WO2016039336A1 - 電池用カーボンブラック、混合粉末、電池用塗工液、電池用電極および電池 - Google Patents
電池用カーボンブラック、混合粉末、電池用塗工液、電池用電極および電池 Download PDFInfo
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- WO2016039336A1 WO2016039336A1 PCT/JP2015/075457 JP2015075457W WO2016039336A1 WO 2016039336 A1 WO2016039336 A1 WO 2016039336A1 JP 2015075457 W JP2015075457 W JP 2015075457W WO 2016039336 A1 WO2016039336 A1 WO 2016039336A1
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- battery
- carbon black
- electrode
- polymer dispersant
- dbp absorption
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to battery carbon black, mixed powder, battery coating liquid, battery electrode, and battery.
- the lithium ion secondary battery in which the negative electrode is formed using a material capable of occluding and releasing lithium ions can suppress the deposition of dendride compared to the lithium battery in which the negative electrode is formed using metallic lithium. Therefore, there is an advantage that a battery having a high capacity and a high energy density can be provided while safety is improved by preventing a short circuit of the battery.
- the content of the conductive agent in the electrode mixture is typically 2 mass percent or less, and more preferably 1 mass percent or less.
- carbon black which is a conductive agent, is required to exhibit sufficient electronic conductivity even when added in a small amount.
- Patent Document 1 as carbon black for non-aqueous secondary batteries having excellent conductivity and dispersibility, BET specific surface area, DBP absorption amount, electrical resistivity, sulfur content and volatile component content are disclosed. Carbon blacks each in a predetermined range are disclosed.
- the compounded material is required to be uniformly dispersed from the viewpoint of improving the performance of the lithium ion secondary battery.
- Patent Document 2 discloses a method for producing a positive electrode mixture characterized by performing two-stage kneading of solid kneading and dilution dispersion.
- Carbon black has a structure in which primary particles close to a spherical shape are connected on a bead as a common structure, and such a structure is called a structure.
- a structure In general, the smaller the primary particle size, the more electrical contacts exist in the same mass of the conductive agent, and the electronic conductivity is improved. Also, the longer the structure is connected, the greater the distance that can be conducted without contact resistance, so that the electron conductivity is improved.
- the length of the structure is indirectly evaluated using a DBP absorption amount generally measured in accordance with JIS K6217-4.
- carbon black with a small primary particle size and a long structure is excellent in conductivity, but has an aspect that it is difficult to disintegrate and easily aggregate because the interaction between particles is large. Therefore, in general, a method of applying a coating liquid in which an active material, a conductive agent and a binder are dispersed in water or an organic solvent is applied to a metal foil at the time of manufacturing an electrode. Carbon black having a small primary particle size and a long structure is used. When used as a conductive agent, the conductive agent agglomerates remain in the coating liquid, resulting in unevenness of the electrodes, and the coating liquid is too viscous to be applied.
- an object of the present invention is to provide a carbon black for a battery excellent in conductivity and dispersibility.
- An object of the present invention is to provide an excellent battery electrode and a battery excellent in high output characteristics.
- the present invention employs the following means in order to solve the above problems.
- the number average primary particle size is 20 nm or more and 40 nm or less, the ratio of the DBP absorption amount to the compression DBP absorption amount is 2.2 or less, and the compression DBP absorption amount is 100 mL / 100 g or more and 200 mL / 100 g or less.
- Carbon black for batteries (2)
- the carbon black for batteries according to (1) which is acetylene black.
- a battery coating solution comprising an active material, a polymer binder, and the battery carbon black described in (1) or (2).
- the battery coating solution according to (3) further comprising a polymer dispersant.
- a mixed powder comprising at least one selected from the group consisting of: (8) The mixed powder according to (7), wherein the content of the polymer dispersant is 0.05 mg or more and 0.5 mg or less per 1 m 2 with respect to the total surface area of the carbon black.
- a battery coating solution comprising the mixed powder according to (7) or (8), an active material, and a polymer binder.
- a battery electrode comprising: a metal foil; and a coating film containing the carbon black for battery according to (1) or (2) formed on the metal foil.
