WO2016088880A1 - 電極用導電性組成物、非水系電池用電極及び非水系電池 - Google Patents
電極用導電性組成物、非水系電池用電極及び非水系電池 Download PDFInfo
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M10/052—Li-accumulators
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Definitions
- the present invention relates to a conductive composition for electrodes, a non-aqueous battery electrode, and a non-aqueous battery.
- Non-aqueous electrolytes including carbonate-based organic electrolytes such as ethylene carbonate and diethyl carbonate, have a wider potential window than aqueous electrolytes. For this reason, the non-aqueous battery using these non-aqueous electrolytes can exhibit a higher voltage than the conventional aqueous battery using an aqueous electrolyte.
- lithium ion secondary batteries in which positive and negative electrodes are formed using a material capable of occluding and releasing lithium ions are excellent in capacity density in addition to high voltage, and as a result, can provide batteries with high energy density and output density. Has advantages.
- Patent Document 1 discloses a positive electrode material for a lithium ion secondary battery in which the surface of the positive electrode material is coated with a phosphorus compound.
- Patent Document 2 discloses a carbonate compound having a fluorine atom in an electrolytic solution.
- Patent Document 3 discloses a nonaqueous electrolyte battery in which at least a part of active material particles and a conductive material are covered with lithium ion conductive glass.
- Patent Document 4 discloses a lithium ion secondary battery in which a surface layer of a positive electrode current collector is coated with lithium fluoride.
- Carbon black has been conventionally used as a conductive agent for secondary batteries.
- a positive electrode active material having a high potential is used as described above, the carbon black that is a conductive agent has a large contact area with the electrolytic solution, which is a cause of facilitating side reactions such as oxidative decomposition of the electrolytic solution. It has become.
- Patent Documents 1 and 2 None of the methods described in Patent Documents 1 and 2 has improved carbon black, and the effect of suppressing side reactions is insufficient. In addition, in the methods described in Patent Documents 3 and 4, since the surface of carbon black is coated, there is a possibility that sufficient electronic conductivity cannot be ensured.
- the present invention is a non-aqueous battery using a positive electrode active material used at a high potential, and in particular, an electrode conductivity that suppresses side reactions such as a decomposition reaction of an electrolytic solution in a lithium ion secondary battery. It is an object of the present invention to provide a composition, a non-aqueous battery electrode using the composition, and a non-aqueous battery excellent in output characteristics and durability.
- the present invention employs the following means in order to solve the above problems.
- It contains carbon black, an active material capable of occluding and releasing cations, and a binder, and the localized electron spin density per unit surface area of the carbon black at 23 ° C. is 18.0 ⁇ 10 16. pieces / m 2 or less, the BET specific surface area of carbon black is less than 30 m 2 / g or more 120 m 2 / g, electrode conductive composition.
- a x M y Ni z Mn ( 2-y-z) O 4 (1) (Wherein A is one or more elements selected from the group consisting of Li, Na and K, and M is one or more elements selected from the group consisting of Ti, V, Cr, Fe, Co and Zn, or 2 or more, and x, y, and z satisfy 0 ⁇ x ⁇ 1, 0 ⁇ y, 0 ⁇ z, and y + z ⁇ 2, respectively.) (3) The conductive composition for electrodes according to (1) or (2), wherein the carbon black is acetylene black. (4) A non-aqueous battery electrode comprising: a metal foil; and a coating film of the conductive composition for an electrode according to any one of (1) to (3) provided on the metal foil. (5) A nonaqueous battery comprising the nonaqueous battery electrode according to (4) on at least one of a positive electrode and a negative electrode.
- non-aqueous batteries using a conductive composition for electrodes containing carbon black having a specific range of localized electron spin density and BET specific surface area have excellent output characteristics and high potential. It has been found that even when a positive electrode active material is used, side reactions such as a decomposition reaction of the electrolytic solution are suppressed, and the durability is excellent.
- FIG. 1 is a diagram showing a method for calculating the conduction electron spin number and the localized electron spin number from the total electron spin number at each temperature.
- FIG. 2 is an ESR spectrum (differential form) of the carbon black of Example 1.
- the conductive composition for an electrode according to this embodiment is a composition containing carbon black, an active material capable of occluding and releasing cations, and a binder.
- the carbon black according to the present embodiment may be selected from acetylene black, furnace black, channel black, and the like, like carbon black as a general battery conductive agent. Among these, acetylene black having excellent crystallinity and purity is more preferable.
- the localized electron spin density of carbon black defined as follows is strongly related to side reactions such as the decomposition reaction of the electrolyte.
- the localized electron spin density per unit surface area (D 1 [units / m 2 ]) of carbon black in the present embodiment is the number of localized electron spins per unit mass (N l [units / g]).
- a BET [m 2 / g]) is a value defined as shown in Equation (2).
- N is the total number of electron spins per unit mass of carbon black
- Nc is the number of conduction electron spins per unit mass of carbon black.
- N The total number of electron spins (N) per unit mass of carbon black is a value defined as in equation (3).
- N I / I REF ⁇ ⁇ s (s + 1) ⁇ / ⁇ S (S + 1) ⁇ ⁇ N REF / M (3)
- I is the electron spin resonance (hereinafter referred to as ESR) signal intensity of carbon black
- I REF is the ESR signal intensity of the standard sample
- s the spin of the standard sample.
- the quantum number, N REF is the spin number of the standard sample
- M is the mass of carbon black.
- the type of the standard sample is not particularly limited.
- a polyethylene film in which ions having a known spin quantum number are implanted by an electrochemical method can be used.
