JP6274388B2 - Electrochemical cell and method for producing the same - Google Patents

Description

  The present invention relates to an electrochemical cell, and in particular, an electrochemical cell such as a nonaqueous electrolyte battery or an electric double layer capacitor in which an active material used as a positive electrode or a negative electrode and an electrolytic solution are accommodated in a container, and its It relates to a manufacturing method.

  Conventionally, electrochemical cells such as non-aqueous electrolyte batteries and electric double layer capacitors that can be mounted on the surface are used, for example, as a backup power source for a clock function or a backup power source for a semiconductor memory. Such a small electrochemical cell includes, for example, a pair of electrodes, a separator interposed between the pair of electrodes, and a pair of polarizable electrodes in a container sealed with a lid and a container. And a pair of current collectors that are electrically connected to each other, and an electrolytic solution accommodated in the container.

  On the other hand, the need for large capacity and large current is decreasing due to nonvolatile semiconductor memory, low power consumption of timepiece functional elements, etc. There is an increasing demand for reflow soldering with a small mounting area and a thin shape. In this reflow soldering, for example, a solder cream or the like is applied in advance to a part to be soldered on a printed circuit board, and a part is placed on the part, or a solder ball after placing the part ( Solder bump) is supplied to a soldered part, and a printed circuit board having components mounted in a furnace in a high-temperature atmosphere set so that the soldered part is higher than the melting point of the solder, for example, 250 ° C. or higher, further 300 ° C. or higher. This is a method of performing soldering by melting the solder by passing it through.

  In addition, conventional non-aqueous electrolyte batteries and electric double layer capacitors, which are conventional electrochemical cells, have a round shape like a coin or button, so external terminals are welded to the case in advance for reflow soldering. Since it is necessary, the cost has been increased in terms of an increase in the number of parts and the number of manufacturing steps. Conventionally, there has been a limit to miniaturization, for example, it is necessary to provide a space for external terminals on a substrate. For this reason, a non-aqueous electrolyte battery, an electric double layer capacitor, or the like having a configuration in which a base ceramic container is used as an exterior body that accommodates an electrode and an electrolytic solution and an external terminal is provided has been studied (for example, (See Patent Document 1).

  However, in an electrochemical cell such as a non-aqueous electrolyte battery or an electric double layer capacitor having a conventional configuration as described in Patent Document 1, a positive electrode current collector formed of tungsten, nickel, gold or the like is electrolyzed inside the container. Since it is in contact with the liquid and a voltage is applied, there is a problem that it is dissolved and disconnected by electrolytic corrosion.

  Furthermore, in recent years, customer demands for electric double layer capacitors mounted on energy harvesting devices (energy harvesting devices) have increased, and electric double layer capacitors for backup applications for conventional portable devices In comparison, it is required to maintain stable performance when used in a harsh environment where temperature changes and humidity changes are significantly large.

  In order to solve the above problems, a chip-type electrochemical cell in which a protective layer made of a conductive adhesive is provided between a positive electrode current collector and a positive electrode has been proposed (for example, Patent Document 2). reference). According to the technique described in Patent Document 2, by forming a protective layer covering the positive electrode current collector with a conductive adhesive, a dense and thick film can be formed at low cost, and a highly reliable electrochemical cell is provided. can get.

  In addition, an electrochemical cell having a configuration in which an electrode mainly composed of activated carbon is joined to a current collector through a carbon-based conductive adhesive layer containing a polyimide resin or a polyamideimide resin as a binder component has also been proposed ( For example, see Patent Document 3). According to the technique described in Patent Document 3, capacity degradation and internal resistance increase when charging / discharging cycles are repeated are small, and operational reliability during long-term use is enhanced.

JP 2001-216852 A JP 2006-303381 A JP 2004-048055 A

  On the other hand, when the electrochemical cell having the conventional configuration is subjected to reflow soldering as described above and exposed to a high temperature atmosphere, the electrode and the current collector are separated. The contact resistance between the electrode and the current collector increases and the internal resistance increases. This is particularly noticeable when reflow is repeated in the process using a chip-type electrochemical cell, in particular, a heat-resistant electric double layer capacitor using an electrode having a high electrolyte impregnation property. And when the internal resistance of an electrochemical cell rose, there existed a problem that charging / discharging efficiency fell and an element characteristic fell.

  Moreover, even when a protective layer having a conventional structure is formed on an electrode as in the electrochemical cells described in Patent Documents 2 and 3, it is exposed to a high-temperature atmosphere by performing reflow soldering. In this case, as described above, there is a problem that peeling occurs between each of the electrode, the protective film, and the current collector, the internal resistance increases, and the charge / discharge efficiency decreases.

The present invention has been made in view of the above problems, and even when exposed to a severe high-temperature atmosphere similar to repeated heat treatment corresponding to reflow soldering, electrode peeling or the like occurs. In addition, the electrochemical cell can prevent an increase in internal resistance, has high charge / discharge efficiency, is highly reliable even in harsh usage environments that require heat resistance, and has excellent electrical characteristics. For the purpose.
Moreover, this invention aims at providing the manufacturing method of said electrochemical cell.

In order to solve the above problems, an electrochemical cell of the present invention includes a positive electrode current collector, a negative electrode current collector, a positive electrode, a negative electrode, a separator that separates the positive electrode and the negative electrode, an electrolyte solution, The positive electrode, the negative electrode, the separator, and a base container that stores the electrolyte solution, and a lid that seals the container, and is electrically connected to the positive electrode current collector and the negative electrode current collector. An electrochemical cell that can be charged / discharged via each external terminal, wherein the container has a container bottom and a container wall, and the positive electrode and the negative electrode are connected to the container on the container bottom side. And the positive electrode current collector is disposed on the container bottom side of the positive electrode, and the negative electrode current collector is disposed on the negative electrode side. The positive electrode, the positive electrode current collector and the container bottom. In a heating burned material of polyamic acid, the average particle size is 23~36nm carbon, and mixtures comprising a good conductive protective layer of fine particles is provided in the graphite, the is the positive electrode and the positive electrode collector the It is electrically connected through a protective layer.

The electrochemical cell of the present invention includes a positive electrode current collector, a negative electrode current collector, a positive electrode, a negative electrode, a separator separating the positive electrode and the negative electrode, an electrolyte, the positive electrode and the negative electrode. A base container that houses the separator and the electrolyte solution, and a lid that seals the container, through each external terminal electrically connected to the positive electrode current collector and the negative electrode current collector An electrochemical cell capable of charging / discharging, wherein the container includes a container bottom, a container wall, a spacer disposed between the container bottom and the container wall, and the spacer passes therethrough. The positive electrode current collector has a groove, and the surface formed between the container bottom and the spacer and exposed to the groove has a polyamic acid heat-fired product and an average particle size. 23~36nm of carbon, and a fine of graphite Coated with a mixture to consist of good conductive protective layer of the child, the positive electrode and the positive electrode current collector is characterized by comprising electrically connected via the protective layer.

  As in the above configuration, the polyamic acid calcined product and carbon are formed in the groove provided in the spacer disposed between the positive electrode and the positive electrode current collector and the container bottom, or between the positive electrode and the positive electrode current collector. And a mixture of fine particles of graphite are provided with a good-electricity protective layer, and the positive electrode and the positive electrode current collector are electrically connected via the protective layer, so heat treatment corresponding to reflow soldering is performed. Even when exposed to a high temperature atmosphere, adhesion between the current collector, the protective layer and the electrode is strong, and an increase in contact resistance and internal resistance due to peeling can be prevented. Thereby, it is possible to provide an electrochemical cell having high charge / discharge efficiency and excellent heat resistance and electrical characteristics.

Moreover, as for the said protective layer, it is more preferable that the heat-firing thing of the said polyamic acid is a polyimide which has a low linear expansion coefficient.
By using polyimide with a low coefficient of linear expansion for the heat-fired product of polyamic acid, the resin does not melt even when reheated, and it also has excellent chemical resistance, so when exposed to a high temperature atmosphere Even if it exists, the effect | action which raises the adhesive force between each of a collector, a protective layer, and an electrode becomes more remarkable, and it becomes what was excellent in heat resistance and an electrical property.

The protective layer, the carbon, carbon black, and more preferably contains at least one or more of Ca over carbon fibers and carbon nanotubes.
These carbons can be mixed with graphite fine particles to reduce the resistance value of the paste forming the protective layer. In addition, as described above, even when exposed to a high-temperature atmosphere, the action of increasing the adhesion between the current collector, the protective layer and the electrode becomes more remarkable, and the heat resistance and electrical characteristics are excellent. It will be a thing.

The protective layer more preferably has a specific surface area of the graphite fine particles of 20 m ² / g or less and an average particle size of 10 μm or less.
The graphite fine particles are a material having very high electrical conductivity, and furthermore, by using a material having a specific surface area and an average particle size within the above range, a sufficient capacity can be secured, and as in the above case, a current collector The action of increasing the fixing force between the protective layer and the electrode becomes more prominent, and the heat resistance and electrical characteristics are excellent.