- the content of the polymer dispersant in the coating film is 0.05 mg or more and 0.5 mg or less per m 2 with respect to the total surface area of the carbon black.
- the present inventors have found that the carbon black for a battery in which the ratio of the DBP absorption amount to the compressed DBP absorption amount is in a specific range is excellent in dispersibility, and that the primary particle diameter and the compressed DBP absorption amount are appropriate It has been found that high conductivity and dispersibility can be achieved at the same time. In addition, it has been found that dispersibility is further improved by using an appropriate polymer dispersant together.
- the battery electrode produced using these has a low resistance, and the battery has a feature of excellent high output characteristics.
- FIG. 1 is a transmission electron micrograph of carbon black for a battery of Example 4.
- FIG. 2 is a transmission electron micrograph of acetylene black of Comparative Example 1.
- the carbon black for batteries of this embodiment has a number average primary particle size of 20 nm to 40 nm, a ratio of DBP absorption to compression DBP absorption of 2.2 or less, and a compression DBP absorption of 100 mL / 100 g or more. It is carbon black for batteries characterized by being 200 mL / 100 g or less.
- the ratio of the DBP absorption amount to the compressed DBP absorption amount means a value obtained by dividing the DBP absorption amount by the compressed DBP absorption amount (DBP absorption amount / compressed DBP absorption amount).
- the carbon black in the present embodiment is 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 number average primary particle size of the carbon black for battery in this embodiment is 20 nm or more and 40 nm or less.
- the number average primary particle diameter is 20 nm or more and 40 nm or less.
- the DBP absorption amount of the carbon black for batteries in the present embodiment is a value measured according to JIS K6217-4.
- the compressed DBP absorption amount is a value measured by the same method as the DBP absorption amount for a compressed sample produced according to JIS K6217-4 Annex A.
- the ratio of the DBP absorption amount to the compressed DBP absorption amount of the battery carbon black in the present embodiment is 2.2 or less.
- a large DBP absorption value compared to the compressed DBP absorption amount means that the amount of agglomerated particles that are destroyed when producing a compressed sample is large, and that more energy is required to break them up. . Therefore, by setting the ratio of the DBP absorption amount to the compressed DBP absorption amount to 2.2 or less, the energy necessary for crushing the agglomerated particles can be suppressed, and the dispersibility becomes good.
- Compressed DBP absorption of the carbon black for batteries in this embodiment is 100 mL / 100 g or more and 200 mL / 100 g or less, and more preferably 110 mL / 100 g or more and 140 mL / 100 g or less.
- the compressed DBP absorption amount is 100 mL / 100 g or more, the structure used as a conductive agent has a sufficient length, and good conductivity can be obtained.
- it by setting it as 200 mL / 100g or less, aggregation by the entanglement of structures is suppressed and a dispersibility becomes favorable.
- the battery carbon black can be dispersed in a medium together with an active material and a polymer binder and used as a battery coating solution.
- active materials composite oxides having a layered rock salt structure such as lithium cobaltate, lithium nickelate, nickel cobalt lithium manganate, nickel cobalt lithium aluminum oxide, etc., and spinels such as lithium manganate and nickel manganate are used for the positive electrode.
- composite oxides having an olivine structure such as lithium complex phosphate, lithium iron phosphate, lithium manganese phosphate, and lithium manganese phosphate.
- Active materials for negative electrodes 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 oxidation such as lithium titanate.
- the polymer binder include polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene copolymer, polyvinyl alcohol, acrylonitrile-butadiene copolymer, and carboxylic acid-modified (meth) acrylic acid ester copolymer. Examples include polymers.
- polyvinylidene fluoride is preferred from the viewpoint of oxidation resistance when used for the positive electrode, and polyvinylidene fluoride or styrene-butadiene copolymer is preferred from the viewpoint of adhesive strength when used for the negative electrode.
- Examples of the dispersion medium for the electrode coating liquid include water, N-methylpyrrolidone, cyclohexane, methyl ethyl ketone, and methyl isobutyl ketone.
- N-methylpyrrolidone is preferable from the viewpoint of solubility, and water is preferable when using a styrene-butadiene copolymer.
- the electrode coating solution may further contain a polymer dispersant.
