×103Pa)において1,800rpmで1.5分間攪拌混合することにより、正極用スラリーを調製した。 6.1.3. Preparation and Evaluation of Positive Electrode Slurry and Negative Electrode Slurry (1) Preparation of Positive Electrode Slurry An electricity storage device obtained as above in a biaxial planetary mixer (trade name “TK Hibismix 2P-03” manufactured by PRIMIX Corporation) The binder composition S1 was added in an amount corresponding to 1.5 parts by mass in terms of the water-soluble polymer (A), and a commercially available nickel / manganese / cobalt acid lithium (nickel (D50 value) of 10 μm) Ni), cobalt (Co), manganese (Mn) ratio 1: 1: 1) 100 parts by mass of active material particles, 3 parts by mass of acetylene black, 0.5 parts by mass of sodium vanadate and 4 parts by mass of water were added, Stirring was performed at 90 rpm for 1 hour. After adding water to the obtained paste to adjust the solid content concentration to 70%, using a stirring defoaming machine (trade name “Awatori Nentaro” manufactured by Shinky Co., Ltd.) for 2 minutes at 200 rpm. The slurry for positive electrode was prepared by stirring and mixing at 800 rpm for 5 minutes and further under vacuum (about 5.0 × 10 3 Pa) at 1,800 rpm for 1.5 minutes.
二軸型プラネタリーミキサー(プライミクス株式会社製、商品名「TKハイビスミックス 2P-03」)に、上記で得られた蓄電デバイス用バインダー組成物S1を水溶性重合体(A)換算で1質量部に相当する量を投入し、負極活物質としてグラファイト100質量部(固形分換算)、およびアセチレンブラック4質量部、イオン交換水53質量部を投入し、60rpmで1時間撹拌を行った。さらに水40質量部を投入した後、撹拌脱泡機(株式会社シンキー製、製品名「あわとり練太郎」)を使用して、200rpmで2分間、次いで1,800rpmで5分間、さらに真空下(約5.0×103Pa)において1,800rpmで1.5分間撹拌・混合することにより、負極用スラリーを調製した。 (2) Preparation of slurry for negative electrode A biaxial planetary mixer (product name “TK Hibismix 2P-03” manufactured by PRIMIX Co., Ltd.) was charged with the water-soluble polymer binder composition S1 for an electricity storage device obtained above. (A) An amount corresponding to 1 part by mass is introduced, 100 parts by mass of graphite (in terms of solid content), 4 parts by mass of acetylene black, and 53 parts by mass of ion-exchanged water are introduced as the negative electrode active material. Stir for hours. After adding 40 parts by mass of water, using a stirring defoamer (product name “Awatori Nertaro” manufactured by Sinky Co., Ltd.) for 2 minutes at 200 rpm, then 5 minutes at 1,800 rpm, and further under vacuum A slurry for negative electrode was prepared by stirring and mixing at 1,800 rpm for 1.5 minutes at (about 5.0 × 10 3 Pa).
上記で得られた正極用および負極用スラリーの曳糸性を、以下のようにして測定した。まず、容器の底辺に直径5.2mmの開口部が存在するザーンカップ(太佑機材株式会社製、ザーンビスコシティーカップNo.5)を準備した。このザーンカップの開口部を閉じた状態で、上記で調製したスラリーを40g流し込んだ。開口部を開放するとスラリーが流れ出した。このとき、開口部を開放した瞬間の時間をT0とし、スラリーが流れ出る際に糸を曳くようにして流出し続けた時間を目視で測定し、この時間をTAとした。さらに、糸を曳かなくなってからも測定を継続し、スラリーが流れ出なくなるまでの時間TBを測定した。測定した各値T0、TAおよびTBを下記式(5)に代入して曳糸性を求めた。このスラリーの曳糸性は、上述したように30~80%である場合に集電体上への塗布性が良好であると判断することができる。その結果を表3に併せて示した。
曳糸性(%)=((TA-T0)/(TB-T0))×100 ・・・・・(5) (3) Measurement of the spinnability of the slurry The spinnability of the positive electrode slurry and the negative electrode slurry obtained above was measured as follows. First, a Zaan cup (Dazai Equipment Co., Ltd., Zaan Bisco City Cup No. 5) having an opening with a diameter of 5.2 mm at the bottom of the container was prepared. With the Zahn cup opening closed, 40 g of the slurry prepared above was poured. When the opening was opened, the slurry flowed out. In this case, the time instant of opening the opening and T 0, the time continued to flow out so as to draw the yarn when the slurry flows measured visually, the time was T A. Moreover, to continue the measurement from no longer attracted yarn was measured time T B until the slurry no longer flow out. The measured values T 0 , T A and T B were substituted into the following formula (5) to determine the spinnability. As described above, when the slurry has a spinnability of 30 to 80%, it can be determined that the coating property on the current collector is good. The results are also shown in Table 3.
Spinnability (%) = ((T A −T 0 ) / (T B −T 0 )) × 100 (5)
(1)正極の製造
アルミニウム箔からなる集電体の表面に、上記で調製した正極用スラリーを、乾燥後の膜厚が110μmとなるようにドクターブレード法によって均一に塗布し、120℃で10分間乾燥した。その後、膜(活物質層)の密度が3.0g/cm3になるようにロールプレス機によりプレス加工することにより、正極を得た。 6.1.4. Production and Evaluation of Positive Electrode and Negative Electrode (1) Production of Positive Electrode The positive electrode slurry prepared above is uniformly applied to the surface of the current collector made of aluminum foil by a doctor blade method so that the film thickness after drying becomes 110 μm. It was applied and dried at 120 ° C. for 10 minutes. Then, the positive electrode was obtained by pressing with a roll press so that the density of a film | membrane (active material layer) might be 3.0 g / cm < 3 >.
