WO2016031220A1 - Method of manufacturing lithium-ion secondary battery electrode sheet - Google Patents
Method of manufacturing lithium-ion secondary battery electrode sheet Download PDFInfo
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- WO2016031220A1 WO2016031220A1 PCT/JP2015/004225 JP2015004225W WO2016031220A1 WO 2016031220 A1 WO2016031220 A1 WO 2016031220A1 JP 2015004225 W JP2015004225 W JP 2015004225W WO 2016031220 A1 WO2016031220 A1 WO 2016031220A1
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- active material
- particles
- current collector
- granulated particles
- material particles
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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
- H01M4/139—Processes of manufacture
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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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
- 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
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a method of manufacturing a lithium-ion secondary battery electrode sheet.
- the term “secondary battery” refers to a repeatedly rechargeable battery in general.
- the term “lithium-ion secondary battery” refers to a secondary battery that uses lithium ions as the electrolyte ions and implements charging and discharging by the transfer of electric charge which is associated with the transfer of the lithium ions between the positive and negative electrodes.
- the lithium-ion secondary battery is one type of non-aqueous electrolyte secondary battery, which uses a non-aqueous electrolyte comprising a non-aqueous solvent in which an electrolyte salt is dissolved.
- JP 2004-079370 A discloses a method of obtaining an electrode sheet in which a layer of active material particles is formed on a current collector.
- the method involves coating the current collector with a mixture paste containing active material particles and a binder, drying the paste, and pressing the resultant material.
- the step of drying the mixture paste requires a large amount of energy, which increases the manufacturing cost.
- JP 2014-078497 A discloses a method of manufacturing a lithium-ion secondary battery electrode sheet in which a layer of active material particles is formed on a current collector, by feeding particles containing the active material particles and a binder onto the current collector and then pressing the particles and the current collector.
- This manufacturing method can simplify or eliminate the drying step, and in that respect, it can keep the manufacturing cost low.
- Patent Literature 1 in the manufacturing method in which a layer of active material particles is formed from the mixture paste, it is desirable to set the pressing pressure based on the weight of the mixture paste per unit area after drying and the thickness of the active material layer after pressing (i.e., the density of the active material layer).
- the layer of the active material particles is formed from granulated particles, as disclosed in Patent Literature 2, the resulting layer of the active material particles may not have sufficient peel strength even if the pressing is carried out under the same conditions as those used in the case where the layer of the active material particles is formed from the mixture paste.
- a method of manufacturing a lithium-ion secondary battery electrode sheet proposed herein includes the following steps 1 through 5: 1. Preparing a current collector. 2. Preparing granulated particles containing active material particles and a binder. 3. Feeding the granulated particles onto the current collector. 4. Leveling the granulated particles fed on the current collector. 5. Pressing the leveled granulated particles.
- the ratio (t/D50) be less than 1, where D50 is the mean particle size of the granulated particles fed onto the current collector and t is the thickness of a layer of the active material particles that has been formed subsequent to the step of pressing. This makes it possible to consistently obtain a lithium-ion secondary battery electrode sheet in which the formed active material particle layer has a high peel strength.
- the ratio (t/D50) be greater than 0.5. In this case, unevenness in the weight per unit area of the active material particles is likely to be kept small.
- Fig. 1 is a schematic view illustrating a manufacturing apparatus 10 that embodies a method of manufacturing a lithium-ion secondary battery electrode sheet proposed herein.
- Fig. 2 is a schematic view schematically illustrating a granulated particle 13a.
- Fig. 3 is a schematic view schematically illustrating the state of the granulated particles 13a before they are pressed.
- Fig. 4 is a schematic view schematically illustrating the state of the granulated particles 13a after they have been pressed.
- Fig. 5 is a photograph showing a surface of a layer 14 of active material particles 13a1 that is formed after the granulated particles 13a have been pressed.
- Fig. 1 is a schematic view illustrating a manufacturing apparatus 10 that embodies a method of manufacturing a lithium-ion secondary battery electrode sheet proposed herein.
- Fig. 2 is a schematic view schematically illustrating a granulated particle 13a.
- Fig. 3 is a schematic view schematically illustrating the
- FIG. 6 is a schematic view schematically illustrating the state of granulated particles 13a before they are pressed in a manufacturing method of a comparative example.
- Fig. 7 is a schematic view schematically illustrating the state of the granulated particles 13a after they have been pressed in the manufacturing method of the comparative example.
- Fig. 8 is a photograph showing a surface of a layer 14 of the active material particles 13a1 after the granulated particles 13a have been pressed in the manufacturing method of the comparative example.
- Figs. 9A to 9F illustrate the procedure of preparing samples.