- the method for determining the spin number (N REF ) of the standard sample is not particularly limited.
- a method of measuring the concentration of ions having a known spin quantum number by titration can be used.
- the number of conduction electron spins (N c ) per unit mass of carbon black is a value defined as in equation (4).
- N A / T + N c (4)
- A is a constant and T is the absolute temperature [K] of carbon black.
- the localized electron spin density per unit surface area at 23 ° C. of the carbon black according to the present embodiment is 18.0 ⁇ 10 16 pieces / m 2 or less, and 1.0 ⁇ 10 14 to 13.0 ⁇ 10 16 pieces / m 2 is preferable, and 1.0 ⁇ 10 14 to 9.0 ⁇ 10 16 pieces / m 2 is more preferable.
- the smaller the localized electron spin density the smaller the number of sites called lattice defects and edges that are liable to cause a side reaction such as a decomposition reaction of the electrolytic solution, so that the effect of suppressing the side reaction can be obtained.
- the BET specific surface area of the carbon black according to this embodiment is 30 m 2 / g or more and 120 m 2 / g or less, and more preferably 40 to 80 m 2 / g. Since side reactions such as the decomposition reaction of the electrolyte solution occur on the surface of carbon black, the smaller the BET specific surface area of carbon black, the smaller the reaction field. Therefore, side reactions are suppressed when the BET specific surface area is 120 m 2 / g or less. Effect is obtained. On the other hand, if the BET specific surface area becomes too small, side reactions such as an electrolyte decomposition reaction are suppressed, but the formation of an electronic conductive path becomes disadvantageous and the battery characteristics represented by rate characteristics and cycle life are impaired.
- the surface area is preferably 30 m 2 / g or more.
- the aggregate structure (structure) of carbon black according to this embodiment is not particularly limited, but a larger structure is preferable from the viewpoint of improving conductivity, and a binder composition and a nonaqueous battery electrode are manufactured.
- the structure is generally evaluated indirectly using the DBP absorption amount measured in accordance with JIS K6217-4 or the DBP absorption amount of the compressed sample.
- the DBP absorption amount of the carbon black according to this embodiment is preferably 80 to 250 g / 100 mL, and the DBP absorption amount of the compressed sample is preferably 55 to 190 g / 100 mL.
- the volume resistivity of the carbon black according to the present embodiment is not particularly limited, but it is preferably as low as possible from the viewpoint of further improving the conductivity.
- the volume resistivity measured under 7.5 MPa compression is preferably 0.30 ⁇ ⁇ cm or less, and more preferably 0.25 ⁇ ⁇ cm or less.
- the ash content and water content of the carbon black according to the present embodiment are not particularly limited, but are preferably as small as possible from the viewpoint of further suppressing side reactions.
- the ash content in the carbon black is preferably 0.04% by mass or less
- the water content in the carbon black is preferably 0.10% by mass or less.
- the active material according to the present embodiment is selected from a positive electrode active material from which cations are released during charging and a negative electrode active material into which cations are inserted during charging, and the cation is preferably lithium ion, sodium ion, or potassium ion, Among these, lithium ions are particularly preferable in practical use.
- the positive electrode active material may be any positive electrode active material that can occlude and release cations.
- composite oxides having a layered rock salt structure such as lithium cobaltate, lithium nickelate, nickel cobalt lithium manganate, nickel cobalt lithium aluminum oxide, and spinel structures such as lithium manganate and nickel manganate
- composite oxides having an olivine structure such as lithium iron phosphate, lithium manganese phosphate, and lithium iron manganese phosphate.
- A is one or more elements selected from the group consisting of Li, Na and K
- M is one or two elements selected from the group consisting of Ti, V, Cr, Fe, Co and Zn. More than a seed.
- x, y, and z satisfy 0 ⁇ x ⁇ 1, 0 ⁇ y, 0 ⁇ z, and y + z ⁇ 2, respectively.
- the negative electrode active material may be any negative electrode active material that can occlude and release cations.
- Examples of the negative electrode active material include carbon-based materials such as artificial graphite, natural graphite, soft carbon, and hard carbon, metal-based materials alloyed with alkali metals such as silicon and tin, and metal composite oxides such as lithium titanate. .
- binder examples include polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene copolymer, polyvinyl alcohol, acrylonitrile-butadiene copolymer, and carboxylic acid-modified (meth) acrylic acid ester copolymer.
- Molecule polyvinylidene fluoride is preferable from the viewpoint of oxidation resistance when used for the positive electrode, and polyvinylidene fluoride or styrene-butadiene copolymer is preferable from the viewpoint of adhesion when used for the negative electrode.
- Examples of the dispersion medium for the electrode conductive composition of the present embodiment include water, N-methyl-2-pyrrolidone, cyclohexane, methyl ethyl ketone, and methyl isobutyl ketone.
- N-methyl-2-pyrrolidone is preferable from the viewpoint of solubility, and when using a styrene-butadiene copolymer, water is preferable.
- a mixing machine such as a raking machine, a universal mixer, a Henschel mixer or a ribbon blender, or a medium stirring type such as a bead mill, a vibration mill or a ball mill
- a mixing machine such as a raking machine, a universal mixer, a Henschel mixer or a ribbon blender, or a medium stirring type such as a bead mill, a vibration mill or a ball mill
- the manufactured electrode coating liquid is preferably subjected to vacuum defoaming at a stage before coating in order to ensure smoothness without causing defects in the coating film. If air bubbles are present in the coating solution, the coating film will be defective when applied to the electrode, which may impair smoothness.