銅箔からなる集電体の表面に、上記で調製した負極用スラリーを、乾燥後の膜厚が110μmとなるようにドクターブレード法によって均一に塗布し、120℃で20分間乾燥した。その後、膜(活物質層)の密度が1.5g/cm3となるようにロールプレス機を使用してプレス加工することにより、負極を得た。 (2) Production of Negative Electrode The negative electrode slurry prepared above was uniformly applied to the surface of a current collector made of copper foil by a doctor blade method so that the film thickness after drying was 110 μm. Dried for minutes. Then, the negative electrode was obtained by pressing using a roll press so that the density of a film | membrane (active material layer) might be 1.5 g / cm < 3 >.
上記で得られた正極板、負極板を、それぞれ幅2cm×長さ10cmに切り出し、幅方向に直径2mmの丸棒に沿って正極板を折り曲げ回数100回にて繰り返し折り曲げ試験を行った。丸棒に沿った部分のクラックの大きさを目視により観察し計測し、クラック率を測定した。クラック率は、下記式(6)によって定義した。
クラック率(%)=
(クラックの入った長さ(mm)÷極板全体の長さ(mm))×100 ・・・・(6)
クラック率は四捨六入することにより5%刻みで評価し、差を明確にしやすくした。ここで、柔軟性や密着性に優れた電極板はクラック率が低い。クラック率は0%であることが望ましいが、正極板と負極板とをセパレーターを介して渦巻き状に捲回して極板群を製造する場合には、クラック率が20%までなら許容される。しかし、クラック率が20%より大きくなると、極板が切れ易くなり極板群の製造が不可能となり、極板群の生産性が低下する。このことから、クラック率が20%までが良好な範囲であると考えられる。その結果を表3に併せて示した。 (3) Evaluation of crack rate of electrode plate Each of the positive electrode plate and the negative electrode plate obtained above was cut into 2 cm width × 10 cm length, and the positive electrode plate was bent 100 times along a round bar having a diameter of 2 mm in the width direction. The bending test was repeatedly performed. The size of the crack along the round bar was visually observed and measured, and the crack rate was measured. The crack rate was defined by the following formula (6).
Crack rate (%) =
(Cracked length (mm) ÷ total length of electrode plate (mm)) × 100 (6)
The crack rate was evaluated in 5% increments by rounding off to make it easier to clarify the difference. Here, the electrode plate excellent in flexibility and adhesion has a low crack rate. The crack rate is preferably 0%. However, when the electrode plate group is manufactured by winding the positive electrode plate and the negative electrode plate in a spiral shape through a separator, the crack rate is allowed up to 20%. However, when the crack rate is greater than 20%, the electrode plates are easily cut, making it impossible to manufacture the electrode plate group, and the productivity of the electrode plate group is lowered. From this, it is considered that the crack rate is good within 20%. The results are also shown in Table 3.
(1)リチウムイオン電池セルの組立て
露点が-80℃以下となるようAr置換されたグローブボックス内で、上記で製造した負極を直径15.95mmに打ち抜き成形したものを、2極式コインセル(宝泉株式会社製、商品名「HSフラットセル」)上に載置した。次いで、直径24mmに打ち抜いたポリプロピレン製多孔膜からなるセパレーター(セルガード株式会社製、商品名「セルガード#2400」)を載置し、さらに、空気が入らないように電解液を500μL注入した後、上記で製造した正極を直径16.16mmに打ち抜き成形したものを載置し、前記2極式コインセルの外装ボディーをネジで閉めて封止することにより、リチウムイオン電池セル(蓄電デバイス)を組み立てた。ここで使用した電解液は、エチレンカーボネート/エチルメチルカーボネート=1/1(質量比)の溶媒に、LiPF6を1モル/Lの濃度で溶解した溶液である 6.1.5. Assembling and Evaluation of Lithium Ion Battery Cell (1) Assembling of Lithium Ion Battery Cell In the glove box substituted with Ar so that the dew point is −80 ° C. or less, the negative electrode produced above was punched and molded to a diameter of 15.95 mm Was placed on a bipolar coin cell (trade name “HS flat cell” manufactured by Hosen Co., Ltd.). Next, a separator made of a polypropylene porous membrane punched into a diameter of 24 mm (trade name “Celguard # 2400” manufactured by Celgard Co., Ltd.) was placed, and after injecting 500 μL of an electrolyte solution so that air did not enter, A lithium ion battery cell (power storage device) was assembled by placing the positive electrode manufactured in the above-described method by punching and molding the positive electrode to a diameter of 16.16 mm, and sealing the outer body of the bipolar coin cell with a screw. The electrolytic solution used here is a solution obtained by dissolving LiPF 6 at a concentration of 1 mol / L in a solvent of ethylene carbonate / ethyl methyl carbonate = 1/1 (mass ratio).
上記で製造したリチウムイオン電池セルにつき、定電流(0.2C)にて充電を開始し、電圧が4.2Vになった時点で引き続き定電圧(4.2V)にて充電を続行し、電流値が0.01Cとなった時点を充電完了(カットオフ)として、0.2Cでの充電容量を測定した。次いで、定電流(0.2C)にて放電を開始し、電圧が2.7Vになった時点を放電完了(カットオフ)とし、0.2Cでの放電容量を測定した。 (2) Evaluation of charge / discharge rate characteristics With respect to the lithium ion battery cell produced above, charging was started at a constant current (0.2 C), and when the voltage reached 4.2 V, the constant voltage (4.2 V) was continued. ) Was continued, and when the current value reached 0.01C, the charging was completed (cut off), and the charge capacity at 0.2C was measured. Next, discharge was started at a constant current (0.2 C), and when the voltage reached 2.7 V, the discharge was completed (cut off), and the discharge capacity at 0.2 C was measured.
