JP2013042053A - Energy device electrode structure, manufacturing method of the same, and energy device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an energy device electrode structure which improves the reliability and a manufacturing method of the energy device electrode structure, and to provide an energy device to which the energy device electrode structure is applied.SOLUTION: An energy device electrode structure 2 includes: a collecting electrode 10; an undercoat layer 12 disposed on the collecting electrode 10; and an active material electrode layer 14 disposed on the undercoat layer 12 and including a first binder having a melting point higher than 200°C and high temperature resistant properties. The invention provides the energy device electrode structure 2, a manufacturing method of the energy device electrode structure, and an energy device to which the energy device electrode structure is applied.

Description

  The present invention relates to an energy device electrode structure, a manufacturing method thereof, and an energy device, and more particularly, to an energy device electrode structure with improved reliability, a manufacturing method thereof, and an energy device to which the energy device electrode structure is applied.

  Conventionally, as an energy device, a laminate-type power storage device, an electric double layer capacitor, and the like are known (for example, see Patent Documents 1 to 3).

  Moreover, the manufacturing method of the electrode for electric double layer capacitors which obtains the electrode which has a high-density electrode layer by a calendar process is also disclosed (for example, refer patent document 4).

JP 2000-12407 A JP 2001-338848 A JP 2003-217646 A JP 2005-191424 A

  In the method for producing an electrode for an electric double layer capacitor in Patent Document 4, a step of forming an undercoat layer containing a binder that can be bound to conductive particles on a collecting electrode, and a conductive particle, binder, And applying a coating solution for an electrode layer containing a solvent and activated carbon to form an electrode layer. Furthermore, in the step of forming the electrode layer, after applying the electrode layer coating solution, drying at 200 ° C. or lower so that the amount of residual solvent contained in the layer on the collecting electrode is 5 to 35% by weight; Then, after drying, there is a step of performing a roll press and a step of further performing vacuum drying.

  In each of the above steps, since the heat resistance of the applied binder is low, the electrode layer is deteriorated when drying at high temperature. Moreover, since high temperature drying cannot be performed, it is difficult to reduce the residual moisture content. In addition, when roll pressing is performed in a state containing a residual solvent, an active material such as activated carbon adheres to the roll pressing machine, and the electrode layer is easily peeled off from the collecting electrode (aluminum foil). Moreover, there exists modification | denaturation and deterioration by the heat | fever of an electrode layer, adhesiveness with an undercoat layer worsens, and an electrode layer will peel off.

  An object of the present invention is to provide an energy device electrode structure with improved reliability, a method for manufacturing the same, and an energy device to which the energy device electrode structure is applied.

  According to one aspect of the present invention, a collector electrode, an undercoat layer disposed on the collector electrode, and a first binder disposed on the undercoat layer and having a high temperature heat resistance higher than 200 ° C. There is provided an energy device electrode structure comprising an active material electrode layer.

  According to another aspect of the present invention, a step of forming an undercoat layer on the collector electrode, a step of drying the undercoat layer, and forming an active material electrode layer containing a first binder on the undercoat layer There is provided a method for manufacturing an energy device electrode structure, the method comprising: a step of drying, a step of drying the active material electrode layer, and a step of roll pressing a laminated structure including the collector electrode, the undercoat layer, and the active material electrode layer. Is done.

  According to another aspect of the present invention, there is provided an electric double layer capacitor comprising the above energy device electrode structure in a positive / negative active material electrode structure.

  According to another aspect of the present invention, there is provided a lithium ion capacitor comprising the energy device electrode structure described above in a positive / negative active material electrode structure.

  According to another aspect of the present invention, there is provided a lithium ion battery comprising the above-mentioned energy device electrode structure in a positive / negative active material electrode structure.

  ADVANTAGE OF THE INVENTION According to this invention, the energy device electrode structure with improved reliability, its manufacturing method, and the energy device to which this energy device electrode structure is applied can be provided.