- the conductive composition for an electrode of the present embodiment can contain components other than carbon black, a positive electrode active material, a negative electrode active material, and a binder as long as the above-described effects are obtained.
- a positive electrode active material for the purpose of further improving conductivity, carbon nanotubes, carbon nanofibers, graphite, graphene, graphene oxide, carbon fibers, elemental carbon, glassy carbon, metal particles, and the like may be included in addition to the carbon black.
- polyvinyl pyrrolidone polyvinyl imidazole, polyethylene glycol, polyvinyl alcohol, polyvinyl butyral, carboxymethyl cellulose, acetyl cellulose, a carboxylic acid-modified (meth) acrylic acid ester copolymer and the like may be included.
- the present invention may relate to a non-aqueous battery electrode comprising a metal foil and a coating film of the above-described electrode conductive composition provided on the metal foil.
- the metal foil may be, for example, an aluminum foil when used as a positive electrode. Moreover, when using as a negative electrode, copper foil etc. may be sufficient, for example.
- the shape of the metal foil is not particularly limited. From the viewpoint of facilitating workability, the thickness of the metal foil is preferably 5 to 30 ⁇ m.
- the electrode conductive composition coating film is, for example, slot die method, lip method, reverse roll method, direct roll method, blade method, knife method, extrusion method, curtain method, gravure method, bar method, dip method. Further, it may be formed by applying a conductive composition for an electrode on a metal foil by a method such as a squeeze method. Of these, the slot die method, the lip method, and the reverse roll method are preferable.
- the coating method may be appropriately selected according to the solution physical properties, drying properties, etc. of the binder.
- the coating film of the conductive composition for electrodes may be formed on one side of the metal foil or on both sides.
- the electrode conductive composition When forming the coating film of the electrode conductive composition on both surfaces of the metal foil, the electrode conductive composition may be sequentially applied to the metal foil one side at a time, or may be simultaneously applied to both surfaces of the metal foil. .
- the application mode of the electrode conductive composition may be continuous, intermittent, or striped.
- the thickness, length, and width of the coating film of the electrode conductive composition may be appropriately determined according to the size of the battery.
- the thickness of the coating film may be in the range of 10 ⁇ m to 500 ⁇ m.
- the coating film of the electrode conductive composition may be formed by applying and drying the electrode conductive composition.
- the conductive composition for an electrode can be dried using, for example, means such as hot air, vacuum, infrared rays, far infrared rays, electron beams, and low-temperature air, alone or in combination.
- the non-aqueous battery electrode may be pressed as necessary.
- a generally adopted method may be used, and for example, a die pressing method, a calendar pressing method (cold or hot roll) and the like are preferable.
- the pressing pressure in the calender pressing method is not limited, but is preferably 0.02 to 3 ton / cm, for example.
- the present invention may also relate to a non-aqueous battery comprising the non-aqueous battery electrode on at least one of a positive electrode and a negative electrode.
- the non-aqueous battery may be, for example, a lithium ion secondary battery, a sodium ion secondary battery, a magnesium ion secondary battery, a nickel hydrogen secondary battery, or an electric double layer capacitor.
- the present invention also provides a carbon black having a localized electron spin density per unit surface area at 23 ° C. of 18.0 ⁇ 10 16 atoms / m 2 or less and a BET specific surface area of 30 m 2 / g or more and 120 m 2 / g or less. It may relate to the conductive agent for non-aqueous batteries.
- the present invention may also relate to the use of the carbon black as a conductive agent for non-aqueous batteries.
- the present invention may also relate to the use of the carbon black for the production of a non-aqueous battery electrode, and may relate to materials for the production of the carbon black non-aqueous battery.
- Example 1 (Carbon black)
- carbon black acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.) having a localized electron spin density of 5.0 ⁇ 10 16 atoms / m 2 per unit surface area at 23 ° C. and a BET specific surface area of 68 m 2 / g. AB powder) was used.
- the localized electron spin density and BET specific surface area per unit surface area of acetylene black were measured by the following methods.
- the localized electron spin density at 23 ° C. of the acetylene black was measured by the following method. First, using an electron spin resonance measuring apparatus (ESP350E manufactured by Bruker) under the conditions of a central magnetic field of 3383 Gauss and a magnetic field sweep width of 200 Gauss, the sample temperature is ⁇ 263 ° C., ⁇ 253 ° C., ⁇ 233 ° C., ⁇ 173 ° C., ⁇ 113 ° C. The ESR signal of carbon black at ⁇ 53 ° C. and 23 ° C. was measured. Since the ESR signal is output in a differential form as shown in FIG. 2, the ESR signal intensity is calculated by integrating the ESR signal twice over the entire region.
- ESR signal intensity is calculated by integrating the ESR signal twice over the entire region.
- the ESR signal intensity of an ion-implanted polyethylene film having a known spin number was measured under the same conditions, and this was used as a standard sample for carbon at each temperature.
- the total electron spin number of black was calculated.
- a graph with the total electron spin number on the vertical axis and the reciprocal of the sample temperature expressed in absolute temperature on the horizontal axis was created, and the conduction electron spin number was calculated as an intercept of the regression line calculated using the method of least squares.
- the localized electron spin density was calculated by dividing the localized electron spin number obtained by subtracting the value of the conduction electron spin number from the value of the total electron spin number at 23 ° C. by the BET specific surface area of acetylene black.
- the mixture was mixed using a revolutionary mixer (manufactured by Shinky Co., Ltd., Awatori Nertaro ARV-310) to obtain a conductive composition for electrodes.
