WO2018180405A1 - 電極構成体固定用接着剤及び電気化学素子 - Google Patents
電極構成体固定用接着剤及び電気化学素子 Download PDFInfo
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- WO2018180405A1 WO2018180405A1 PCT/JP2018/009400 JP2018009400W WO2018180405A1 WO 2018180405 A1 WO2018180405 A1 WO 2018180405A1 JP 2018009400 W JP2018009400 W JP 2018009400W WO 2018180405 A1 WO2018180405 A1 WO 2018180405A1
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- Prior art keywords
- adhesive
- layer
- electrode
- negative electrode
- electrolytic solution
- Prior art date
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Images
Classifications
-
- 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
- H01M10/04—Construction or manufacture in general
- H01M10/049—Processes for forming or storing electrodes in the battery container
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/105—Pouches or flexible bags
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
-
- 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
- H01M10/04—Construction or manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2453/00—Presence of block copolymer
-
- 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
-
- 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 an electrode assembly fixing adhesive and an electrochemical device, and more particularly to an electrochemical device such as a secondary battery and an adhesive for fixing an electrode configuration including an electrode in the electrochemical device. .
- Electrochemical elements such as secondary batteries are used in various technical fields.
- a lithium ion secondary battery can be repeatedly charged and discharged and has a high energy density. Therefore, the lithium ion secondary battery is particularly useful in fields such as a mobile phone, a notebook personal computer, and an electric vehicle.
- Electrochemical elements such as secondary batteries usually include a positive electrode member, a separator member, and a negative electrode member having a film shape. These members usually constitute an electrode structure in a stacked or wound state, and the electrode structure is stored in an exterior body of the element.
- an exterior body it has been proposed to use a film such as a laminate film from the viewpoint of improvement in capacity and weight reduction. Such a film is used as a so-called pouch-type exterior body.
- Electrochemical elements having a pouch-type exterior body usually have tabs extending from the current collectors of the positive electrode member and the negative electrode member.
- the tab extends from the inside of the device to the outside while being sandwiched between the heat-sealed film edges.
- Such a tab can serve as a pole terminal of the element and to hold the electrode structure in a desired position inside the element.
- the electrode structure itself is not fixed by such a structure. When such a configuration is employed, the electrode structure may be damaged by an impact applied to the device when the device is used. The occurrence of such damage can be a problem especially when the battery is large.
- JP 2003-151512 A (corresponding publication: US Patent Application Publication No. 2004/045597) JP 2001-93576 A Japanese Patent No. 4440573 WO2016 / 080143 (corresponding publication: US Patent Application Publication No. 2017/346130)
- the object of the present invention is to reduce the thickness of the element and achieve miniaturization, and to achieve effective fixing between the electrode structure and the pouch-type exterior body. It is to provide an agent.
- a further object of the present invention is to provide an electrochemical device that can be easily downsized and has high durability against impact.
- the present inventor has studied to provide an adhesive layer on the inner surface of the exterior body, thereby fixing the electrode structure, instead of fixing with the double-sided tape.
- an adhesive layer on the inner surface of the exterior body, thereby fixing the electrode structure, instead of fixing with the double-sided tape.
- Electrode composition including a positive electrode member, a separator member, and a negative electrode member, an electrolytic solution, and an adhesive for fixing an electrode composition used for an electrochemical element including a pouch-type exterior body that stores the electrode structure and the electrolytic solution
- An electrode assembly fixing adhesive having a swelling degree with respect to an electrolytic solution of 50% or less.
- the adhesive for fixing an electrode structure according to [1] comprising a styrene block copolymer and a diene polymer.
- An electrochemical element including a positive electrode member, an electrode structure including a separator member and a negative electrode member, an electrolytic solution, and a pouch-type exterior body storing the electrode structure and the electrolytic solution,
- the electrochemical element further includes an adhesive layer that is interposed between the inner surface of the exterior body and the electrode structure to bond them, An electrochemical element having a swelling degree of the adhesive layer with respect to the electrolytic solution of 50% or less.
- the adhesive layer includes a styrene block copolymer and a diene polymer.
- an adhesive for fixing an electrode structure which can reduce the thickness of the element and achieve miniaturization, and can achieve effective fixing between the electrode structure and the pouch-type exterior body;
- an electrochemical device that can be easily downsized and has high durability against impact.
- FIG. 1 is a top view schematically showing an example of the electrochemical device of the present invention.
- FIG. 2 is a vertical cross-sectional view showing a cross section of the electrochemical device shown in FIG. 1 cut along a vertical cross section along line L1.
- the adhesive for fixing an electrode structure of the present invention is used for an electrochemical element including a positive electrode member, an electrode structure including a separator member and a negative electrode member, an electrolytic solution, and a pouch-type exterior body that stores the electrode structure and the electrolytic solution. It is an adhesive.
- the electrochemical element of the present invention is an electrochemical element including an electrode structure including a positive electrode member, a separator member, and a negative electrode member, an electrolytic solution, and a pouch-type exterior body that stores the electrode structural body and the electrolytic solution. It further includes an adhesive layer that is interposed between the inner surface of the exterior body and the electrode structure to bond them together.
- FIG. 1 is a top view schematically showing an example of the electrochemical element of the present invention
- FIG. 2 is a longitudinal section showing a section obtained by cutting the electrochemical element shown in FIG. 1 along a line L1.
- FIG. 1 and 2 show a state where the electrochemical element is horizontally mounted.