- Fig. 10 is a graph illustrating the relationship between the ratio (t/D50) and the peel strength (N/m) in each of samples.
- Fig. 1 is a schematic view illustrating a manufacturing apparatus 10 that embodies a method of manufacturing a lithium-ion secondary battery electrode sheet proposed herein.
- the manufacturing apparatus 10 has a conveyor device 21, a coating device 22, a feeding device 24, a squeegee 25, and pressure rollers 26 and 27.
- the arrow F in the figure indicates the conveying direction, as appropriate.
- the conveyor device 21 is a device for conveying a current collector 11.
- the coating device 22 is a device for applying a binder solution 12.
- the feeding device 24 is a device for feeding granulated particles 13a (see Fig. 2). The details of these devices that constitute the manufacturing apparatus 10 will be described later.
- Fig. 2 is a view schematically illustrating the granulated particle 13a.
- a method of manufacturing a lithium-ion secondary battery electrode sheet proposed herein includes the following steps 1 through 5: 1. preparing a current collector 11; 2. preparing granulated particles 13a containing active material particles and a binder; 3. feeding the granulated particles 13a onto the current collector 11; 4. leveling the granulated particles 13a fed on the current collector 11; and 5. pressing the leveled granulated particles 13a.
- the current collector 11 is prepared.
- the current collector 11 prepared here is a member for obtaining electricity in the electrode sheet.
- the material suitable as the current collector 11 used for a lithium-ion secondary battery is a material that has good electron conductivity and is capable of existing stably within the battery.
- the current collector 11 also requires being lightweight, predetermined mechanical strength, processability, and so forth.
- an aluminum foil is used as the current collector 11 for the positive electrode of a lithium-ion secondary battery.
- a copper foil is used as the current collector 11 for the negative electrode thereof. In the example shown in Fig.
- a strip-shaped metal foil (specifically, an aluminum foil (thickness 15 ⁇ m) or a copper foil (thickness 10 ⁇ m)) is prepared as the current collector foil.
- the strip-shaped metal foil as the current collector foil be prepared in such a condition as to be coiled around a winding core.
- the manufacturing apparatus 10 shown in Fig. 1 is provided with a step of conveying the strip-shaped current collector 11 along its longitudinal direction.
- the current collector foil 11 as the strip-shaped current collector is conveyed by the conveyor device 21 along a predetermined conveyance passage.
- Such a strip-shaped current collector foil 11 is suitable for subjecting it to a predetermined treatment while it is being conveyed in a roll-to-roll process, as illustrated in Fig. 1.
- the current collector need not be a metal foil.
- the current collector 11 may be an electrically conductive resin film.
- the term “preparing” may mean, for example, obtaining a required material from a manufacturer of the material as appropriate.
- the granulated particles 13a are prepared. It is desirable that the granulated particles 13a prepared here contain at least active material particles 13a1 and a binder 13a2 (i.e., the first binder), as illustrated in Fig. 2.
- the granulated particles 13a can be obtained by, for example, granulating a mixture (suspension) in which the active material particles 13a1 and the binder 13a2 are mixed with a solvent by a spray drying method. In the spray drying method, the mixture is sprayed in a dry atmosphere. At this stage, the particles contained in each of the sprayed droplets are merged into roughly one aggregate and formed into a larger particle. Therefore, depending on the size of the droplets, the solid content contained in the granulated particle 13a can vary, and also, the size, mass, and the like of the granulated particle 13a can vary.
- the droplets to be sprayed contain at least the active material particles 13a1 and the binder 13a2. It is also possible that the droplets to be sprayed may contain materials other than the active material particles 13a1 and the binder 13a2. For example, a conductive agent and/or a thickening agent may be contained therein. It is desirable that the granulated particles 13a prepared here have a mean particle size of from about 60 ⁇ m to 100 ⁇ m.
- the term “mean particle size” means a particle size at a cumulative volume of 50% in the particle size distribution determined by a laser scattering and diffraction method using a particle size analyzer, in other words, a 50% volume average particle size, unless otherwise specifically mentioned.
- the cumulative volume of 50% in the particle size distribution i.e., the 50% volume average particle size
- D50 the cumulative volume of 50% in the particle size distribution
- the 50% volume average particle size is measured by a dry measurement method using a laser diffraction/scattering particle size analyzer (for example, Microtrac MT-3200II, made by Nikkiso Co., Ltd.) without dispersing the particles by compressed air.
- a laser diffraction/scattering particle size analyzer for example, Microtrac MT-3200II, made by Nikkiso Co., Ltd.
- the method of manufacturing an electrode sheet proposed herein is applicable to various types of electrode sheets.