- This conductive composition for electrodes was applied to a 20 ⁇ m thick aluminum foil using a Baker type applicator, dried, then pressed and cut to obtain an electrode for a lithium ion battery.
- a lithium ion battery electrode prepared using the electrode conductive composition as a positive electrode was cut into a length of 40 mm and a width of 40 mm, and a negative electrode was cut into the negative electrode into a length of 44 mm and a width of 44 mm.
- An olefin fiber non-woven fabric was used as the separator for electrical isolation, and an aluminum laminate film was used as the exterior to make a laminated battery.
- EC ethylene carbonate, manufactured by Aldrich
- DEC diethyl carbonate, manufactured by Aldrich
- LiPF 6 lithium hexafluorophosphate
- the lithium ion battery produced above was evaluated as follows. The results are shown in Table 1. In addition, all evaluation of the battery was performed in a constant temperature room of 25 ⁇ 1 ° C. Further, unless otherwise specified, the evaluation value is an arithmetic average value of the evaluation values of the three batteries.
- a positive electrode active material amount (g) present on the positive electrode was determined from the mass of the positive electrode, and a value (mA) obtained by dividing this by 140 was defined as a current value “1C”.
- Constant current / constant voltage charging is performed with a current of 0.2C and an upper limit voltage of 5.0V, and further a constant current discharge is performed with a current of 0.2C and a lower limit voltage of 3.0V.
- the ratio (%) was defined as Coulomb efficiency.
- Coulomb efficiency it means that there are few side reactions, such as a decomposition reaction of electrolyte solution, so that Coulomb efficiency is high.
- rate characteristics were measured with the following capacity.
- the lithium ion battery after measuring the Coulomb efficiency was subjected to constant current / constant voltage charging with a current of 0.2 C and an upper limit voltage of 5.0 V, and then a constant current discharge with a current of 0.2 C and a lower limit voltage of 3.0 V. This was repeated for 4 cycles, and the discharge capacity at the 4th cycle was recorded as the 0.2 C discharge capacity.
- a constant current discharge with a current of 5 C and a lower limit voltage of 3.0 V is defined as 4 cycles.
- the discharge capacity at the fourth cycle was recorded as 5C discharge capacity.
- the ratio (%) of the 5C discharge capacity to the 0.2C discharge capacity was defined as the rate characteristic value. It should be noted that the larger the rate characteristic value, the lower the battery resistance and the better the output characteristic.
- Example 2 The acetylene black of Example 1 was applied to furnace black having a localized electron spin density of 8.1 ⁇ 10 16 atoms / m 2 per unit surface area at 23 ° C. and a BET specific surface area of 63 m 2 / g (Timcal Graphite and A conductive composition for electrodes, a lithium ion battery electrode and a lithium ion battery were prepared in the same manner as in Example 1 except that the product was changed to SuperPLi (manufactured by Carbon Co., Ltd.), and each evaluation was performed. The results are shown in Table 1.
- Example 3 Acetylene gas was mixed at 18 m 3 / hour, oxygen gas was 4 m 3 / hour, and hydrogen gas was mixed at 8 m 3 / hour, and installed at the top of a carbon black production furnace (furnace length 5 m, furnace diameter 0.5 m).
- Example 1 Except having changed the acetylene black of Example 1 into the sample A, the electroconductive composition for electrodes, the electrode for lithium ion batteries, and the lithium ion battery were produced by the same method as Example 1, and each evaluation was implemented. The results are shown in Table 1.
- Example 4 The acetylene black of Example 1 was a acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.) having a localized electron spin density of 16.4 ⁇ 10 16 atoms / m 2 per unit surface area at 23 ° C. and a BET specific surface area of 39 m 2 / g. Except having changed to HS100), the electroconductive composition for electrodes, the electrode for lithium ion batteries, and the lithium ion battery were produced by the same method as Example 1, and each evaluation was implemented. The results are shown in Table 1.
- Example 5 Using acetylene black of Example 4 as a raw material, heat treatment was performed at 1800 ° C. for 1 hour in a high-frequency furnace under a nitrogen atmosphere, the local electron spin density was 17.6 ⁇ 10 16 pieces / m 2 , and the BET specific surface area was 34 m. Sample B, 2 / g, was obtained. Except having changed the acetylene black of Example 1 into the sample B, the electroconductive composition for electrodes, the electrode for lithium ion batteries, and the lithium ion battery were produced by the method similar to Example 1, and each evaluation was implemented. The results are shown in Table 1.
- ⁇ Comparative Example 1> Acetylene black of Example 1, 23 localization per unit surface area electron spin density 3.3 ⁇ 10 16 pieces in ° C. / m 2, acetylene black has a BET specific surface area of 133m 2 / g (manufactured by Denki Kagaku Kogyo Kabushiki Kaisha, Except having changed into FX35), the electroconductive composition for electrodes, the electrode for lithium ion batteries, and the lithium ion battery were produced by the method similar to Example 1, and each evaluation was implemented. The results are shown in Table 2.
- Example 2 The acetylene black of Example 1 is furnace black (manufactured by Denki Kagaku Kogyo Co., Ltd.) having a localized electron spin density of 19.6 ⁇ 10 16 per unit surface area at 23 ° C./m 2 and a BET specific surface area of 25 m 2 / g.
- a conductive composition for electrodes, an electrode for lithium ion batteries, and a lithium ion battery were prepared in the same manner as in Example 1 except that the evaluation was performed. The results are shown in Table 2.
- a non-aqueous battery excellent in output characteristics and durability can be suppressed by suppressing side reactions such as decomposition reaction of an electrolytic solution even when a positive electrode active material having a high potential is used. Obtainable.