- Polymeric dispersants include polyvinyl pyrrolidone, copolymers having vinyl pyrrolidone units, polyvinyl imidazole, polyethylene glycol, polyvinyl alcohol, polyvinyl butyral, carboxymethyl cellulose, acetyl cellulose, and carboxylic acid-modified (meth) acrylic acid ester copolymers. It is preferable to use at least one selected from Among these, it is more preferable to include at least one selected from polyvinylpyrrolidone and a copolymer having a vinylpyrrolidone unit (also referred to as a copolymer containing polyvinylpyrrolidone). Of these, polyvinylpyrrolidone is preferred. By including the polymer dispersant, the dispersibility of the carbon black for a battery is further improved.
- the content of the polymer dispersant is preferably 0.05 mg or more and 0.5 mg or less per 1 m 2 with respect to the total surface area of the carbon black for batteries, and more preferably 0.2 mg or more and 0.5 mg or less. preferable.
- the amount is 0.05 mg or more, the polymer dispersant exhibits a sufficient dispersion effect, and the dispersibility of the battery carbon black is further improved.
- covers the active material surface and obstructs a charge transfer reaction is suppressed, and the high resistance of a battery is suppressed.
- the electrode coating liquid containing the polymer dispersant As one form for obtaining the electrode coating liquid containing the polymer dispersant, it can be provided in the form of a mixed powder in which the carbon black for a battery and the polymer dispersant are mixed in advance.
- the battery manufacturer can obtain an electrode coating solution containing the polymer dispersant by simply applying it to a conventional process without using the polymer dispersant.
- a mixing apparatus for producing the electrode coating liquid a mixing machine such as a rough machine, a universal mixer, a Henschel mixer or a ribbon blender, or a medium stirring type mixer such as a bead mill, a vibration mill or a ball mill is used. It can be carried out.
- 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 battery coating liquid can contain components other than the battery carbon black, the active material, the polymer binder, and the polymer dispersant as long as the effects of the present invention are not impaired.
- carbon nanotubes, carbon nanofibers, graphite, graphene, carbon fibers, elemental carbon, glassy carbon, metal particles, and the like may be included in addition to battery carbon black for the purpose of further improving the conductivity.
- the method for producing the mixed powder includes a dry mixing method or a wet mixing method using a solvent such as water.
- a mixer such as a V-type mixer, a high-speed stirring mixer, a universal mixer, a flash blender, or a tumbler mixer can be used.
- the present invention may relate to a battery coating solution containing the battery carbon black.
- the battery coating solution may include the battery carbon black and the dispersion medium.
- the battery coating solution may further contain the active material.
- the battery transfer solution may further contain the polymer binder.
- the battery coating solution may further contain the polymer dispersant.
- the present invention may also relate to a mixed powder comprising the battery carbon black and the polymer dispersant.
- the present invention may also relate to a battery electrode comprising a metal foil and a coating film containing the carbon black for the battery formed on the metal foil.
- the coating film may be formed from the battery coating solution.
- the coating film is formed, for example, by applying and drying the battery coating solution.
- the coating film may further contain the active material.
- the coating film may further contain the polymer binder.
- the coating film may further contain the polymer dispersant.
- Examples of the coating method for battery coating liquid include 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 and squeeze. It may be law. Of these, the slot die method, the lip method, and the reverse roll method are preferable.
- the coating method for the battery coating solution may be selected according to the physical properties, drying properties, etc. of the battery coating solution. Thereby, a favorable surface state of the coating layer can be obtained.
- Application of the battery coating solution to the metal foil may be performed on one side or both sides, and in the case of both sides, it may be applied sequentially on one side or on both sides simultaneously.
- the application may be continuous, intermittent, or striped. What is necessary is just to determine suitably the application
- the coating thickness of the battery coating solution that is, the thickness of the coating film can be in the range of 10 ⁇ m to 500 ⁇ m.
- the method for drying the battery coating solution is not particularly limited, and for example, drying methods using hot air, vacuum, infrared rays, far infrared rays, electron beams, low-temperature air, etc. can be used alone or in combination.
- the metal foil may be, for example, an aluminum foil when used as a positive electrode. Moreover, when using metal foil as a negative electrode, copper foil etc. may be sufficient, for example.