- the ratio of the thickness to the width of the element is shown larger than the actual element.
- the electrochemical element 100 is a secondary battery, and includes an electrode structure 130 and a pouch-type exterior body that stores the electrode structure.
- the pouch-type exterior body is an exterior body for an electrochemical element having a bag shape.
- the bag-like shape can usually be a flat bag shape.
- the bag shape can be formed by overlapping a pair of films and heat-sealing the edge portion.
- the method for forming the bag shape is not limited to this, and it can be formed by any method.
- a bag-like shape can be formed by a method of folding a sheet of film and heat-sealing the edge portion, or forming a tubular film and heat-sealing the edge portion.
- the pouch-type exterior body includes an upper surface side exterior body 110U and a lower surface side exterior body 110D.
- the upper surface side exterior body 110 ⁇ / b> U and the lower surface side exterior body 110 ⁇ / b> D are joined by being heat sealed in the surrounding area 111.
- Electrochemical element 100 further includes an electrolytic solution.
- a part of the electrolytic solution exists in a state where the gap 160 and other gaps in the element are filled, and the other part exists in a state where each component in the outer package is infiltrated.
- the electrode assembly 130 includes a negative electrode member 131 (N), a positive electrode member 133 (P), a negative electrode member 135 (N), a positive electrode member 137 (P), and a negative electrode member.
- 139 (N) are alternately overlapped, and a separator member 132 (S), a separator member 134 (S), a separator member 136 (S), and a separator member 138 (S) are interposed therebetween.
- the electrode assembly can exhibit a function as an electrochemical element such as a secondary battery.
- the structure of the electrode structure is not limited to this, and the number of positive electrode members and negative electrode members may be more or less than the example of FIG.
- the electrode structure may have a wound body structure. For example, by winding a laminate having a layer configuration of negative electrode member / separator member / positive electrode member / separator member, a wound body structure having a structure in which the positive electrode member and the negative electrode member overlap with each other via the separator member is obtained. be able to.
- the electrode assembly 130 further includes a binding member 141 that binds the positive electrode member, the negative electrode member, and the separator member on the outer periphery thereof.
- the material constituting the binding member 141 may be the same material that can be used as the separator member from the viewpoint of ensuring the insulation of the electrode assembly 130.
- the structure of the electrode structure is not limited to this.
- the material of the binding member may be a material other than the material that can be used as the separator member.
- the layer on the outer surface of the electrode assembly may be entirely a negative electrode member layer, the whole may be a separator member layer, or a part thereof may be a negative electrode member layer. The other part may be a layer of a separator member.
- the electrode assembly may include a separator member binding member that further surrounds the entire periphery of the structure in which the positive electrode member, the negative electrode member, and the separator member overlap.
- a separator member binding member that further surrounds the entire periphery of the structure in which the positive electrode member, the negative electrode member, and the separator member overlap.
- a part or all of the layer on the outer surface of the electrode assembly may be a layer of the positive electrode member.
- the electrochemical element 100 is interposed between the inner surface of the upper surface side exterior body 110U and the electrode structure 130, and adheres to the adhesive layer 150U, and the inner surface of the lower surface side exterior body 110D and the electrode structure 130. It further includes an adhesive layer 150D interposed between and adhering them.
- each of the adhesive layers 150U and 150D includes only one adhesive layer.
- the adhesive layer 150U is in direct contact with both the upper surface side exterior body 110U and the electrode structure 130, and the adhesive layer 150D is in direct contact with both the lower surface side exterior body 110D and the electrode structure 130.
- the adhesive layer is in direct contact with both the exterior body and the electrode structure, whereby reliable adhesion with a thin layer can be achieved as compared with the adhesion with the double-sided tape in the prior art.
- the adhesive layer is in direct contact with both the exterior body and the electrode structure, it is possible to achieve sufficient fixation of the electrode structure as compared with the adhesion by the double-sided tape in the prior art.
- sufficient fixing of the electrode structure can be achieved by using the specific adhesive layer defined in the present invention. Thereby, it is possible to increase the durability against impact while reducing the thickness of the element and achieving miniaturization.
- the thickness of the adhesive layer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less.
- a sufficient shear adhesive force can be expressed.
- the thickness is equal to or less than the upper limit, the volume and weight of the adhesive layer in the electrochemical element can be suppressed, and as a result, the capacity per volume and weight of the electrochemical element can be increased. In addition, the manufacturing cost of the electrochemical element can be reduced.
- the adhesive layer is provided over the entire interface between the electrode assembly 130 and the exterior body, but the mode of the adhesive layer is not limited to this.
- the adhesive layer may be provided only in a partial region of the interface between the electrode structure 130 and the exterior body. More specifically, the adhesive layer may be provided at an interval according to a predetermined pattern at the interface between the electrode structure 130 and the exterior body.
- a part of the surface layer in contact with the adhesive layers 150U and 150D of the electrode assembly 130 is a layer of the negative electrode members 131 (N) and 139 (N), and the other part is It is a layer of the binding member 141.
- the layer on the surface of the electrode structure that is in contact with the adhesive layer may be a separator member layer, a negative electrode member layer, or a part of the separator member. It may be a layer and the other part may be a layer of the negative electrode member.
- a part or all of the surface layer in contact with the adhesive layer may be a layer of the positive electrode member.
- the electrochemical device 100 further includes a positive electrode tab 120P and a negative electrode tab 120N as optional components.