More preferably, the protective layer has a mixing ratio of the carbon and the graphite fine particles in the range of 8:30 to 19:19 ( 5: 5 ) .
By making the mixing ratio of carbon and graphite fine particles in the above range, the effect of preventing peeling between the current collector, the protective layer and the electrode, and the effect of reducing contact resistance become more prominent as described above. Excellent in electrical properties and electrical characteristics.

  In addition, the protective layer may have a configuration in which a binder component including a fired product of polyamic acid used at the time of formation has a solid content in a range of 40 wt% or more and less than 80 wt%.

Moreover, you may employ | adopt the structure by which the aluminum layer which protects this positive electrode collector is provided on the said positive electrode collector.
As described above, by providing the aluminum layer on the positive electrode current collector, the positive electrode current collector made of tungsten or the like is protected by aluminum which is a valve action metal, so that the corrosion resistance of the positive electrode current collector is further improved. Is possible.

The electrochemical cell manufacturing method of the present invention is a method for manufacturing any one of the above electrochemical cells, wherein the positive electrode is formed on the positive electrode current collector formed on the bottom of the container in the container. Forming the separator on the positive electrode, and then forming the negative electrode so as to be connected to the separator, thereby connecting the positive electrode and the negative electrode through the separator, and further, An electrode disposing step for forming the negative electrode current collector on the negative electrode side, an injecting step for injecting the electrolytic solution into the container, and overlapping the lid on the negative electrode, thereby opening the opening of the container to the lid A sealing step of covering and sealing with, and further, the electrode placement step is performed between the positive electrode and the positive electrode current collector and the container bottom, or between the container bottom and the container wall. Placed between It is, and the positive electrode and the groove extending through the spacer provided between the positive electrode current collector, and heating the calcined product of the polyamic acid, the average particle size is 23~36nm carbon, and a mixture of graphite particles And a step of forming a good-electricity protective layer comprising:

  As described above, the electrode placement step is performed by heating and baking the polyamic acid between the positive electrode and the positive electrode current collector and the bottom of the container, or in the groove portion passing through the spacer provided between the positive electrode and the positive electrode current collector. Each of the current collector, the protective layer, and the electrode in a continuous high-temperature atmosphere by adopting a method including a step of forming a good electric protective layer comprising a mixture of carbon and graphite fine particles. The adhesion force between them can be increased. As a result, no peeling occurs between the current collector, the protective layer, and the electrode, and an increase in contact resistance and internal resistance associated therewith can be prevented. The cell can be manufactured.

  Further, the electrode disposing step is less than 3 times the solid content after solidification after mixing the binder containing the heat-fired product of polyamic acid and the mixture of fine particles of carbon and graphite in the step of forming the protective layer. The paste is prepared by adding a diluting solvent in an addition amount to be, and then the paste is exposed on the cathode current collector and the bottom of the container or in the groove formed in the spacer. It is good also as the process of heat-hardening, after apply | coating on a collector.

  By making the step of forming the protective layer in the electrode placement step the above appropriate conditions, the adhesion force between the current collector, the protective layer and the electrode can be increased, so that peeling does not occur and contact resistance / internal The effect of preventing an increase in resistance can be obtained more remarkably.

  According to the electrochemical cell of the present invention, by providing the protective film having a configuration in which the selection of materials and the mixing ratio are optimized as described above, the same harshness as repeated heat treatment corresponding to reflow soldering is performed. Even when exposed to a high temperature atmosphere, the current collector, the protective layer, and the electrodes are firmly fixed to each other, and an increase in contact resistance and internal resistance due to peeling can be prevented. Thereby, it is possible to provide an electrochemical cell that has high charge / discharge efficiency, high reliability, and excellent electrical characteristics even in a severe use environment that requires heat resistance.

  Moreover, according to the method for producing an electrochemical cell of the present invention, as described above, a spacer provided between the positive electrode and the positive electrode current collector and the container bottom, or between the positive electrode and the positive electrode current collector is penetrated. Current collector, protective layer in a continuous high-temperature atmosphere by including a step of forming a good-electricity protective layer comprising a heat-fired product of polyamic acid and a mixture of fine particles of carbon and graphite in the groove portion And the adhesion between each of the electrodes can be increased. Thereby, peeling does not occur between each of the current collector, the protective layer, and the electrode, and an increase in contact resistance and internal resistance associated therewith can be prevented. Therefore, it is possible to produce an electrochemical cell that is excellent in handling in the process, has a high yield, has excellent charge / discharge efficiency, and has excellent heat resistance and electrical characteristics.

FIG. 1 is a cross-sectional view schematically showing a nonaqueous electrolyte battery and an electric double layer capacitor which are the first embodiment of the electrochemical cell of the present invention. FIG. 2 is a cross-sectional view schematically showing a nonaqueous electrolyte battery and an electric double layer capacitor according to a second embodiment of the electrochemical cell of the present invention. FIG. 3 is a cross-sectional view schematically showing a nonaqueous electrolyte battery and an electric double layer capacitor which are the third embodiment of the electrochemical cell of the present invention. FIG. 4 is a cross-sectional view schematically showing a nonaqueous electrolyte battery and an electric double layer capacitor which are the fourth embodiment of the electrochemical cell of the present invention. FIG. 5 is a cross-sectional view schematically showing a nonaqueous electrolyte battery and an electric double layer capacitor which are the fifth embodiment of the electrochemical cell of the present invention. FIG. 6 is a view schematically showing a non-aqueous electrolyte battery and an electric double layer capacitor, which are the sixth embodiment of the electrochemical cell of the present invention. FIG. 6 (a) is a longitudinal sectional view, and FIG. ) Is a cross-sectional view showing a pattern of internal wiring. FIG. 7 is a cross-sectional view schematically showing a nonaqueous electrolyte battery and an electric double layer capacitor which are the seventh embodiment of the electrochemical cell of the present invention. FIG. 8 is a diagram for explaining an example of a non-aqueous electrolyte battery and an electric double layer capacitor which are embodiments of the electrochemical cell of the present invention. FIG. 8A is a diagram showing a binder (solid state) in a paste forming a protective layer. 8) is a graph showing the relationship between the blending ratio and the resistance value when heat treatment corresponding to reflow soldering is performed 10 times. FIG. 8B shows the data shown in the graph of FIG. It is a graph which shows the heat processing conditions at the time of obtaining. FIG. 9 is a diagram for explaining an example of a non-aqueous electrolyte battery and an electric double layer capacitor which are embodiments of the electrochemical cell of the present invention. For the blending ratio of the solvent in the paste forming the protective layer and reflow soldering, FIG. It is a graph which shows the relationship with the resistance value when performing the corresponding heat processing 10 times. FIG. 10 is a diagram for explaining an example of a non-aqueous electrolyte battery and an electric double layer capacitor which are embodiments of the electrochemical cell of the present invention, in which graphite fine particles in a mixture of carbon and graphite fine particles forming a protective layer are shown. It is a graph which shows the relationship between a compounding ratio and the resistance value at the time of performing the heat processing corresponded to reflow soldering 10 times. FIG. 11 is a diagram for explaining an example of a non-aqueous electrolyte battery and an electric double layer capacitor which are embodiments of the electrochemical cell of the present invention, and the mixing ratio of graphite fine particles in the entire paste forming the protective layer, and reflow It is a graph which shows the relationship with the resistance value when the heat processing corresponded to soldering is performed 10 times. FIG. 12 is a diagram for explaining an example of a non-aqueous electrolyte battery and an electric double layer capacitor which are embodiments of the electrochemical cell of the present invention. The particle size (D50) of graphite fine particles forming the protective layer, and reflow soldering. It is a graph which shows the relationship with the resistance value at the time of performing the heat processing corresponded to attachment 10 times. FIG. 13 is a diagram for explaining an example of a non-aqueous electrolyte battery and an electric double layer capacitor which are embodiments of the electrochemical cell of the present invention, for specific surface area of graphite fine particles forming a protective layer, and reflow soldering. It is a graph which shows the relationship with the resistance value when performing the corresponding heat processing 10 times. FIG. 14 is a diagram for explaining an example of a non-aqueous electrolyte battery and an electric double layer capacitor which are embodiments of the electrochemical cell of the present invention. The particle size D90 of the graphite fine particles forming the protective layer (the integrated value is 90%). It is a graph which shows the relationship between the resistance value at the time of performing the heat processing corresponding to reflow soldering 10 times. FIG. 15 is a diagram for explaining an example of a non-aqueous electrolyte battery and an electric double layer capacitor which are embodiments of the electrochemical cell of the present invention, and corresponds to oil absorption in the paste forming the protective layer and reflow soldering. It is a graph which shows the relationship with the resistance value at the time of performing heat processing 10 times. FIG. 16 is a diagram for explaining an example of a nonaqueous electrolyte battery and an electric double layer capacitor which are embodiments of the electrochemical cell of the present invention, and shows the specific surface area of graphite fine particles forming a protective layer and the internal resistance. It is a graph which shows a relationship. FIG. 17 is a diagram for explaining an example of a non-aqueous electrolyte battery and an electric double layer capacitor which are embodiments of the electrochemical cell of the present invention, and the average particle diameter of graphite fine particles forming the protective layer, the internal resistance, It is a graph which shows the relationship. FIG. 18 is a diagram for explaining an example of a non-aqueous electrolyte battery and an electric double layer capacitor which are embodiments of the electrochemical cell of the present invention, and shows the number of heat treatments by heat treatment corresponding to reflow soldering and the internal resistance. It is a graph which shows a relationship. FIG. 19 is a diagram for explaining an example of a non-aqueous electrolyte battery and an electric double layer capacitor which are embodiments of the electrochemical cell of the present invention, and shows the relationship between the number of heat treatments corresponding to reflow soldering and the internal resistance. It is a graph to show. FIG. 20 is a diagram for explaining a conventional nonaqueous electrolyte battery and an electric double layer capacitor, and is a graph showing the relationship between the number of heat treatments corresponding to reflow soldering and the internal resistance. FIG. 21 is a diagram for explaining a conventional nonaqueous electrolyte battery and an electric double layer capacitor, and is a graph showing the relationship between the number of heat treatments corresponding to reflow soldering and the internal resistance. FIG. 22 is a diagram for explaining a conventional non-aqueous electrolyte battery and electric double layer capacitor, and is a graph showing the relationship between the number of heat treatments corresponding to reflow soldering and the internal resistance. FIG. 23 is a diagram for explaining a conventional non-aqueous electrolyte battery and an electric double layer capacitor, and is a graph showing the relationship between the number of heat treatments corresponding to reflow soldering and the internal resistance. FIG. 24 is a diagram for explaining a conventional non-aqueous electrolyte battery and an electric double layer capacitor, and is a graph showing the relationship between the number of heat treatments corresponding to reflow soldering and the internal resistance.

