WO2013172257A1 - 集電体、電極構造体、非水電解質電池及び蓄電部品、集電体の製造方法 - Google Patents
集電体、電極構造体、非水電解質電池及び蓄電部品、集電体の製造方法 Download PDFInfo
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- WO2013172257A1 WO2013172257A1 PCT/JP2013/063130 JP2013063130W WO2013172257A1 WO 2013172257 A1 WO2013172257 A1 WO 2013172257A1 JP 2013063130 W JP2013063130 W JP 2013063130W WO 2013172257 A1 WO2013172257 A1 WO 2013172257A1
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Definitions
- the present invention relates to a current collector, an electrode structure, a nonaqueous electrolyte battery, a power storage component (such as an electric double layer capacitor and a lithium ion capacitor) excellent in safety, and a manufacturing method thereof.
- a power storage component such as an electric double layer capacitor and a lithium ion capacitor
- Lithium ion batteries used in vehicles are required to be provided with a so-called shutdown function that stops charging and discharging spontaneously and safely in the event of an accident such as a failure.
- the separator is normally designed to stop at an abnormal heat generation by melting at about 110 to 140 ° C. to close the micropores and blocking Li ions.
- the shutdown by the separator is incomplete and the temperature further rises above the melting point of the separator, or due to an increase in the external temperature, the separator melts and an internal short circuit occurs. In such a case, the shutdown function of the separator can no longer be expected, and the battery will go into thermal runaway.
- a technique for forming a positive temperature coefficient resistor on a current collector has been proposed.
- Patent Document 1 discloses that the surface of the current collector has a crystalline thermal function having a function of a positive temperature coefficient resistor whose resistance value increases as the temperature rises.
- a technique for coating with a conductive layer containing a plastic resin, a conductive agent, and a binder is disclosed. According to this technology, when the internal temperature of the battery reaches the melting point of the crystalline thermoplastic resin due to the heat generated when the battery is overcharged, the resistance of the conductive layer increases rapidly, blocking the flow of electricity through the current collector. By doing so, the shutdown function is exhibited.
- Patent Document 2 the insulating elastic particles are arranged between the electrodes in an elastically deformed state, and when heat exceeding the glass transition temperature is applied, the elastic deformation is released and the electrodes are separated from each other.
- a fuse element based on the principle that conduction is interrupted is disclosed.
- Patent Document 1 exhibits a certain degree of shutdown function, but is insufficient for practical use, and further enhancement of the shutdown function is desired.
- Patent Document 2 The technique described in Patent Document 2 is practically inconvenient because it cannot be reused once the elastic deformation is released.
- this technique in order to hold the insulating elastic particles in an elastically deformed state, the insulating elastic particles are pressed between the electrodes in a state where the insulating elastic particles are sandwiched between a pair of electrodes, and the surrounding matrix resin in that state is pressed.
- the current collector does not have a pair of electrodes, it is not easy to employ this technique for the current collector.
- the present invention has been made in view of such circumstances, and a current collector, an electrode structure, a non-aqueous electrolyte battery, a power storage component, which can be easily manufactured and has a shutdown function excellent in safety. And the manufacturing method of an electrical power collector is provided.
- a current collector having a resin layer on at least one surface of a conductive substrate, wherein the resin layer substantially contains a conductive agent in a thermosetting resin base material containing a conductive agent.
- the thermoplastic resin particles not contained in the particle are dispersed, the value of the mass ratio of (the thermoplastic resin particles) / (the conductive agent) is 0.3 to 1.5, and (the average thickness of the conductive agent) ) / (Average thickness of thermoplastic resin particles) is provided as a current collector of 0.3 to 4.0.
- the inventors of the present invention have made extensive studies in order to exhibit a shutdown function of a nonaqueous electrolyte battery or the like. As it is difficult to introduce into the body, it can be introduced into the current collector, and the shutdown function can be appropriately exhibited, so that the conductive agent is substantially contained in the thermosetting resin base material containing the conductive agent.
- the present inventors have come up with a resin layer in which thermoplastic resin particles not contained are dispersed. And when such a configuration was actually tried, it can be manufactured relatively easily, and the thermoplastic resin particles expand as the temperature rises. It was found that the shutdown function is demonstrated.
- thermoplastic resin particle / (conductive agent) mass ratio and (average thickness of conductive agent) / (average thickness of thermoplastic resin particles) were identified. Only when it is in the range, it has been found that the low resistance at room temperature and the shutdown function is properly exhibited at the time of temperature rise, exhibiting excellent solvent resistance, and the present invention has been completed.
- the present invention utilizes the fact that the coefficient of thermal expansion is different between the thermosetting resin base material containing the conductive agent and the thermoplastic resin particles substantially not containing the conductive agent. Since it is not necessary to arrange the elastic particles in an elastically deformed state, the elastic particles can be easily introduced into the current collector.
- the value of (average thickness of the conductive agent) / (average thickness of the thermosetting resin base material) is 1.0 to 3.0.
- the thermoplastic resin particles are water-insoluble.
- a value of (average thickness of the thermoplastic resin particles) / (average thickness of the thermosetting resin base material) is 1.0 to 3.0.
- the value of the mass ratio of (the conductive agent) / (the thermosetting resin base material) is 0.1 to 0.5.
- the value of the mass ratio of (the thermoplastic resin particles) / (the thermosetting resin base material) is 0.09 to 0.4.
- the thermosetting resin base material is formed from a resin composition including a thermosetting resin, a curing agent, and a conductive agent.
- the thermosetting resin is made of a mixture or copolymer containing at least one of polyacrylic acid resin, nitrified cotton resin, and chitosan resin.
- the conductive agent is made of carbon black.
- the thermoplastic resin particles include at least one selected from polyethylene resins, polypropylene resins, polyvinylidene fluoride resins, polyvinyl butyral resins, and modified products thereof.
- an electrode structure including an active material layer or an electrode material layer on the resin layer of the current collector described above, and a nonaqueous electrolyte battery or a power storage component using the electrode structure are provided.
- the method includes a step of applying a resin layer material to at least one surface of a conductive substrate and baking at 120 to 230 ° C., wherein the resin layer material includes a thermosetting resin
- a method for producing a current collector comprising a curing agent, a thermosetting resin liquid containing a conductive agent, and a thermoplastic resin powder dispersed in the liquid.