The typical cross-section figure of the energy device electrode structure which concerns on 1st Embodiment. The typical cross-section figure of the energy device electrode structure which concerns on the modification 1 of 1st Embodiment. The typical cross-section figure of the energy device electrode structure which concerns on the modification 2 of 1st Embodiment. The typical cross-section figure of the energy device electrode structure which concerns on the modification 3 of 1st Embodiment. The figure showing the chemical formula of polytetrafluoroethylene (PTFE) as a binder applied to the energy device electrode structure which concerns on 1st Embodiment. The SEM photograph example of the active material electrode layer which applied polytetrafluoroethylene (PTFE) as a binder applied to the energy device electrode structure which concerns on 1st Embodiment. The typical explanatory view of the active material electrode layer to which polytetrafluoroethylene (PTFE) is applied as a binder applied to the energy device electrode structure concerning a 1st embodiment. The figure showing the chemical formula of polyvinylidene fluoride (PVdF) as a binder of a comparative example. The SEM photograph example of the active material electrode layer which applied the polyvinylidene fluoride (PVdF) as a binder of a comparative example. (A) Schematic explanatory drawing of the active material electrode layer which applied the polyvinylidene fluoride (PVdF) as a binder of a comparative example, (b) Detailed drawing of the detail of FIG. 10 (a). The figure showing chemical formula of aramid resin (polymetaphenylene isophthalamide) as a binder applied to the energy device electrode structure concerning a 1st embodiment. The SEM photograph example of the active material electrode layer which applied the aramid resin (polymetaphenylene isophthalamide) as a binder in the energy device electrode structure which concerns on 1st Embodiment. (A) In the energy device electrode structure which concerns on 1st Embodiment, the typical explanatory drawing of the active material electrode layer which applied the aramid resin (polymetaphenylene isophthalamide) as a binder, (b) of FIG. 13 (a) Detailed view of details. It is a manufacturing method of the energy device electrode structure which concerns on 1st Embodiment, Comprising: Typical sectional structure drawing (the 1) explaining 1 process of (a) manufacturing method, (b) 1 process of manufacturing method is demonstrated (2), (c) Schematic cross-sectional structure diagram explaining one process of the manufacturing method (3), (d) Schematic cross-sectional structure diagram explaining one process of the manufacturing method (2) 4). It is a manufacturing method of the energy device electrode structure which concerns on 1st Embodiment, Comprising: Typical sectional structure drawing (the 5) explaining 1 process of a manufacturing method, (b) 1 process of manufacturing method is demonstrated FIG. 6 is a schematic cross-sectional structure diagram (No. 6). FIG. 3 is a schematic cross-sectional structure diagram illustrating one step of the method for manufacturing the energy device electrode structure according to the first embodiment and illustrating a roll press step. It is a manufacturing method of the energy device electrode structure which concerns on 2nd Embodiment, Comprising: The typical bird's-eye view structural drawing (the 1) explaining 1 process of (a) manufacturing method, (b) 1 process of manufacturing method is demonstrated (C) a schematic bird's-eye view structural diagram for explaining one process of the manufacturing method (part 3), and (d) a schematic bird's-eye view structural diagram for explaining one process of the manufacturing method (part 2). 4). It is a manufacturing method of the energy device electrode structure which concerns on 2nd Embodiment, Comprising: (a) Schematic bird's-eye drawing explaining the 1 process of a manufacturing method (the 5), (b) 1 process of a manufacturing method Schematic bird's-eye view structure diagram (No. 6) to explain. FIG. 10 is a schematic cross-sectional structure diagram that explains one step of a method for manufacturing an energy device electrode structure according to a second embodiment, and illustrates a roll press step. The typical section structure figure of the electric double layer capacitor to which the energy device electrode structure concerning an embodiment is applied. The typical cross-section figure of the lithium ion capacitor to which the energy device electrode structure which concerns on embodiment is applied. The typical cross-section figure of the lithium ion battery to which the energy device electrode structure which concerns on embodiment is applied.

  Next, embodiments of the present invention will be described with reference to the drawings. In the following description of the drawings, the same or similar parts are denoted by the same or similar reference numerals. However, it should be noted that the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, and the like are different from the actual ones. Therefore, specific thicknesses and dimensions should be determined in consideration of the following description. Moreover, it is a matter of course that portions having different dimensional relationships and ratios are included between the drawings.

  Further, the embodiments described below exemplify apparatuses and methods for embodying the technical idea of the present invention, and the embodiments of the present invention include the material, shape, structure, The layout is not specified as follows. Various modifications can be made to the embodiment of the present invention within the scope of the claims.

[First Embodiment]
As shown in FIG. 1, the energy device electrode structure 2 according to the first embodiment is disposed on the collector electrode 10, the undercoat layer 12 disposed on the collector electrode 10, and the undercoat layer 12. And an active material electrode layer 14 including a first binder 22 having a high temperature heat resistance with a melting point higher than 200 ° C.

  As shown in FIG. 2, the energy device electrode structure 2 according to the first modification of the first embodiment includes a collector electrode 10, an undercoat layer 12 disposed on the collector electrode 10, and an undercoat layer 12. And the active material electrode layer 14 including the first binder 22 having a high temperature heat resistance greater than 200 ° C., and the undercoat layer 12 includes the second binder 24, and includes the first binder 22 and the second binder 22. The binder 24 has different melting points.