Hereinafter, first and second embodiments of a nonaqueous electrolyte battery and an electric double layer capacitor will be given as embodiments of the electrochemical cell of the present invention, and their respective configurations and manufacturing methods will be described in detail with reference to the drawings. .
The electrochemical cell described in the present invention specifically refers to a nonaqueous electrolyte battery, an electric double layer capacitor, or the like in which an active material used as a positive electrode or a negative electrode and an electrolytic solution are accommodated in a container. Also in the present embodiment, these will be described as examples.

[First Embodiment]
A nonaqueous electrolyte battery and an electric double layer capacitor, which are the first embodiment of the electrochemical cell of the present invention, and a manufacturing method thereof will be described below with reference to the drawings.

“Electric Double Layer Capacitors (Nonaqueous Electrolyte Batteries)”
The electric double layer capacitor (non-aqueous electrolyte battery) A according to the first embodiment shown in FIG. 1 is a so-called chip type, and is approximately 2 to 3 mm long × 2 to 3 mm wide × 0.2 to 1 mm high. It is a rectangular parallelepiped. The electric double layer capacitor A includes a positive electrode current collector 7, a negative electrode current collector 6, a positive electrode 9, a negative electrode 8, a separator 10 that separates the positive electrode 9 and the negative electrode 8, an electrolyte, A base container (container) 1A for storing the negative electrode 8, the separator 10, and the electrolytic solution, and a lid 4 for sealing the container 1A are electrically connected to the positive electrode current collector 7 and the negative electrode current collector 6. In addition, charging / discharging is possible through each of the external terminals 70 and 60.

  In the electric double layer capacitor A of the present embodiment, the container 1A has the container bottom 11 and the container wall 12 so that the positive electrode 9 and the negative electrode 8 are arranged on the container bottom 11 side. The positive electrode current collector 7 is disposed on the container bottom 11 side of the positive electrode 9 and the negative electrode current collector 6 is disposed on the negative electrode 8 side. Between the electric body 7 and the container bottom 11, a good-electricity protective layer 18A made of a heat-fired product of polyamic acid and a mixture of fine particles of carbon and graphite is provided, and the positive electrode 9 and the positive electrode current collector 7 Are electrically connected via the protective layer 18A. In addition, an electrolytic solution (not shown) is accommodated in the container 1A, and the positive electrode 9, the negative electrode 8, and the separator 10 are impregnated with the above electrolytic solution.

(Container and lid)
As shown in FIG. 1, the container 1 </ b> A has a bottomed rectangular tube shape having a container bottom part 11 and a container wall part 12, and is made of, for example, a ceramic material. In addition, a seal ring 3 using a Kovar material having a thermal expansion coefficient close to that of a ceramic material is joined to the container 1A with a brazing material 5 such as silver brazing or gold brazing at the periphery of the opening on the container wall 12. ing. And in the electric double layer capacitor A of this embodiment, it is comprised in the state by which the cover 4 and the container 1A were sealed via the seal ring 3. FIG.
Although it does not specifically limit as thickness of each site | part of 1 A of containers, For example, it can be set as about 0.15-0.25 mm.

Examples of the material of the container 1A including the container bottom 11 and the container wall 12 include heat-resistant materials having insulating properties such as glass, plastic, and alumina, in addition to the above ceramic materials.
Examples of the seal ring 3 include those in which nickel plating is applied to Kovar or the like.
Examples of the brazing material 5 include conventionally known brazing materials such as gold brazing and silver brazing.

  The lid 4 is obtained by applying nickel plating to a conductive metal flat plate such as a nickel-iron alloy containing about 50% by mass of nickel, such as Kovar (alloy of iron, nickel and cobalt) or 42 alloy. is there. This nickel plating serves as a bonding material when welding with the seal ring 3.

Here, the lid 4 and the seal ring 3 have the same linear expansion coefficient in order to prevent the sealing portion from being fragile due to the degree of expansion of the material at the time of joining and the stress at the time of shrinkage caused by cooling after joining. It is preferable to use a material having Similarly, for the seal ring 3 and the container 1A, in order to prevent the container 1A from being damaged by residual stress due to heat, it is preferable to select a material having a close linear expansion coefficient. At this time, for example, alumina (Al ₂ O ₃ ) used as the main component of the container 1A has a representative value of linear expansion coefficient (400 ° C.) of 7.1 × 10 ⁻⁶ K ⁻¹ , and the lid 4 or the seal Kovar used as the main component of the ring 3 has a representative value of the linear expansion coefficient of 4.9 × 10 ⁻⁶ K ⁻¹ .

(Positive electrode and negative electrode)
In the electric double layer capacitor A of the present embodiment, a positive electrode 9 and a negative electrode 8 that are a pair of electrodes are disposed to face each other with a separator 10 in a concave container 1A. The positive electrode 9 is disposed on the container bottom 11 side in the container 1A, and is electrically connected to the positive electrode current collector 7 through a protective layer 18A described later, and a part of the positive electrode 9 is disposed through the protective layer 18A. 11 is adhered. Further, in the example shown in FIG. 1, the negative electrode 8 is bonded and electrically connected to the inner surface side of the lid 4 through the adhesive layer 13.

  As the positive electrode 9 and the negative electrode 8, for example, activated carbon powder obtained by performing activation treatment using water vapor or alkali alone or in combination on organic materials such as sawdust, coconut shell, pitch, coke, and phenol resin, It can be used by press molding or rolling with a suitable binder. In addition, phenol, rayon, acrylic, and pitch fibers are infusibilized and carbonized to obtain activated carbon or activated carbon fibers that are made into a felt, fiber, paper, or sintered body. May be used. Polyaniline (PAN) or polyacene can also be used.

  Further, as the positive electrode 9, conventionally known active materials such as lithium-containing manganese oxide, lithium-containing cobalt oxide, lithium-containing nickel oxide, lithium-containing titanium oxide, molybdenum trioxide, niobium pentoxide, What mixed conventionally well-known binder and graphite which is a conductive support agent can be used.

  Moreover, as the negative electrode 8 used for a secondary battery, a suitable binder and graphite which is a conductive auxiliary agent can be mixed and used for conventionally known active materials such as carbon, silicon and silicon oxide.

(Positive electrode current collector and negative electrode current collector)
As in the example shown in FIG. 1, the positive electrode current collector 7 is electrically connected to the positive electrode 9 via a protective layer 18 </ b> A described later, and is disposed on the container bottom 11 side of the positive electrode 9. The positive electrode current collector 7 is electrically connected with an external terminal 70 provided on the container bottom 11.
Further, the negative electrode current collector 6 is disposed on the negative electrode 8 side as in the example shown in FIG. 1, and is electrically connected to the negative electrode 8 through the brazing material 5, the seal ring 3, the lid 4, and the adhesive layer 13. And electrically connected to an external terminal 60 extending from the container wall 12 toward the container bottom 11.

  As these positive electrode current collector 7 and negative electrode current collector 6, a conductive material usually used in this field can be used without any limitation. The material for each of these current collectors must be selected in consideration of electrolytic corrosion depending on the type of electrolyte used. For example, tungsten, molybdenum, nickel, aluminum, gold, silver, copper, iron, chromium, It can be composed of an alloy such as 42 alloy or stainless steel, or a laminate of a plurality of these, and can be appropriately selected. Here, in particular, when aluminum is used as the current collector material, there is a problem that the conventional conductive paste is liable to be peeled off from the electrode. By using the protective layer made of paste, the effect of effectively fixing is exhibited.