- the resin layer material comprises (1) an aqueous emulsion of a thermosetting resin, (2) a mixture of the emulsion and the conductive agent, and (3) a mixture obtained in step (2).
- the emulsion is added to the mixture, (4) the thermoplastic resin powder is mixed with the mixed solution obtained in step (3), and (5) the curing agent is mixed with the mixed solution obtained in step (4).
- the conductive agent has a mass ratio value of (the conductive agent) / (the thermosetting resin + the curing agent + the conductive agent) of 0.1 to 0.5. To be mixed.
- the current collector 1 of the present invention is a current collector 1 having a conductive resin layer (current collector resin layer) 5 on at least one surface of a conductive substrate 3.
- the resin layer 5 is obtained by dispersing thermoplastic resin particles 13 substantially not containing the conductive agent 11 in the thermosetting resin base material 7 containing the conductive agent 11.
- arrows A, B, and C indicate the thickness of the thermosetting resin base material, the thickness of the thermoplastic resin particles, and the thickness of the conductive agent, respectively.
- the thickness of the thermosetting resin base material 7 means the thickness of the resin layer 5 at a portion where the thermoplastic resin particles 13 and the conductive agent 11 are not present.
- an active material layer or an electrode material layer 15 is formed on the resin layer 5 of the current collector 1 of the present invention, so that it can be used for a non-aqueous electrolyte battery such as a lithium ion battery.
- An electrode structure 17 suitable for a double layer capacitor or a lithium ion capacitor can be formed.
- Conductive base material As the conductive base material of the present invention, various metal foils for non-aqueous electrolyte batteries, electric double layer capacitors, or lithium ion capacitors can be used. Specifically, various metal foils for positive electrode and negative electrode can be used, and for example, aluminum, aluminum alloy, copper, stainless steel, nickel and the like can be used. Among these, aluminum, an aluminum alloy, and copper are preferable from the balance between high conductivity and cost.
- the thickness of the conductive substrate is not particularly limited, but is preferably 5 ⁇ m or more and 50 ⁇ m or less. If the thickness is less than 5 ⁇ m, the strength of the foil is insufficient and it may be difficult to form a resin layer or the like.
- the resin layer 5 is formed on the conductive substrate 3.
- the resin layer 5 of the present invention is preferably configured separately from the active material layer, and not only improves the adhesion between the conductive substrate and the active material layer, but also has a shutdown function. And can be suitably used for the production of non-aqueous electrolyte batteries, power storage components and the like having excellent safety.
- the resin layer 5 of the present invention is obtained by dispersing thermoplastic resin particles 13 substantially not containing a conductive agent in a thermosetting resin base material 7 containing a conductive agent 11.
- the thickness of the resin layer 5 is not particularly limited, but is preferably 0.3 to 20 ⁇ m. If the thickness is less than 0.3 ⁇ m, the resistance is not sufficiently lowered during abnormal heat generation, and the shutdown function is not exhibited. When it exceeds 20 ⁇ m, the resistance at the normal time becomes high and the performance at the high rate is lowered.
- the thickness of the resin layer 5 is, for example, 0.3, 0.5, 1, 2, 5, 10, 15, 20 ⁇ m, and may be within a range between any two of the numerical values exemplified here. Good.
- the thermosetting resin base material 7 can be formed by heating and curing a resin composition including a thermosetting resin, a curing agent, and a conductive agent 11.
- This resin composition is composed of a conductive agent 11 and a curing agent in an aqueous solution containing an aqueous emulsion of a thermosetting resin (dissolved in water containing a surfactant after the thermosetting resin is dissolved in an organic solvent).
- the thermosetting resin is not particularly limited as long as it is cured when reacted with a curing agent.
- a mixture containing at least one of polyacrylic acid resin, nitrified cotton resin, and chitosan resin is used.
- a copolymer for example, a polyacrylic acid-polyacrylate ester copolymer.
- the polyacrylic acid-based resin is a resin formed from a monomer mainly composed of acrylic acid or methacrylic acid, or a derivative thereof. Specifically, polyacrylic acid, polyacrylic ester, It is a mixture or copolymer containing at least one of methacrylic acid and polymethacrylic acid ester.
- the polyacrylic acid resin contains a copolymer with a hydroxyacrylic acid ester resin or a polyacrylonitrile resin in addition to at least one of polyacrylic acid, polyacrylic acid ester, polymethacrylic acid, and polymethacrylic acid ester. It may be a thing.
- the nitrified cotton-based resin is a resin containing nitrified cotton as a resin component, and may be composed only of nitrified cotton or may contain nitrified cotton and another resin.
- Nitrified cotton is a kind of cellulose which is a polysaccharide, but is characterized by having a nitro group.
- Nitrified cotton is a cellulose having a nitro group, but it is not known as a use for an electrode as compared with other celluloses such as CMC, and is conventionally used as a raw material for resin films and paints.
- the nitrogen concentration of the nitrified cotton used in the present invention is preferably 10 to 13%, particularly preferably 10.5 to 12.5%.
- the nitrogen concentration is too low, it may not be sufficiently dispersed depending on the type of the conductive material. If the nitrogen concentration is too high, the nitrified cotton becomes chemically unstable and is dangerous for use in a battery. Since the nitrogen concentration depends on the number of nitro groups, the nitrogen concentration can be adjusted by adjusting the number of nitro groups.
- the viscosity of the above nitrified cotton is usually 1 to 6.5 seconds, particularly 1.0 to 6 seconds, and the acid content is 0.006% or less, particularly 0.005% or less, as measured according to JIS K-6703. It is recommended that When deviating from these ranges, the dispersibility of the conductive material and the battery characteristics may deteriorate.
- the chitosan resin is a resin containing a chitosan derivative as a resin component.
- a chitosan derivative as a resin component.
- the chitosan derivative is, for example, hydroxyalkyl chitosan. Specifically, hydroxyethyl chitosan, hydroxypropyl chitosan, hydroxybutyl chitosan, glycerylated chitosan is preferable, and glycerylated chitosan is particularly preferable.
- the chitosan resin preferably contains an organic acid.
- organic acids include pyromellitic acid and terephthalic acid.
- the addition amount of the organic acid is preferably 20 to 300% by mass, more preferably 50 to 150% by mass with respect to 100% by mass of the chitosan derivative. This is because if the addition amount of the organic acid is too small, the chitosan derivative is not sufficiently cured, and if the addition amount of the organic acid is too large, the flexibility of the resin layer is lowered.