  As shown in FIG. 3, the schematic cross-sectional structure of the energy device electrode structure 2 according to Modification 2 of the first embodiment includes a collector electrode 10, an undercoat layer 12 disposed on the collector electrode 10, and An active material electrode layer 14 including a first binder 26 disposed on the undercoat layer 12 and having a high temperature heat resistance greater than 200 ° C., the first binder 26 being an aramid resin, And a second binder 28 different from the aramid resin. Here, the aramid resin can be formed of, for example, polymetaphenylene isophthalamide. The second binder 28 can be formed of, for example, polytetrafluoroethylene (PTFE). In addition to PTFE, for example, a resin that is the same fluororesin as PTFE and has a branched portion or a crosslinked portion in the structure of PTFE is also applicable. For example, a resin having PMVE (perfluoromethylvinyl ether) at a branch portion of the PTFE structure.

  As shown in FIG. 4, a schematic cross-sectional structure of the energy device electrode structure 2 according to Modification 3 of the first embodiment includes a collector electrode 10, an undercoat layer 12 disposed on the collector electrode 10, and An active material electrode layer 14 including a first binder 30 disposed on the undercoat layer 12 and having a high temperature heat resistance greater than 200 ° C., the undercoat layer 12 having a first melting point equal to that of the first binder 30. 2 binders 32 are included. Further, both the first binder and the second binder may be formed of an aramid resin. Here, the aramid resin can be formed of, for example, polymetaphenylene isophthalamide.

  In the energy device electrode structure 2 according to the first embodiment and the first to third modifications thereof, as illustrated in FIGS. 1 to 4, by the laminated structure including the undercoat layer 12 and the active material electrode layer 14, An active material electrode structure 16 is formed.

  In the energy device electrode structure 2 according to the first embodiment and the first to third modifications thereof, a highly heat-resistant binder having a melting point higher than 200 ° C., one of the undercoat layer 12 and the active material electrode layer 14, or A laminated structure applied to both layers is formed. As such a heat-resistant binder having a melting point higher than 200 ° C., for example, an aramid resin can be applied. The melting point of the aramid resin is, for example, about 250 ° C., which is sufficiently higher than 200 ° C., so that the active material electrode layer 14 / undercoat layer 12 including the aramid binder has high heat resistance. .

  In the energy device electrode structure 2 according to the first embodiment and the first to third modifications thereof, a highly heat-resistant binder having a melting point higher than 200 ° C., one of the undercoat layer 12 and the active material electrode layer 14, or By applying to both layers, deterioration and modification | denaturation by high temperature drying of a binder application layer can be prevented, and the adhesiveness of the collector electrode 10 and active material electrode structure 16 which consist of each interlayer and aluminum foil etc. can be maintained. It is possible to reduce peeling due to deterioration / denaturation.

  As a binder applied to the energy device electrode structure 2 according to the first embodiment, the chemical formula of polytetrafluoroethylene (PTFE) is expressed as shown in FIG. An example of an SEM photograph of an active material electrode layer to which PTFE is applied is represented as shown in FIG. 6, and a schematic explanatory diagram of the active material electrode layer in FIG. 6 is represented as shown in FIG. As shown in FIG. 6, the active material electrode layer to which PTFE is applied as a binder has activated carbon AC bonded to each other in a fibril (fibrous) form. Further, as schematically shown in FIG. 7, in the electrolytic solution 40, an active material electrode layer in which the activated carbon AC surface is bonded in a fibrous form with PTFE is obtained. The melting point of PTFE is, for example, about 260 ° C. Since PTFE has high heat resistance, it can be applied as a binder for an undercoat layer or an active material electrode layer.

  As a binder of the comparative example, the chemical formula of polyvinylidene fluoride (PVdF) is represented as shown in FIG. Further, an SEM photograph example of an active material electrode layer to which PVdF is applied is represented as shown in FIG. 9, and the active material electrode layer of FIG. 9 is schematically represented as shown in FIG. Details of the details of 10 (a) are expressed as shown in FIG. 10 (b). In the active material electrode layer to which PVdF is applied as a binder, PVdF coats the activated carbon AC surface and bonds the activated carbon AC to each other. Therefore, PVdF itself is not visible in FIG. Further, as schematically shown in FIGS. 10 (a) and 10 (b), in the electrolytic solution 40, PVdF covers the surface of the activated carbon AC, and the activated carbon AC is bonded by surface bonding. A material electrode layer is obtained. The melting point of PVdF is, for example, about 150 ° C.