- the method can be applied either to the positive electrode sheet or to the negative electrode sheet in a lithium-ion secondary battery.
- the active material particles 13a1 contained in the granulated particles 13a may vary depending on the electrode sheet to be manufactured.
- the active material particles for the positive electrode are used for the active material particles 13a1.
- the active material particles for the negative electrode are used for the active material particles 13a1.
- the lithium-ion secondary battery is taken as an example.
- the active material particles 13a1 used in the positive electrode of the lithium-ion secondary battery include: oxides containing lithium and one or more transition metal elements (i.e., lithium-transition metal oxide), such as lithium nickel oxide (for example, LiNiO 2 ), lithium cobalt oxide (for example, LiCoO 2 ), and lithium manganese oxide (LiMn 2 O 4 ); and phosphates containing lithium and one or more transition metal elements, such as lithium manganese phosphate (LiMnPO 4 ) and lithium iron phosphate (LiFePO 4 ).
- transition metal elements i.e., lithium-transition metal oxide
- LiNiO 2 lithium nickel oxide
- LiCoO 2 lithium cobalt oxide
- LiMn 2 O 4 lithium manganese oxide
- phosphates containing lithium and one or more transition metal elements such as lithium manganese phosphate (LiMnPO 4 ) and lithium iron phosphate (LiF
- positive electrode active material particles are used in particulate form and may be referred to as positive electrode active material particles, as appropriate.
- the positive electrode active material particles may be used either alone or in combination. Because these positive electrode active material particles have low electrical conductivity, the positive electrode active material layer contains a conductive agent in order to enhance the electrical conductivity. In this case, it is desirable that the conductive agent be contained in droplets that are sprayed in spray drying.
- the active material particles used in the negative electrode of the lithium-ion secondary battery include carbon-based materials, such as graphite carbons and amorphous carbons, lithium-transition metal oxides, and lithium-transition metal nitrides. These are used in particulate form and may be referred to as negative electrode active material particles, as appropriate.
- the negative electrode active material particles may be used either alone or in combination.
- the negative electrode active material layer may contain a conductive agent in order to enhance the electrical conductivity. In this case, it is desirable that the conductive agent be contained in droplets that are sprayed in spray drying.
- Examples of the conductive agent include carbon materials, such as carbon powder and carbon fiber. It is possible to use one of the just-mentioned examples of the conductive agents either alone or in combination with another one or more of the examples.
- Examples of the carbon powder include powders of acetylene black, oil-furnace black, graphitized carbon black, carbon black, Ketjen Black, and graphite. Such conductive agents are preferably added when active material particles 13a1 with poor electrical conductivity are used to form conductive paths between the active material particles 13a1 and the current collector foil 11.
- ⁇ Binder 13a2> the binder 13a2 that is to be added to the granulated particles 13a in the step of preparing granulated particles 13a.
- the granulated particles 13a are preferably granulated by a spray drying method. For this reason, a polymer that can be dissolved or dispersed in a solvent is used as the binder 13a2 that is to be added to the granulated particles 13a.
- Examples of the polymer that can be dissolved or dispersed in an aqueous solvent include rubber materials (such as styrene-butadiene copolymer (SBR) and acrylic acid-modified SBR resin (SBR latex)), vinyl acetate copolymers, and acrylate polymers.
- Examples of the polymer that can be dissolved or dispersed in a non-aqueous solvent include polyvinylidene fluoride (PVDF). It is also possible to use a cellulose-based polymer, a fluoropolymer (such as polytetrafluoroethylene (PTFE)), or the like, as the binder 13a2 that is to be added to the granulated particles 13a. Note that although examples of the binder 13a2 that is to be added to the granulated particles 13a are shown herein, the binder 13a2 that is to be added to the granulated particles 13a is not limited to the examples shown herein.
- Step 3 the granulated particles 13a are fed onto the current collector 11.
- a binder solution 12 is applied onto the current collector 11 before the granulated particles 13a are supplied, as illustrated in Fig. 1.
- the binder solution 12 prepared here is a solution in which a binder is mixed with a solvent. From the viewpoint of reducing the environmental load, it is preferable to use what is called an aqueous solvent as the solvent for the binder solution 12. In this case, water or a mixed solvent mainly composed of water is used.
- the solvent of the binder solution 12 is not limited to what is called an aqueous solvent, but may be what is called an organic-based solvent.
- An example of the organic-based solvent is N-methylpyrrolidone (NMP).
- the binder contained in the binder solution 12 be one that can be dispersed in a solvent.
- preferable examples include styrene-butadiene rubber (SBR) and polyacrylic acid (PAA), because the solvent is an aqueous solvent.
- preferable examples of the binder include polyvinylidene fluoride (PVDF) and polyacrylic acid (PAA).