  As described above, the external terminal 70 electrically connected to the positive electrode current collector 7 and the external terminal electrically connected to the negative electrode current collector 6 are provided on the external bottom surface and the external side surface of the container 1A. 60 is provided. These external terminals 60 and 70 become external terminals when the electric double layer capacitor A is mounted on the circuit board by reflow soldering. These external terminals 60 and 70 can be formed integrally with the negative electrode current collector 6 and the positive electrode current collector 7, respectively, and can be made of the same material. Further, since the exposed surfaces of the external terminals 60 and 70 are reflow soldered to the circuit board, it is preferable to perform nickel plating or gold plating (not shown) as necessary. When such a plating method is used, if the method using an electrolytic plating bath is used, the entire exposed surface of the positive electrode current collector 7, the negative electrode current collector 6, the brazing material 5 and the seal ring 3 is also plated. The

  In the case where the external terminal 70 and the external terminal 60 are formed on the outer surface of the container 1A by passing the positive electrode current collector 7 and the negative electrode current collector 6 from the inside of the concave container 1A to the outside, the container 1A and By adopting a material with good adhesiveness for each current collector, it becomes excellent in airtightness. For example, when ceramic is used as the material of the container 1A, tungsten or molybdenum that can withstand the sintering temperature of the ceramic is used for each current collector and terminal. In addition, when a thermosetting resin such as epoxy or polyimide, or a thermoplastic resin such as polystyrene, polyphenylene sulfide, polyester, polyamide, or polyether is used as the material of the container 1A, When 42 alloy having a small expansion coefficient is used as the material of each current collector, the adhesion between the container 1A and each current collector 6 and 7 is improved by heat during reflow. By configuring the combination of the materials of the base container (container) 1A, each of the current collectors 6 and 7 and each of the external terminals 60 and 70 as described above, the airtightness when passing through the reflow furnace is excellent. It can be a chemical cell.

(Separator)
The separator 10 is interposed between the positive electrode 9 and the negative electrode 8, and an insulating film having high ion permeability and mechanical strength is used. As the separator 10, considering the mounting process in the reflow furnace and the thermal influence due to the welding of the lid 4, it is preferable to use glass fibers from the viewpoint of heat stability, for example, borosilicate glass, quartz glass, lead Examples thereof include glass fiber laminates such as glass. Moreover, it is also possible to use a nonwoven fabric made of a resin such as polyphenylene sulfide, polyamide, polyimide, polyethylene terephthalate, or polytetrafluoroethylene for the separator 10. Among these, it is preferable to use a fiber laminate made of glass as the separator 10, and it is more preferable to use a product made of borosilicate glass. Since the fiber laminate made of glass has excellent mechanical strength in addition to the above heat stability, and has a large ion permeability, the effect of reducing the internal resistance and improving the discharge capacity is obtained.

  Moreover, although the hole diameter of the separator 10, thickness, etc. are not specifically limited, It is a matter determined based on the electric current value of the apparatus in which an electrochemical cell is used. A ceramic porous body can also be used.

(Protective layer)
The protective layer 18A used in the electrochemical cell according to the present invention, that is, the electric double layer capacitor (nonaqueous electrolyte battery) A of the present embodiment, is composed of a fired product of polyamic acid and a mixture of fine particles of carbon and graphite. It consists of a good electric film. In the present invention, by using the above material for the protective layer 18A interposed between the positive electrode 9 and the positive electrode current collector 7, the fixing force between each of the current collector, the protective layer, and the electrode in a high temperature environment. Since the heat resistance is improved and the heat resistance is improved, electrode peeling or the like can be prevented from occurring even when continuously exposed to a severe high temperature atmosphere in the reflow soldering process. Therefore, it is possible to suppress an increase in the contact resistance between the positive electrode 9 and the positive electrode current collector 7, and thus it is possible to suppress the internal resistance as an electrochemical cell to a low level.

  Specifically, the polyamic acid heat-fired product and the mixture of carbon and graphite fine particles used for the protective layer 18A described above use a material having a low coefficient of linear expansion, such as polyimide, as the polyamic acid heat-fired product. It is preferable. The polyimide described here is, for example, contained in a resin binder or the like used when producing a paste for forming the protective layer 18A, and specifically includes an insulating varnish.

  Since the protective layer 18A is obtained by using a material containing a thermosetting resin such as polyimide as a binder in the manufacturing method described later, the electric double layer for reflow soldering does not melt even when reheated. This is suitable for electrochemical cells such as capacitors and nonaqueous electrolyte batteries. In addition, since polyimide is excellent in chemical resistance such as an electrolytic solution, it is very suitable as a resin binder used when preparing a paste for forming the protective layer 18A.

  Moreover, in this embodiment, it is preferable that the protective layer 18 </ b> A after heating and baking has a component of the binder containing the heated and fired product of polyamic acid used at the time of formation in a range of about 40 wt% or more and less than 80 wt% of solid content. .

  In the present embodiment, by using polyimide having a low coefficient of linear expansion for the heat-fired product of polyamic acid, the fixing force between each of the current collector, the protective layer, and the electrode is further strengthened in a high temperature atmosphere. Since peeling can be prevented, an increase in contact resistance between the positive electrode 9 and the positive electrode current collector 7 is suppressed, and an effect of suppressing the internal resistance is obtained more remarkably.

  The protective layer 18A preferably employs carbon containing at least one of carbon black, graphite, carbon fiber, and carbon nanotube as the carbon used in the mixture of carbon and graphite fine particles. Although these carbons have lower electronic conductivity than graphite, it is possible to reduce the resistance value of the entire protective layer 18A when carbon having a small particle diameter enters the gap. Further, as described above, the adhesion between the positive electrode and the positive electrode current collector in a high-temperature atmosphere can be prevented from increasing, and each can be prevented from peeling off, thereby reducing the contact resistance between the positive electrode 9 and the positive electrode current collector 7. In addition, the effect of suppressing the internal resistance is more remarkably obtained.

The protective layer 18A preferably has a specific surface area of 20 m ² / g or less, which is used in a mixture of carbon and graphite fine particles. Moreover, in the protective layer 18A, the average particle size of the graphite fine particles is more preferably 10 μm or less. Graphite is known as a material having very high electrical conductivity. Further, by limiting its specific surface area and average particle size to the above range, sufficient capacity can be secured and, similarly to the above, a high temperature atmosphere. Since the adhesion between the positive electrode and the positive electrode current collector below can be prevented from increasing and the separation of each can be prevented, the contact resistance between the positive electrode 9 and the positive electrode current collector 7 can be reduced, and the internal resistance can be kept low. Is more prominently obtained.

  In the present invention, since the above-mentioned mixture of carbon and graphite fine particles is used as the protective layer 18A, a remarkable effect of reducing the resistance value of the entire protective layer 18A is obtained.

  The protective layer 18A in the present embodiment is more preferably a mixture of carbon and graphite fine particles in which the mixing ratio is in the range of 0:10 to 5: 5. By setting the mixing ratio of carbon and graphite fine particles in the above range, the above-described effect of preventing the peeling between the positive electrode and the positive electrode current collector in a high temperature atmosphere and the effect of reducing the contact resistance can be obtained more remarkably.

  Moreover, as thickness of 18 A of protective layers, it is preferable to set it as the grade of the range of 3-100 micrometers, for example. If the thickness of the protective layer 18A is 3 μm or less, pinholes may be generated in the film. On the other hand, if the thickness of the protective layer 18A exceeds 100, it is necessary to reduce the thickness of the positive electrode 9 and the negative electrode 8 due to the size and the like in the container 1A, so that the electric double layer capacitor (nonaqueous electrolyte battery) Capacity will drop. In general, the thickness of the coating film is larger than the particle size of the raw material used. Therefore, when the upper limit of the average particle size of the graphite fine particles is usually 10 μm, the thickness of the protective layer 18A is 10 μm or more. .

  Here, when the polyamic acid that is a polyimide precursor is polymerized by heating, the solvent is volatilized during the heating process, so that “su” is likely to be generated. Further, 1-2 mol from the polyamic acid that is the precursor. In addition to the above, it is easy to generate “su”. For this reason, when the polyimide obtained by heating and baking polyamic acid is used for the protective layer 18A, the above-mentioned mixture of carbon and graphite fine particles is applied once, dried and solidified, and then once more. By applying the above-mentioned mixture of carbon and graphite fine particles, a dense and stable protective layer can be formed.

(Electrolyte)
In the electric double layer capacitor (nonaqueous electrolyte battery) A of the present embodiment, the electrolyte solution (not shown) that is accommodated in the container 1A and impregnated in the positive electrode 9, the negative electrode 8, and the separator 10 is not particularly limited. For example, liquids, solids, gels, etc. can be used without any limitation. Examples of the organic solvent used in the liquid and gel electrolytes include acetonitrile (AN), diethyl ether (DEE), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), 1, Examples include 2-dimethoxyethane (DME), tetrahydrofuran (THF), propylene carbonate (PC), ethylene carbonate (EC), γ-butyrolactone (γBL), sulfolane (SL), symmetric chain sulfone, and asymmetric chain sulfone. These can be used singly or in combination of one or more.