  The chemical formula of an aramid resin (polymetaphenylene isophthalamide) as a binder applied to the energy device electrode structure 2 according to the first embodiment is expressed as shown in FIG. An example of an SEM photograph of an active material electrode layer to which an aramid resin (polymetaphenylene isophthalamide) is applied as a binder is shown as shown in FIG. 12, and the active material electrode layer of FIG. 12 is shown in FIG. The details of FIG. 13 (a) are expressed in detail as shown in FIG. 13 (b). In an active material electrode layer to which an aramid resin (polymetaphenylene isophthalamide) is applied as a binder, the aramid resin AR is bonded to the activated carbon AC by point bonding. Further, as schematically shown in FIGS. 13 (a) and 13 (b), in the electrolytic solution 40, the aramid resin AR adheres to the surface of the activated carbon AC, and the activated carbon AC is bonded to each other by point bonding. An active material electrode layer is obtained. The melting point of the aramid resin (polymetaphenylene isophthalamide) is, for example, about 250 ° C.

(Production method)
FIGS. 14A to 14D and FIG. 15A are schematic cross-sectional structures for explaining one process of the manufacturing method of the energy device electrode structure according to the first embodiment. ) To FIG. 15 (b). Moreover, it is a schematic cross-sectional structure for explaining one step of the method for manufacturing the energy device electrode structure according to the first embodiment, and the schematic cross-sectional structure for explaining the roll press step is expressed as shown in FIG. Is done.

  The manufacturing method of the energy device electrode structure according to the first embodiment is as shown in FIGS. 14 (a) to 14 (d), FIGS. 15 (a) to 15 (b), and FIG. A step of applying the undercoat layer coating solution 120 on the electrode 10, a step of drying the undercoat layer coating solution 120 to form the undercoat layer 12, and a first binder on the undercoat layer 12. The step of forming the active material electrode layer coating solution 140, the step of drying the active material electrode layer coating solution 140 to form the active material electrode layer 14, the collector electrode 10, the undercoat layer 12, and the active material electrode And a step of roll-pressing the laminated structure composed of the layers 14.

  Further, the step of drying the active material electrode layer 14 may include vacuum drying.

  In addition, the roll pressing step may be combined with a heating step.

  Hereinafter, each process of the manufacturing method of the energy device electrode structure which concerns on 1st Embodiment is demonstrated in detail.

(A) First, as shown in FIG. 14A, the collector electrode 10 is prepared. The collector electrode 10 can be formed using, for example, an aluminum foil, a copper foil, or the like.

(B) Next, as shown in FIG. 14B, an undercoat layer coating solution 120 is applied to a portion of the collector electrode 10. The components of the undercoat layer coating solution 120 include a conductive additive such as acetylene black and kerosene black, a binder such as an aramid binder, and these solvents. As apparent from FIG. 14B, the collector electrode 10 is exposed in the uncoated portion of the undercoat layer coating solution 120 on the collector electrode 10. As shown in FIG. 14B, the undercoat layer coating solution 120 contains residual moisture 34.

(C) Next, as shown in FIG. 14C, the undercoat layer coating solution 120 is dried to form the undercoat layer 12 on the collector electrode 10. In the drying step shown in FIG. 14 (c), the removal of the solvent and the reduction of the residual moisture 34 are performed.

(D) Next, as shown in FIG. 14D, an active material electrode layer coating solution 140 is applied on the undercoat layer 12. The active material electrode layer coating solution 140 is a mixture of a conductive additive such as acetylene black and kerosene black, a binder such as an aramid binder, these solvents, and activated carbon. As is clear from FIG. 14D, the collector electrode 10 is exposed at an uncoated portion of the active material electrode layer coating liquid 140 on the collector electrode 10. The active material electrode layer coating liquid 140 contains residual moisture 34 as shown in FIG.

(E) Next, as shown in FIG. 15A, the active material electrode layer coating solution 140 is dried to form the active material electrode layer 14 on the undercoat layer 12 on the collector electrode 10. Here, the step of drying the active material electrode layer coating solution 140 may be performed by vacuum drying. As a result, as shown in FIG. 15A, the thickness of the active material electrode layer 14 after drying is D2, and the thickness of the undercoat layer 12 after drying is D1. Here, as a specific numerical example, the thickness of the active material electrode layer 14 before drying is, for example, about 50 μm, and the thickness D2 of the active material electrode layer 14 after drying is, for example, about 35 μm. It is.

(F) Next, as shown in FIG. 16, the laminated structure including the collector electrode 10, the undercoat layer 12, and the active material electrode layer 14 is roll-pressed using roll press machines 18u and 18d. The roll press machine 18 is arranged on the work table 20 and can adjust the width between the rolls 18u and 18d by adjusting the height of the upper roll 18u with respect to the lower roll 18d. In addition, this roll press process may use together the heating process using a heater.

  As a result of the roll pressing step, as shown in FIG. 15B, the thickness of the active material electrode layer 14 is d2, and the thickness of the undercoat layer 12 is d1. Here, as a specific numerical example, the thickness d2 of the active material electrode layer 14 is, for example, about 28 μm. Thus, the reason why the thickness of the active material electrode layer 14 is reduced is that the adhesiveness between the activated carbon ACs is increased by roll press.