- PVDF polyvinylidene fluoride
- PAA polyacrylic acid
- an acrylic resin e.g., polymethyl methacrylate
- ⁇ Step of Coating Binder Solution 12 It is desirable that the binder solution 12 be applied onto the current collector 11 in a predetermined pattern.
- the binder solution 12 is applied onto a predetermined region in the current collector 11.
- the binder solution 12 be applied thinly onto the current collector 11, for example, at a thickness of from about 1 ⁇ m to 20 ⁇ m, and be applied by gravure printing or the like.
- a direct gravure roll coater can be used as the coating device 22.
- Such a coating device 22 allows the binder solution 12 to be transferred onto the current collector 11 by direct gravure printing using the gravure roller 22a having minute patterns engraved on the surface thereof.
- the gravure roller 22a have, for example, a plurality of grooves having a print depth of about from 10 ⁇ m to 30 ⁇ m (for example, 20 ⁇ m), a width of 50 ⁇ m, and a pitch of 200 ⁇ m, along an oblique line inclined with respect to the rotational axis.
- the pattern of grooves formed in the gravure roller 22a may be a horizontal striped pattern or a grid pattern.
- the grid pattern may be, for example, such a pattern in which oblique lines are combined with a grid pattern.
- the horizontal striped pattern may be such that the binder solution 12 is applied along the width direction of the strip-shaped current collector 11 and at a predetermined interval along the length direction thereof.
- the width and the pitch of the grooves of the gravure roller 22a may be varied in a variety of ways.
- the strip-shaped current collector 11 be conveyed with the treatment surface to be coated with the binder solution 12 (i.e., the surface on which the active material layer is to be formed) facing downward, and that the gravure roller 22a be applied to the current collector 11 in such a condition.
- the lower side of the gravure roller 22a is immersed in the binder solution 12 stored in a reservoir 22b.
- a backing roller 22c is applied to the opposite side of the current collector 11 to the surface thereof with which the gravure roller 22a makes contact.
- the binder solution 12 stored in the reservoir 22b is continuously transferred to the current collector 11 through the gravure roller 22a. It is desirable that the binder solution 12 be applied to the current collector 11 at a thickness of, for example, from about 1 ⁇ m to about 10 ⁇ m.
- the current collector foil 11 strip-shaped current collector foil
- the feeding device 24, the squeegee 25, and the pressure rollers 26 and 27 are disposed in that order in the conveyance passage of the current collector foil 11.
- the granulated particles 13a are fed onto the current collector 11 by the feeding device 24.
- the feeding device 24 is provided with a hopper 24a for storing the granulated particles 13a.
- the hopper 24a be provided with an adjusting device for adjusting the amount of the granulated particles 13a to be supplied.
- the hopper 24a should desirably adjust the feeding amount of the granulated particles 13a according to, for example, the conveying speed of the current collector 11, to feed an appropriate amount of the granulated particles 13a onto the current collector foil 11.
- the granulated particles 13a are fed in the form of an aggregate (powder material 13) in which a plurality of granulated particles 13a are gathered.
- the granulated particles 13a that have been fed on the current collector foil 11 is leveled.
- the thickness of the granulated particles 13a fed on the current collector foil 11 i.e., the thickness of the powder material 13 of the granulated particles 13a
- the squeegee 25 is provided on the downstream side of the feeding device 24 (i.e., on the downstream side in the conveyance passage of the current collector foil). The squeegee 25 adjusts the thickness of the granulated particles 13a that have been fed on the current collector foil 11.
- the squeegee 25 includes a roller squeegee 25a and a backing roller 25b that are disposed so as to sandwich the granulated particles 13a fed on the current collector foil 11 therebetween in the thickness direction.
- the squeegee 25 herein is composed of a roller-shaped member, it may be composed of a blade-shaped member.
- the gap between the squeegee 25 and the conveyed current collector foil 11 be adjusted to, for example, from about 100 ⁇ m to about 300 ⁇ m (preferably from about 150 ⁇ m to about 250 ⁇ m), although it may depend on the particle size and the weight per unit area (designed weight per unit area) of the granulated particles 13a.
- the granulated particles 13a that have been leveled are pressed against the current collector 11.
- the pressure rollers 26 and 27 are members for sandwiching the granulated particles 13a and the current collector foil 11 therebetween in the conveyance passage in which the strip-shaped current collector foil 13a is conveyed.
- the manufacturing method of forming the layer 14 of the active material particles 13a1 on the current collector 11 using the granulated particles 13a may not be able to obtain sufficient strength and sufficient adhesive strength in the resulting layer of the active material particles 13a1.