上記で製造したリチウムイオン電池セルを25℃の恒温槽に入れ、定電流(0.2C)にて充電を開始し、電圧が4.1Vになった時点で引き続き定電圧(4.1V)にて充電を続行し、電流値が0.01Cとなった時点を充電完了(カットオフ)とした。次いで、定電流(0.2C)にて放電を開始し、電圧が2.5Vになった時点を放電完了(カットオフ)とした(エージング充放電)。 (3) Measurement of rate characteristics, remaining capacity rate, and rate of increase in resistance The lithium ion battery cell produced above was placed in a thermostatic bath at 25 ° C., and charging was started at a constant current (0.2 C). When the voltage reached 1 V, charging was continued at a constant voltage (4.1 V), and when the current value reached 0.01 C, charging was completed (cut off). Next, discharging was started at a constant current (0.2 C), and the time when the voltage reached 2.5 V was regarded as discharging completion (cut-off) (aging charge / discharge).
5Cレート特性(%)=(C2/C1)×100 ・・・・・(7)
なお、5Cレート特性の値が大きいほど、高速放電においても良好な出力特性得られると判断することができるが、特に5Cレート特性の値が60%以上である場合、良好と判断できる。 The cell after the discharge capacity (initial) measurement was placed in a constant temperature bath at 25 ° C., charging was started at a constant current (0.2 C), and when the voltage reached 4.1 V, the constant voltage (4.1 V) was continued. The charging was continued at), and the time when the current value reached 0.01 C was regarded as the completion of charging (cutoff). Subsequently, the discharge capacity C2 when discharging by a constant current (5.0C) system was measured. And using these measured values, 5C rate characteristic (%) of the lithium ion secondary battery was computed by following formula (7). The results are also shown in Table 3.
5C rate characteristics (%) = (C2 / C1) × 100 (7)
It can be determined that the larger the value of the 5C rate characteristic, the better the output characteristic can be obtained even in the high-speed discharge, but it can be determined that the value is particularly good when the value of the 5C rate characteristic is 60% or more.
残存容量率(%)=(C2/C1)×100 ・・・・・(8)
抵抗上昇率(%)=((EISb-EISa)/EISa)×100 ・・・・(9)
この残存容量率が75%以上であり、かつ、抵抗上昇率300%以下であるとき、耐久性は良好であると評価することができる。 The respective measured values were substituted into the following formula (8) and the following formula (9) to determine the remaining capacity rate and the resistance increase rate, respectively. The results are also shown in Table 3.
Remaining capacity ratio (%) = (C2 / C1) × 100 (8)
Resistance increase rate (%) = ((EISb−EISa) / EISa) × 100 (9)
When this remaining capacity ratio is 75% or more and the resistance increase rate is 300% or less, it can be evaluated that the durability is good.
上記実施例1の「6.1.1.水溶性重合体(A)の合成と評価」において、単量体の組成と開始剤の量を適宜に変更し、上記実施例1の「6.1.2.蓄電デバイス用バインダー組成物の調製および評価」において、化合物(B)の種類および添加量を適宜に変更したほかは実施例1と同様にして、表1~表2に示す組成の重合体を含む水溶液(蓄電デバイス用バインダー組成物S2~S24)を調製し、得られた水溶性重合体(A)の分子量を測定した。その結果を表1~表2に併せて示した。 6.2. Examples 2 to 24, Comparative Examples 1 to 4
In “6.1.1. Synthesis and Evaluation of Water-Soluble Polymer (A)” in Example 1 above, the composition of the monomer and the amount of the initiator were appropriately changed, and “6. In “1.2. Preparation and Evaluation of Binder Composition for Electricity Storage Device”, the compositions shown in Tables 1 and 2 were changed in the same manner as in Example 1 except that the type and amount of the compound (B) were appropriately changed. An aqueous solution containing the polymer (binder compositions S2 to S24 for electricity storage devices) was prepared, and the molecular weight of the obtained water-soluble polymer (A) was measured. The results are also shown in Tables 1 and 2.
すなわち、粉砕した二酸化ケイ素粉末(平均粒子径10μm)と炭素粉末(平均粒子径35μm)との混合物を、温度を1100~1600℃の範囲に調整した電気炉中で、窒素気流下(0.5NL/分)、10時間の加熱処理を行い、組成式SiOx(X=0.5~1.1)で表される酸化ケイ素の粉末(平均粒子径8μm)を得た。この酸化ケイ素の粉末300gをバッチ式加熱炉内に仕込み、真空ポンプにより絶対圧100Paの減圧を維持しながら、300℃/hの昇温速度にて室温(25℃)から1100℃まで昇温した。次いで、加熱炉内の圧力を2,000Paに維持しつつ、メタンガスを0.5NL/分の流速にて導入しながら、1100℃、5時間の加熱処理(黒鉛被膜処理)を行った。黒鉛被膜処理終了後、50℃/hの降温速度で室温まで冷却することにより、黒鉛被膜酸化ケイ素の粉末約330gを得た。この黒鉛被膜酸化ケイ素は、酸化ケイ素の表面が黒鉛で被覆された導電性の粉末(活物質)であり、その平均粒子径は10.5μmであり、得られた黒鉛被膜酸化ケイ素の全体を100質量%とした場合の黒鉛被膜の割合は2質量%であった。 The “Si-containing” active material described in Table 4 was prepared as follows.