- the negative electrode tab 120N is electrically connected to the negative electrodes 131 (N), 135 (N), and 139 (N) through the lead 121, and functions as a negative electrode in the electrochemical element 100.
- the positive electrode tab 120 ⁇ / b> P is electrically connected to the positive electrode 133 (P) and the positive electrode 137 (P) via a lead (not shown), and functions as a positive electrode in the electrochemical element 100.
- the positive electrode tab 120P and the negative electrode tab 120N are fixed by being sandwiched between heat seals in the peripheral region 111 of the pouch-type exterior body.
- the electrode assembly 130 is mechanically supported inside the pouch-type exterior body by the positive electrode tab 120P and the negative electrode tab 120N via leads.
- the swelling degree with respect to the electrolyte solution of the adhesive for fixing an electrode assembly of the present invention and the adhesive layer in the electrochemical element of the present invention is within a specific range.
- the degree of swelling of an adhesive is the degree of swelling of a film obtained by drying the adhesive. More specifically, the adhesive is dried to form a film having a thickness of about 1 mm, a rectangular test piece of 2 cm ⁇ 2 cm is cut out from the film, and the degree of swelling of the test piece is measured, whereby the adhesive is obtained. The degree of swelling can be obtained. Furthermore, this measured value can be employed as the degree of swelling of the adhesive layer in the electrochemical device using the adhesive.
- the degree of swelling of the measurement object (adhesive or adhesive layer) of the swelling degree with respect to the electrolytic solution is the rate of change in weight caused by immersing the measurement object in the electrolytic solution.
- the degree of swelling can be determined by performing immersion treatment for 72 hours at a temperature of 60 ° C. in a state in which a test piece to be measured is immersed in an electrolytic solution, and measuring a change in weight before and after the treatment.
- an electrolytic solution used in an electrochemical element to be used for the adhesive of the present invention is employed.
- the adhesive is swollen using the electrolytic solution. The degree can be measured.
- the degree of swelling of the adhesive of the present invention with respect to the electrolytic solution is 50% or less, preferably 20% or less, and more preferably 15% or less.
- the lower limit of the degree of swelling is ideally 0%, but can usually be 0.1% or more.
- the adhesive having such a degree of swelling is, for example, an adhesive containing a styrene block copolymer and a diene polymer, which will be described in detail below, and parameters of each polymer (type of constituent unit, ratio, molecular weight, etc.). ) And the content ratio can be appropriately adjusted.
- the adhesive can exhibit tackiness at ⁇ 30 ° C. to 100 ° C. By exhibiting tackiness in such a temperature range, it can be usefully used as an adhesive in an electrochemical element such as a secondary battery.
- the glass transition temperature Tg of the adhesive layer is not particularly limited, but is preferably ⁇ 30 ° C. or lower. By having a glass transition temperature in such a range, flexibility can be maintained and adhesiveness can be maintained over a wide range of operating temperatures.
- the lower limit of the glass transition temperature is not particularly limited, but may be, for example, ⁇ 60 ° C. or higher.
- the adhesive layer used in the present invention exhibits a high shear adhesive force in bonding with the electrode structure in a wet state.
- the shear adhesive strength in such a wet state is preferably 0.05 N / mm 2 or more, more preferably 0.1 N / mm 2 or more.
- the adhesion in the wet state is an adhesion in a state where the adhesive layer and the layer to be bonded are wetted by the electrolytic solution.
- the adhesive exhibiting such shear adhesive force is, for example, an adhesive containing a styrene block copolymer and a diene polymer, which will be described in detail below, by appropriately adjusting the parameters and content ratio of each polymer. It can be obtained.
- the upper limit of the shear adhesive strength in the wet state is not particularly limited, but may be, for example, 10 N / mm 2 or less.
- the shear adhesive force between the adhesive layer and the exterior material is also preferably a high value equal to or higher than the shear adhesive force between the adhesive layer and the electrode structure described above. However, normally, the shear adhesive force between the adhesive layer and the exterior material can be easily obtained sufficiently higher than the shear adhesive force between the adhesive layer and the electrode structure.
- a test laminate was prepared by adhering the outer surface layer of the electrode assembly and the exterior material through an adhesive layer, and this was immersed in an electrolyte solution, and then a tensile test. It can obtain
- an electrolytic solution used for the immersion an electrolytic solution used in an electrochemical element to be used with the adhesive of the present invention is employed.
- Adhesive material The material which comprises an adhesive agent is not specifically limited, It can be set as the arbitrary materials which have the property described above.
- the adhesive includes a styrenic block copolymer and a diene polymer.
- Such an adhesive is usually a rubber-based adhesive.
- the diene polymer is a polymer containing units having a structure obtained by polymerizing diene or a derivative thereof.
- the diene polymer is not limited depending on the production method.
- the diene polymer include natural rubber, polybutadiene, polyisoprene, polychloroprene, ethylene-propylene copolymer, and acrylonitrile-butadiene copolymer.
- a polymer with low polarity is preferable from the viewpoint of setting the degree of swelling in the electrolyte to a desired low value.
- polybutadiene and polyisoprene are preferable, and polybutadiene is particularly preferable.
- the styrenic block copolymer is a multi-block type block copolymer composed of a polystyrene block and a diene polymer block that repeats AB type, ABA type, or AB.
- a polystyrene block here is a block containing the unit which has a structure obtained by superposing
- the polystyrene block is not limited depending on the production method.