- the shape of the metal foil is not particularly limited, but the thickness is preferably 5 to 30 ⁇ m from the viewpoint of easy workability.
- the electrode may be pressed as necessary.
- a generally adopted method can be used, and a die pressing method and a calendar pressing method (cold or hot roll) are particularly preferable.
- the press pressure in the calendar press method is not particularly limited, but is preferably 0.02 to 3 ton / cm.
- the present invention may also relate to a battery provided with the battery electrode.
- the battery may be a lithium ion secondary battery, a nickel hydride secondary battery, an electric double layer capacitor, or the like.
- a battery electrode manufacturing method comprises: applying the battery coating solution onto a metal foil; and providing the battery electrode with the metal foil and a coating film formed from the battery coating solution. The process of obtaining may be included.
- the present invention may also relate to the use of the carbon black as a carbon black for a battery.
- the present invention may also relate to the use of the carbon black for the production of a battery coating solution.
- the present invention may further relate to the use of the carbon black for the manufacture of a battery.
- Example 1 Carbon carbon black
- furnace black manufactured by Timcal Graphite and Carbon having a number average primary particle size of 40 nm, a DBP absorption of 234 mL / 100 g, and a compressed DBP absorption of 115 mL / 100 g was used.
- the DBP absorption amount and the compressed DBP absorption amount were measured by the following methods.
- the DBP absorption amount was measured by a method according to JIS K6217-4, and the compressed DBP absorption amount was measured by a measurement method similar to the DBP absorption amount for a compressed sample prepared by a method according to JIS K6217-4 Annex A. .
- the number average primary particle size was measured using a transmission electron microscope JEM-2000FX (manufactured by JEOL Ltd.), and five images with a magnification of 100,000 were taken and taken into image resolving software (Nireco Corp., “Luzex AP”). The number average primary particle diameter was determined for the extracted 200 or more primary particles, and the arithmetic average value thereof was calculated.
- Electrode coating solution evaluation of dispersibility (electrode coating solution)
- the dispersibility of the electrode coating solution was evaluated by a method using a crush gauge described in JIS K5600-2-5. Specifically, a scraper was used to apply the coating solution, and the graduations were measured at locations where three or more linear traces of 10 mm or more continuous on the sample surface were arranged in one groove. The lower the numerical value, the better the dispersibility.
- Electrode appearance The dispersibility of the carbon black for the battery was judged by the appearance of the positive electrode for the lithium secondary battery. Specifically, five 100 mm square electrodes were prepared and evaluated according to the following scale. Excellent: Neither streak-like coating marks nor aggregates were observed on the electrode surface. Good: A streaky coating mark or an aggregate of less than 1 mm was observed on one or more electrode surfaces. Defective: Agglomerates of 1 mm or more were observed on one or more electrode surfaces.
- a positive electrode for a lithium secondary battery is cut out into a disk shape having a diameter of 14 mm, and both surfaces are sandwiched between flat electrodes made of SUS304, using an electrochemical measurement system (Solartron, function generator 1260 and potentiogalvanostat 1287). The resistance against 1 Hz alternating current between the electrodes was measured and found to be 26 ⁇ .
- a positive electrode for the lithium secondary battery was used as the positive electrode, metal lithium (manufactured by Honjo Metal Co., Ltd.) was used as the negative electrode, and a non-woven fabric made of olefin fiber was used as a separator to electrically isolate them, thereby obtaining a CR-2032 type coin battery.
- electrolyte EC (ethylene carbonate, manufactured by Aldrich), MEC (methyl ethyl carbonate, manufactured by Aldrich) was mixed in a volume ratio of 1: 2, and lithium hexafluorophosphate (LiPF6, manufactured by Stella Chemifa). ) was dissolved at 1 mol / L.
- Examples 2 to 4> Except for changing the furnace black of Example 1 to acetylene black (SB50L, FX35, AB powder form, manufactured by Denki Kagaku Kogyo Co., Ltd.) having the number average primary particle size, DBP absorption, and compressed DBP absorption shown in Table 1.