- the curing agent is not particularly limited as long as the thermosetting resin is crosslinked and cured, and examples thereof include melamine or a derivative thereof and blocked urea.
- Melamine derivatives can be obtained by, for example, condensing melamine and formaldehyde to methylolate melamine (optionally further polynuclearized by addition reaction), and then alkylate methylol group with alcohol (eg, methyl alcohol or butyl alcohol) as necessary. Or can be manufactured.
- Derivatives of melamine include fully alkyl type in which the methylol group is almost completely alkylated, imino type in which many non-methylol hydrogen groups remain, and methylol type in which the proportion of non-alkylated methylol groups is large.
- Fully alkylated melamine has no methylol group or imino group, has a methylol group that is completely etherified with a monohydric alcohol having usually 1 to 4 carbon atoms, such as methanol, n-butanol, and isobutanol.
- the degree of condensation usually means 2 or less.
- melamine derivatives are trimethoxymethylated melamine and hexamethoxymethylated melamine.
- Blocked urea can be produced by reacting urea and methylol obtained by condensation reaction of urea and formaldehyde with a blocking agent such as alcohol (eg, methyl alcohol or butyl alcohol).
- the conductive agent 11 used in the present invention known carbon powder, metal powder and the like can be used, and among them, carbon black such as furnace black, acetylene black and ketjen black is preferable.
- the average thickness of the conductive agent 11 is not particularly limited, but the value of (average thickness of conductive agent 11) / (average thickness of thermosetting resin base material 7) is 1.0 to 3.0. Is preferred. When this value is too small, it becomes difficult for the conductive agent 11 in the resin layer 5 and the active material to come into contact with each other, and the resistance at room temperature increases. On the other hand, if this value is too large, the particles of the conductive agent 11 are not easily separated even when the temperature is raised, and the shutdown function is hardly exhibited.
- the average thickness of the conductive agent 11 can be obtained from an image obtained by photographing a cross section of a coating film produced by an ultramicrotome or ion milling with a field emission scanning electron microscope (SEM). If the particle shape is unclear, at least carbon and oxygen images are taken and measured by EDX (energy dispersive X-ray spectrometer) simultaneously with SEM observation. This is because the conductive agent contains only carbon, whereas the thermosetting resin film contains a functional group and a component derived from the curing agent (oxygen, nitrogen, etc.), and therefore can be distinguished.
- SEM field emission scanning electron microscope
- the blending amount of the conductive agent 11 is not particularly limited, but the value of the mass ratio of (conductive agent 11) / (thermosetting resin base material 7) is preferably 0.1 to 0.5. If the blending amount of the conductive agent 11 is too small, the number of contact points between the particles of the conductive agent 11 is small, and the electrical resistance at normal temperature is increased. When there is too much compounding quantity of the electrically conductive agent 11, the contact of the particle
- thermoplastic resin particles 13 are dispersed in the thermosetting resin base material 7, are made of a thermoplastic resin, and do not substantially contain the conductive agent 11. “Substantially free” means that a small amount of the conductive agent 11 is allowed as long as it does not form a conductive path in the thermoplastic resin particles 13.
- (conductive agent 11) / (Thermoplastic resin particle 13) means that the mass ratio is 0.02 or less, preferably 0.01 or less. Since the conductive agent is not substantially contained, there is no conductive path through the thermoplastic resin particles 13.
- the thermal expansion coefficient of the conductive agent is usually smaller than the thermal expansion coefficient of the resin
- the thermal expansion coefficient of the thermoplastic resin particles 13 substantially not including the conductive agent is thermosetting including the conductive agent. It tends to be larger than the thermal expansion coefficient of the resin base material 7. Therefore, when the temperature is raised in a state where the active material layer 15 is formed on the resin layer 5, the thermoplastic resin particles 13 are greatly expanded to change from the state of FIG. 4 to the state of FIG. The particles are separated from each other, the conductive path is blocked, and the shutdown function is effectively exhibited.
- thermoplastic resin particles 13 The mass ratio value of (thermoplastic resin particles 13) / (conductive agent 11) is 0.3 to 1.5. If this value is too small, even if there are too few thermoplastic resin particles relative to the conductive agent and the thermoplastic particles expand, it is not possible to disconnect all the conductive agents. Too little agent will increase the electrical resistance.
- the value of (average thickness of conductive agent 11) / (average thickness of thermoplastic resin particles 13) is 0.3 to 4.0. If this value is too small, the active material layer 15 and the resin layer 5 are less likely to come into contact with each other and the resistance becomes high. If this value is too large, the conductive agent 11 is too much and the thermoplastic resin particles 13 expand. All the conductive agents 11 are not disconnected, and the shutdown function does not function properly.
- the value of (average thickness of thermoplastic resin particles 13) / (average thickness of thermosetting resin base material 7) is preferably 1.0 to 3.0. This is because if this value is too small, the shutdown function is insufficient, and if this value is too large, the adhesion between the resin layer and the substrate and the solvent resistance are insufficient.
- the value of the mass ratio of (thermoplastic resin particle 13) / (thermosetting resin base material 7) is 0.09 to 0.4. If this value is too small, the shutdown function tends to be insufficient, and if this value is too large, the area of the thermosetting resin portion becomes small, the coating film adhesion becomes insufficient, and the solvent resistance decreases. .
- thermoplastic resin of the present invention is not particularly limited as long as it can exhibit a shutdown function by thermal expansion in accordance with the above principle, but is preferably water-insoluble from the viewpoint of ease of resin layer formation.
- polyethylene It consists of 1 or more types chosen from a resin, a polypropylene resin, a polyvinylidene fluoride resin, a polyvinyl butyral resin, or those modified products.
- the method for producing a current collector of the present invention comprises a step of applying a resin layer material to at least one surface of the conductive substrate 3 and baking at 120 to 230 ° C.
- the resin layer material is (1) An aqueous emulsion of a thermosetting resin is prepared, (2) Mixing the emulsion and the conductive agent, (3) Add the emulsion to the mixture obtained in step (2), (4) The thermoplastic resin powder is mixed with the liquid mixture obtained in step (3), (5) Step (4) formed by a method comprising a step of mixing a curing agent with the obtained mixed liquid, The conductive agent is mixed so that the mass ratio of (the conductive agent) / (the thermosetting resin + the curing agent + the conductive agent) is 0.1 to 0.5.