That is, a mixture of pulverized silicon dioxide powder (average particle size 10 μm) and carbon powder (average particle size 35 μm) was heated in a nitrogen stream (0.5 NL) in an electric furnace adjusted to a temperature in the range of 1100 to 1600 ° C. / Min.) Heat treatment was performed for 10 hours to obtain a silicon oxide powder (average particle size of 8 μm) represented by the composition formula SiO x (X = 0.5 to 1.1). 300 g of this silicon oxide powder was charged into a batch-type heating furnace, and the temperature was raised from room temperature (25 ° C.) to 1100 ° C. at a temperature raising rate of 300 ° C./h while maintaining a reduced pressure of 100 Pa absolute pressure with a vacuum pump. . Subsequently, heat treatment (graphite coating treatment) was performed at 1100 ° C. for 5 hours while introducing methane gas at a flow rate of 0.5 NL / min while maintaining the pressure in the heating furnace at 2,000 Pa. After the completion of the graphite coating treatment, the powder was cooled to room temperature at a temperature decrease rate of 50 ° C./h to obtain about 330 g of graphite-coated silicon oxide powder. This graphite-coated silicon oxide is a conductive powder (active material) in which the surface of silicon oxide is coated with graphite, and its average particle diameter is 10.5 μm. The ratio of the graphite film in the case of mass% was 2 mass%.
下表1~表2に、各蓄電デバイス用バインダー組成物に含まれる重合体の単量体組成および分子量、化合物(B)の含有割合、評価結果を示す。下表3~表4に、正極、負極用スラリーの組成および各評価結果を示す。 6.3. Evaluation results of Examples 1 to 24 and Comparative Examples 1 to 4 In Tables 1 to 2 below, the monomer composition and molecular weight of the polymer contained in each binder composition for an electricity storage device, the content ratio of the compound (B), An evaluation result is shown. Tables 3 to 4 below show the compositions of the positive and negative electrode slurries and the evaluation results.
・AMM:アクリルアミド
・MAMM:メタクリルアミド
・NMAM:N-メチロールアクリルアミド
・ATBS:アクリルアミドt-ブチルスルホン酸
・AA:アクリル酸
・MAA:メタクリル酸
・VS:ビニルスルホン酸
・AS:アリルスルホン酸
・MAS:メタアリルスルホン酸
・MMA:メタクリル酸メチル
・MA:アクリル酸メチル
・BA:アクリル酸n-ブチル
・EA:アクリル酸エチル
・HEMA:メタクリル酸2-ヒドロキシエチル
・AN:アクリロニトリル
・MAN:メタクリロニトリル
・DMAEA:ジメチルアミノエチルアクリレート
・DMAEA-Q:ジメチルアミノエチルアクリレート塩化メチル4級塩
・2VP:2-ビニルピリジン
・1VI:1-ビニルイミダゾール
・DAA:ジアリルアミン
表1および表2における「-」の表記は、該当する成分を使用しなかったか、あるいは該当する操作を行わなかったことを示す。 The abbreviations of the components in Tables 1 and 2 have the following meanings, respectively.
AMM: acrylamide MAMMA: methacrylamide NMAM: N-methylol acrylamide ATBS: acrylamide t-butyl sulfonic acid AA: acrylic acid MAA: methacrylic acid VS: vinyl sulfonic acid AS: allyl sulfonic acid MAS: Methallylsulfonic acid, MMA: methyl methacrylate, MA: methyl acrylate, BA: n-butyl acrylate, EA: ethyl acrylate, HEMA: 2-hydroxyethyl methacrylate, AN: acrylonitrile, MAN: methacrylonitrile, DMAEA: dimethylaminoethyl acrylate, DMAEA-Q: dimethylaminoethyl acrylate methyl chloride quaternary salt, 2VP: 2-vinylpyridine, 1VI: 1-vinylimidazole, DAA: diallylamine Tables 1 and 2 The notation “-” in indicates that the corresponding component was not used or the corresponding operation was not performed.
・NMC(111):ユミコア社製、ニッケル・マンガン・コバルト酸リチウム(ニッケル(Ni):コバルト(Co):マンガン(Mn)が1:1:1)、グレード名「MX-10」
・NMC(532):ユミコア社製、ニッケル・マンガン・コバルト酸リチウム(ニッケル(Ni):コバルト(Co):マンガン(Mn)が5:3:2)、グレード名「TX-10」
・AB:アセチレンブラック(電気化学工業株式会社製、デンカブラック50%プレス)
・黒鉛:日立化成工業株式会社製、商品名「MAG」
・NaVO3:和光純薬工業株式会社製、メタバナジン(V)酸ナトリウム Abbreviations of each component in Tables 3 to 4 have the following meanings, respectively.
NMC (111): manufactured by Umicore, nickel, manganese, lithium cobaltate (nickel (Ni): cobalt (Co): manganese (Mn) is 1: 1: 1), grade name “MX-10”
NMC (532): manufactured by Umicore, nickel, manganese, lithium cobalt oxide (nickel (Ni): cobalt (Co): manganese (Mn) is 5: 3: 2), grade name "TX-10"
AB: Acetylene black (Denka Black 50% press, manufactured by Denki Kagaku Kogyo Co., Ltd.)