- a battery coating solution, an electrode and a secondary battery were prepared in the same manner as in Example 1, and each evaluation was performed. The results are shown in Table 1. Moreover, when the carbon black for batteries of Example 4 was observed with a transmission electron microscope, the transmission electron micrograph shown in FIG. 1 was obtained.
- Examples 5 to 9 The furnace black of Example 1 was changed to acetylene black (SB50L, manufactured by Denki Kagaku Kogyo Co., Ltd.) having a number average primary particle size of 37 nm, a DBP absorption of 218 mL / 100 g, and a compressed DBP absorption of 111 mL / 100 g.
- Polyvinylpyrrolidone manufactured by Junsei Co., Ltd., PVP K-30
- a battery coating solution, an electrode and a secondary battery were prepared in the same manner as in Example 1 and evaluated. Carried out.
- the total surface area of acetylene black was determined by multiplying the BET specific surface area measured using a nitrogen adsorption specific surface area meter (Macsorb 1201) by the total mass of acetylene black. The results are shown in Table 2.
- Example 10 (Production of mixed powder) Acetylene black (SB50L manufactured by Denki Kagaku Kogyo Co., Ltd.) and polyvinylpyrrolidone (manufactured by Pure Chemical Co., PVP K-30) having a number average primary particle size of 37 nm, DBP absorption of 218 mL / 100 g, and compressed DBP absorption of 111 mL / 100 g.
- the mixture was mixed using a V-type mixer (VM-10, manufactured by Dalton) at a ratio such that the content of polyvinylpyrrolidone per 1 m 2 of acetylene black surface area was 0.17 mg to obtain a mixed powder.
- V-type mixer VM-10, manufactured by Dalton
- a battery coating solution, an electrode, and a secondary battery were produced in the same manner as in Example 1 except that the furnace black in Example 1 was changed to the mixed powder, and each evaluation was performed. The results are shown in Table 2.
- Example 1 The furnace black of Example 1 is furnace black (manufactured by Timcal Graphite and Carbon) or acetylene black (Denki Kagaku Kogyo Co., Ltd.) having the number average primary particle size, DBP absorption, and compression DBP absorption shown in Table 3.
- a battery coating solution, an electrode, and a secondary battery were prepared in the same manner as in Example 1 except that the product was changed to “manufactured”, and each evaluation was performed.
- the battery coating solution used in Comparative Example 1 was used, the dispersibility was poor and the electrode plate resistance was also high. Also in the battery evaluation, the 5C discharge capacity was below the measurement limit.
- the results are shown in Table 3.
- the acetylene black of the comparative example 1 was observed with the transmission electron microscope, the transmission electron micrograph shown in FIG. 2 was obtained.
- ⁇ Comparative example 2> Using acetylene black having a number average primary particle size of 48 nm as carbon black, a battery coating solution, an electrode and a secondary battery were prepared in the same manner as in Example 1, and each evaluation was performed. Although the battery coating solution used in Comparative Example 2 was excellent in dispersibility, it exhibited a high value of electrode plate resistance. Also in the battery evaluation, the 5C discharge capacity was below the measurement limit. The results are shown in Table 3.
- the carbon black for batteries of the examples of the present invention is excellent in conductivity and dispersibility, and the electrode produced using these has low resistance, and the battery has high output characteristics. It turned out to be excellent. Moreover, it turned out that the same effect is acquired also by providing with the form of mixed powder.
- the positive electrode, the negative electrode, and the lithium ion secondary battery using various active materials other than the present Example also showed good evaluation results regardless of the type of the active material and the polymer dispersant.
- the carbon black for a battery of the present invention is excellent in conductivity and dispersibility, and further, by using this, a battery having a low resistance and a high output characteristic can be obtained. Further, by providing the mixed powder in the form of a powder, the battery manufacturer can obtain the above effects without changing the conventional process.