  In the manufacturing method of the energy device electrode structure according to the first embodiment, by applying a high heat-resistant binder as the binder, high temperature drying (temperature higher than 200 ° C.) can be performed, so that the residual moisture content is reduced. can do.

  Moreover, in the manufacturing method of the energy device electrode structure according to the first embodiment, since the roll press can be performed after drying at a high temperature and removing the solvent, the peeling of the active material or the like during the roll press is reduced. be able to.

  Moreover, in the manufacturing method of the energy device electrode structure according to the first embodiment, the residual moisture content can be further reduced by roll pressing while applying heat.

  According to the first embodiment, there is provided an energy device electrode structure having improved reliability by suppressing deterioration / denaturation due to high temperature drying of the binder application layer, preventing peeling of the active material electrode layer, and a method for manufacturing the same. be able to.

[Second Embodiment]
The energy device electrode structure 2 according to the second embodiment includes a laminated structure having undercoat layers 12u and 12d and active material electrode layers 14u and 14d on both front and back surfaces of the collector electrode 10. Furthermore, a structure in which such a stacked structure is repeatedly stacked may be provided.

  As shown in FIG. 18B, the energy device electrode structure 2 according to the second embodiment includes a collector electrode 10, undercoat layers 12u and 12d disposed on the collector electrode 10, and an undercoat layer 12u. The active material electrode layers 14u and 14d including the first binder 22 (similar to FIG. 1) disposed on 12d and having a high temperature heat resistance higher than 200 ° C. are provided.

  Similarly to FIG. 2, the energy device electrode structure 2 according to the first modification of the second embodiment includes a collector electrode 10, undercoat layers 12u and 12d disposed on the collector electrode 10, and an undercoat layer 12u. An active material electrode layer 14u, 14d including a first binder 22 disposed on 12d and having a high temperature heat resistance greater than 200 ° C., and the undercoat layers 12u, 12d include a second binder 24, The first binder 22 and the second binder 24 have different melting points.

  Similar to FIG. 3, the schematic cross-sectional structure of the energy device electrode structure 2 according to the second modification of the second embodiment includes the collector electrode 10 and the undercoat layers 12 u and 12 d disposed on the collector electrode 10. The active material electrode layers 14u and 14d including the first binder 26 disposed on the undercoat layers 12u and 12d and having a high temperature heat resistance higher than 200 ° C., and the first binder 26 is an aramid resin, Undercoat layer 12u * 12d contains the 2nd binder 28 different from an aramid resin. Here, as the aramid resin, for example, polymetaphenylene isophthalamide can be applied. In addition, for example, polytetrafluoroethylene (PTFE) can be applied to the second binder 28.

  Similar to FIG. 4, the schematic cross-sectional structure of the energy device electrode structure 2 according to the third modification of the second embodiment includes the collector electrode 10 and the undercoat layers 12 u and 12 d disposed on the collector electrode 10. The active material electrode layers 14u and 14d including the first binder 30 disposed on the undercoat layers 12u and 12d and having a high-temperature heat resistance having a melting point higher than 200 ° C. are provided. A second binder 32 having the same melting point as that of the binder 30 is included. Further, both the first binder and the second binder may be formed of an aramid resin. Here, as the aramid resin, for example, polymetaphenylene isophthalamide can be applied.

  In the energy device electrode structure 2 according to the second embodiment and its modifications 1 to 3, as shown in FIG. 18B and FIGS. 1 to 3, the undercoat layers 12u and 12d and the active material electrode The active material electrode structures 16u and 16d are formed by a laminated structure including the layers 14u and 14d.

  In the energy device electrode structure 2 according to the second embodiment and the first to third modifications thereof, a high heat-resistant binder having a melting point higher than 200 ° C. is used as an undercoat layer 12u · 12d and active material electrode layers 14u · 14d. A laminated structure applied to one or both layers is formed. As such a heat-resistant binder having a melting point higher than 200 ° C., for example, an aramid resin can be applied. The melting point of the aramid resin is, for example, about 250 ° C., and is sufficiently higher than 200 ° C. Therefore, the active material electrode layers 14 u and 14 d / undercoat layers 12 u and 12 d containing the aramid binder have high heat resistance. Will have.

  In the energy device electrode structure 2 according to the second embodiment and the first to third modifications thereof, a high heat-resistant binder having a melting point higher than 200 ° C. is used as an undercoat layer 12u · 12d and active material electrode layers 14u · 14d. By applying to one or both of these layers, deterioration and modification due to high temperature drying of the binder application layer can be prevented, and adhesion between the collector electrode 10 made of each layer and aluminum foil and the active material electrode structures 16u and 16d Property can be maintained, and peeling due to deterioration / denaturation can be reduced.