- the layer 14 of the active material particles 13a1 is formed by leveling the granulated particles 13a fed on the current collector 11 and, in the step of pressing, pressing the leveled granulated particles 13a hard from above. At this stage, if the pressing pressure is adjusted so that the formed layer 14 of the active material particles 13a1 will have a predetermined density, the formed layer 14 of the active material particles 13a1 may not have sufficient strength and sufficient adhesive strength.
- the pressing pressure may be determined based on the weight of the mixture paste per unit area after drying and the thickness of the active material layer after pressing (i.e., the density of the active material layer).
- the formed layer 14 of the active material particles 13a1 may not have sufficient strength and sufficient adhesive strength even if the pressing pressure is set in the same way as in the case of forming the layer of the active material particles from a mixture paste.
- the active material particles and the binder are dispersed in the coated mixture paste. Then, the drying is carried out with the binder having entered the gaps between the active material particles. Furthermore, the pressing is performed for the dried material, in which the binder has entered in the gaps between the active material particles. This ensures a sufficient contact area of the bonder with the active material particles and the current collector, so that sufficient bonding strength can be ensured between the active material particles and between the active material particles and the current collector.
- the pressing pressure may be determined based on the weight of the mixture paste per unit area and the thickness of the active material layer after pressing (i.e., the density of the active material layer). That is, in the manufacturing method in which the active material particle layer is formed from the mixture paste, the mixture layer is formed while the solvent (liquid) that forms the paste is being dried. In this case, the active material layer is adhered to the current collector to some degree before the step of pressing, because the number of contact points of the binder is increased in the step of drying.
- the granulated particles 13a are produced by spray-drying a mixture (suspension) containing the active material particles 13a1 and the binder 13a2, as described above.
- the binder 13a2 contained in the granulated particles 13a has been dried with the binder 13a2 adhering to the active material particles 13a1.
- the granulated particles 13a are merely placed on the current collector 11. Under this condition, the active material particles 13a1 contained in a single granulated particle 13a are bonded to each other by the binder 13a2. However, different granulated particles 13a are not bonded to each other by the binder 13a2.
- the layer 14 of the active material particles 13a1 is formed from the granulated particles 13a, it is necessary to bond the active material particles 13a1 contained in different granulated particles 13a to each other and the active material particles 13a1 to the current collector 11 with sufficient strength in the step of pressing.
- the granulated particles 13a that have been dried in advance are adhered to each other in the step of pressing, to form the layer 14 of the active material particles 13a1. For this reason, in order to ensure sufficient peel strength, adhesion must be brought about between the granulated particles 13a by the pressing.
- the states of the active material particles 13a1 and the binder 13a2 prior to the pressing are different between the case where the layer 14 of the active material particles 13a1 is formed from the granulated particles 13a and the case where the layer of the active material particles are formed from a mixture paste (not shown).
- the mechanisms of how the active material particles 13a1 are bonded to each other before forming the layer of the active material particles are also different.
- Figs. 3 and 4 schematically illustrate the step of pressing the granulated particles 13a in the method of manufacturing a lithium-ion secondary battery electrode sheet proposed herein.
- Fig. 3 is a view schematically illustrating the state of the granulated particles 13a before they are pressed.
- Fig. 4 is a view schematically illustrating the state of the granulated particles 13a after they have been pressed.
- Fig. 3 is a view schematically illustrating the state of the granulated particles 13a before they are pressed.
- Fig. 4 is a view schematically illustrating the state of the granulated particles 13a after they have been pressed.
- FIG. 5 is a photograph showing a surface of the layer 14 of the active material particles 13a1 that is formed after the granulated particles 13a have been pressed.
- Figs. 6 and 7 schematically illustrate the step of pressing granulated particles 13a in a comparative example of the method of manufacturing a lithium-ion secondary battery electrode sheet.
- Fig. 6 is a view schematically illustrating the state of the granulated particles 13a before they are pressed.
- Fig. 7 is a view schematically illustrating the state of the granulated particles 13a after they have been pressed.
- Fig. 8 is a photograph showing a surface of a layer 14 of the active material particles 13a1 after the granulated particles 13a have been pressed in the comparative example of the manufacturing method.
- the present inventors propose that, in the step of feeding the granulated particles 13a, the ratio (t/D50) should be set in the range (t/D50) ⁇ 1, where D50 is the mean particle size of the granulated particles 13a fed onto the current collector 11 and t is the thickness of the layer 14 of the active material particles 13a1 that has been formed subsequent to the step of pressing.
- D50 is the mean particle size of the granulated particles 13a fed onto the current collector 11
- t is the thickness of the layer 14 of the active material particles 13a1 that has been formed subsequent to the step of pressing.