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Abstract
Description
(1)個数平均1次粒子径が20nm以上40nm以下であり、圧縮DBP吸収量に対するDBP吸収量の比が2.2以下、かつ、圧縮DBP吸収量が100mL/100g以上200mL/100g以下である、電池用カーボンブラック。
(2)アセチレンブラックである、(1)に記載の電池用カーボンブラック。
(3)活物質と、高分子結着剤と、(1)又は(2)に記載の電池用カーボンブラックと、を含む、電池用塗工液。
(4)さらに高分子分散剤を含む、(3)に記載の電池用塗工液。
(5)前記高分子分散剤が、ポリビニルピロリドンおよびビニルピロリドン単位を有する共重合体からなる群より選択される少なくとも1種を含む、(4)に記載の電池用塗工液。
(6)前記高分子分散剤の含有量が、カーボンブラックの全表面積に対して1m2あたり0.05mg以上0.5mg以下である、(4)又は(5)に記載の電池用塗工液。
(7)高分子分散剤と、(1)又は(2)に記載の電池用カーボンブラックと、を含み、前記高分子分散剤がポリビニルピロリドンおよびビニルピロリドン単位を有する共重合体からなる群より選択される少なくとも1種を含む、混合粉末。
(8)前記高分子分散剤の含有量が、カーボンブラックの全表面積に対して1m2あたり0.05mg以上0.5mg以下である、(7)に記載の混合粉末。
(9)(7)又は(8)に記載の混合粉末と、活物質と、高分子結着剤と、を含む、電池用塗工液。
(10)金属箔と、該金属箔上に形成された(1)又は(2)に記載の電池用カーボンブラックを含む塗膜と、を備える、電池用電極。
(11)前記塗膜が、活物質および高分子結着剤をさらに含む、(10)に記載の電池用電極。
(12)前記塗膜が、高分子分散剤をさらに含む、(10)又は(11)に記載の電池用電極。
(13)前記高分子分散剤が、ポリビニルピロリドンおよびビニルピロリドン単位を有する共重合体からなる群より選択される少なくとも1種を含む、(12)に記載の電池用電極。
(14)前記塗膜における前記高分子分散剤の含有量が、カーボンブラックの全表面積に対して1m2あたり0.05mg以上0.5mg以下である、(12)又は(13)に記載の電池用電極。
(15)(10)~(15)のいずれかに記載の電池用電極を備える電池。
(16)(3)~(6)および(9)のいずれかに記載の電池用塗工液を金属箔上に塗布して、前記金属箔と前記電池用塗工液から形成された塗膜とを備える電池用電極を得る工程を含む、電池用電極の製造方法。
(電池用カーボンブラック)
電池用カーボンブラックとして、個数平均1次粒子径40nm、DBP吸収量234mL/100g、圧縮DBP吸収量115mL/100g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)を用いた。なお、DBP吸収量および圧縮DBP吸収量は、以下の方法により測定した。
DBP吸収量はJIS K6217-4に準拠する方法で測定し、圧縮DBP吸収量はJIS K6217-4附属書Aに準拠する方法で作製した圧縮試料について、DBP吸収量と同様の測定法で測定した。
個数平均1次粒子径は透過電子顕微鏡JEM-2000FX(日本電子社製)を用いて100000倍の画像5枚を撮影し、画像解折ソフト(ニレコ社製、「ルーゼックスAP」)に取り込んだ。抽出した200個以上の1次粒子について個数平均1次粒子径を求め、それらの算術平均値を算出した。
ファーネスブラック5質量部に、活物質としてリン酸鉄リチウム(Aleees社製)を90質量部、高分子結着剤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1120」)を溶質量で5質量部、さらに分散媒としてN-メチルピロリドン(キシダ化学社製)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、塗工液を得た。この塗工液を、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、リチウム二次電池用正極電極を得た。
電極用塗工液の分散性をJIS K5600-2-5に記載されるつぶゲージを用いた方法で評価した。具体的には、スクレパーを用い、塗工液を塗布し、試料面に10mm以上連続した線状痕が、一つの溝について3本以上並んだ箇所の目盛りを測定した。分散性は数値が低い程、良好な分散性を意味する。