- an aqueous emulsion of a thermosetting resin is prepared.
- the aqueous emulsion can be prepared, for example, by dissolving a thermosetting resin in an organic solvent and then dispersing it in water containing a surfactant.
- the conductive agent may not be properly dispersed.
- a relatively small amount of the emulsion and the conductive agent are mixed and stirred to sufficiently disperse the conductive agent.
- the conductive agent is mixed so that the value of the mass ratio of (conductive agent) / (thermosetting resin + curing agent + conductive agent) is 0.1 to 0.5. If this amount is too small, the resistance at room temperature will be large, and if it is too large, the shutdown function will not be properly exhibited.
- thermoplastic resin powder is mixed and sufficiently dispersed in a state where the conductive agent is sufficiently dispersed in an appropriate amount of the aqueous emulsion.
- the thermoplastic resin powder is preferably added in a dry state, but the powder may be mixed in a state of being dispersed in a medium such as water.
- curing agent is mixed in the obtained liquid mixture.
- the curing agent is mixed so that the solid content mass ratio of (curing agent) / (thermosetting resin) is 0.02 to 0.5.
- the resin layer material is obtained through the above steps.
- the curing agent is mixed after mixing the thermoplastic resin powder, but the curing agent may be mixed first.
- the resin layer material is applied onto a conductive substrate and baked at 120 to 230 ° C.
- the baking temperature is, for example, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230 ° C., and is within a range between any two of the numerical values exemplified here. Also good.
- a roll coater As a coating method, a roll coater, a gravure coater, a slit die coater or the like can be used, but is not particularly limited.
- the baking time is not particularly limited, but is, for example, 60 to 240 seconds.
- Electrode Structure The electrode structure of the present invention can be obtained by forming an active material layer or an electrode material layer on at least one surface of the current collector of the present invention.
- the electrode structure for an electrical storage component in which the electrode material layer is formed will be described later.
- an electrode structure (battery component) for a non-aqueous electrolyte battery for example, a lithium ion secondary battery, using the electrode structure, a separator, a non-aqueous electrolyte solution, etc.
- a battery component for a non-aqueous electrolyte battery, for example, a lithium ion secondary battery
- a member other than the current collector can be a known nonaqueous battery member.
- the active material layer formed as an electrode structure in the present invention may be conventionally proposed for non-aqueous electrolyte batteries.
- the current collector of the present invention using aluminum as the positive electrode, LiCoO 2 , LiMnO 2 , LiNiO 2 or the like as the active material, carbon black such as acetylene black as the conductive agent, and PVDF as a binder
- the positive electrode structure of the present invention can be obtained by applying and drying a paste dispersed in water-dispersed PTFE.
- the negative electrode structure for example, graphite, graphite, mesocarbon microbeads or the like are used as the active material for the current collector of the present invention using copper as the conductive base material, and these are used as a thickener CMC. After the dispersion, the paste mixed with SBR as a binder is applied and dried as an active material layer forming material, whereby the negative electrode structure of the present invention can be obtained.
- Nonaqueous electrolyte battery The present invention may be a nonaqueous electrolyte battery.
- the non-aqueous electrolyte battery of the present invention is sandwiched between separators impregnated with an electrolyte for a non-aqueous electrolyte battery having a non-aqueous electrolyte between the positive electrode structure and the negative electrode structure having the current collector of the present invention as a constituent element.
- a water electrolyte battery can be constructed.
- the nonaqueous electrolyte and the separator those used for known nonaqueous electrolyte batteries can be used.
- carbonates or lactones can be used as a solvent.
- a solution obtained by dissolving LiPF 6 or LiBF 4 as an electrolyte in a mixed solution of EC (ethylene carbonate) and EMC (ethyl methyl carbonate) is used.
- EC ethylene carbonate
- EMC ethyl methyl carbonate
- the separator for example, a film having a microporous made of polyolefin can be used.
- Power storage components (electric double layer capacitors, lithium ion capacitors, etc.)
- an electric double layer capacitor or the like is safer than a secondary battery, but the current collector of the present invention can be applied for the purpose of improving high rate characteristics.
- the electric double layer capacitor, lithium ion capacitor, etc. of the present invention can also be applied to power storage components such as electric double layer capacitors and lithium ion capacitors that require high-speed charge / discharge at a large current density. is there.
- the electrode structure for a power storage component of the present invention is obtained by forming an electrode material layer on the current collector of the present invention. By using this electrode structure and a separator, an electrolytic solution, etc., an electric double layer capacitor, a lithium ion capacitor, etc. A power storage component can be manufactured.
- members other than the current collector can be members for known electric double layer capacitors or lithium ion capacitors.
- the electrode material layer can be made of an electrode material, a conductive agent, and a binder for both the positive electrode and the negative electrode.
- an electricity storage component can be obtained after forming the electrode material layer on at least one side of the current collector of the present invention to form an electrode structure.
- the electrode material those conventionally used as electrode materials for electric double layer capacitors and lithium ion capacitors can be used.
- carbon powder or carbon fiber such as activated carbon or graphite can be used.
- the conductive agent carbon black such as acetylene black can be used.
- the binder for example, PVDF (polyvinylidene fluoride), SBR (styrene butadiene rubber), water-dispersed PTFE, or the like can be used.
- the electric storage component of the present invention can constitute an electric double layer capacitor or a lithium ion capacitor by fixing the electrode structure of the present invention with a separator interposed therebetween and allowing the electrolyte to penetrate into the separator.
- the separator for example, a polyolefin microporous film, an electric double layer capacitor nonwoven fabric, or the like can be used.
- carbonates and lactones can be used as the solvent in the electrolyte, and the electrolyte includes tetraethylammonium salt and triethylmethylammonium salt as the cation, and hexafluorophosphate and tetrafluoroborate as the anion.
- a lithium ion capacitor is a combination of a negative electrode of a lithium ion battery and a positive electrode of an electric double layer capacitor.
- aqueous emulsion (solid content: 30% by mass) was prepared by dissolving the thermosetting resin shown in Table 1 in an organic solvent and then dispersing it in water containing a surfactant.