(Production method)
FIGS. 17A to 17D and FIG. 18A are schematic bird's-eye views that explain one process of the manufacturing method of the energy device electrode structure according to the second embodiment. ) To FIG. 18 (b). Moreover, it is a schematic cross-sectional structure for explaining one step of the manufacturing method of the energy device electrode structure according to the second embodiment, and the schematic cross-sectional structure for explaining the roll press step is expressed as shown in FIG. Is done.

  In the manufacturing method of the energy device electrode structure according to the second embodiment, the step of forming the undercoat layers 12u and 12d on the collector electrode 10 is performed on both the front and back surfaces of the collector electrode 10.

  The step of forming the active material electrode layers 14u and 14d containing the first binder on the undercoat layers 12u and 12d is performed on the undercoat layers 12u and 12d formed on the front and back surfaces of the collector electrode 10.

  Hereinafter, each process of the manufacturing method of the energy device electrode structure which concerns on 2nd Embodiment is demonstrated in detail.

(A) First, the collector electrode 10 is prepared as shown in FIG. The collector electrode 10 can be formed using, for example, an aluminum foil, a copper foil, or the like.

(B) Next, as shown in FIG. 17 (b), undercoat layer coating solutions 120 u and 120 d are applied to a part of the front and back surfaces of the collector electrode 10. The components of the undercoat layer coating liquids 120u and 120d include a conductive additive such as acetylene black and kerosene black, a binder such as an aramid binder, and these solvents. As apparent from FIG. 17B, the collector electrode 10 is exposed at the uncoated portions of the undercoat layer coating liquids 120 u and 120 d on the collector electrode 10. The undercoat layer coating solutions 120u and 120d contain residual moisture 34 as shown in FIG.

(C) Next, as shown in FIG. 17C, the undercoat layer coating solutions 120 u and 120 d are dried to form the undercoat layers 12 u and 12 d on the collector electrode 10. In the drying step shown in FIG. 17 (c), the removal of the solvent and the reduction of the residual moisture 34 are performed.

(D) Next, as shown in FIG. 17D, the active material electrode layer coating liquids 140u and 140d are applied on the undercoat layers 12u and 12d. The coating liquids 140u and 140d for the active material electrode layer are a mixture of a conductive additive such as acetylene black and kerosene black, a binder such as an aramid binder, these solvents, and activated carbon. As is apparent from FIG. 17D, the collector electrode 10 is exposed at the uncoated portions of the active material electrode layer coating liquids 140u and 140d on the collector electrode 10. The active material electrode layer coating liquids 140u and 140d contain residual moisture 34 as shown in FIG.

(E) Next, as shown in FIG. 18A, the active material electrode layer coating liquids 140 u and 140 d are dried, and the active material electrode layers 14 u and 14 d are formed on the undercoat layers 12 u and 12 d on the collector electrode 10. 14d is formed. Here, the step of drying the active material electrode layer coating liquids 140u and 140d may be performed by vacuum drying. As a result, as shown in FIG. 18A, the thickness of the dried active material electrode layers 14u and 14d is D2, and the thickness of the dried undercoat layers 12u and 12d is D1. Here, as a specific numerical example, the thickness of the active material electrode layers 14u and 14d before drying is, for example, about 50 μm, and the thickness D2 of the active material electrode layers 14u and 14d after drying is For example, it is about 35 μm.

(F) Next, as shown in FIG. 19, a laminated structure including the collector electrode 10, the undercoat layers 12 u and 12 d and the active material electrode layers 14 u and 14 d is roll-pressed using a roll press machine 18. The roll press machine 18 is arranged on the work table 20 and can adjust the width between the rolls 18u and 18d by adjusting the height of the upper roll 18u with respect to the lower roll 18d. This roll press process may be used in combination with a heating process using a heater or the like.

  As a result of the roll pressing step, as shown in FIG. 18B, the thickness of the active material electrode layers 14u and 14d is d2, and the thickness of the undercoat layers 12u and 12d is d1. Here, as a specific numerical example, the thickness d2 of the active material electrode layers 14u and 14d is, for example, about 28 μm. The reason why the thickness of the active material electrode layers 14u and 14d is thus reduced is that the adhesion between the activated carbons AC is increased by roll pressing.

  In the manufacturing method of the energy device electrode structure according to the second embodiment, by applying a high heat-resistant binder as the binder, high temperature drying (temperature higher than 200 ° C.) can be performed, so that the residual moisture content is reduced. can do.

  Moreover, in the manufacturing method of the energy device electrode structure according to the second embodiment, it is possible to carry out a roll press after drying at a high temperature and removing the solvent, thereby reducing the peeling of the active material or the like during the roll press. be able to.

  Moreover, in the manufacturing method of the energy device electrode structure according to the second embodiment, the residual moisture content can be further reduced by roll pressing while applying heat.