Abstract
Description
(1)カーボンブラックと、カチオンを吸蔵及び放出することが可能な活物質と、バインダーと、を含み、前記カーボンブラックの23℃における単位表面積あたりの局在電子スピン密度が18.0×1016個/m2以下であり、前記カーボンブラックのBET比表面積が30m2/g以上120m2/g以下である、電極用導電性組成物。
(2)前記活物質がスピネル型の結晶構造を持つ式(1)で表される複合金属酸化物である、(1)に記載の電極用導電性組成物。
AxMyNizMn(2-y-z)O4 (1)
(式中、AはLi、Na及びKからなる群より選ばれる元素の一種又は二種以上であり、MはTi、V、Cr、Fe、Co及びZnからなる群より選ばれる元素の一種又は二種以上であり、x、y及びzはそれぞれ0<x≦1、0≦y、0<z、及び、y+z<2を満たす。)
(3)前記カーボンブラックがアセチレンブラックである、(1)又は(2)に記載の電極用導電性組成物。
(4)金属箔と、前記金属箔上に設けられた(1)~(3)のいずれか一つに記載の電極用導電性組成物の塗膜と、を備える、非水系電池用電極。
(5)(4)に記載の非水系電池用電極を、正極及び負極のうち少なくとも一方に備えた非水系電池。
本実施形態におけるカーボンブラックの単位表面積あたりの局在電子スピン密度(Dl[個/m2])は単位質量あたりの局在電子スピン数(Nl[個/g])をBET比表面積(aBET[m2/g])で割った式(2)のように定義される値である。
Dl=Nl/aBET=(N-Nc)/aBET (2)
但し、Nはカーボンブラックの単位質量あたりの総電子スピン数、Ncはカーボンブラックの単位質量あたりの伝導電子スピン数である。
カーボンブラックの単位質量あたりの総電子スピン数(N)は、式(3)のように定義される値である。
N=I/IREF×{s(s+1)}/{S(S+1)}×NREF/M (3)
但し、Iはカーボンブラックの電子スピン共鳴(以下ESR)信号強度、IREFは標準試料のESR信号強度、Sはカーボンブラックのスピン量子数(すなわちS=1/2)、sは標準試料のスピン量子数、NREFは標準試料のスピン数、Mはカーボンブラックの質量である。
標準試料の種類は特に限定されるものではないが、例えば電気化学的な方法によりスピン量子数が既知のイオンを注入されたポリエチレンフィルムなどを用いることができる。また、標準試料のスピン数(NREF)を決定する方法は特に限定されるものではないが、例えば滴定法によりスピン量子数が既知のイオンの濃度を測定する方法を用いることができる。
カーボンブラックの単位質量あたりの伝導電子スピン数(Nc)は式(4)のように定義される値である。
N=A/T+Nc (4)
但し、Aは定数、Tはカーボンブラックの絶対温度[K]である。
すなわち、カーボンブラックの伝導電子スピン数(Nc)は、例えば下記のようにして決定することができる。まず、2点以上の異なる温度でカーボンブラックの総電子スピン数(N)を測定する。次いで図1のように、Nを縦軸に、絶対温度単位で表した測定温度の逆数(1/T)を横軸にとったグラフを作成する。次いでそのグラフの回帰直線を最小自乗法により求め、その切片の値(すなわち1/T=0に外挿した値)をNcとする方法である。
AxMyNizMn(2-y-z)O4 (1)
但し、AはLi、Na及びKからなる群より選ばれる元素の一種又は二種以上であり、またMはTi、V、Cr、Fe、Co及びZnからなる群より選ばれる元素の一種又は二種以上である。また、x、y及びzはそれぞれ0<x≦1、0≦y、0<z、及び、y+z<2を満たす。
(カーボンブラック)
本実施例ではカーボンブラックとして、23℃における単位表面積あたりの局在電子スピン密度5.0×1016個/m2、BET比表面積が68m2/gであるアセチレンブラック(電気化学工業社製、AB粉状)を用いた。なお、アセチレンブラックの単位表面積あたりの局在電子スピン密度及びBET比表面積は、以下の方法により測定した。
前記アセチレンブラックの23℃における局在電子スピン密度は、下記の方法で測定した。まず電子スピン共鳴測定装置(Bruker社製 ESP350E)を用いて、中心磁場3383Gauss、磁場掃引幅200Gaussの条件で、試料温度-263℃、-253℃、-233℃、-173℃、-113℃、-53℃及び23℃におけるカーボンブラックのESR信号を測定した。ESR信号は図2のような微分形式で出力されるため、これを全領域で2回積分することにより、ESR信号強度を算出した。次いで、既知のスピン数をもつイオン注入されたポリエチレンフィルム(厚み300μm、スピン数5.5×1013個/g)のESR信号強度を同一条件で測定し、これを標準試料として各温度におけるカーボンブラックの総電子スピン数を算出した。次いで縦軸に総電子スピン数、横軸に絶対温度で表した試料温度の逆数を取ったグラフを作成し、最小自乗法を用いて算出した回帰直線の切片として、伝導電子スピン数を算出した。次いで23℃における総電子スピン数の値から伝導電子スピン数の値を減じることで得られる局在電子スピン数をアセチレンブラックのBET比表面積で割ることによって、局在電子スピン密度を算出した。
前記アセチレンブラックのBET比表面積は、窒素吸着比表面積計(マウンテック社製、Macsorb1201)を用い、吸着ガスとして窒素を用いて相対圧p/p0=0.30±0.04の条件で測定した。
前記アセチレンブラック5質量部に、活物質としてスピネル型ニッケルマンガン酸リチウム(LiNi0.5Mn1.5O4、宝泉社製)を90質量部、バインダーとしてポリフッ化ビニリデン溶液(呉羽化学社製、「KFポリマー(登録商標)1120」、固形分濃度12質量%)を溶質量で5質量部、さらに分散媒としてN-メチル-2-ピロリドン(キシダ化学社製)30質量部を加えて自転公転式混合機(シンキー社製、あわとり練太郎ARV-310)を用いて混合し、電極用導電性組成物を得た。この電極用導電性組成物を、ベーカー式アプリケーターを用いて厚さ20μmのアルミニウム箔に塗布、乾燥し、その後、プレス、裁断して、リチウムイオン電池用電極を得た。