- the aqueous solution having a solid content of 30% by mass has a somewhat high viscosity, pure water is further added to the thermosetting resin emulsion aqueous solution in order to facilitate mixing during the additional addition, and the solid content is 25% by mass.
- An aqueous solution for additional addition was also prepared.
- a conductive agent was mixed with the prepared aqueous emulsion, stirred with a disper at 3000 rpm for 20 minutes, then added with an aqueous emulsion, and then with a disper at 4000 rpm. Stir for 30 minutes.
- thermoplastic resin powder was mixed with the obtained mixed liquid, and stirred at 3000 rpm for 20 minutes with a disper.
- the average particle size of the thermoplastic resin powder is the particle size at an integrated value of 50% in the particle size distribution determined by the laser diffraction / scattering method.
- ⁇ Average thickness of conductive agent The average thickness of the conductive agent was obtained by cutting a coated plate with an ultramicrotome to obtain a cross-section of the coating film, and then shooting an SEM image (electron microscope image) with an FE-SEM (field emission scanning electron microscope). The thickness at 20 points was measured from the cross-sectional photograph, and the average thickness was calculated from the average value.
- thermosetting resin base material was measured by observing the cross section of the resin layer with an FE-SEM.
- the average thickness of the thermosetting resin base material was determined from the average value of the film thickness of 20 points in a portion where neither the thermoplastic resin particles nor the conductive material was present.
- the average thickness of the thermoplastic resin particles was determined as an average value of 30 points.
- ⁇ Electric resistance of resin layer> While heating the sample in steps of 20 ° C. to 10 ° C., the sample was sandwiched between electrodes plated with gold at the top and bottom, and the amount of direct current flowing at a constant voltage was measured to determine the resistance at each electrode temperature. The lowest temperature at which the resistance starts to rise is defined as the resistance increase start temperature. Moreover, the value which divided the maximum resistance value by the resistance value in 20 degreeC was made into resistance ratio.
- Comparative Example 4 since the average particle size of the thermoplastic resin powder was too large, the electrical resistance at room temperature was high. Also, adhesion and solvent resistance were not good. In Comparative Example 5, since the blending amount of the thermoplastic resin powder was too small, the shutdown function was not properly exhibited. In Comparative Example 6, since the blending amount of the thermoplastic resin powder was excessive, the area of the thermosetting resin portion was small, the adhesion of the resin layer was insufficient, and the solvent resistance was lowered. In Comparative Example 7, since the compounding amount of the curing agent is too small, curing of the thermosetting resin base material becomes insufficient, resulting in a substantially thermoplastic resin, and good adhesion and solvent resistance. Was not
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Abstract
Description