- styrenic block copolymers examples include styrene-butadiene AB type block copolymers, styrene-butadiene-styrene ABA type block copolymers, styrene-isoprene AB type block copolymers, and styrene-isoprene. -ABA block copolymers of styrene.
- the proportion of the styrene block copolymer may be 1 to 50 parts by weight with respect to 100 parts by weight of the diene polymer.
- the weight average molecular weight of the polymer constituting the adhesive is not particularly limited, but is preferably 10,000 to 1,500,000, more preferably 100,000 to 1,000,000. When the molecular weight is equal to or more than the lower limit, good shear adhesive force and cohesive force can be obtained. When the molecular weight is not more than the above upper limit, the viscosity of the adhesive can be kept at a low value suitable for coating.
- the adhesive may be either a crosslinked type or a non-crosslinked type.
- the cross-linking adhesive may contain a cross-linking agent in addition to the polymer.
- the crosslinking agent can be appropriately selected according to the type of the crosslinkable functional group possessed by the polymer. Examples include epoxy crosslinking agents, isocyanate crosslinking agents, metal chelate crosslinking agents, metal alkoxide crosslinking agents, metal salt crosslinking agents, amine crosslinking agents, hydrazine crosslinking agents, aldehyde crosslinking agents, and These combinations are mentioned.
- the ratio of the crosslinking agent in the adhesive may be 0 to 10 parts by weight with respect to 100 parts by weight of the polymer.
- the adhesive may contain additives in addition to the components listed above.
- additives include ultraviolet absorbers, tackifiers, softeners (plasticizers), anti-aging agents, stabilizers, fillers, pigments, dyes, and silane coupling agents.
- tackifiers include rosin and derivatives thereof, polyterpenes, terpene phenol resins, coumarone-indene resins, petroleum resins, styrene resins, and xylene resins.
- softeners include liquid polyethers, glycol esters, liquid polyterpenes, liquid polyacrylates, phthalic acid esters, and trimellitic acid esters. The ratio of these additives in the adhesive may be 0 to 10 parts by weight with respect to 100 parts by weight of the polymer.
- the adhesive can contain a solvent, and the solvent can be appropriately selected according to the type of other components used. Examples thereof include toluene, xylene, mesitylene, hexane, cyclohexane, heptane, octane, isooctane and the like.
- the ratio of the solvent in the adhesive can be appropriately adjusted so that the solid content ratio of the obtained adhesive (the ratio of the component remaining when the adhesive is dried to form the adhesive layer) is within a desired range.
- the method for forming the adhesive layer using the adhesive is not particularly limited, and any method can be adopted.
- the adhesive is provided on the inner surface of the exterior material, the surface of the electrode structure, or both surfaces, and the exterior material and the electrode structure are bonded via the adhesive, and further required. Accordingly, by drying the adhesive, an adhesive layer can be formed between the exterior material and the electrode structure. Drying of the adhesive may be performed prior to bonding or after bonding.
- methods for providing an adhesive on the surface to be bonded include a printing method, a casting method, and a coating method.
- the printing method is preferable from the viewpoint that a thin adhesive can be easily provided at a desired position on the surface to be bonded. Examples of the printing method include a stamp method and a transfer method.
- the stamp method is a method of providing a stamp with an adhesive on a target surface by pressing the stamp onto the surface of the target.
- the transfer method is a method in which an adhesive on a base material such as a film is attached to the surface to be bonded, and the adhesive on the base material is transferred to the target surface.
- the material which comprises the positive electrode member which comprises an electrode structure, a negative electrode member, a separator member, and another member is not specifically limited, A known material can be selected arbitrarily.
- the negative electrode member may be a member including a current collector and a negative electrode active material layer provided on the surface thereof.
- the negative electrode active material layer may be a layer containing a negative electrode active material, a binder resin, and an additive.
- the negative electrode active material include graphite such as artificial graphite when the electrochemical element is a lithium ion secondary battery.
- the binder resin include rubber materials such as styrene-butadiene rubber.
- Examples of the material of the separator member include resins generally used as constituent elements of the separator member, such as polyethylene resin and polypropylene resin.
- the material which comprises an exterior material is not specifically limited, A film-form material can be selected arbitrarily.
- the surface layer located on the inside of the element is preferably a layer having heat sealability. That is, it is preferably a layer that can be melted by heating and thereby achieve adhesion to the opposing member.
- an exterior material including a layer having heat sealability the device can be easily manufactured.
- the multilayer film which has a resin layer as a layer of both surfaces, and has a metal thin film layer as an internal layer is mentioned.
- resin which comprises a resin layer resin generally used as a component of a laminate film, such as polyethylene resin and polypropylene resin, is mentioned.
- An example of the metal thin film layer is an aluminum thin film layer.
- an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is usually used.
- a lithium salt is used in a lithium ion secondary battery.
- lithium salts LiPF 6 and the like.
- the organic solvent an organic solvent capable of dissolving the supporting electrolyte can be appropriately selected. Examples of the organic solvent in the lithium ion secondary battery include ethylene carbonate (EC), diethyl carbonate (DEC), and a mixture thereof.
- the electrochemical device of the present invention is a step of preparing an electrode structure, a step of providing an adhesive on the surface of the exterior material inside the device (the surface facing the interior of the device when used as the exterior material of the device), It can be manufactured by a manufacturing method including a step of putting the electrode structure into the exterior body, a step of filling the inside of the exterior body with an electrolytic solution, and a step of sealing the exterior body.