活物質として黒鉛粉末(日立化成社製 MAG-D)98質量部、バインダーとしてポリフッ化ビニリデン溶液を溶質量で2質量部、さらに分散媒としてN-メチル-2-ピロリドン30質量部を加えて自転公転式混合機を用いて混合し、負極用バインダー組成物を得た。これをベーカー式アプリケーターを用いて厚さ15μmの銅箔に塗布、乾燥し、その後、プレス、裁断して、負極電極を得た。
正極として前記電極用導電性組成物を用いて作製したリチウムイオン電池用電極を縦40mm、横40mmに裁断したもの、負極として前記負極電極を縦44mm、横44mmに裁断したものを用い、これらを電気的に隔離するセパレータとしてオレフィン繊維製不織布、外装としてアルミラミネートフィルムを用いてラミネート型電池とした。電解液にはEC(エチレンカーボネート、Aldrich社製)、DEC(ジエチルカーボネート、Aldrich社製)を体積比で1:2に混合した溶液中に六フッ化リン酸リチウム(LiPF6、ステラケミファ社製)を1mol/L溶解したものを用いた。
上記で作製したリチウムイオン電池について、次のようにして評価を行った。結果を表1に示す。尚、電池の評価は全て25±1℃の恒温室内で行った。また、特に記載のない場合は、評価値は3個の電池の評価値の算術平均値である。
まず正極の質量から正極上に存在する正極活物質量(g)を求め、これを140で除した値(mA)を電流値「1C」とした。電流を0.2C、上限電圧を5.0Vとして定電流・定電圧充電を行い、さらに電流を0.2C、下限電圧を3.0Vとして定電流放電を行い、この際の充電容量に対する放電容量の比(%)をクーロン効率とした。尚、クーロン効率が高いほど、電解液の分解反応などの副反応が少ないことを意味する。
出力特性の評価として、次の容量でレート特性の測定を行った。クーロン効率測定後のリチウムイオン電池について、電流を0.2C、上限電圧を5.0Vとして定電流・定電圧充電を行った後、電流を0.2C、下限電圧を3.0Vとして定電流放電を行うことを1サイクルとしてこれを4サイクル繰り返し、4サイクル目の放電容量を0.2C放電容量として記録した。次いで電流を0.2C、上限電圧を5.0Vとして定電流・定電圧充電を行ったあと、電流を5C、下限電圧を3.0Vとして定電流放電を行うことを1サイクルとしてこれを4サイクル繰り返し、4サイクル目の放電容量を5C放電容量として記録した。そして前記0.2C放電容量に対する5C放電容量の比(%)をレート特性値とした。尚、レート特性値が大きいほど電池の抵抗が低く、出力特性に優れることを意味する。
寿命の評価として、次の要領でサイクル特性の測定を行った。レート特性測定後のリチウムイオン電池について、電流を1C、上限電圧を5.0Vとして定電流・定電圧充電を行ったあと、電流を1C、下限電圧を3.0Vとして定電流を行うことを1サイクルとしてこれを200サイクル繰り返し、1サイクル目の放電容量に対する200サイクル目の放電容量の比(%)をサイクル特性値とした。200サイクル未満で放電容量が0となった場合は、その電池のサイクル特性値は0として3個の電池の算術平均値を計算した。
実施例1のアセチレンブラックを、23℃における単位表面積あたりの局在電子スピン密度8.1×1016個/m2、BET比表面積が63m2/gであるファーネスブラック(ティムカル・グラファイト・アンド・カーボン社製、SuperPLi)に変更した以外は、実施例1と同様な方法で電極用導電性組成物、リチウムイオン電池用電極及びリチウムイオン電池を作製し、各評価を実施した。結果を表1に示す。
アセチレンガスを18m3/時、酸素ガスを4m3/時、水素ガスを8m3/時の条件で混合し、カーボンブラック製造炉(炉長5m、炉直径0.5m)の炉頂に設置されたノズルから噴霧し、アセチレンの熱分解及び燃焼反応を利用して局在電子スピン密度12.1×1016個/m2、BET比表面積が52m2/gであるサンプルAを製造した。実施例1のアセチレンブラックをサンプルAに変更した以外は、実施例1と同様な方法で電極用導電性組成物、リチウムイオン電池用電極及びリチウムイオン電池を作製し、各評価を実施した。結果を表1に示す。
実施例1のアセチレンブラックを、23℃における単位表面積あたりの局在電子スピン密度16.4×1016個/m2、BET比表面積が39m2/gであるアセチレンブラック(電気化学工業社製、HS100)に変更した以外は、実施例1と同様な方法で電極用導電性組成物、リチウムイオン電池用電極及びリチウムイオン電池を作製し、各評価を実施した。結果を表1に示す。
実施例4のアセチレンブラックを原料とし、窒素雰囲気下で高周波炉にて、1800℃で1時間の熱処理を行い、局在電子スピン密度17.6×1016個/m2、BET比表面積が34m2/gであるサンプルBを得た。実施例1のアセチレンブラックをサンプルBに変更した以外は、実施例1と同様な方法で電極用導電性組成物、リチウムイオン電池用電極及びリチウムイオン電池を作製し、各評価を実施した。結果を表1に示す。
実施例1のアセチレンブラックを、23℃における単位表面積あたりの局在電子スピン密度3.3×1016個/m2、BET比表面積が133m2/gであるアセチレンブラック(電気化学工業社製、FX35)に変更した以外は、実施例1と同様な方法で電極用導電性組成物、リチウムイオン電池用電極及びリチウムイオン電池を作製し、各評価を実施した。結果を表2に示す。
実施例1のアセチレンブラックを、23℃における単位表面積あたりの局在電子スピン密度19.6×1016個/m2、BET比表面積が25m2/gであるファーネスブラック(電気化学工業社製)に変更した以外は、実施例1と同様な方法で電極用導電性組成物、リチウムイオン電池用電極及びリチウムイオン電池を作製し、各評価を実施した。結果を表2に示す。
Claims (5)
- カーボンブラックと、カチオンを吸蔵及び放出することが可能な活物質と、バインダーと、を含み、
前記カーボンブラックの23℃における単位表面積あたりの局在電子スピン密度が18.0×1016個/m2以下であり、
前記カーボンブラックのBET比表面積が30m2/g以上120m2/g以下である、電極用導電性組成物。 - 前記活物質がスピネル型の結晶構造を持つ式(1)で表される複合金属酸化物である、請求項1に記載の電極用導電性組成物。
AxMyNizMn(2-y-z)O4 (1)