・ Graphite: Made by Hitachi Chemical Co., Ltd., trade name “MAG”
NaVO 3 : manufactured by Wako Pure Chemical Industries, Ltd., sodium metavanadate (V)
6.4.1.保護膜用スラリーの調製
フィラーとして酸化チタン(製品名「KR380」、チタン工業株式会社製、ルチル型、平均粒子径0.38μm)を水500質量部に対して100質量部、上記実施例1で得られた蓄電デバイス用バインダー組成物S1をフィラー100質量部に対して水溶性重合体(A)換算で5質量部に相当する量を、T.K.フィルミックス(R)56-50型(プライミクス株式会社製)を用いて混合分散処理を行い、酸化チタンが分散された保護膜用スラリーを調製した。このようにして得られた保護膜用スラリーの曳糸性を実施例1と同様にして評価した。 6.4. Example 25
6.4.1. Preparation of slurry for protective film Titanium oxide (product name “KR380”, manufactured by Titanium Industry Co., Ltd., rutile type, average particle size 0.38 μm) is 100 parts by mass with respect to 500 parts by mass of water. An amount corresponding to 5 parts by mass of the obtained binder composition S1 for an electricity storage device in terms of a water-soluble polymer (A) with respect to 100 parts by mass of the filler was calculated using T.P. K. Using a Mixmix (R) type 56-50 (manufactured by PRIMIX Co., Ltd.), a mixture dispersion treatment was performed to prepare a slurry for a protective film in which titanium oxide was dispersed. The spinnability of the protective film slurry thus obtained was evaluated in the same manner as in Example 1.
二軸型プラネタリーミキサー(プライミクス株式会社製、商品名「TKハイビスミックス 2P-03」)に電気化学デバイス電極用バインダー(株式会社クレハ製、商品名「KFポリマー#1120」)4.0質量部(固形分換算)、導電助剤(電気化学工業株式会社製、商品名「デンカブラック50%プレス品」)3.0質量部、正極活物質として粒径5μmのLiCoO2(ハヤシ化成株式会社製)100質量部(固形分換算)、N-メチルピロリドン(NMP)36質量部を投入し、60rpmで2時間攪拌を行った。得られたペーストにNMPを投入し、固形分を65%に調製した後、攪拌脱泡機(株式会社シンキー製、商品名「泡とり練太郎」)を使用して、200rpmで2分間、1800rpmで5分間、さらに真空下において1800rpmで1.5分間攪拌混合することにより、正極用スラリーを調製した。アルミニウム箔よりなる集電体の表面に、得られた正極用スラリーを、乾燥後の膜厚が120μmとなるようにドクターブレード法によって均一に塗布し、120℃で20分間乾燥処理した。その後、活物質層の密度が3.0g/cm3となるようにロールプレス機でプレス加工することにより、正極を得た。 6.4.2. 3. Production of positive electrode Biaxial planetary mixer (product name “TK Hibismix 2P-03” manufactured by PRIMIX Corporation) and binder for electrochemical device electrode (product name “KF polymer # 1120” manufactured by Kureha Co., Ltd.) 0 parts by mass (converted to solid content), 3.0 parts by mass of conductive assistant (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “DENKA BLACK 50% press product”), LiCoO 2 having a particle diameter of 5 μm as a positive electrode active material (Hayashi Kasei) 100 parts by mass (made by Co., Ltd.) and 36 parts by mass of N-methylpyrrolidone (NMP) were added and stirred at 60 rpm for 2 hours. After adding NMP to the obtained paste to adjust the solid content to 65%, using a stirring defoaming machine (trade name “Awatori Netaro”, manufactured by Shinky Co., Ltd.), 2 minutes at 200 rpm, 1800 rpm The slurry for positive electrode was prepared by stirring and mixing for 5 minutes at 1800 rpm for 1 minute at 1800 rpm. The obtained positive electrode slurry was uniformly applied to the surface of a current collector made of aluminum foil by a doctor blade method so that the film thickness after drying was 120 μm, followed by drying treatment at 120 ° C. for 20 minutes. Then, the positive electrode was obtained by pressing with a roll press so that the density of an active material layer might be 3.0 g / cm < 3 >.
二軸型プラネタリーミキサー(プライミクス株式会社製、商品名「TKハイビスミックス 2P-03」)に、ポリフッ化ビニリデン(PVDF)4質量部(固形分換算)、負極活物質としてグラファイト100質量部(固形分換算)、N-メチルピロリドン(NMP)80質量部を投入し、60rpmで1時間撹拌を行った。その後、さらにNMP20質量部を投入した後、撹拌脱泡機(株式会社シンキー製、製品名「あわとり練太郎」)を使用して、200rpmで2分間、次いで1,800rpmで5分間、さらに真空下において1,800rpmで1.5分間撹拌・混合することにより、負極用スラリーを調製した。 6.4.3. Negative electrode Biaxial planetary mixer (product name “TK Hibismix 2P-03” manufactured by PRIMIX Corporation), 4 parts by mass of polyvinylidene fluoride (PVDF) (in terms of solid content), and 100 parts by mass of graphite as a negative electrode active material ( 80 parts by mass of N-methylpyrrolidone (NMP) was added, and the mixture was stirred at 60 rpm for 1 hour. Then, after adding 20 parts by mass of NMP, using a stirring defoaming machine (product name “Awatori Netaro” manufactured by Shinky Co., Ltd.) for 2 minutes at 200 rpm, then for 5 minutes at 1,800 rpm, further vacuum Below, the slurry for negative electrodes was prepared by stirring and mixing for 1.5 minutes at 1,800 rpm.