- the electrode structure can be prepared by superposing the positive electrode member and the negative electrode member via a separator member, and performing a process such as bending or winding in accordance with the battery shape. By such an operation, an electrode structure having a structure such as a laminate or a wound body can be obtained. In addition, before or after these operations, a step of attaching a tab to the positive electrode member and the negative electrode member via a lead or directly can be performed.
- the process of heat-sealing the exterior material into a bag-like shape can be performed before, after, or both of the operations of putting the electrode structure into the exterior body.
- the tab may be sandwiched between the exterior bodies so that a part of the tab is exposed to the outside of the element through the heat seal. .
- the opening of the pouch-type exterior body is sealed with heat to obtain an electrochemical element.
- the heating temperature at the time of heat sealing is usually 120 to 150 ° C.
- ⁇ Evaluation item ⁇ (1. degree of swelling)
- the adhesive was placed in a Teflon (registered trademark) petri dish and dried to prepare a film having a thickness of about 1 mm.
- a 2 cm ⁇ 2 cm rectangular test piece was cut out from this film, and the weight W0 of the test piece was measured.
- a droplet of the electrolytic solution adhering to the periphery of the test piece was wiped off, and the weight W1 of the test piece was measured.
- Spherical artificial graphite 100 parts as negative electrode active material, styrene butadiene rubber (particle diameter 180 nm, glass transition temperature ⁇ 40 ° C.) 1 part as negative electrode binder resin, 1 part carboxymethyl cellulose as thickener, An appropriate amount of water was stirred with a planetary mixer to prepare a negative electrode slurry composition.
- a copper foil having a thickness of 15 ⁇ m was prepared as a current collector.
- the negative electrode slurry composition was applied to both sides of a copper foil. The coating thickness was adjusted so that the coating amount after drying was 10 mg / cm 2 . After application, the slurry composition layer was dried at 60 ° C. for 20 minutes, followed by drying at 120 ° C.
- This negative electrode original fabric was rolled with a roll press to produce a sheet-like negative electrode comprising a negative electrode active material layer and a copper foil.
- the density of the negative electrode active material layer in the obtained negative electrode was 1.8 g / cm 3 per layer.
- a polypropylene microporous film having a thickness of 20 ⁇ m was prepared.
- Example 1 A rectangular sample of 15 mm ⁇ 15 mm was cut out from the negative electrode or the separator.
- Example 3 Comparative Example 1 and Comparative Example 3
- a negative electrode sample was used
- Example 2 Example 4 and Comparative Example 2
- a separator sample was used.
- One surface of the sample was bonded to the adhesive layer of the multilayer (1). Bonding was performed by applying a load by reciprocating a 2 kg weight roller. Furthermore, the other surface of the sample was bonded to a SUS board via a double-sided tape.
- a test laminate having a layer structure of (SUS plate) / (double-sided tape) / (sample (negative electrode or separator)) / (adhesive layer) / (exterior material) was obtained.
- a plurality of test laminates were prepared, one part was subjected to a shear test in a dry state, and the other part was subjected to a shear test in a wet state.
- Example 1 (3. Impact test) (3-1. Preparation of test simulation battery)
- a negative electrode was wound around the SUS plate for one and a half times, and the end of the negative electrode was fastened with a polyimide tape to prepare a test piece (N) whose negative electrode was the outermost layer. Separately from the test piece (N), the negative electrode is wound around the SUS plate for one and a half turns, the end of the negative electrode is fastened with polyimide tape, and the separator is further wound about one and a half turns, and the end of the separator is polyimide tape.
- the outermost layer was a separator test piece (S). In Example 1, Example 3, Comparative Example 1 and Comparative Example 3, the test piece (N) was used, and in Example 2, Example 4 and Comparative Example 2, the test piece (S) was used.
- the same exterior material for pouch type batteries as that used in (2. Shear adhesive strength) was prepared.
- the adhesive obtained in the examples and comparative examples is applied to a 15 cm ⁇ 15 cm region on the surface of the battery inside of the packaging material, the adhesive is dried, an adhesive layer is formed, and the packaging material with the adhesive layer is formed. Obtained.
- the thickness of the adhesive layer was as shown in Table 1 in each of the examples and comparative examples.
- the test piece (N) or the test piece (S) was placed in a state where the test piece (N) or the test piece (S) was interposed between the pair of outer packaging materials with an adhesive layer, and the peripheral portion of the outer packaging material was heat sealed. Before completely sealing the exterior material, 2 ml of the electrolyte was injected. As the electrolytic solution, the same one as prepared in (1. Swelling degree) was used. By this operation, a test simulation battery was produced.
- test simulation battery (3-2. Impact test) The obtained test simulation battery was dropped on a concrete floor from a height of 1 m, thereby imposing an impact on the test simulation battery. The impact was imposed five times on one test simulation battery. After completing the impact imposition, the test simulation battery was disassembled and the electrolyte was taken out. The presence or absence of the negative electrode active material dropped in the electrolyte was observed.
- Example 1 (Adhesive A: negative electrode) A styrene-isoprene-styrene ABA type block copolymer having a styrene content of 30 wt%, an isoprene content of 70 wt%, and a molecular weight Mw of 150,000 was prepared. 5 parts of the copolymer and 95 parts of polybutadiene having a molecular weight of 250,000 were dissolved in xylene. By this operation, an adhesive A having a solid content concentration of 10 wt% was obtained. The obtained adhesive A was subjected to the measurement of the degree of swelling, the measurement of the shear adhesive force between the exterior material and the negative electrode, and the impact test of the test simulated battery equipped with the test piece (N).