すなわち、本発明によれば、導電性基材の少なくとも片面に樹脂層を有する集電体であって、前記樹脂層は、導電剤を含む熱硬化性樹脂母材中に、導電剤を実質的に含まない熱可塑性樹脂粒子が分散されており、(前記熱可塑性樹脂粒子)/(前記導電剤)の質量比の値が0.3~1.5であり、かつ(導電剤の平均厚さ)/(熱可塑性樹脂粒子の平均厚さ)の値が0.3~4.0である集電体が提供される。
好ましくは、(前記導電剤の平均厚さ)/(前記熱硬化性樹脂母材の平均厚さ)の値が1.0~3.0である。
好ましくは、前記熱可塑性樹脂粒子は、水不溶性である。
好ましくは、(前記熱可塑性樹脂粒子の平均厚さ)/(前記熱硬化性樹脂母材の平均厚さ)の値が1.0~3.0である。
好ましくは、(前記導電剤)/(前記熱硬化性樹脂母材)の質量比の値は、0.1~0.5である。
好ましくは、(前記熱可塑性樹脂粒子)/(前記熱硬化性樹脂母材)の質量比の値は、0.09~0.4である。
好ましくは、前記熱硬化性樹脂母材は、熱硬化性樹脂と、硬化剤と、導電剤を含む樹脂組成物から形成される。
好ましくは、前記熱硬化性樹脂は、ポリアクリル酸系樹脂、硝化綿系樹脂、キトサン系樹脂の中の1種以上を含む混合物又は共重合体からなる。
好ましくは、前記導電剤は、カーボンブラックからなる。
好ましくは、前記熱可塑性樹脂粒子は,ポリエチレン系樹脂,ポリプロピレン系樹脂,ポリフッ化ビニリデン系樹脂,ポリビニルブチラール系樹脂またはそれらの変性物中から選ばれる1種以上からなる。
好ましくは、前記樹脂層材料は、(1)熱硬化性樹脂の水性エマルションを作製し、(2)前記エマルションと前記導電剤を混合し、(3)工程(2)で得られた混合液に対して前記エマルションを追加し、(4)工程(3)で得られた混合液に対して前記熱可塑性樹脂粉末を混合し、(5)工程(4)得られた混合液に対して硬化剤を混合する工程を備える方法によって形成され、前記導電剤は、(前記導電剤)/(前記熱硬化性樹脂+前記硬化剤+前記導電剤)の質量比の値が0.1~0.5になるように混合される。
以下、図1~図5を用いて、本発明の実施形態について説明する。
図1~図2に示すように、本発明の集電体1は、導電性基材3の少なくとも片面に導電性を有する樹脂層(集電体用樹脂層)5を有する集電体1であり、樹脂層5は、導電剤11を含む熱硬化性樹脂母材7中に、導電剤11を実質的に含まない熱可塑性樹脂粒子13が分散されてなる。図2において、矢印A、B、Cは、それぞれ、熱硬化性樹脂母材の厚さ、熱可塑性樹脂粒子の厚さ、導電剤の厚さを示している。図2から明らかなように、熱硬化性樹脂母材7の厚さとは、熱硬可塑性樹脂粒子13と導電剤11が存在していない部位での樹脂層5の厚さを意味する。
以下、各構成要素について詳細に説明する。
本発明の導電性基材としては、非水電解質電池用、電気二重層キャパシタ用、又はリチウムイオンキャパシタ用の各種金属箔が使用可能である。具体的には、正極用、負極用の種々の金属箔を使用することができ、例えば、アルミニウム、アルミニウム合金、銅、ステンレス、ニッケルなどが使用可能である。その中でも導電性の高さとコストのバランスからアルミニウム、アルミニウム合金、銅が好ましい。導電性基材の厚さとしては、特に制限されるものではないが、5μm以上、50μm以下であることが好ましい。厚さが5μmより薄いと箔の強度が不足して樹脂層等の形成が困難になる場合がある。一方、50μmを超えるとその分、その他の構成要素、特に活物質層あるいは電極材層を薄くせざるを得ず、特に非水電解質電池や、電気二重層キャパシタ又はリチウムイオンキャパシタ等の蓄電部品とした場合、活物質層の厚さを薄くせざるを得ず必要十分な容量が得られなくなる場合がある。
本発明では導電性基材3の上に、樹脂層5を形成する。本発明の樹脂層5は、正極用として使用する場合、特に活物質層とは別に構成されることが好ましく、導電性基材と活物質層との密着性を向上させるだけでなく、シャットダウン機能を備えることができ、安全性に優れた非水電解質電池、蓄電部品等の製造に好適に使用することができる。
熱硬化性樹脂母材7は、熱硬化性樹脂と、硬化剤と、導電剤11を含む樹脂組成物を加熱して硬化させることによって形成することができる。この樹脂組成物は、熱硬化性樹脂の水性エマルション(熱硬化性樹脂を有機溶剤に溶解させた後、界面活性剤を含む水中に分散させたもの)を含む水溶液中に導電剤11及び硬化剤を混合することによって作製することができる。熱硬化性樹脂は、硬化剤と反応させたときに硬化するものであれば特に限定されず、例えば、ポリアクリル酸系樹脂、硝化綿系樹脂、キトサン系樹脂の中の1種以上を含む混合物又は共重合体からなり、例えば、ポリアクリル酸-ポリアクリル酸エステル共重合体である。
熱可塑性樹脂粒子13は、熱硬化性樹脂母材7中に分散されており、熱可塑性樹脂からなり、導電剤11を実質的に含まない。「実質的に含まない」とは、熱可塑性樹脂粒子13中に導電経路を形成しない程度の分量であれば導電剤11が少量含まれることを許容する意味であり、例えば、(導電剤11)/(熱可塑性樹脂粒子13)の質量比が0.02以下、好ましくは0.01以下であることを意味する。導電剤を実質的に含んでいないので、熱可塑性樹脂粒子13を通じた導電経路は存在していない。また、通常、導電剤の熱膨張率は樹脂の熱膨張率よりも小さいので、導電剤を実質的に含んでいない熱可塑性樹脂粒子13の熱膨張率は、導電剤を含んでいる熱硬化性樹脂母材7の熱膨張率よりも大きくなりやすい。そのため、樹脂層5上に活物質層15が形成された状態で昇温されると、熱可塑性樹脂粒子13が大きく膨張して、図4の状態から図5の状態になって、導電剤11の粒子同士が離間され、導電経路が遮断され、シャットダウン機能が効果的に発揮される。
本発明の集電体の製造方法は、導電性基材3の少なくとも片面に樹脂層材料を塗布し、120~230℃で焼き付けを行う工程を備え、前記樹脂層材料は、熱硬化性樹脂と、硬化剤と、導電剤を含む熱硬化性樹脂液と、この液中に分散された熱可塑性樹脂粉末とを含む。
(1)熱硬化性樹脂の水性エマルションを作製し、
(2)前記エマルションと前記導電剤を混合し、
(3)工程(2)で得られた混合液に対して前記エマルションを追加し、
(4)工程(3)で得られた混合液に対して前記熱可塑性樹脂粉末を混合し、
(5)工程(4)得られた混合液に対して硬化剤を混合する工程を備える方法によって形成され、
前記導電剤は、(前記導電剤)/(前記熱硬化性樹脂+前記硬化剤+前記導電剤)の質量比の値が0.1~0.5になるように混合される。
まず、熱硬化性樹脂の水性エマルションを作製する。水性エマルションは、例えば、熱硬化性樹脂を有機溶剤に溶解させた後、界面活性剤を含む水中に分散させることによって作製することができる。
また、導電剤は、(導電剤)/(熱硬化性樹脂+硬化剤+導電剤)の質量比の値が0.1~0.5となるように混合する。この量が少なすぎると常温時の抵抗が大きくなり、多すぎるとシャットダウン機能が適切に発揮されにくくなる。
以上の工程で、導電剤を適切な量の水性エマルション中に十分に分散させた状態で、ここに、熱可塑性樹脂粉末を混合し、十分に分散させる。熱可塑性樹脂粉末は、乾燥した状態で添加することが好ましいが、この粉末を水などの媒体中に分散させた状態で混合してもよい。
次に、得られた混合液中に硬化剤を混合する。硬化剤は、(硬化剤)/(熱硬化性樹脂)の固形分質量比
が0.02~0.5になるように混合する。以上の工程で、樹脂層材料が得られる。