露点が-80℃以下となるようAr置換されたグローブボックス内で、上記で製造した負極を直径15.95mmに打ち抜き成形したものを、2極式コインセル(宝泉株式会社製、商品名「HSフラットセル」)上に載置した。次いで、直径24mmに打ち抜いたポリプロピレン製多孔膜からなるセパレーター(セルガード株式会社製、商品名「セルガード#2400」)を載置し、さらに、空気が入らないように電解液を500μL注入した後、上記で製造した正極を直径16.16mmに打ち抜き成形したものを正極に形成された保護膜とセパレーターとが相対するように載置し、前記2極式コインセルの外装ボディーをネジで閉めて封止することにより、リチウムイオン電池セル(蓄電デバイス)を組み立てた。ここで使用した電解液は、エチレンカーボネート/エチルメチルカーボネート=1/1(質量比)の溶媒に、LiPF6を1モル/Lの濃度で溶解した溶液である。このようにして得られた蓄電デバイスについて、上記実施例1と同様にして充放電レート特性の評価を行った。 6.4.4. Assembly of lithium ion battery cell In a glove box substituted with Ar so that the dew point is -80 ° C. or less, the negative electrode produced above was punched and molded to a diameter of 15.95 mm. And product name “HS flat cell”). Next, a separator made of a polypropylene porous membrane punched into a diameter of 24 mm (trade name “Celguard # 2400” manufactured by Celgard Co., Ltd.) was placed, and after injecting 500 μL of an electrolyte solution so that air did not enter, The positive electrode manufactured in the above is punched and molded to a diameter of 16.16 mm and placed so that the protective film formed on the positive electrode and the separator face each other, and the outer body of the bipolar coin cell is closed with a screw and sealed. Thus, a lithium ion battery cell (electric storage device) was assembled. The electrolytic solution used here is a solution obtained by dissolving LiPF 6 at a concentration of 1 mol / L in a solvent of ethylene carbonate / ethyl methyl carbonate = 1/1 (mass ratio). Thus, about the obtained electrical storage device, it carried out similarly to the said Example 1, and evaluated charge / discharge rate characteristic.
上記実施例25において、使用した蓄電デバイス用バインダー組成物を表5に記載したものにそれぞれ変更し、使用したフィラーを表5に記載のものとした以外は、実施例25と同様にして保護膜用スラリーを調製し、その曳糸性について評価した。また、上記実施例25において、使用した保護膜用スラリーを表5に記載のものとした以外は、実施例25と同様にして正極を作製し、そのクラック率を評価した。さらに、上記実施例25と同様にして負極を作製した後、蓄電デバイスを製造し、同様に充放電レート特性を評価した。これらの評価結果を表5に併せて示した。 6.5. Examples 26 to 28, Comparative Examples 5 to 6
In Example 25 above, the protective film was used in the same manner as in Example 25, except that the binder composition for an electricity storage device used was changed to that shown in Table 5 and the filler used was that shown in Table 5. Slurry was prepared and its spinnability was evaluated. Further, a positive electrode was produced in the same manner as in Example 25 except that the protective film slurry used in Example 25 was changed to that shown in Table 5, and the crack rate was evaluated. Furthermore, after producing a negative electrode in the same manner as in Example 25, an electricity storage device was produced, and charge / discharge rate characteristics were similarly evaluated. These evaluation results are also shown in Table 5.
上記実施例25において、使用した蓄電デバイス用バインダー組成物を表6に記載したものにそれぞれ変更し、使用したフィラーを表6に記載のものとした以外は、上記実施例25と同様にして保護膜用スラリーを調製し、その曳糸性について評価した。その評価結果を表6に併せて示した。 6.6. Examples 29 to 31 and Comparative Examples 7 to 8
In Example 25, the binder composition for an electricity storage device used was changed to that shown in Table 6, and the same procedure as in Example 25 was applied except that the filler used was that shown in Table 6. A membrane slurry was prepared and evaluated for spinnability. The evaluation results are also shown in Table 6.
上記実施例25で調製した保護膜用スラリーを、ポリプロピレン製多孔膜からなるセパレーター(セルガード株式会社製、商品名「セルガード#2400」)の片面に乾燥後の厚さが10μmになるようにワイヤーバーを用いて塗工し、次いで90℃で20分間乾燥することにより、保護膜付きセパレーターを得た。このようにして得られた保護膜付きセパレーターについて、上記実施例25と同様にして保護膜のクラック率を評価した。その評価結果を表7に併せて示した。 6.7. Example 32
A wire bar was prepared by applying the slurry for the protective film prepared in Example 25 on one side of a separator (trade name “Celguard # 2400” manufactured by Celgard Co., Ltd.) made of a polypropylene porous film so that the thickness after drying was 10 μm. And then dried at 90 ° C. for 20 minutes to obtain a separator with a protective film. About the separator with a protective film thus obtained, the crack rate of the protective film was evaluated in the same manner as in Example 25. The evaluation results are also shown in Table 7.
上記実施例32において、使用した蓄電デバイス用バインダー組成物およびフィラーを表7に記載のものに変更して保護膜用スラリーを調製した以外は、上記実施例32と同様にして保護膜付きセパレーター、正極、負極、蓄電デバイスを製造し、同様に評価した。その結果を表5に併せて示した。 6.8. Examples 33 to 39, Comparative Examples 9 to 10
In Example 32, a separator with a protective film was prepared in the same manner as in Example 32 except that the slurry for protective film was prepared by changing the binder composition and filler for the electricity storage device used to those shown in Table 7. A positive electrode, a negative electrode, and an electricity storage device were manufactured and evaluated in the same manner. The results are also shown in Table 5.