- Example 2 (Adhesive A: Separator)
- the adhesive A obtained in Example 1 was subjected to the measurement of the shear adhesive force between the exterior material and the separator, and the impact test of the test simulation battery equipped with the test piece (S).
- Adhesive B negative electrode
- An acrylic acid ester copolymer (weight average molecular weight (Mw) 450,000) obtained by polymerizing 85 parts by weight of 2-ethylhexyl acrylate and 15 parts by weight of butyl acrylate was prepared.
- the copolymer was dissolved in xylene to obtain an adhesive B having a solid content concentration of 10 wt%.
- the obtained adhesive B was subjected to the measurement of the degree of swelling, the measurement of the shear adhesive strength between the exterior material and the negative electrode, and the impact test of the test simulation battery equipped with the test piece (N).
- Example 4 (Adhesive B: Separator)
- the adhesive B obtained in Example 3 was subjected to measurement of the shear adhesive force between the exterior material and the separator, and the impact test of the test simulation battery equipped with the test piece (S).
- Adhesive C negative electrode
- An acrylic ester copolymer (weight average molecular weight (Mw) 500,000) obtained by polymerizing 60 parts by weight of butyl acrylate and 40 parts by weight of 2-ethylhexyl acrylate was prepared.
- the copolymer was dissolved in xylene to prepare an adhesive C having a solid content concentration of 10 wt%.
- the obtained adhesive C was subjected to the measurement of the degree of swelling, the measurement of the shear adhesive strength between the exterior material and the negative electrode, and the impact test of the test simulation battery equipped with the test piece (N).
- Comparative Example 2 (Adhesive C: Separator)
- the adhesive C obtained in Comparative Example 1 was subjected to measurement of the shear adhesive force between the exterior material and the separator, and the impact test of the test simulation battery equipped with the test piece (S).
- Electrochemical element 110D Lower surface side exterior body 110U: Upper surface side exterior body 111: Surrounding area 120N: Negative electrode tab 120P: Positive electrode tab 121: Lead 130: Electrode structure 131 (N): Negative electrode member 132 (S): Separator Member 133 (P): Positive electrode member 134 (S): Separator member 135 (N): Negative electrode member 136 (S): Separator member 137 (P): Positive electrode member 138 (S): Separator member 139 (N): Negative electrode member 141: Bundling member 150D: Adhesive layer 150U: Adhesive layer 160: Gaps
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Abstract
Description
即ち、本発明によれば、下記のものが提供される。
〔2〕 スチレン系ブロック共重合体及びジエン系重合体を含む、〔1〕に記載の電極構成体固定用接着剤。