Examples of the electrolyte contained in the liquid electrolyte and the gel electrolyte include (C ₂ H ₅ ) ₄ PBF ₄ {abbreviation: TEA}, (C ₃ H ₇ ) ₄ PBF ₄ , (CH ₃ ) (C ₂ H ₅ ) ₃ NBF ₄ {abbreviation: TEMA}, (C ₂ H ₅ ) ₄ NBF ₄ , (C ₂ H ₅ ) ₄ PPF ₆ , (C ₂ H ₅ ) ₄ PCF ₃ SO ₄ , (C ₂ H ₅ ) ₄ NPF ₆ , Lithium perchlorate (LiClO ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium borofluoride (LiBF ₄ ), lithium arsenic hexafluoride (LiAsF ₆ ), lithium trifluorometasulfonate (LiCF ₃ SO ₃ ) Bistrifluoromethylsulfonylimide lithium [LiN (CF ₃ SO ₂ ) ₂ ], thiocyanate, aluminum fluoride, lithium salt, etc. can be used. It is not limited to these.

As the gel electrolyte, a polymer electrolyte impregnated with a liquid electrolyte can be used. Polyethylene oxide, polymethyl methacrylate, and polyvinylidene fluoride are suitable as the polymer gel, but are not limited thereto.
Moreover, room temperature molten salt also called ionic liquid can also be used for electrolyte solution. In this case, an organic solvent may be mixed with the room temperature molten salt to adjust the electrical conductivity at room temperature or low temperature. The above-mentioned room temperature molten salt consists of a combination of a cation and an anion.

  Imidazolium cations, tetraalkylammonium cations, pyridinium cations, pyrazolium cations, pyrrolium cations, pyrrolinium cations, and pyrrolidinium cations are suitable as room temperature molten salts for use in capacitors. Among them, 1-ethyl-3-methylimidazolium cation (EMI +) has a particularly high electric conductivity and is suitable for an electrolytic solution of a capacitor.

The imidazolium cation includes a dialkyl imidazolium cation and a trialkyl imidazolium cation. Specifically, 1,3-dimethylimidazolium cation (DMI ⁺ ), 1-ethyl-3-methylimidazolium cation (EMI ⁺ ), 1-methyl-3-ethylimidazolium cation (MEI ⁺ ), 1- Methyl-3-butylimidazolium cation (MBI ⁺ ), 1-butyl-3-methylimidazolium cation (BMI ⁺ ), 1,2,3-trimethylimidazolium cation (TMI ⁺ ), 1,2-dimethyl-3 -Ethylimidazolium cation (DMEI ⁺ ), 1,2-dimethyl-3-propylimidazolium cation (DMPI ⁺ ), 1-butyl-2,3-dimethylimidazolium cation (BDMI ⁺ ) and the like can be used. However, it is not limited to these.

Examples of the pyridinium cation include N-ethylpyridinium cation (EP ⁺ ), Nn-butylpyridinium cation, Ns-butylpyridinium cation, Nn-propylpyridinium cation, 1-ethyl-2-methylpyridinium cation, 1 Although -n-hexyl-2-methylpyridinium cation, 1-n-butyl-4-methylpyridinium cation, 1-n-butyl-2,4-dimethylpyridinium cation, etc. can be used, it is not limited to these.

  Examples of the pyrazolium cation include 1,2-dimethylpyrazolium cation, 1-ethyl-2-methylpyrazolium cation, 1-propyl-2-methylpyrazolium cation, 1-butyl-2-methylpyrazo Examples include, but are not limited to, a lithium cation.

  Examples of the pyrrolium cation include 1,1-dimethylpyrrolium cation, 1-ethyl-1-methylpyrrolium cation, 1-methyl-1-propylpyrrolium cation, 1-butyl-1-methylpyrrolium cation and the like. However, it is not limited to these.

  Examples of the pyrrolium cation include 1,2-dimethylpyrrolium cation, 1-ethyl-2-methylpyrrolium cation, 1-propyl-2-methylpyrrolium cation, 1-butyl-2-methylpyrrolium cation and the like. However, it is not limited to these.

  Examples of pyrrolidinium cations include 1,1-dimethylpyrrolidinium cation, 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, and 1-butyl-1-methylpyrrolidinium. Examples thereof include, but are not limited to, nium cations.

Anions include AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , HF ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , CH ₃ CO ₂ ⁻ , CF ₃ CO ₂ ⁻ , C ₃ F ₇ CO ₂ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , N (CF ₃ SO ₂ ) ₂ ⁻ , N _{(C 2 F 5 SO 2)} 2 -, C (CF 3 SO 2) 3 -, N (CN) 2 - is used.

  Further, the amount of the electrolytic solution in the container 1A is not particularly limited, and the protective layer 18A of the present embodiment is obtained when a solvent having a high boiling point is used or when a solvent having a low boiling point is used. In any case, since strong binding can be maintained, it may be appropriately determined in consideration of the type of non-aqueous solvent, container size, porosity, and the like.

  According to the electric double layer capacitor (nonaqueous electrolyte battery) A of the present embodiment, in particular, between the positive electrode 9 and the positive electrode current collector 7 and the container bottom 11, Further, a protective layer 18A composed of a mixture of carbon and graphite fine particles is provided, and the positive electrode 9 and the positive electrode current collector 7 are electrically connected via the protective layer 18A. By using the above material for the protective layer 18A interposed between the positive electrode 9 and the positive electrode current collector 7, the adhesion between the current collector, the protective layer and the electrode in a high temperature environment is increased, and the heat resistance Therefore, it is possible to prevent electrode peeling or the like from occurring even when continuously exposed to a severe high-temperature atmosphere in the reflow soldering process. Therefore, it is possible to suppress an increase in the contact resistance between the positive electrode 9 and the positive electrode current collector 7, and thus it is possible to suppress the internal resistance as an electrochemical cell to a low level, and the charge / discharge efficiency is high, and the heat resistance and An electrochemical cell having excellent electrical characteristics can be provided.

  In the present invention, as the positive electrode current collector 7 and the negative electrode current collector 6, in addition to the materials described above, for example, a foam metal is used in addition to a current collector using an aluminum vapor deposition layer as a support material. Conventionally used current collector materials such as current collector materials (see, for example, Japanese Patent Application Laid-Open No. 2006-164947 and Japanese Patent No. 318853 proposed by the present applicant) can be used without any limitation. . And in this invention, even when it is a case where the positive electrode collector which consists of such a material is used, by providing the protective layer 18A similarly to the above, in the environment exposed continuously to severe high temperature atmosphere In addition, since electrode peeling and the like can be prevented and the internal resistance can be suppressed, an electrochemical cell having high charge / discharge efficiency and excellent heat resistance and electrical characteristics can be realized.

"Production method"
Next, the manufacturing method of the electric double layer capacitor (nonaqueous electrolyte battery) which is the electrochemical cell of this invention is demonstrated.
The manufacturing method of the electric double layer capacitor which is a preferable aspect of the present embodiment is a method of manufacturing the electric double layer capacitor A having the above-described configuration, and the positive electrode is formed on the positive electrode current collector 7 formed on the container bottom 11 in the container 1A. After forming 9, the separator 10 is formed on the positive electrode 9, and then the negative electrode 8 is formed so as to be connected to the separator 10, thereby connecting the positive electrode 9 and the negative electrode 8 through the separator 10, The “electrode placement step” for forming the negative electrode current collector 6 on the negative electrode 8 side in the container 1A, the “injection step” for injecting the electrolyte into the container 1A, and the lid 4 on the negative electrode are overlaid. The “sealing process” in which the opening 1a of 1A is covered with the lid 4 and sealed is provided.

Further, in the electrode arrangement process of the present embodiment, as shown in the example shown in FIG. 1, after the positive electrode 9 is formed on the positive electrode current collector 7, the separator 10 and the negative electrode 8 are sequentially stacked on the positive electrode 9. The positive electrode 9 and the negative electrode 8 are disposed to face each other with the separator 10 interposed therebetween, and the negative electrode current collector 6 is formed on the negative electrode 8 side in the container 1A.
And the above-mentioned electrode arrangement | positioning process is further between the positive electrode 9, the positive electrode electrical power collector 7, and the container bottom part 11 from the heat-baking thing of polyamic acid as mentioned above, and the mixture of carbon and the fine particle of graphite. The method includes a step of forming a good electric protective layer 18A.
In addition, in the manufacturing method of the electric double layer capacitor (nonaqueous electrolyte battery) which is the electrochemical cell of this invention, except the point provided with the process of forming 18 A of protective layers included in the electrode arrangement | positioning process as said method. The same conditions and procedures as in the past can be employed.

  In this embodiment, first, a base container (container) 1A provided with a positive electrode current collector 7 (including an external terminal 70) and a negative electrode current collector 6 (including an external terminal 60) is prepared. Next, the seal ring 3 is joined to the peripheral edge of the opening of the container 1 </ b> A, that is, the upper end surface 12 a of the container wall 12 by the brazing material 5. Next, nickel plating (not shown) is applied so as to cover the seal ring 3, the brazing material 5, and the upper end surface 12a. Examples of the nickel plating include electrolytic nickel plating and electroless nickel plating.