本発明の集電体の少なくとも片面に活物質層又は電極材層を形成することによって、本発明の電極構造体を得ることができる。電極材層を形成した蓄電部品用の電極構造体については後述する。まず、活物質層を形成した電極構造体の場合、この電極構造体とセパレータ、非水電解質溶液等を用いて非水電解質電池用、例えばリチウムイオン二次電池用の電極構造体(電池用部品を含む)を製造することができる。本発明の非水電解質電池用電極構造体および非水電解質電池において集電体以外の部材は、公知の非水電池用部材を用いることが可能である。
ここで、本発明において電極構造体として形成される活物質層は、従来、非水電解質電池用として提案されているものでよい。例えば、正極としてはアルミニウムを用いた本発明の集電体に、活物質としてLiCoO2、LiMnO2、LiNiO2等を用い、導電剤としてアセチレンブラック等のカーボンブラックを用い、これらをバインダであるPVDFや水分散型PTFEに分散したペーストを塗工・乾燥させることにより、本発明の正極構造体を得ることができる。
負極の電極構造体とする場合に、導電性基材として銅を用いた本発明の集電体に活物質として例えば黒鉛、グラファイト、メソカーボンマイクロビーズ等を用い、これらを増粘剤であるCMCに分散後、バインダであるSBRと混合したペーストを活物質層形成用材料として塗工・乾燥させることにより、本発明の負極構造体を得ることができる。
本発明は非水電解質電池であってもよい。この場合、本発明の集電体を使用する以外には特に制限されるものではない。例えば、本発明の集電体を構成要素とする前記正極構造体と負極構造体の間に非水電解質を有する非水電解質電池用電解液を含浸させたセパレータで挟むことにより、本発明の非水電解質電池を構成することができる。非水電解質およびセパレータは公知の非水電解質電池用として用いられているものを使用可能である。電解液は溶媒として、カーボネート類やラクトン類等を用いることができ、例えば、EC(エチレンカーボネイト)とEMC(エチルメチルカーボネイト)の混合液に電解質としてLiPF6やLiBF4を溶解したものを用いることができる。セパレータとしては例えばポリオレフィン製のマイクロポーラスを有する膜を用いることができる。
一般に電気二重層キャパシタ等は二次電池に比較すると安全であるが、ハイレート特性向上などの目的から、本発明の集電体を適用することが可能である。本発明の電気二重層キャパシタ、リチウムイオンキャパシタ等は、本発明の集電体を大電流密度での高速の充放電が必要な電気二重層キャパシタやリチウムイオンキャパシタ等の蓄電部品にも適応可能である。本発明の蓄電部品用電極構造体は本発明の集電体に電極材層を形成することによって得られ、この電極構造体とセパレータ、電解液等によって、電気二重層キャパシタやリチウムイオンキャパシタ等の蓄電部品を製造することができる。本発明の電極構造体および蓄電部品において集電体以外の部材は、公知の電気二重層キャパシタ用やリチウムイオンキャパシタ用の部材を用いることが可能である。
表1に示す熱硬化性樹脂を有機溶剤に溶解させた後、界面活性剤を含む水中に分散させることによって、水性エマルション(固形分30質量%)を作製した。また、この固形分30質量%の水溶液はやや粘度が高いので、追加添加の際に混合を容易にするために、この熱硬化性樹脂エマルション水溶液にさらに純水を添加し、固形分25質量%の追加添加用水溶液も作製した。
次に、表1に示すように、作製した水性エマルションに導電剤を混合し、ディスパーにて回転数3000回転で20分攪拌し、その後、水性エマルションを追加し、ディスパーにて回転数4000回転で30分攪拌した。
次に、表1に示すように、得られた混合液に対して熱可塑性樹脂粉末を混合し、ディスパーにて3000回転で20分攪拌した。熱可塑性樹脂粉末の平均粒径は、レーザー回折・散乱法によって求めた粒度分布における積算値50%での粒径である。
次に、表1に示すように、得られた混合液に対して硬化剤を混合し、ディスパーにて3000回転で20分攪拌し、樹脂層材料を得た。
上記の樹脂層材料導電剤を、厚さ20μmのアルミニウム箔(JIS A1085)の両面に厚さバーコーターにて塗布し、直ちに熱風炉で乾燥して焼き付けを行なって、集電体の試料を作製した。焼付は、大気雰囲気、風速1~3m/s、設定雰囲気温度160℃、在炉時間120秒で行った。
導電剤の平均厚さは、ウルトラミクロトームにて塗装板を切断して塗膜断面を出した後,FE-SEM(電界放射型走査電子顕微鏡)にてSEM像(電子顕微鏡像)を撮影し,断面写真から20点の厚さを測定し、その平均値から平均厚さを算出した。
熱硬化性樹脂母材の厚さは、樹脂層断面をFE-SEMにて観察して測定した。熱硬化性樹脂母材の平均厚さは、熱可塑性樹脂粒子と導電材がどちらも存在しない部分の膜厚20点の平均値から求めた。また、熱可塑性樹脂粒子の平均厚さは、30点の平均値として求めた。
試料を20℃から10℃刻みに加熱しながら、上下を金めっきした電極で試料を挟み、一定電圧で流れる直流電流量を測定することにより、電極各温度での抵抗を求めた。抵抗が上昇し始める最低温度を抵抗増加開始温度とした。また、20℃での抵抗値で最大抵抗値を割った値を抵抗比とした。
試料表面に電気絶縁用ポリエステルテープ(日東電工製NP-Tテープ)、幅10mmを貼り付け、手で押し付けて良く密着させた後、勢い良く剥がし、剥離面を観察した。
◎:変化無しの樹脂層
○:表層のみ剥離または引き剥がしたテープ面に導電剤が付着している樹脂層
×:一部または全てアルミ界面から剥離している樹脂層
NMP溶液に、室温で60秒浸漬し、取り出し後に表面に付着したNMPを手早く拭き取り、直ちにスクラッチ試験を行った。スクラッチ試験はガーゼを10枚重ねた2ポンドハンマーを往復させ、樹脂層に変化(脱色、剥離、樹脂層厚さ減少)が生じた回数を記録した。往復回数は最大20回とした。
全ての実施例では、常温時には電気抵抗が小さく、昇温に伴って電気抵抗が増大し、シャットダウン機能が適切に発揮された。また、密着性及び耐溶剤性も良好であった。
比較例1では、導電剤配合量が過少であるので、導電剤同士の連絡点数が少なく、常温時の電気抵抗が高かった。
比較例2では、導電剤配合量が過剰であるので、昇温時にも導電剤同士の接触が保たれ、シャットダウン機能が適切に発揮されなかった。また、密着性・耐溶剤性も良好でなかった。
比較例3では、熱可塑性樹脂粉末の平均粒径が小さすぎるため、シャットダウン機能が適切に発揮されなかった。
比較例4では、熱可塑性樹脂粉末の平均粒径が大きすぎるため、常温時の電気抵抗が高かった。また、密着性・耐溶剤性も良好でなかった。
比較例5では、熱可塑性樹脂粉末の配合量が過少であるので、シャットダウン機能が適切に発揮されなかった。
比較例6では、熱可塑性樹脂粉末の配合量が過剰であるので、熱硬化性樹脂部分の面積が小さく、樹脂層の密着性が不十分になり、耐溶剤性が低下した。
比較例7では、硬化剤の配合量が過少であるので、熱硬化性樹脂母材の硬化が不十分になって、実質的に熱可塑性樹脂になってしまい、密着性・耐溶剤性が良好でなかった
3:導電性基材
5:樹脂層(集電体用樹脂層)
7:熱硬化性樹脂母材
11:導電剤
13:熱可塑性樹脂粒子
15:活物質層又は電極材層
17:電極構造体
Claims (15)
- 導電性基材の少なくとも片面に樹脂層を有する集電体であって、前記樹脂層は、導電剤を含む熱硬化性樹脂母材中に、導電剤を実質的に含まない熱可塑性樹脂粒子が分散されており、(前記熱可塑性樹脂粒子)/(前記導電剤)の質量比の値が0.3~1.5であり、かつ(導電剤の平均厚さ)/(熱可塑性樹脂粒子の平均厚さ)の値が0.3~4.0である集電体。
- (前記導電剤の平均厚さ)/(前記熱硬化性樹脂母材の平均厚さ)の値が1.0~3.0である請求項1に記載の集電体。
- 前記熱可塑性樹脂粒子は、水不溶性である請求項1又は2に記載の集電体。