〔3〕 前記電極構成体において、前記正極部材、前記セパレーター部材及び前記負極部材は、積層体構造又は巻回体構造を有する、〔1〕又は〔2〕に記載の電極構成体固定用接着剤。
〔4〕 正極部材、セパレーター部材及び負極部材を含む電極構成体、電解液、並びに前記電極構成体及び前記電解液を格納するパウチ型外装体を含む電気化学素子であって、
前記電気化学素子は、前記外装体の内側の表面と前記電極構成体との間に介在しこれらを接着する接着剤層をさらに含み、
前記接着剤層の、前記電解液に対する膨潤度が50%以下である電気化学素子。
〔5〕 前記接着剤層が、前記外装体及び前記電極構成体の両方に直接接する、〔4〕に記載の電気化学素子。
〔6〕 前記接着剤層が、スチレン系ブロック共重合体及びジエン系重合体を含む、〔4〕又は〔5〕に記載の電気化学素子。
〔7〕 前記電極構成体において、前記正極部材、前記セパレーター部材及び前記負極部材は、積層体構造又は巻回体構造を有する、〔4〕~〔6〕のいずれか1項に記載の電気化学素子。
〔8〕 前記電極構成体の、前記接着剤層に接する表面の層が、前記セパレーター部材の層を含む、〔4〕~〔7〕のいずれか1項に記載の電気化学素子。
〔9〕 前記電極構成体の、前記接着剤層に接する表面の層が、前記負極部材の層を含む、〔4〕~〔8〕のいずれか1項に記載の電気化学素子。
本発明の電極構成体固定用接着剤は、正極部材、セパレーター部材及び負極部材を含む電極構成体、電解液、並びに電極構成体及び電解液を格納するパウチ型外装体を含む電気化学素子に用いる接着剤である。また、本発明の電気化学素子は、正極部材、セパレーター部材及び負極部材を含む電極構成体、電解液、並びに電極構成体及び電解液を格納するパウチ型外装体を含む電気化学素子であって、外装体の内側の表面と電極構成体との間に介在しこれらを接着する接着剤層をさらに含む。
本発明の電極構成体固定用接着剤、及び本発明の電気化学素子における接着剤層は、その電解液に対する膨潤度が、特定の範囲内である。本願において、接着剤の膨潤度とは、接着剤を乾燥させて膜としたものについての膨潤度である。より具体的には、接着剤を乾燥させて厚さ約1mmの膜とし、この膜から、2cm×2cmの矩形の試験片を切り出し、かかる試験片についての膨潤度を測定することにより、接着剤の膨潤度を求めうる。さらにこの測定値を、当該接着剤を用いた電気化学素子における接着剤層の膨潤度として採用しうる。
接着剤を構成する材料は、特に限定されず、上に述べた性質を有する任意の材料としうる。好ましい例において、接着剤は、スチレン系ブロック共重合体及びジエン系重合体を含む。このような接着剤は、通常、ゴム系の接着剤とされる。
電極構成体を構成する正極部材、負極部材、セパレーター部材及びその他の部材を構成する材料は、特に限定されず、既知の材料を任意に選択しうる。
外装材を構成する材料は、特に限定されず、フィルム状の材料を任意に選択しうる。
外装材は、素子内部側に位置する表面の層がヒートシール性を有する層であることが好ましい。即ち、加熱により溶融させ、それにより対向する部材との接着を達成しうる層であることが好ましい。ヒートシール性を有する層を備える外装材を採用することにより、素子の製造を容易に行うことができる。外装材の例としては、両表面の層として樹脂層を有し、内部の層として金属薄膜層を有する複層フィルムが挙げられる。樹脂層を構成する樹脂の例としては、ポリエチレン樹脂、及びポリプロピレン樹脂等の、ラミネートフィルムの構成要素として一般的に用いられる樹脂が挙げられる。金属薄膜層の例としては、アルミニウム薄膜層が挙げられる。
電解液としては、通常、有機溶媒に支持電解質を溶解した有機電解液が用いられる。支持電解質としては、例えば、リチウムイオン二次電池においてはリチウム塩が用いられる。リチウム塩の例としては、LiPF6が挙げられる。有機溶媒としては、支持電解質を溶解できる有機溶媒を適宜選択しうる。リチウムイオン二次電池における有機溶媒の例としては、エチレンカーボネート(EC)、ジエチルカーボネート(DEC)、及びこれらの混合物が挙げられる。
本発明の電気化学素子は、電極構成体を調製する工程、外装材の素子内部側の表面(素子の外装材として使用する際に、素子内部側に向ける表面)に、接着剤を設ける工程、電極構成体を外装体の内部に入れる工程、外装体の内部に電解液を充填する工程、及び外装体を封口する工程を含む製造方法により製造しうる。
以下の説明において、量を表す「%」及び「部」は、別に断らない限り重量基準である。また、以下に説明する操作は、別に断らない限り、常温及び常圧の条件において行った。
(1.膨潤度)
接着剤をテフロン(登録商標)シャーレに入れて乾燥させて厚さ約1mmの膜を作製した。この膜から、2cm×2cmの矩形の試験片を切り出し、試験片の重量W0を測定した。
試験片を、電解液(溶媒:EC/DEC=1/1(体積比)、LiPF6 1Mを含む)に浸漬した状態で、温度を60℃とし、72時間浸漬処理を行った。
浸漬処理終了後、試験片を電解液中で室温に冷却し、電解液から取り出した。試験片の周囲に付着した電解液の液滴をふき取り、試験片の重量W1を測定した。膨潤度S(%)を、式S=((W1-W0)/W0)×100から求めた。
(2-1.試験用積層体の作製)
パウチ型電池用の外装材(外層が厚さ15μmのナイロン層、バリヤ層が厚さ25μmのアルミ箔、内層が厚さ30μmのポリエチレンからなるもの)を用意した。外装材の電池内部側の表面(電池外装材として使用する際に、電池内部側に向ける、ポリエチレン層の表面)に、接着剤をコーターを用いて塗布し、接着剤を乾燥させ、厚さ5μmの接着剤層を形成した。この操作により、(接着剤層)/(外装材)の層構成を有する複層物(1)を得た。
集電体として、厚さ15μmの銅箔を用意した。上記負極用スラリー組成物を銅箔の両面に塗布した。塗布厚みは、乾燥後の塗布量が10mg/cm2になるよう調整した。塗布後、スラリー組成物の層を60℃で20分間乾燥させ、続いて120℃で20分間乾燥させた。その後、150℃で2時間加熱処理を行い、負極原反を得た。
この負極原反をロールプレスで圧延し、負極活物質層及び銅箔からなるシート状の負極を作製した。得られた負極における負極活物質層の密度は、1層あたり1.8g/cm3であった。
試験用積層体の外装材とSUS板とを支持して、引っ張り試験機を用いてせん断接着力を測定した。引っ張り速度は10mm/分とした。