  Specifically, first, the tungsten paste is printed on two ceramic green sheets and then sintered, whereby the external terminal 70 and the external terminal 60 are placed on the container bottom 11 and the container wall 12 of the concave container 1A. A positive electrode current collector 7 and a negative electrode current collector 6 are formed. At this time, the seal ring 3 made of Kovar having a thermal expansion coefficient close to that of the ceramic is joined to the container wall 12 with a brazing material 5 made of silver brazing, gold brazing, or the like. Moreover, since the bottom surfaces of the negative electrode current collector 6 and the positive electrode current collector 7 are reflow soldered to the circuit board, it is preferable to perform nickel plating or gold plating in advance. When such a plating method is used, if the method using an electrolytic plating bath is adopted, the entire surface of the brazing material 5 and the seal ring 3 is also plated in addition to the positive electrode current collector 7 and the negative electrode current collector 6. The

Next, in the electrode arrangement process of the present embodiment, as shown in FIG. 1, a polyamic acid fired product, specifically polyimide, is formed on the positive electrode current collector 7 formed on the container bottom 11 of the container 1A. A protective layer 18A is formed by applying a paste made of a mixture of carbon and graphite fine particles, followed by heat curing. At this time, since the paste before curing contains a lot of air and may cause pinholes, it can be defoamed using a vacuum (vacuum) device or a planetary stirring and defoaming machine. After that, it is preferable to fill and use the container without touching the atmosphere. Further, when applying such a paste, it is applied using a dispenser or the like so as to completely cover the positive electrode current collector 7.
Next, the positive electrode 9 is placed on the paste applied in the above procedure, and is heated and cured by a conventionally known method. At this time, if the paste is heat-cured in a vacuum, the solvent, air, and moisture generated by the polymerization in the paste are released and the dense protective layer 18A can be formed. By the process of performing such heating, removal of the solvent and dehydration ring closure reaction (imidization) proceed.

  In the present invention, in applying the paste for forming the protective layer 18A as described above, first, a binder containing polyimide and a mixture of fine particles of carbon and graphite are mixed and then solidified after solidification. The dilution solvent can be added in an addition amount that is less than 3 times the above, and the conditions for adjusting the paste can be obtained.

  Here, examples of the binder containing a heat-fired product of polyamic acid used for the paste for forming the protective layer 18A include thermosetting polyimide, polyamideimide resin, and polyimide precursor mixed solution. Here, the “polyamic acid” described in the present invention is “an intermediate of thermal condensation composed of an acid anhydride and a diamine”.

In the present invention, it is preferable that impurities contained in carbon and graphite are removed, and it is particularly preferable that fiber metal such as Fe is suppressed to 100 ppm or less. In the X-ray diffraction (XRD) analysis of graphite and carbon, the central value of the lattice spacing (d ₀₀₂ ) of the (002) plane is preferably in the range of 0.30 nm to 0.40 nm, and 0.33 nm to 0 A range of .38 nm is more preferred.
Further, as the fine particles of graphite used in the present invention, for example, those subjected to expansion treatment can be used.

  In the present embodiment, although detailed illustration is omitted, first, only the protective layer 18A is formed by heat curing, and then a conductive adhesive is applied thereon to dispose the positive electrode 9, and then conductive bonding is performed. A method of bonding the protective layer 18A and the positive electrode 9 by forming an adhesive layer (not shown) by curing the agent may be employed. As the conductive adhesive used here, the same material as the adhesive layer 13 for bonding the negative electrode 8 and the lid 4 described above can be used.

  In addition, the film thickness of 18 A of protective layers can be adjusted with the application quantity and viscosity of a paste. Here, the high-viscosity paste becomes a mountain shape when applied with a dispenser, and a uniform film thickness cannot be obtained. Therefore, it is diluted with a solvent such as N-methyl-2pyrrolidone (abbreviation: NMP). May be. The viscosity after dilution is preferably about 0.05 to 50 Ps · s. By making the paste low viscosity, the shape after application becomes flat and the protective layer 18A having a uniform thickness is formed. be able to.

  Next, after placing the separator 10 on the positive electrode 9, an arbitrary amount of electrolyte is injected into the container 1A (injection step). In this case, the injection amount of the electrolytic solution is determined in consideration of the type of the nonaqueous solvent, the container size, the porosity, and the like. Here, when a glass fiber laminate is used as the separator 10, the separator 10 may be heated in advance before injecting the electrolytic solution. By heating the separator 10, the adsorbed water and various organic substances on the surface of the glass fiber laminate can be removed by oxidation or volatilization, so that the separator 10 is impregnated more rapidly and rapidly.

  Next, a conductive adhesive is applied to the inner surface side of the lid 4, that is, the surface that becomes the container 1 </ b> A side to form the adhesive layer 13, and the negative electrode 8 is adhered to the inner surface side of the lid 4 by the adhesive layer 13. Then, after the adhesive layer 13 is cured, the lid 4 to which the negative electrode 8 is bonded is placed on the seal ring 3 provided in the opening of the container 1 </ b> A so that the negative electrode 8 contacts the separator 10. Alternatively, after the negative electrode 8 is placed in contact with the separator 10, the lid 4 provided with the adhesive layer 13 is placed on the seal ring 30 in advance to bond between the negative electrode 8 and the lid 4 ( Electrode placement process and encapsulation process).

  Next, the lid 4 and the seal ring 3 are welded, and the inside of the container 1A is sealed with the lid 4 and the container 1A (enclosing step). At this time, the method for welding the lid 4 and the seal ring 3 is not particularly limited, and examples thereof include seam welding by resistance welding. When such seam welding is used, the nickel plating of the lid 4 and the nickel plating covering the seal ring 3 are welded.

The electric double layer capacitor (nonaqueous electrolyte battery) A of this embodiment is obtained by the procedure as described above.
In the above procedure, the method of sealing the lid 4 and the container 1A is described as a method of welding the nickel plating of the lid 4 and the nickel plating of the seal ring 3, but this is not a limitation. For example, The lid 4 and the seal ring 3 may be joined directly by a brazing material. As the brazing material in this case, the same material as the brazing material 5 used between the container 1A and the seal ring 3 as described above can be used.

  In the present invention, in particular, the process of forming the protective layer in the electrode placement process is performed under appropriate conditions and procedures as described above, so that the product is continuously put in a high-temperature atmosphere such as a reflow soldering apparatus. Even when the exposure is repeated, the adhesion between the positive electrode current collector 7, the protective layer 18A, and the positive electrode 9 is increased. Therefore, no peeling occurs between the positive electrode 9 and the positive electrode current collector 7, and an increase in contact resistance and internal resistance associated therewith is prevented, and the electric double layer capacitor (non-aqueous electrolyte) having excellent charge / discharge efficiency is prevented. Battery) A can be manufactured. Moreover, according to the manufacturing method of this invention, it is excellent also in the handleability in a process and a yield is high.

  In the present embodiment, as described above, an example is described in which the protective layer 18A is formed on the container bottom 11 and the positive electrode current collector 7 in the container 1A made of a ceramic material, and the positive electrode 9 is formed thereon. However, the present invention is not limited to this. For example, a protective layer composed of a heat-fired polyamic acid as described above and a mixture of fine particles of carbon and graphite is formed on a positive electrode current collector, and a positive electrode is formed on the protective layer. It is also possible to employ a method for producing an electrochemical cell (electric double layer capacitor, nonaqueous electrolyte battery) by assembling in a container. When such a method is adopted, detailed illustration is omitted, but for example, a method described below can be employed.

First, an expanded metal that is a metal foil made of aluminum or the like is prepared as a current collector (positive electrode current collector). Here, as the metal foil, an etching metal, a punching metal, an expanded metal, or the like can be used, and an expanded metal is particularly preferable. And after apply | coating the electrically conductive paste for forming the above protective layers on this, it dries at the temperature of about 200-300 degreeC. Next, the current collector coated with the conductive paste is pressed by roll rolling to produce a sheet-like member having a protective layer formed on the positive electrode current collector.
Next, a slurry containing an active material for forming a positive electrode as described above is further applied on the protective layer formed on the sheet-like member, and then dried to pressed under the same conditions as described above. Thus, a sheet-like member composed of the positive electrode current collector, the protective layer, and the positive electrode is obtained. Alternatively, a sheet-like member composed of a positive electrode current collector, a protective layer, and a positive electrode as described above can also be produced by a method of adhering an electrode sheet prepared in advance on a protective layer formed on a sheet-like member. Is possible.

  Then, the sheet-like member as described above is appropriately cut into electrode sizes, and after the leads and tabs are attached by an ultrasonic welding method, the above-described sheet-like member, separator, and negative electrode are sequentially combined and placed in a container. Then, after putting electrolyte solution in a container and degassing an internal reaction gas, an electrochemical cell can be manufactured by sealing with a lid.