(式中、AはLi、Na及びKからなる群より選ばれる元素の一種又は二種以上であり、MはTi、V、Cr、Fe、Co及びZnからなる群より選ばれる元素の一種又は二種以上であり、x、y及びzはそれぞれ0<x≦1、0≦y、0<z、及び、y+z<2を満たす。) - 前記カーボンブラックがアセチレンブラックである、請求項1又は2に記載の電極用導電性組成物。
- 金属箔と、
前記金属箔上に設けられた請求項1~3のいずれか一項に記載の電極用導電性組成物の塗膜と、
を備える、非水系電池用電極。 - 請求項4に記載の非水系電池用電極を、正極及び負極のうち少なくとも一方に備えた非水系電池。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016186065A1 (ja) * | 2015-05-19 | 2016-11-24 | デンカ株式会社 | シリカ被覆カーボンブラック、それを用いた電極用組成物、二次電池用電極および二次電池 |
CN106654234A (zh) * | 2017-02-06 | 2017-05-10 | 深圳市斯诺实业发展股份有限公司 | 一种锂电池正极材料及其制备方法 |
CN106784735A (zh) * | 2017-02-06 | 2017-05-31 | 安徽鹰龙工业设计有限公司 | 一种锂电池用复合正极材料及其制备方法 |
WO2018037910A1 (ja) * | 2016-08-24 | 2018-03-01 | デンカ株式会社 | 電池用カーボンブラック、電極用導電性組成物、電池用電極、および電池 |
Families Citing this family (1)
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---|---|---|---|---|
KR101937900B1 (ko) | 2018-02-07 | 2019-01-14 | 주식회사 엘지화학 | 신규한 도전재, 상기 도전재를 포함하는 전극, 상기 전극을 포함하는 이차 전지, 및 상기 도전재의 제조 방법 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63163085A (ja) * | 1986-12-24 | 1988-07-06 | 三菱油化株式会社 | 給排水用樹脂管 |
JP2010225366A (ja) * | 2009-03-23 | 2010-10-07 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
JP2011129442A (ja) * | 2009-12-21 | 2011-06-30 | Hitachi Ltd | リチウムイオン二次電池用正極及びリチウムイオン二次電池 |
JP2013109896A (ja) * | 2011-11-18 | 2013-06-06 | Toyota Motor Corp | 電極材料及び電極材料の製造方法 |
JP2014193996A (ja) * | 2013-02-27 | 2014-10-09 | Toyo Ink Sc Holdings Co Ltd | カーボンブラック分散液およびその利用 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3804898B2 (ja) * | 1999-05-13 | 2006-08-02 | 電気化学工業株式会社 | 非水系二次電池電極の導電剤、電極及び非水系二次電池 |
JP4029266B2 (ja) | 2001-12-04 | 2008-01-09 | 株式会社ジーエス・ユアサコーポレーション | 非水電解質電池および非水電解質電池の製造法 |
JP4697770B2 (ja) * | 2004-08-30 | 2011-06-08 | Jx日鉱日石エネルギー株式会社 | 炭素材料及びそれを用いた非水電解液二次電池 |
WO2008038930A1 (en) * | 2006-09-25 | 2008-04-03 | Lg Chem, Ltd. | Non-aqueous electrolyte and electrochemical device comprising the same |
JP5368685B2 (ja) * | 2007-07-31 | 2013-12-18 | 電気化学工業株式会社 | アセチレンブラック、その製造方法及び用途 |
JP5657348B2 (ja) * | 2010-11-04 | 2015-01-21 | Jx日鉱日石エネルギー株式会社 | リチウムイオン二次電池負極用炭素材料およびそれを使用した非水系二次電池 |
WO2012137119A2 (de) * | 2011-04-04 | 2012-10-11 | Basf Se | Elektrochemische zellen, die ionenaustauscher enthalten |
JP5544342B2 (ja) | 2011-09-21 | 2014-07-09 | 株式会社日立製作所 | リチウムイオン二次電池 |
KR101718057B1 (ko) * | 2012-08-02 | 2017-03-20 | 삼성에스디아이 주식회사 | 양극 활물질 및 이를 채용한 양극과 리튬전지 |
JP6070204B2 (ja) * | 2013-01-17 | 2017-02-01 | 日本ゼオン株式会社 | 電気化学素子電極用導電性接着剤組成物 |
WO2014119256A1 (ja) * | 2013-01-29 | 2014-08-07 | 三洋電機株式会社 | 非水電解質二次電池用負極活物質、当該負極活物質を用いた非水電解質二次電池用負極、及び当該負極を用いた非水電解質二次電池 |
US10559828B2 (en) * | 2013-02-04 | 2020-02-11 | Zeon Corporation | Slurry for lithium ion secondary battery positive electrodes |