- the mean particle size (D50) of the granulated particles 13a be greater than the thickness t of the layer 14 of the active material particles 13a1 after pressing.
- the weight per unit area and the mean particle size of the granulated particles 13a be determined so that the ratio (t/D50) is in the range (t/D50) ⁇ 1.
- the mean particle size (D50) of the granulated particles 13a is greater than the thickness t of the layer 14 of the active material particles 13a1 after pressing, as illustrated in Fig. 3, the particle configuration of the granulated particles 13a is destroyed at the time of the pressing, as illustrated in Figs. 4 and 5. Accordingly, the binder 13a2 contained in the granulated particles 13a is squashed between the active material particles 13a1. As a result, the contact area between the active material particles 13a1 and the binder 13a2 is increased.
- the binder 13a2 adheres between the active material particles 13a1 that were contained in different granulated particles 13a, allowing the active material particles 13a1 to be bonded to each other with sufficient strength. Furthermore, since the active material particles 13a1 are also pressed against the current collector 11, the binder 13a2 is also squashed between the current collector 11 and the active material particles 13a1. As a result, sufficient bonding strength is also ensured between the current collector 11 and the active material particles 13a1.
- the current collector 11 is coated with the binder solution 12. For this reason, it is easy to obtain sufficient bonding strength between the current collector 11 and the active material particles 13a1. It is also possible that the granulated particles 13a to be fed onto the current collector 11 may contain granulated particles 13a that have a smaller particle size than the thickness t of the layer 14 of the active material particles 13a1 after pressing. It is also possible that granulated particles 13a whose particle configuration has not destroyed after pressing may remain partially in the granulated particles 13a to be fed onto the current collector 11. Thus, in the case of powder molding, the particle size of the granulated particles 13a may be determined so that the granulated particles 13a can be destroyed (i.e., squashed) with each other.
- the binder 13a2 contained in the granulated particles 13a is squashed between the active material particles 13a1, and the adhesion strength thereof is obtained. As a result, a required bonding strength between the active material particles 13a1 can be obtained.
- the ratio (t/D50) of the thickness t of the layer 14 of the active material particles 13a1 after pressing and the mean particle size (D50) of the granulated particles 13a is in the range (t/D50) > 1.
- the mean particle size (D50) of the granulated particles 13a is smaller than the thickness t of the layer 14 of the active material particles 13a1 after pressing.
- the particle configuration remains unbroken in a relatively large proportion of the granulated particles 13a, as illustrated in Figs. 7 and 8.
- the binder 13a2 may not serve its function sufficiently. Consequently, sufficient peel strength may not be obtained.
- Figs. 9A to 9F show the procedure of preparing the samples.
- an aluminum foil 201 having a thickness of 15 ⁇ m and 200 mm ⁇ 200 mm dimensions is prepared, as shown in Fig. 9A.
- the binder solution 202 is applied to a widthwise center portion of such an aluminum foil 201 over a width of 160 mm.
- the portion coated with the binder solution 202 is covered by a mask 203.
- An opening 203a with dimensions of 100 mm ⁇ 100 mm is formed at a central portion of the mask 203, and the aluminum foil 201 coated with the binder solution 202 is exposed from the opening 203a.
- D50 mean particle size
- the aluminum foil 201 provided with the granulated particles 204a that were adjusted so as to have a predetermined weight per unit area is passed through the gap between the pressure rollers 206 and 207, as illustrated in Fig. 9F.
- the pressing pressure was adjusted so that the density of the layer 205 of the active material particles formed from the granulated particles 204a became 1.35 g/cm 3 .
- Fig. 10 is a graph illustrating the relationship between the ratio (t/D50) and the peel strength (N/m) in each of the samples.
- the peel strength is evaluated by a value determined by the 90-degree peeling test according to JIS K 6854.
- the thickness t ( ⁇ m) of the layer 205 of the active material particles after pressing is evaluated by the mean value of the thickness values at arbitrary four points in each sample, which are measured by a film thickness gauge 547-315 manufactured by Mitutoyo Corp.
- sample 1 had a weight per unit area of 8.5 (mg/cm 2 ), a ratio (t/D50) of 0.83, and a peel strength of 1.9 (N/m).
- Sample 2 had a weight per unit area of 9.8 (mg/cm 2 ), a ratio (t/D50) of 0.97, and a peel strength of 1.1 (N/m).
- Sample 3 had a weight per unit area of 11.5 (mg/cm 2 ), a ratio (t/D50) of 1.11, and a peel strength of 0.7 (N/m).
- Sample 4 had a weight per unit area of 13.1 (mg/cm 2 ), a ratio (t/D50) of 1.26, and a peel strength of 0.55 (N/m).