  In order to sequentially combine the sheet-like member, the separator, and the negative electrode as described above, the sheet-like member may be formed in advance as a long member and wound as necessary. In such a case, the structure of the sheet-like member in an electrochemical cell having a configuration in which electrodes are wound in a container, for example, a structure described in Japanese Patent No. 3405380, Japanese Patent No. 4448963, etc. It is possible to apply. In addition, for example, the structure of the sheet-like member can be applied to a structure in which electrodes are stacked in multiple layers as described in JP-A-2005-149882.

  When a lead is attached as an external terminal to the sheet-like member, for example, a stainless steel case is used as a container, and a seal made of PPS (polyphenylene sulfide) or the like is provided between the stainless steel case and the lead. By providing the member, it is possible to improve the sealing performance of the electrochemical cell. In addition, for joining the stainless steel container and the lid in such a case, a method of joining by welding or a seal member can be employed. As an example of the stainless steel case in this case, for example, a case composed of a base container and a flat bottom plate as described in JP-A-2005-183700 is cited. Further, as described in Japanese Patent Application Laid-Open No. 2011-210900 and Japanese Patent Application Laid-Open No. 2011-228409, a flat plate provided with a deep-bottom container and a through-hole for leading a lead (external terminal) out of the container. The sheet-like member can also be applied in the case of including a stainless steel case composed of a lid.

  Furthermore, the configuration of the sheet-like member can be applied to a coin-type or button-type non-aqueous electrolyte battery and an electric double layer capacitor.

[Second Embodiment]
A nonaqueous electrolyte battery and an electric double layer capacitor according to a second embodiment of the electrochemical cell of the present invention will be described below with reference to the drawings. In the following description, the same reference numerals are assigned to the same components as those of the electric double layer capacitor (nonaqueous electrolyte battery) A in the first embodiment described above, and detailed description thereof is omitted.

  The electric double layer capacitor (nonaqueous electrolyte battery) B according to the second embodiment of the present invention shown in FIG. 2 is similar to the electric double layer capacitor A according to the first embodiment, and includes a positive electrode current collector 7 and a negative electrode current collector. Body 6, positive electrode 9, negative electrode 8, separator 10 that separates positive electrode 9 and negative electrode 8, electrolyte solution (not shown), and base container that stores positive electrode 9, negative electrode 8, separator 10, and electrolyte solution ( (Container) 1B and a lid 4 for sealing the container 1B, and can be charged and discharged through the external terminals 70 and 60 electrically connected to the positive electrode current collector 7 and the negative electrode current collector 6. It is made into the composition.

  Furthermore, in the electric double layer capacitor B of the present embodiment, the container 1B includes a container bottom part 11, a container wall part 12, and a spacer 14 disposed between the container bottom part 11 and the container wall part 12, It has a groove 15 through which the spacer 14 penetrates. In the electric double layer capacitor B of the present embodiment, the positive electrode current collector 7 is formed between the container bottom part 11 and the spacer 14 and the surface exposed to the groove part 15 is obtained by heating and baking the polyamic acid. The positive electrode 9 and the positive electrode current collector 7 are electrically connected to each other through the protective layer 10A. The positive electrode 9 and the positive electrode current collector 7 are covered with a protective layer 18B made of a mixture of fine particles of carbon and graphite. This is different from the electric double layer capacitor A in the first embodiment.

  In the conventional electrochemical cell, the electrolyte solution may permeate from the end of the protective layer and reach the positive electrode current collector due to its structure. For this reason, in this embodiment, as shown in FIG. 2, a groove 15 is formed in the spacer 14 provided in the vicinity of the bottom of the base container (container) 1B, and protection is provided by embedding a conductive adhesive in the groove 15. A method of forming the layer 18B is employed. Thereby, since the distance from the upper end part of the protective layer 18B to the positive electrode current collector 7 is increased, the possibility of the electrolyte penetrating to reach the positive electrode current collector 7 is surely reduced. The groove 15 may adopt a configuration in which a spacer 14 made of a ceramic sheet is added between the container bottom 11 and the container wall 12.

  Moreover, also in the method for manufacturing the electric double layer capacitor B of the present embodiment, as an electrode arrangement process, the polyamic acid is heated in the groove portion 15 penetrating the spacer 14 provided between the positive electrode 9 and the positive electrode current collector 7. A method including a step of forming a good-electricity protective layer 18B made of a fired product and a mixture of fine particles of carbon and graphite can be employed. The conditions and procedures for forming the protective layer 18B can be the same as those in the first embodiment.

  Similar to the electric double layer capacitor A of the first embodiment, the electric double layer capacitor B of the present embodiment has the above-described configuration in the groove portion 15 penetrating the spacer 14 provided between the positive electrode 9 and the positive electrode current collector 7. The protective layer 18B is provided. As a result, even when the product is repeatedly exposed to a high temperature atmosphere as in a reflow soldering apparatus (reflow furnace), the solid state between each of the positive electrode current collector 7, the protective layer 18B, and the positive electrode 9 can be reduced. The wearing power is increased. Therefore, peeling does not occur between the positive electrode 9 and the positive electrode current collector 7, and it is possible to suppress an increase in contact resistance with this, and thus it is possible to keep the internal resistance as an electrochemical cell low. Thus, an electrochemical cell having high charge / discharge efficiency and excellent heat resistance and electrical characteristics can be realized. Furthermore, since the electric double layer capacitor B of the present embodiment has a structure in which the protective layer 18B is provided in the groove portion 15, the possibility that the electrolyte solution penetrates to reach the positive electrode current collector 7 is reduced, which is favorable. Advantageous electrical characteristics can be maintained.

[Third Embodiment]
A nonaqueous electrolyte battery and an electric double layer capacitor which are the third embodiment of the electrochemical cell of the present invention will be described below with reference to FIG. In addition, in the following description, about the structure which is common with the electric double layer capacitor (nonaqueous electrolyte battery) A and B in 1st, 2nd embodiment mentioned above, while giving the same code | symbol, the detailed description is abbreviate | omitted. .

  The electric double layer capacitor C of the third embodiment of the present invention shown in FIG. 3 is similar to the electric double layer capacitors A and B of the first and second embodiments, and has a positive current collector 17 and a negative current collector 16. A base container (container) that houses the positive electrode 9, the negative electrode 8, the separator 10 that separates the positive electrode 9 and the negative electrode 8, the electrolyte solution (not shown), the positive electrode 9, the negative electrode 8, the separator 10, and the electrolyte solution. 1C and a lid 4 that seals the container 1C, and can be charged and discharged through the external terminals 70 and 60 that are electrically connected to the positive electrode current collector 17 and the negative electrode current collector 6 It is said that.

  In the electric double layer capacitor C of the present embodiment, the positive electrode current collector 17 that is longer than the positive electrode 9 is provided on the container bottom 11C of the container 1C, and the positive electrode current collector 17 is connected to the container 1C. Is extended between the container bottom 11C and the container wall 12C, and is electrically connected to the external terminal 70. Furthermore, the electric double layer capacitor C is provided with a protective layer 18C made of the same material as the protective layers 18A and 18B in the first and second embodiments on the positive electrode current collector 17 having the above-described configuration. The electric body 17 and the positive electrode 9 are joined. Further, in the present embodiment, although detailed illustration in FIG. 3 is omitted, an aluminum layer for protecting the positive electrode current collector 17 is provided on the positive electrode current collector 17 made of tungsten or the like. .

In the present embodiment, the negative electrode current collector 16 is bonded to the lid 4 by the adhesive layer 13, and the peripheral edge of the negative electrode current collector 16 is in contact with the seal ring 3, so that the negative electrode current collector 16 and the external terminal 60 are Are electrically connected.
Similarly to the first and second embodiments, the external terminals 60 and 70 are formed along the outer surface of the container 1C, and the external terminal 60 is formed on the bottom surface of the container bottom 11C along the outer wall surface of the container wall 12C. The external terminal 70 extends to the bottom surface of the container bottom portion 11C along the side end surface of the container bottom portion 11C.

  As described above, according to the electric double layer capacitor C of the present embodiment, a configuration in which the protective layer 18C made of the same material as the protective layers 18A and 18B of the first and second embodiments is provided. Accordingly, as described above, even when the product is continuously exposed to a high temperature atmosphere, the adhesion between the positive electrode current collector 17, the protective layer 18C, and the positive electrode 9 is increased, and the positive electrode 9 and the positive electrode 9 Separation does not occur between the current collector 17 and an increase in contact resistance can be suppressed. Therefore, the internal resistance can be kept low, and the electric double layer capacitor C having high charge / discharge efficiency and excellent heat resistance and electrical characteristics can be realized.

[Fourth Embodiment]
A nonaqueous electrolyte battery and an electric double layer capacitor which are the fourth embodiment of the electrochemical cell of the present invention will be described below with reference to FIG.
The electric double layer capacitor D of the fourth embodiment of the present invention shown in FIG. 4 has a positive electrode current collector 27, a negative electrode current collector 26, and a positive electrode similarly to the electric double layer capacitors A to C of the above embodiments. 9, a negative electrode 8, a separator 10 that separates the positive electrode 9 and the negative electrode 8, an electrolyte solution (not shown), a base container (container) 1D that stores the positive electrode 9, the negative electrode 8, the separator 10, and the electrolyte solution, It is composed of a lid 4 that seals the container 1D, and can be charged and discharged through the external terminals 71 and 61 that are electrically connected to the positive electrode current collector 27 and the negative electrode current collector 26. Yes.