  According to the second embodiment, there is provided an energy device electrode structure having improved reliability by suppressing deterioration / denaturation due to high temperature drying of the binder application layer, preventing peeling of the active material electrode layer, and a manufacturing method thereof. be able to.

(Energy device)
A schematic cross-sectional structure of the electric double layer capacitor 4 to which the energy device electrode structure according to the embodiment is applied is expressed as shown in FIG.

  A schematic cross-sectional structure of the lithium ion capacitor 6 to which the energy device electrode structure according to the embodiment is applied is expressed as shown in FIG.

  A schematic cross-sectional structure of a lithium ion battery 8 to which the energy device electrode structure according to the embodiment is applied is expressed as shown in FIG.

  With reference to FIGS. 20-22, the basic structure of the energy device (for example, electrical storage device) to which the energy device electrode structure which concerns on embodiment is applied is demonstrated. In addition, the energy device electrode structure which concerns on the modifications 1-3 of embodiment is applicable similarly. 20 to 22, the electrolyte is soaked and ions are charged and discharged through the separator 30, but the illustration of the electrolyte is omitted.

  The electric double layer capacitor 4 provided with the energy device electrode structure according to the embodiment in the active material electrode structure of positive and negative electrodes is a separator through which only ions of the electrolytic solution pass between the active material electrode layer 14a and the active material electrode layer 14b. 30 is interposed. Active material electrode layers 14a and 14b are disposed on the collector electrodes 10a and 10b via undercoat layers 12a and 12b. The collector electrodes 10a and 10b are connected to a power supply voltage. In FIG. 20, the active material electrode structure is formed by the laminated structure of the undercoat layer 12a and the active material electrode layer 14a and the laminated structure of the undercoat layer 12b and the active material electrode layer 14b, respectively.

  As the separator 30, polypropylene or the like can be used when heat resistance is not required, and cellulose-based material can be used when heat resistance is required.

  The electric double layer capacitor 4 to which the energy device electrode structure according to the embodiment is applied is impregnated with an electrolytic solution, and only ions of the electrolytic solution move through the separator 30 during charging and discharging.

  The electric double layer capacitor to which the energy device electrode structure according to the embodiment is applied includes an LED flash, a power source for driving a motor (for example, for toys), a storage element for an electric vehicle (for example, for regeneration and starter), a solar cell, It can be applied to energy storage elements from vibration power generation, power storage elements for high-power communication, environment-resistant storage elements (for example, storage elements for roads, railways, bicycle lights), and the like.

  In the lithium ion capacitor 6 to which the energy device electrode structure according to the embodiment is applied, a separator 30 through which only ions of the electrolytic solution pass is interposed between the active material electrode layer 36 and the active material electrode layer 14b. On the collector electrodes 11a and 10b, active material electrode layers 36 and 14b are arranged via undercoat layers 12a and 12b. The collector electrodes 10a and 10b are connected to a power supply voltage. Here, the collector electrode 11a is formed from, for example, copper foil, and the collector electrode 10b is formed from, for example, aluminum foil. In FIG. 21, the active material electrode structure is formed by the laminated structure of the undercoat layer 12a and the active material electrode layer 36 and the laminated structure of the undercoat layer 12b and the active material electrode layer 14b, respectively.

  The active material electrode layer 36 on the negative electrode side is formed from, for example, Li-doped carbon (activated carbon) containing a binder such as an aramid binder.

  The lithium ion capacitor 6 is impregnated with an electrolytic solution, and only ions of the electrolytic solution move through the separator 30 during charging and discharging.

  The lithium ion capacitor to which the energy device electrode structure according to the embodiment is applied can be applied to an energy storage element from a solar cell or wind power generation, a power source for driving a motor, or the like.

  In the lithium ion battery 8 to which the energy device electrode structure according to the embodiment is applied, a separator 30 through which only ions of the electrolytic solution pass is interposed between the active material electrode layer 36 and the active material electrode layer 38. Active material electrode layers 36 and 38 are disposed on the collector electrodes 11a and 10b via the undercoat layers 12a and 12b. The collector electrodes 10a and 10b are connected to a power supply voltage. Here, the collector electrode 11a is formed from, for example, copper foil, and the collector electrode 10b is formed from, for example, aluminum foil. In FIG. 22, an active material electrode structure is formed by the laminated structure of the undercoat layer 12a and the active material electrode layer 36 and the laminated structure of the undercoat layer 12b and the active material electrode layer 38, respectively.

The active material electrode layer 38 on the positive electrode side is formed of, for example, LiCoO ₂ containing a binder such as an aramid binder. The active material electrode layer 36 on the negative electrode side is formed from, for example, Li-doped carbon (activated carbon) containing a binder such as an aramid binder.