- the ratio (t/D50) of the thickness t of the layer 205 of the active material particles after pressing to the mean particle size (D50) of the granulated particles 204a fed on the aluminum foil 201 serving as the current collector is, the higher the peel strength.
- the thickness t of the layer 205 of the active material particles after pressing can be adjusted by varying the weight per unit area of the granulated particles 13a.
- the ratio (t/D50) be less than 1, where D50 is the mean particle size (D50) of the granulated particles 204a and t is the thickness of the layer 205 of the active material particles after pressing. In this case, there is a tendency that the layer 205 of the active material particles formed in the lithium-ion secondary battery electrode sheet results in a high peel strength consistently.
- the mean particle size (D50) of the granulated particles 204a be sufficiently large relative to the thickness t of the layer 205 of the active material particles after pressing.
- the mean particle size (D50) of the granulated particles 204a is excessively large relative to the thickness t of the layer 205 of the active material particles after pressing, it is likely to cause unevenness in the weight per unit area.
- the mean particle size (D50) of the granulated particles 204a not be excessively large relative to the thickness t of the layer 205 of the active material particles after pressing.
- the ratio (t/D50) be in the range 0.5 ⁇ (t/D50) ⁇ 1 in the step of pressing the granulated particles 204a, according to the discovery by the present inventors.
- the thickness t of the layer 14 of the active material particles 13a1 after the step of pressing the granulated particles 13a be equal to or greater than two times the mean particle size (D50) of the active material particles 13a1 contained in the granulated particles 13a.
- the thickness t of the layer of the active material particles after the step of pressing is ensured to be large relative to the mean particle size (D50) of the active material particles 13a1 contained in the granulated particles 13a. Therefore, the layer 14 of the active material particles is likely to be formed appropriately.
- the layer of the active material particles 13a1 is formed by feeding the granulated particles 13a onto a predetermined region of the current collector 11 in the width direction, leveling the granulated particles 13a, and pressing the granulated particles 13a, while the strip-shaped current collector 11 is being conveyed along the longitudinal direction.
- the method of manufacturing a lithium-ion secondary battery electrode sheet proposed herein is not limited to such an embodiment.
- a current collector 201 having a predetermined shape is prepared (see Fig. 9A).
- granulated particles 204a are fed onto the current collector 201 (see Fig. 9C).
- the method of manufacturing a lithium-ion secondary battery electrode sheet proposed herein is applicable, not only to the case in which predetermined processes are carried out while the current collector 201 is being conveyed in a roll-to-roll process, but also to the case in which the layer 205 of the active material particles is formed on each single sheet of the current collector 201, in other words, to a sheet-by-sheet system.
- the electrode sheet manufactured by the manufacturing method proposed herein offers good productivity.
- the manufacturing method proposed herein can yield an electrode sheet with stable product quality. Therefore, it can be used suitably for such applications that require mass productivity and stable performance.
- An example of such applications is a power source (driving power source) for electric motors incorporated in vehicles.
- the types of the vehicles are not particularly limited, and examples include plug-in hybrid vehicles (PHVs), hybrid vehicles (HVs), electric vehicles (EVs), electric trucks, small-sized motorcycles, power assisted bicycles, electric powered wheelchairs, and electric railroads.
- the non-aqueous electrolyte secondary battery may be used in the form of a battery module, in which a plurality of the batteries are connected in series and/or in parallel to each other.
Abstract
Description
1. Preparing a current collector.
2. Preparing granulated particles containing active material particles and a binder.
3. Feeding the granulated particles onto the current collector.
4. Leveling the granulated particles fed on the current collector.
5. Pressing the leveled granulated particles.
Here, in the step of feeding the granulated particles, it is desirable that the ratio (t/D50) be less than 1, where D50 is the mean particle size of the granulated particles fed onto the current collector and t is the thickness of a layer of the active material particles that has been formed subsequent to the step of pressing. This makes it possible to consistently obtain a lithium-ion secondary battery electrode sheet in which the formed active material particle layer has a high peel strength.