上記実施例32において、使用した蓄電デバイス用バインダー組成物およびフィラーを表8に記載のものに変更して保護膜用スラリーを調製し、保護膜付きセパレーターの保護膜面が負極側になるようにした以外は、上記実施例32と同様にして保護膜付きセパレーター、正極、負極、蓄電デバイスを製造し、同様に評価した。その結果を表8に併せて示した。 6.9. Examples 40 to 42, Comparative Examples 11 to 12
In the above Example 32, the binder composition and filler for the electricity storage device used were changed to those shown in Table 8 to prepare a slurry for the protective film, so that the protective film surface of the separator with the protective film was on the negative electrode side. A separator with a protective film, a positive electrode, a negative electrode, and an electricity storage device were produced in the same manner as in Example 32 except that the evaluation was performed in the same manner. The results are also shown in Table 8.
下表5~下表8に、保護膜用スラリーの組成および各評価結果を示す。 6.10. Evaluation results of Examples 25 to 42 and Comparative Examples 5 to 12 Tables 5 to 8 below show the composition of the slurry for the protective film and each evaluation result.
・酸化チタン:製品名「KR380」(チタン工業株式会社製、ルチル型、平均粒子径0.38μm)をそのまま使用に供するか、または製品名「KR380」をめのう乳鉢で粉砕し、ふるいを用いて分級することにより、平均粒子径が0.08μm、0.12μmである酸化チタンをそれぞれ調製して使用に供した。
・酸化アルミニウム:製品名「AKP‐3000」(住友化学株式会社製、平均粒子径0.74μm)、または製品名「AL-160SG-3」(昭和電工株式会社製、平均粒子径0.98μm)を使用に供した。
・酸化ジルコニウム:製品名「UEP酸化ジルコニウム」(第一希元素化学工業株式会社製、平均粒子径0.67μm)
・シリカ:製品名「シーホスター(R) KE-S50」(株式会社日本触媒製、平均粒子径0.54μm)を使用に供した。
・酸化マグネシウム:製品名「PUREMAG(R) FNM-G」(タテホ化学工業株式会社製、平均粒子径0.50μm) The fillers described in Tables 5 to 8 are as follows.
Titanium oxide: The product name “KR380” (manufactured by Titanium Industry Co., Ltd., rutile type, average particle size 0.38 μm) is used as it is, or is ground in a mortar with the product name “KR380” and used with a sieve. By classification, titanium oxides having an average particle diameter of 0.08 μm and 0.12 μm were prepared and used.
Aluminum oxide: Product name “AKP-3000” (manufactured by Sumitomo Chemical Co., Ltd., average particle size 0.74 μm), or product name “AL-160SG-3” (manufactured by Showa Denko Co., Ltd., average particle size 0.98 μm) Was used.
Zirconium oxide: Product name “UEP zirconium oxide” (Daiichi Rare Element Chemical Industries, Ltd., average particle size 0.67 μm)
Silica: The product name “Seahoster KE-S50” (manufactured by Nippon Shokubai Co., Ltd., average particle size 0.54 μm) was used.
Magnesium oxide: Product name “PUREMAG® FNM-G” (manufactured by Tateho Chemical Co., Ltd., average particle size 0.50 μm)
Claims (18)
- (メタ)アクリルアミドに由来する繰り返し単位を含有し、かつ、重量平均分子量(Mw)が3×105~6×106である水溶性重合体(A)と、
液状媒体(C)と、
を含有する、蓄電デバイス用バインダー組成物。 A water-soluble polymer (A) containing a repeating unit derived from (meth) acrylamide and having a weight average molecular weight (Mw) of 3 × 10 5 to 6 × 10 6 ;
A liquid medium (C);
The binder composition for electrical storage devices containing this. - 前記水溶性重合体(A)の重量平均分子量(Mw)/数平均分子量(Mn)が3~30である、請求項1に記載の蓄電デバイス用バインダー組成物。 The binder composition for an electricity storage device according to claim 1, wherein the water-soluble polymer (A) has a weight average molecular weight (Mw) / number average molecular weight (Mn) of 3 to 30.
- 不飽和カルボン酸、不飽和アミド、およびこれらの塩よりなる群から選択される少なくとも1種の化合物(B)をさらに含有する、請求項1または請求項2に記載の蓄電デバイス用バインダー組成物。 The binder composition for an electricity storage device according to claim 1 or 2, further comprising at least one compound (B) selected from the group consisting of unsaturated carboxylic acids, unsaturated amides, and salts thereof.
- 前記水溶性重合体(A)100質量部中に含有される前記(メタ)アクリルアミドに由来する繰り返し単位の割合が40~100質量部である、請求項1ないし請求項3のいずれか一項に記載の蓄電デバイス用バインダー組成物。 The ratio of the repeating unit derived from the (meth) acrylamide contained in 100 parts by mass of the water-soluble polymer (A) is 40 to 100 parts by mass. The binder composition for electrical storage devices as described.
- 前記水溶性重合体(A)100質量部中に含有される、前記(メタ)アクリルアミドに由来する繰り返し単位の割合が40~90質量部であり、かつ、カチオン性単量体に由来する繰り返し単位の割合が10~30質量部である、請求項1ないし請求項4のいずれか一項に記載の蓄電デバイス用バインダー組成物。 The proportion of the repeating unit derived from (meth) acrylamide contained in 100 parts by mass of the water-soluble polymer (A) is 40 to 90 parts by mass, and the repeating unit derived from a cationic monomer. The binder composition for an electricity storage device according to any one of claims 1 to 4, wherein the ratio of is 10 to 30 parts by mass.