  The lithium ion battery 8 is impregnated with the electrolytic solution, and only ions of the electrolytic solution move through the separator 30 during charging and discharging.

  The lithium ion battery to which the energy device electrode structure according to the embodiment is applied can be applied to a battery for a portable device, a power storage element for electric vehicles (during steady operation), a large-scale power storage element (for general household use), and the like.

  ADVANTAGE OF THE INVENTION According to this invention, degradation and modification | denaturation by high temperature drying of a binder application layer can be suppressed, peeling of an active material electrode layer can be prevented, and the energy device electrode structure and its manufacturing method which improved reliability can be provided.

  Moreover, the energy device to which this energy device electrode structure is applied can be provided.

[Other embodiments]
As described above, the embodiments have been described. However, it should not be understood that the description and drawings constituting a part of this disclosure limit the present invention. From this disclosure, various alternative embodiments, examples and operational techniques will be apparent to those skilled in the art.

  As described above, the present invention naturally includes various embodiments not described herein. Therefore, the technical scope of the present invention is defined only by the invention specifying matters according to the scope of claims reasonable from the above description.

  The energy device of the present invention can be applied as an LED-flash module, a communication (high output) module, a solar cell module, a power supply module, a backup power supply for toys, and the like. In addition, as a backup power source for LSIs, watches, digital still cameras, digital video cameras, personal computers, mobile phones, toys, etc., it is a micro that stores low output energy from solar power generation, dynamo power generation, vibration power generation, thermoelectric elements, power generation, etc. It is applicable as an energy storage element, a coupling capacitor, a smoothing capacitor, or the like.

2 ... Energy device electrode structure 4 ... Electric double layer capacitor 6 ... Lithium ion capacitor 8 ... Lithium ion batteries 10, 10a, 10b, 11a ... Collector electrodes 12, 12u, 12d, 12a, 12b ... Undercoat layers 14, 14u, 14d , 14a, 14b, 36, 38 ... active material electrode layers 16, 16u, 16d ... active material electrode structure 18 ... roll press machine 18u, 18d ... roll 20 ... work table 22, 24, 26, 28, 30, 32 ... binder 34 ... Residual moisture 40 ... Electrolytic solution 120, 120u, 120d ... Undercoat layer coating solution 140, 140u, 140d ... Active material electrode layer coating solution AC ... Activated carbon AR ... Aramid resin PTFE ... Polytetrafluoroethylene PVdF ... Polyfluorinated Vinylidene D1, D2, d1, d2 ... thickness

Claims (15)

A collector electrode;
An undercoat layer disposed on the collector electrode;
An active device electrode layer comprising a first binder disposed on the undercoat layer and having a high temperature heat resistance having a melting point higher than 200 ° C.   The energy device electrode structure according to claim 1, wherein the undercoat layer includes a second binder, and the first binder and the second binder have different melting points.   The energy device electrode structure according to claim 1, wherein the first binder is an aramid resin.   The energy device electrode structure according to claim 1, wherein the undercoat layer includes a second binder, and the first binder and the second binder have the same melting point.   The energy device electrode structure according to claim 4, wherein both the first binder and the second binder are aramid resins.   The energy device electrode structure according to claim 3 or 5, wherein the aramid resin is polymetaphenylene isophthalamide.   The energy device electrode structure according to claim 2, wherein the second binder is polytetrafluoroethylene (PTFE). Applying an undercoat layer coating solution on the collector electrode;
Drying the undercoat layer coating solution to form an undercoat layer;
Applying an active material electrode layer coating solution containing a first binder on the undercoat layer;
Drying the active material electrode layer coating solution to form an active material electrode layer;
And a step of roll-pressing a laminated structure composed of the collector electrode, the undercoat layer, and the active material electrode layer.   The method for manufacturing an energy device electrode structure according to claim 8, wherein the step of drying the active material electrode layer includes vacuum drying.   The method for producing an energy device electrode structure according to claim 8, wherein the roll pressing step uses a heating step in combination.   9. The method for manufacturing an energy device electrode structure according to claim 8, wherein the step of applying the undercoat layer coating solution is performed on both the front and back surfaces of the collector electrode.   The method for producing an energy device electrode structure according to claim 11, wherein the step of applying the coating solution for the active material electrode layer is performed on the undercoat layer formed on both the front and back surfaces of the collector electrode. .   An electric double layer capacitor comprising the energy device electrode structure according to claim 1 in an active material electrode structure of positive and negative electrodes.   A lithium ion capacitor comprising the energy device electrode structure according to any one of claims 1 to 7 in an active material electrode structure of positive and negative electrodes.   A lithium ion battery comprising the energy device electrode structure according to any one of claims 1 to 7 in an active material electrode structure of positive and negative electrodes.