電池用カーボンブラックの分散性はリチウム二次電池用正極電極の外観によって判断した。具体的には100mm四方の電極5枚を作製し、以下の尺度で評価した。
優:5枚とも電極面に筋状の塗工跡および凝集塊が観られなかった。
良:1枚以上の電極面に筋状の塗工跡または1mm未満の凝集塊が観られた。
不良:1枚以上の電極面に1mm以上の凝集塊が観察された。
リチウム二次電池用正極電極を直径14mmの円盤状に切り抜き、表裏をSUS304製平板電極によって挟んだ状態で、電気化学測定システム(ソーラトロン社製、ファンクションジェネレーター1260およびポテンショガルバノスタット1287)を用いて両電極間の1Hz交流に対する抵抗を測定したところ、26Ωであった。
前記リチウム二次電池用正極電極を正極として用いて、次のようにしてリチウムイオン二次電池を作製した。
上記で作製したリチウムイオン二次電池について、次のようにして評価を行った。
まず0.7mA/cm2の電流密度、上限電圧4.0Vにて定電流・定電圧充電を行い、次いで0.7mA/cm2の電流密度、下限電圧2.0Vにて定電流放電を行った際の放電容量を測定し、正極活物質量で除した容量密度(mAh/g)を算出した。この容量(mAh)を1時間で充放電可能な電流値を「1C」とした。次いで、電流を0.2C、上限電圧を4.0V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2.0Vとして定電流放電を行うことを5回繰り返し、5回目の定電流放電の際の放電容量を正極活物質量で除した値(mAh/g)を初期容量として算出した。本実施例の電池の初期容量は159mAh/gであった。
高出力特性の評価として、電流を0.2C、上限電圧を4.0Vとして定電流・定電圧充電を行った後、電流を5C、下限電圧を2.0Vとして定電流放電を行い、この際の放電容量を正極活物質量で除した値(mAh/g)を5C放電容量として算出したところ、75mAh/gであった。
実施例1のファーネスブラックを、表1に示す個数平均1次粒子径、DBP吸収量、圧縮DBP吸収量を持つアセチレンブラック(電気化学工業社製 SB50L、FX35、AB粉状)へ変更した以外は、実施例1と同様な方法で電池用塗工液、電極および二次電池を作製し、各評価を実施した。結果を表1に示す。また、実施例4の電池用カーボンブラックについて透過型電子顕微鏡による観測を行ったところ、図1に示す透過型電子顕微鏡写真が得られた。
実施例1のファーネスブラックを、個数平均1次粒子径37nm、DBP吸収量218mL/100g、圧縮DBP吸収量111mL/100gであるアセチレンブラック(電気化学工業社製 SB50L)へ変更し、さらに高分子分散剤としてポリビニルピロリドン(純正科学社製、PVP K-30)を表2に示す量だけ加えて、実施例1と同様な方法で電池用塗工液、電極および二次電池を作製し、各評価を実施した。ただし、アセチレンブラックの全表面積は窒素吸着比表面積計(マウンテック社製、Macsorb1201)を用いて測定したBET比表面積にアセチレンブラックの全質量を乗ずることで求めた。結果を表2に示す。
(混合粉末の作製)
個数平均1次粒子径37nm、DBP吸収量218mL/100g、圧縮DBP吸収量111mL/100gであるアセチレンブラック(電気化学工業社製 SB50L)とポリビニルピロリドン(純正科学社製、PVP K-30)とを、アセチレンブラックの表面積1m2あたりのポリビニルピロリドンの含有量が0.17mgになるような割合で、V型混合機(ダルトン社製、VM-10)を用いて混合し、混合粉末を得た。
実施例1のファーネスブラックを、表3に示す個数平均1次粒子径、DBP吸収量、圧縮DBP吸収量を持つ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)またはアセチレンブラック(電気化学工業社製)へ変更した以外は、実施例1と同様な方法で電池用塗工液、電極および二次電池を作製し、各評価を実施した。比較例1で用いた電池用塗工液を用いた場合、分散性に乏しく、極板抵抗も高い値を示した。また、電池評価においても5C放電容量が測定限界を下回る結果となった。結果を表3に示す。また、比較例1のアセチレンブラックについて透過型電子顕微鏡による観測を行ったところ、図2に示す透過型電子顕微鏡写真が得られた。
個数平均1次粒子径が48nmのアセチレンブラックをカーボンブラックとして用い、実施例1と同様な方法で電池用塗工液、電極および二次電池を作製し、各評価を実施した。比較例2で用いた電池用塗工液は分散性に優れるものの、極板抵抗が高い値を示した。また、電池評価においても5C放電容量が測定限界を下回る結果となった。結果を表3に示す。