Fig. 1 is a schematic view illustrating a
A method of manufacturing a lithium-ion secondary battery electrode sheet proposed herein includes the
1. preparing a
2. preparing granulated
3. feeding the granulated
4. leveling the granulated
5. pressing the leveled granulated
At
At
The method of manufacturing an electrode sheet proposed herein is applicable to various types of electrode sheets. For example, the method can be applied either to the positive electrode sheet or to the negative electrode sheet in a lithium-ion secondary battery. The active material particles 13a1 contained in the
Herein, the lithium-ion secondary battery is taken as an example. Preferable examples of the active material particles 13a1 used in the positive electrode of the lithium-ion secondary battery include: oxides containing lithium and one or more transition metal elements (i.e., lithium-transition metal oxide), such as lithium nickel oxide (for example, LiNiO2), lithium cobalt oxide (for example, LiCoO2), and lithium manganese oxide (LiMn2O4); and phosphates containing lithium and one or more transition metal elements, such as lithium manganese phosphate (LiMnPO4) and lithium iron phosphate (LiFePO4). These are used in particulate form and may be referred to as positive electrode active material particles, as appropriate. The positive electrode active material particles may be used either alone or in combination. Because these positive electrode active material particles have low electrical conductivity, the positive electrode active material layer contains a conductive agent in order to enhance the electrical conductivity. In this case, it is desirable that the conductive agent be contained in droplets that are sprayed in spray drying.
Preferable examples of the active material particles used in the negative electrode of the lithium-ion secondary battery include carbon-based materials, such as graphite carbons and amorphous carbons, lithium-transition metal oxides, and lithium-transition metal nitrides. These are used in particulate form and may be referred to as negative electrode active material particles, as appropriate. The negative electrode active material particles may be used either alone or in combination. The negative electrode active material layer may contain a conductive agent in order to enhance the electrical conductivity. In this case, it is desirable that the conductive agent be contained in droplets that are sprayed in spray drying.
Examples of the conductive agent include carbon materials, such as carbon powder and carbon fiber. It is possible to use one of the just-mentioned examples of the conductive agents either alone or in combination with another one or more of the examples. Examples of the carbon powder include powders of acetylene black, oil-furnace black, graphitized carbon black, carbon black, Ketjen Black, and graphite. Such conductive agents are preferably added when active material particles 13a1 with poor electrical conductivity are used to form conductive paths between the active material particles 13a1 and the
Next, the following describes the binder 13a2 that is to be added to the
At
The
It is desirable that the
The
At step 4, the
At step 5, the
11 -- Current collector (current collector foil)
12 -- Binder solution
13 -- Powder material
13a -- Granulated particle
13a1 -- Active material particle
13a2 -- Binder
14 -- Layer of active material particles 13a1 after pressing
21 -- Conveyor device
21a -- Conveyor roller
22 -- Coating device
22a -- Gravure roller
22b -- Reservoir
22c -- Backing roller
24 -- Feeding device
24a -- Hopper
25 -- Squeegee
26, 27 -- Pressure roller
201 -- Aluminum foil (current collector)
202 -- Binder solution
203 -- Mask
203a -- Opening
204a -- Granulated particles
205 -- Layer of active material particles after pressing
206, 207 -- Pressure roller
F -- Conveying direction
t -- Thickness of the layer of active material particles after pressing
Claims (2)
- A method of manufacturing a lithium-ion secondary battery electrode sheet, comprising the steps of:
preparing a current collector;
preparing granulated particles containing active material particles and a binder;
feeding the granulated particles onto the current collector;
leveling the granulated particles fed on the current collector; and
pressing the leveled granulated particles, wherein
in the step of feeding the granulated particles, the ratio (t/D50) is less than 1, where D50 is the mean particle size of the granulated particles fed onto the current collector and t is the thickness of a layer of the active material particles that has been formed subsequent to the step of pressing.
- The method according to claim 1, wherein the ratio (t/D50) is greater than 0.5.
Priority Applications (3)
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KR1020177008295A KR101888968B1 (en) | 2014-08-29 | 2015-08-21 | Method of manufacturing lithium-ion secondary battery electrode sheet |
CN201580046142.4A CN106663778B (en) | 2014-08-29 | 2015-08-21 | Method for manufacturing electrode plate of lithium ion secondary battery |
US15/506,795 US10658652B2 (en) | 2014-08-29 | 2015-08-21 | Method of manufacturing lithium-ion secondary battery electrode sheet |
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JP2014175920A JP2016051586A (en) | 2014-08-29 | 2014-08-29 | Manufacturing method of electrode for lithium ion secondary battery |
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US (1) | US10658652B2 (en) |
JP (1) | JP2016051586A (en) |
KR (1) | KR101888968B1 (en) |
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US20180108903A1 (en) * | 2016-10-19 | 2018-04-19 | Toyota Jidosha Kabushiki Kaisha | Method for producing negative electrode and secondary battery, and secondary battery |
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CN106663778A (en) | 2017-05-10 |
JP2016051586A (en) | 2016-04-11 |
KR20170044732A (en) | 2017-04-25 |
US20170256780A1 (en) | 2017-09-07 |
KR101888968B1 (en) | 2018-08-17 |
CN106663778B (en) | 2020-04-24 |
US10658652B2 (en) | 2020-05-19 |
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