- 前記水溶性重合体(A)100質量部に対して、前記化合物(B)を0.01~0.5質量部含有する、請求項3ないし請求項5のいずれか一項に記載の蓄電デバイス用バインダー組成物。 The electricity storage device according to any one of claims 3 to 5, comprising 0.01 to 0.5 parts by mass of the compound (B) with respect to 100 parts by mass of the water-soluble polymer (A). Binder composition.
- 前記水溶性重合体(A)が、重合性不飽和二重結合を有する酸、不飽和カルボン酸エステルおよびα,β-不飽和ニトリル化合物よりなる群から選択される少なくとも1種に由来する繰り返し単位をさらに含む、請求項1ないし請求項6のいずれか一項に記載の蓄電デバイス用バインダー組成物。 The water-soluble polymer (A) is a repeating unit derived from at least one selected from the group consisting of an acid having a polymerizable unsaturated double bond, an unsaturated carboxylic acid ester, and an α, β-unsaturated nitrile compound. The binder composition for an electricity storage device according to any one of claims 1 to 6, further comprising:
- 前記重合性不飽和二重結合を有する酸が、アクリル酸、メタクリル酸、イタコン酸、ビニルスルホン酸、アリルスルホン酸およびメタリルスルホン酸よりなる群から選択される少なくとも1種である、請求項7に記載の蓄電デバイス用バインダー組成物。 The acid having a polymerizable unsaturated double bond is at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, vinyl sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid. 2. The binder composition for an electricity storage device according to 1.
- 請求項1ないし請求項8のいずれか一項に記載の蓄電デバイス用バインダー組成物と、活物質と、を含有する蓄電デバイス用スラリー。 The slurry for electrical storage devices containing the binder composition for electrical storage devices as described in any one of Claims 1 thru | or 8, and an active material.
- 蓄電デバイス負極を作製するための蓄電デバイス用スラリーであって、前記活物質の平均粒子径が3μm以上10μm以下である、請求項9に記載の蓄電デバイス用スラリー。 The slurry for electrical storage devices of Claim 9 which is the slurry for electrical storage devices for producing an electrical storage device negative electrode, Comprising: The average particle diameter of the said active material is 3 micrometers or more and 10 micrometers or less.
- 前記活物質が、炭素材料およびケイ素材料の少なくとも一方を含む、請求項10に記載の蓄電デバイス用スラリー。 The slurry for an electrical storage device according to claim 10, wherein the active material contains at least one of a carbon material and a silicon material.
- 蓄電デバイス正極を作製するための蓄電デバイス用スラリーであって、前記活物質の平均粒子径が0.4μm以上7μm以下である、請求項9に記載の蓄電デバイス用スラリー。 The slurry for electrical storage devices of Claim 9 which is the slurry for electrical storage devices for producing an electrical storage device positive electrode, Comprising: The average particle diameter of the said active material is 0.4 micrometer or more and 7 micrometers or less.
- 請求項1ないし請求項8のいずれか一項に記載の蓄電デバイス用バインダー組成物と、フィラーと、を含有する蓄電デバイス用スラリー。 The slurry for electrical storage devices containing the binder composition for electrical storage devices as described in any one of Claims 1 thru | or 8, and a filler.
- 前記フィラーが、シリカ、酸化チタン、酸化アルミニウム、酸化ジルコニウムおよび酸化マグネシウムよりなる群から選択される少なくとも1種の粒子である、請求項13に記載の蓄電デバイス用スラリー。 The slurry for an electricity storage device according to claim 13, wherein the filler is at least one particle selected from the group consisting of silica, titanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide.
- 集電体と、前記集電体の表面上に請求項9ないし請求項12のいずれか一項に記載の蓄電デバイス用スラリーが塗布および乾燥されて形成された層と、を備える蓄電デバイス電極。 An electricity storage device electrode comprising: a current collector; and a layer formed by applying and drying the slurry for an electricity storage device according to any one of claims 9 to 12 on a surface of the current collector.
- 集電体と、前記集電体の表面に形成された活物質層と、を備え、
前記活物質層の表面に請求項13または請求項14に記載の蓄電デバイス用スラリーを塗布および乾燥させて形成された層をさらに備える、蓄電デバイス電極。 A current collector, and an active material layer formed on the surface of the current collector,
The electrical storage device electrode further provided with the layer formed by apply | coating and drying the slurry for electrical storage devices of Claim 13 or Claim 14 on the surface of the said active material layer. - 請求項13または請求項14に記載の蓄電デバイス用スラリーを塗布および乾燥させて形成された層を表面に備えるセパレーター。 A separator provided on the surface thereof with a layer formed by applying and drying the slurry for an electricity storage device according to claim 13 or claim 14.
- 請求項15または請求項16に記載の蓄電デバイス電極および請求項17に記載のセパレーターの少なくとも一方を備える蓄電デバイス。 An electricity storage device comprising at least one of the electricity storage device electrode according to claim 15 or claim 16 and the separator according to claim 17.
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KR1020167000843A KR20160033692A (en) | 2013-07-18 | 2014-07-02 | Binder composition for storage device, slurry for storage device, electrode for storage device, separator, and storage device |
JP2015527250A JPWO2015008626A1 (en) | 2013-07-18 | 2014-07-02 | Binder composition for power storage device, slurry for power storage device, power storage device electrode, separator, and power storage device |
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CN105378989B (en) | 2018-04-27 |
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CN105378989A (en) | 2016-03-02 |
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