試験用積層体を、電解液に浸漬した状態で、温度を60℃とし、72時間処理を行った。電解液としては、(1.膨潤度)で作成したものと同じものを用いた。処理終了後、試験用積層体を電解液中で室温まで冷却し、電解液から取り出した。試験用積層体の外装材とSUS板とを支持して、引っ張り試験機を用いてせん断接着力を測定した。測定の条件は、乾燥状態のせん断接着力の測定と同じとした。
(3-1.試験用模擬電池の作製)
2mm×18cm×18cmのSUS板、並びに(2.せん断接着力)で作製したものと同じ負極及びセパレーターを用意した。SUS板の周囲に、負極を1周半巻き付け、負極の端部をポリイミドテープで留めて、最外層が負極の試験片(N)を作製した。試験片(N)とは別に、SUS板の周囲に、負極を1周半巻き付け、負極の端部をポリイミドテープで留め、その上にさらにセパレーターを1周半巻き付け、セパレーターの端部をポリイミドテープで留めて、最外層がセパレーターの試験片(S)を作製した。実施例1、実施例3、比較例1及び比較例3では試験片(N)を用い、実施例2、実施例4及び比較例2では試験片(S)を用いた。
得られた試験用模擬電池を、1mの高さからコンクリート床に落下させることにより、試験用模擬電池に衝撃を賦課した。衝撃の賦課は、1つの試験用模擬電池に対して5回行った。衝撃の賦課を終了した後、試験用模擬電池を分解し、電解液を取り出した。電解液中に脱落した負極活物質の有無を観察した。
スチレン-イソプレン-スチレンのABA型ブロック共重合体であってスチレンが30wt%イソプレンが70wt%、分子量Mwが150000の共重合体を用意した。
前記共重合体5部と、分子量250000のポリブタジエン95部とをキシレンに溶解した。この操作により、固形分濃度10wt%の接着剤Aを得た。
得られた接着剤Aについて、膨潤度の測定、外装材-負極間のせん断接着力の測定、及び試験片(N)を備えた試験用模擬電池の衝撃試験を行った。
実施例1で得られた接着剤Aについて、外装材-セパレーター間のせん断接着力の測定、及び試験片(S)を備えた試験用模擬電池の衝撃試験を行った。
アクリル酸2-エチルヘキシル85重量部とアクリル酸ブチル15重量部とを重合してなるアクリル酸エステル系共重合体(重量平均分子量(Mw)45万)を用意した。前記共重合体をキシレンに溶解して、固形分濃度10wt%の接着剤Bを得た。
得られた接着剤Bについて、膨潤度の測定、外装材-負極間のせん断接着力の測定、及び試験片(N)を備えた試験用模擬電池の衝撃試験を行った。
実施例3で得られた接着剤Bについて、外装材-セパレーター間のせん断接着力の測定、及び試験片(S)を備えた試験用模擬電池の衝撃試験を行った。
アクリル酸ブチル60重量部とアクリル酸2-エチルヘキシル40重量部とを重合してなるアクリル酸エステル系共重合体(重量平均分子量(Mw)50万)を用意した。前記共重合体をキシレンに溶解して、固形分濃度10wt%の接着剤Cを作製した。
得られた接着剤Cについて、膨潤度の測定、外装材-負極間のせん断接着力の測定、及び試験片(N)を備えた試験用模擬電池の衝撃試験を行った。
比較例1で得られた接着剤Cについて、外装材-セパレーター間のせん断接着力の測定、及び試験片(S)を備えた試験用模擬電池の衝撃試験を行った。
対照のため、接着剤の塗布を行わなかった他は、(3.衝撃試験)と同じ操作により、試験片(N)を備えた試験用模擬電池の衝撃試験を行った。
110D:下面側外装体
110U:上面側外装体
111:周囲領域
120N:負極タブ
120P:正極タブ
121:リード
130:電極構成体
131(N):負極部材
132(S):セパレーター部材
133(P):正極部材
134(S):セパレーター部材
135(N):負極部材
136(S):セパレーター部材
137(P):正極部材
138(S):セパレーター部材
139(N):負極部材
141:結束部材
150D:接着剤層
150U:接着剤層
160:空隙
Claims (9)
- 正極部材、セパレーター部材及び負極部材を含む電極構成体、電解液、並びに前記電極構成体及び前記電解液を格納するパウチ型外装体を含む電気化学素子に用いる電極構成体固定用接着剤であって、電解液に対する膨潤度が50%以下である電極構成体固定用接着剤。
- スチレン系ブロック共重合体及びジエン系重合体を含む、請求項1に記載の電極構成体固定用接着剤。
- 前記電極構成体において、前記正極部材、前記セパレーター部材及び前記負極部材は、積層体構造又は巻回体構造を有する、請求項1又は2に記載の電極構成体固定用接着剤。
- 正極部材、セパレーター部材及び負極部材を含む電極構成体、電解液、並びに前記電極構成体及び前記電解液を格納するパウチ型外装体を含む電気化学素子であって、
前記電気化学素子は、前記外装体の内側の表面と前記電極構成体との間に介在しこれらを接着する接着剤層をさらに含み、
前記接着剤層の、前記電解液に対する膨潤度が50%以下である電気化学素子。 - 前記接着剤層が、前記外装体及び前記電極構成体の両方に直接接する、請求項4に記載の電気化学素子。
- 前記接着剤層が、スチレン系ブロック共重合体及びジエン系重合体を含む、請求項4又は5に記載の電気化学素子。
- 前記電極構成体において、前記正極部材、前記セパレーター部材及び前記負極部材は、積層体構造又は巻回体構造を有する、請求項4~6のいずれか1項に記載の電気化学素子。
- 前記電極構成体の、前記接着剤層に接する表面の層が、前記セパレーター部材の層を含む、請求項4~7のいずれか1項に記載の電気化学素子。
- 前記電極構成体の、前記接着剤層に接する表面の層が、前記負極部材の層を含む、請求項4~8のいずれか1項に記載の電気化学素子。
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JP2020202055A (ja) * | 2019-06-07 | 2020-12-17 | トヨタ自動車株式会社 | 積層型電池 |
CN113491029A (zh) * | 2020-01-03 | 2021-10-08 | 宁德新能源科技有限公司 | 电芯及包含其的电化学装置和电子装置 |
WO2022024717A1 (ja) | 2020-07-28 | 2022-02-03 | 日本ゼオン株式会社 | 電池用接着剤及び電池用接着積層体 |
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