JP2014165131A (ja) * | 2013-02-27 | 2014-09-08 | Nippon Zeon Co Ltd | リチウムイオン二次電池正極用スラリー組成物の製造方法、リチウムイオン二次電池用正極の製造方法、及び、リチウムイオン二次電池 |
JP6062297B2 (ja) | 2013-03-19 | 2017-01-18 | 旭化成株式会社 | 非水電気化学デバイス用電解液及びリチウムイオン二次電池 |
JP2015162356A (ja) | 2014-02-27 | 2015-09-07 | トヨタ自動車株式会社 | 被覆正極活物質、被覆正極活物質の製造方法およびリチウム電池 |
JP6094826B2 (ja) * | 2014-07-16 | 2017-03-15 | トヨタ自動車株式会社 | 非水電解液二次電池とその製造方法および非水電解液 |
-
2015
- 2015-12-04 US US15/532,879 patent/US20180269467A1/en not_active Abandoned
- 2015-12-04 CN CN201580074600.5A patent/CN107210426A/zh active Pending
- 2015-12-04 JP JP2016562696A patent/JP6769878B2/ja active Active
- 2015-12-04 KR KR1020177017476A patent/KR102492457B1/ko active IP Right Grant
- 2015-12-04 WO PCT/JP2015/084168 patent/WO2016088880A1/ja active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63163085A (ja) * | 1986-12-24 | 1988-07-06 | 三菱油化株式会社 | 給排水用樹脂管 |
JP2010225366A (ja) * | 2009-03-23 | 2010-10-07 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
JP2011129442A (ja) * | 2009-12-21 | 2011-06-30 | Hitachi Ltd | リチウムイオン二次電池用正極及びリチウムイオン二次電池 |
JP2013109896A (ja) * | 2011-11-18 | 2013-06-06 | Toyota Motor Corp | 電極材料及び電極材料の製造方法 |
JP2014193996A (ja) * | 2013-02-27 | 2014-10-09 | Toyo Ink Sc Holdings Co Ltd | カーボンブラック分散液およびその利用 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2016186065A1 (ja) * | 2015-05-19 | 2016-11-24 | デンカ株式会社 | シリカ被覆カーボンブラック、それを用いた電極用組成物、二次電池用電極および二次電池 |
JPWO2016186065A1 (ja) * | 2015-05-19 | 2018-04-12 | デンカ株式会社 | シリカ被覆カーボンブラック、それを用いた電極用組成物、二次電池用電極および二次電池 |
WO2018037910A1 (ja) * | 2016-08-24 | 2018-03-01 | デンカ株式会社 | 電池用カーボンブラック、電極用導電性組成物、電池用電極、および電池 |
CN109643802A (zh) * | 2016-08-24 | 2019-04-16 | 电化株式会社 | 电池用碳黑、电极用导电性组合物、电池用电极及电池 |
KR20190040300A (ko) * | 2016-08-24 | 2019-04-17 | 덴카 주식회사 | 전지용 카본 블랙, 전극용 도전성 조성물, 전지용 전극 및 전지 |
JPWO2018037910A1 (ja) * | 2016-08-24 | 2019-06-20 | デンカ株式会社 | 電池用カーボンブラック、電極用導電性組成物、電池用電極、および電池 |
US11098201B2 (en) | 2016-08-24 | 2021-08-24 | Denka Company Limited | Carbon black for batteries, conductive composition for electrodes, electrode for batteries, and battery |
KR102411086B1 (ko) | 2016-08-24 | 2022-06-20 | 덴카 주식회사 | 전지용 카본 블랙, 전극용 도전성 조성물, 전지용 전극 및 전지 |
CN109643802B (zh) * | 2016-08-24 | 2022-08-19 | 电化株式会社 | 电池用碳黑、电极用导电性组合物、电池用电极及电池 |
CN106654234A (zh) * | 2017-02-06 | 2017-05-10 | 深圳市斯诺实业发展股份有限公司 | 一种锂电池正极材料及其制备方法 |
CN106784735A (zh) * | 2017-02-06 | 2017-05-31 | 安徽鹰龙工业设计有限公司 | 一种锂电池用复合正极材料及其制备方法 |
Also Published As
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KR102492457B1 (ko) | 2023-01-30 |
CN107210426A (zh) | 2017-09-26 |
JPWO2016088880A1 (ja) | 2017-10-12 |
JP6769878B2 (ja) | 2020-10-14 |
US20180269467A1 (en) | 2018-09-20 |
KR20170088410A (ko) | 2017-08-01 |
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