- (前記熱可塑性樹脂粒子の平均厚さ)/(前記熱硬化性樹脂母材の平均厚さ)の値が1.0~3.0である請求項1~3の何れか1つに記載の集電体。
- (前記導電剤)/(前記熱硬化性樹脂母材)の質量比の値は、0.1~0.5である請求項1~4の何れか1つに記載の集電体。
- (前記熱可塑性樹脂粒子)/(前記熱硬化性樹脂母材)の質量比の値は、0.09~0.4である請求項1~5の何れか1つに記載の集電体。
- 前記熱硬化性樹脂母材は、熱硬化性樹脂と、硬化剤と、導電剤を含む樹脂組成物から形成される請求項1~6の何れか1つに記載の集電体。
- 前記熱硬化性樹脂は、ポリアクリル酸系樹脂、硝化綿系樹脂、キトサン系樹脂の中の1種以上を含む混合物又は共重合体からなる請求項7に記載の集電体。
- 前記導電剤は、カーボンブラックからなる請求項1~8の何れか1つに記載の集電体。
- 前記熱可塑性樹脂粒子は,ポリエチレン系樹脂,ポリプロピレン系樹脂,ポリフッ化ビニリデン系樹脂,ポリビニルブチラール系樹脂またはそれらの変性物中から選ばれる1種以上からなる請求項1~9の何れか1つに記載の集電体。
- 請求項1~10の何れか1つに記載の集電体の前記樹脂層上に活物質層又は電極材層を備える、電極構造体。
- 請求項11に記載の電極構造体を備える、非水電解質電池又は蓄電部品。
- 導電性基材の少なくとも片面に樹脂層材料を塗布し、120~230℃で焼き付けを行う工程を備え、
前記樹脂層材料は、熱硬化性樹脂と、硬化剤と、導電剤を含む熱硬化性樹脂液と、この液中に分散された熱可塑性樹脂粉末とを含む、集電体の製造方法。 - 前記樹脂層材料は、
(1)熱硬化性樹脂の水性エマルションを作製し、
(2)前記エマルションと前記導電剤を混合し、
(3)工程(2)で得られた混合液に対して前記エマルションを追加し、
(4)工程(3)で得られた混合液に対して前記熱可塑性樹脂粉末を混合し、
(5)工程(4)得られた混合液に対して硬化剤を混合する工程を備える方法によって形成され、
前記導電剤は、(前記導電剤)/(前記熱硬化性樹脂+前記硬化剤+前記導電剤)の質量比の値が0.1~0.5になるように混合される請求項13に記載の集電体の製造方法。 - 前記硬化剤は、(前記硬化剤)/(前記熱硬化性樹脂)の固形分質量比が0.02~0.5になるように混合する請求項14に記載の集電体の製造方法。
Priority Applications (6)
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CN201380021621.1A CN104272509A (zh) | 2012-05-15 | 2013-05-10 | 集电体、电极结构体、非水电解质电池及蓄电部件、集电体的制造方法 |
JP2014515593A JPWO2013172257A1 (ja) | 2012-05-15 | 2013-05-10 | 集電体、電極構造体、非水電解質電池及び蓄電部品、集電体の製造方法 |
EP13790882.8A EP2851981A4 (en) | 2012-05-15 | 2013-05-10 | COLLECTOR, ELECTRODE STRUCTURE, NONAQUEOUS ELECTROLYTE BATTERY, AND ENERGY STORAGE COMPONENT, AND MANUFACTURER MANUFACTURING METHOD |
KR20147035117A KR20150015504A (ko) | 2012-05-15 | 2013-05-10 | 집전체, 전극 구조체, 비수전해질 전지 및 축전 부품, 집전체의 제조 방법 |
US14/399,492 US9786919B2 (en) | 2012-05-15 | 2013-05-10 | Current collector, electrode structure, nonaqueous electrolyte battery and electrical storage device, and method for producing current collector |
HK15105155.3A HK1204712A1 (en) | 2012-05-15 | 2015-05-29 | Collector, electrode structure, nonaqueous electrolyte battery and power storage component, and method for producing collector |
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US (1) | US9786919B2 (ja) |
EP (1) | EP2851981A4 (ja) |
JP (1) | JPWO2013172257A1 (ja) |
KR (1) | KR20150015504A (ja) |
CN (1) | CN104272509A (ja) |
HK (1) | HK1204712A1 (ja) |
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JP2015118865A (ja) * | 2013-12-19 | 2015-06-25 | 株式会社豊田自動織機 | 集電体本体への保護層形成方法、リチウムイオン二次電池用集電体、リチウムイオン二次電池用正極及びリチウムイオン二次電池 |
WO2018179898A1 (ja) * | 2017-03-29 | 2018-10-04 | パナソニックIpマネジメント株式会社 | 二次電池 |
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- 2013-05-10 JP JP2014515593A patent/JPWO2013172257A1/ja active Pending
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- 2013-05-10 CN CN201380021621.1A patent/CN104272509A/zh active Pending
- 2013-05-10 US US14/399,492 patent/US9786919B2/en not_active Expired - Fee Related
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CN111640949A (zh) * | 2020-06-12 | 2020-09-08 | 宁德新能源科技有限公司 | 集流体、电极极片、电化学装置和电子装置 |
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HK1204712A1 (en) | 2015-11-27 |
US9786919B2 (en) | 2017-10-10 |
US20150118553A1 (en) | 2015-04-30 |
JPWO2013172257A1 (ja) | 2016-01-12 |
KR20150015504A (ko) | 2015-02-10 |
EP2851981A1 (en) | 2015-03-25 |
TW201415700A (zh) | 2014-04-16 |
EP2851981A4 (en) | 2016-06-22 |
CN104272509A (zh) | 2015-01-07 |
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