DBP吸収量が254ml/100gのファーネスブラックをカーボンブラックとして用い、実施例1と同様な方法で電池用塗工液、電極および二次電池を作製し、各評価を実施した。比較例3で用いた電池用塗工液は分散性に優れるものの、極板抵抗が高い値を示した。また、電池評価においても5C放電容量が本発明の実施例より低い値となった。結果を表3に示す。
Claims (16)
- 個数平均1次粒子径が20nm以上40nm以下であり、
圧縮DBP吸収量に対するDBP吸収量の比が2.2以下、かつ、圧縮DBP吸収量が100mL/100g以上200mL/100g以下である、電池用カーボンブラック。 - アセチレンブラックである、請求項1に記載の電池用カーボンブラック。
- 活物質と、
高分子結着剤と、
請求項1又は2に記載の電池用カーボンブラックと、
を含む、電池用塗工液。 - さらに高分子分散剤を含む、請求項3に記載の電池用塗工液。
- 前記高分子分散剤が、ポリビニルピロリドンおよびビニルピロリドン単位を有する共重合体からなる群より選択される少なくとも1種を含む、請求項4に記載の電池用塗工液。
- 前記高分子分散剤の含有量が、カーボンブラックの全表面積に対して1m2あたり0.05mg以上0.5mg以下である、請求項4又は5に記載の電池用塗工液。
- 高分子分散剤と、
請求項1又は2に記載の電池用カーボンブラックと、
を含み、
前記高分子分散剤がポリビニルピロリドンおよびビニルピロリドン単位を有する共重合体からなる群より選択される少なくとも1種を含む、混合粉末。 - 前記高分子分散剤の含有量が、カーボンブラックの全表面積に対して1m2あたり0.05mg以上0.5mg以下である、請求項7に記載の混合粉末。
- 請求項7又は8に記載の混合粉末と、
活物質と、
高分子結着剤と、
を含む、電池用塗工液。 - 金属箔と、
該金属箔上に形成された請求項1又は2に記載の電池用カーボンブラックを含む塗膜と、
を備える、電池用電極。 - 前記塗膜が、活物質および高分子結着剤をさらに含む、請求項10に記載の電池用電極。
- 前記塗膜が、高分子分散剤をさらに含む、請求項10又は11に記載の電池用電極。
- 前記高分子分散剤が、ポリビニルピロリドンおよびビニルピロリドン単位を有する共重合体からなる群より選択される少なくとも1種を含む、請求項12に記載の電池用電極。
- 前記塗膜における前記高分子分散剤の含有量が、カーボンブラックの全表面積に対して1m2あたり0.05mg以上0.5mg以下である、請求項12又は13に記載の電池用電極。
- 請求項10~14のいずれか一項に記載の電池用電極を備える電池。
- 請求項3~6および9のいずれか一項に記載の電池用塗工液を金属箔上に塗布して、前記金属箔と前記電池用塗工液から形成された塗膜とを備える電池用電極を得る工程を含む、電池用電極の製造方法。
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KR20190045198A (ko) * | 2016-09-07 | 2019-05-02 | 덴카 주식회사 | 전극용 도전성 조성물 및 이를 이용한 전극, 전지 |
JP2019169272A (ja) * | 2018-03-22 | 2019-10-03 | 三洋化成工業株式会社 | 樹脂集電体、及び、リチウムイオン電池 |
JP7128576B2 (ja) | 2018-03-22 | 2022-08-31 | 三洋化成工業株式会社 | 樹脂集電体、及び、リチウムイオン電池 |
WO2022118921A1 (ja) * | 2020-12-04 | 2022-06-09 | デンカ株式会社 | カーボンブラック、スラリー及びリチウムイオン二次電池 |
WO2023233788A1 (ja) * | 2022-05-30 | 2023-12-07 | デンカ株式会社 | 正極組成物、正極、電池、正極形成用塗液の製造方法、正極の製造方法及び電池の製造方法 |
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CN107636872A (zh) | 2018-01-26 |
JP6581991B2 (ja) | 2019-09-25 |
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