  Further, in the electric double layer capacitor D of the present embodiment, the positive electrode current collector 27 and the external terminal 70 are electrically connected via a via 31 passing through a through hole formed in the container bottom 11D forming the container 1D. ing. In the present embodiment, the negative electrode current collector 26 is bonded to the lid 4 by the adhesive layer 13 as in the third embodiment. Then, the peripheral edge of the negative electrode current collector 26 is in contact with the seal ring 3, so that the negative electrode current collector 26 and the external terminal 60 are electrically connected via the vias 32 that pass through the through holes formed in the container wall 12 </ b> D. Connected configuration.

Further, in the electric double layer capacitor D, the positive electrode current collector 17 is provided on the container bottom 11D of the container 1D, and a protective layer 18D made of the same material as the protective layers 18A to 18C of the above embodiments is provided thereon. By being provided, the positive electrode current collector 27 and the positive electrode 9 are joined. Further, the electric double layer capacitor D of the present embodiment is not shown in detail in FIG. 4, but like the electric double layer capacitor C of the third embodiment, the positive electrode current collector 27 made of tungsten or the like is used. On top of this, an aluminum layer for protecting the positive electrode current collector 27 is provided.
Note that the via 31 and the via 32 can also be formed of a tungsten material, like the current collectors.

  According to the electric double layer capacitor D of the present embodiment, a configuration in which the protective layer 18D having the above configuration is provided is adopted. Thereby, similarly to the electric double layer capacitors A to C of the above embodiments, each of the positive electrode current collector 27, the protective layer 18D, and the positive electrode 9 can be used even when the product is continuously exposed to a high temperature atmosphere. The adhesion force between the positive electrode 9 and the positive electrode current collector 27 is not peeled off, and the increase in contact resistance can be suppressed. Accordingly, it is possible to realize the electric double layer capacitor D that can keep the internal resistance low, have high charge / discharge efficiency, and have excellent heat resistance and electrical characteristics.

[Fifth Embodiment]
A nonaqueous electrolyte battery and an electric double layer capacitor which are the fifth embodiment of the electrochemical cell of the present invention will be described below with reference to FIG.
The electric double layer capacitor E of the fifth embodiment of the present invention shown in FIG. 5 separates the positive electrode current collector 37, the negative electrode current collector 36, the positive electrode 9, the negative electrode 8, the positive electrode 9 and the negative electrode 8. And a base container (container) 1E for housing the positive electrode 9, the negative electrode 8, the separator 10, and the electrolytic solution, and a lid 4 for sealing the container 1E. Charging / discharging can be performed via the external terminals 72 and 62 electrically connected to the electric body 37 and the negative electrode current collector 36.

  In the electric double layer capacitor E, the positive electrode current collector 37 and the external terminal 72 are electrically connected through a via 41 that passes through an L-shaped through hole formed in the container bottom 11E forming the container 1E. Has been. In the present embodiment, the negative electrode current collector 36 is bonded to the lid 4 by the adhesive layer 13 as in the third and fourth embodiments. The peripheral edge of the negative electrode current collector 36 is in contact with the seal ring 3 so that the negative electrode current collector 36 and the external terminal 62 pass through the vertical through-hole formed in the container wall portion 12E, and the container It is configured to be electrically connected via a via 42b formed so as to be embedded in the bottom 11E.

Furthermore, in the electric double layer capacitor E, the positive electrode current collector 37 is provided on the container bottom 11E of the container 1E, and the protective layer 18E made of the same material as that of each of the above embodiments is provided thereon. The current collector 37 and the positive electrode 9 are joined. Further, the electric double layer capacitor E of the present embodiment is not shown in detail in FIG. 5, but like the electric double layer capacitors C and D described above, on the positive electrode current collector 37 made of tungsten or the like. An aluminum layer for protecting the positive electrode current collector 37 is provided.
Note that the via 41 and the via 42 can also be formed of a tungsten material, like the current collectors.

  According to the electric double layer capacitor E, the configuration in which the protective layer 18E having the above configuration is provided is adopted. Therefore, the products are continuously put in a high-temperature atmosphere in the same manner as the electric double layer capacitors A to D in the above embodiments. Even when repeated exposure to the positive electrode current collector 37, the adhesion between the positive electrode current collector 37, the protective layer 18E and the positive electrode 9 is increased, and no peeling occurs between the positive electrode 9 and the positive electrode current collector 37. It is possible to suppress an increase in contact resistance. Accordingly, it is possible to realize the electric double layer capacitor E that can keep the internal resistance low, have high charge / discharge efficiency, and have excellent heat resistance and electrical characteristics.

[Sixth Embodiment]
A nonaqueous electrolyte battery and an electric double layer capacitor, which are the sixth embodiment of the electrochemical cell of the present invention, will be described below with reference to FIGS. 6 (a) and 6 (b).
The electric double layer capacitor G of the sixth embodiment of the present invention shown in FIG. 6A includes a positive electrode 9, a negative electrode 8, a separator 10 that separates the positive electrode 9 and the negative electrode 8, an electrolyte solution (not shown), Each comprising a base container (container) 1G for accommodating the positive electrode 9, the negative electrode 8, the separator 10 and the electrolyte, and a lid 4 for sealing the container 1G, and electrically connected to the positive electrode 9 and the negative electrode 8. The external terminals 72G and 60G can be charged and discharged.

  In the electric double layer capacitor G, the positive electrode 9 and the external terminal 72G are electrically connected via a via 53 and an internal wiring 54 that pass through a through hole formed in the container bottom 11G forming the container 1G. . In the present embodiment, the negative electrode 8 and the external terminal 60 </ b> G are configured to be electrically connected via the brazing material 5, the seal ring 3, the lid 4, and the adhesive layer 13.

  Further, in the electric double layer capacitor G, the upper surface of the via 53 is exposed on the container bottom 11G of the container 1G, and the protective layer 18G made of the same material as that of each of the above embodiments is formed on the upper surface of the via 53 and the container. By being provided so as to continuously cover the bottom 11G, the upper surface of the via 53 and the positive electrode 9 are electrically connected. Further, the electric double layer capacitor G of the present embodiment can be configured such that the protective layer 18G is directly formed on the container bottom 11G where the upper surface of the via 53 is exposed, but is not limited thereto. For example, although detailed illustration is omitted in FIG. 6A, the upper surface of the via 53 is continuously covered so as to continuously cover the upper surface of the via 53 made of tungsten or the like and the container bottom 11G made of ceramic. A configuration in which an aluminum layer for protecting the film is provided and a protective layer 18G is formed on the aluminum layer may be employed. Thus, by providing an aluminum layer (not shown), it is possible to prevent the upper surface of the via 53 from coming into contact with the electrolytic solution.

  Further, as shown in the cross-sectional view of FIG. 6B, a plurality of vias 53 and a plurality of internal wirings 54 are formed, and each of the vias 53 is connected to a different internal wiring 54. In the example shown in FIG. 6B, the two internal wirings 54 are provided so as to branch into a substantially inverted U shape in plan view, and one end side of each of the two internal wirings 54 is connected to the via 53. However, the present invention is not limited to this, and a configuration including more vias and internal wirings may be employed.

When forming the internal wiring 54 as shown in FIGS. 6A and 6B, for example, a through hole having an L-shaped cross section is formed in the container bottom 11G, and the via 53 and the internal are formed inside the through hole. In addition to the method of forming the wiring 54, it is possible to adopt a method in which the container bottom portion 11G has a ceramic laminated structure and internal wiring is formed between the layers.
The via 53 and the internal wiring 54 can be formed from a tungsten material.

  According to the electric double layer capacitor G, since the configuration in which the protective layer 18G having the above configuration is provided is employed, as in each of the above embodiments, even when the product is repeatedly exposed to a high temperature atmosphere. The adhesion between the upper surface of the via 53, the protective layer 18G, and the positive electrode 9 is enhanced, and no peeling occurs between the positive electrode 9 and the upper surface of the via 53, thereby suppressing an increase in contact resistance. . Accordingly, it is possible to realize the electric double layer capacitor G that can keep the internal resistance low, have high charge / discharge efficiency, and have excellent heat resistance and electrical characteristics.

  Further, by exposing only the top surface of the via on the bottom of the container and continuously covering the bottom of the container with a protective layer, corrosion of the via due to contact between the electrolytic solution and the top surface of the via can be prevented. Furthermore, by providing multiple combinations of vias and internal wiring, even if one via is corroded and the corrosion reaches the internal wiring, the combination of other vias and internal wiring Thus, the electrical connection between the positive electrode and the external terminal can be maintained. Therefore, the electric double layer capacitor G having very excellent corrosion resistance can be realized.

[Seventh Embodiment]
A nonaqueous electrolyte battery and an electric double layer capacitor which are the seventh embodiment of the electrochemical cell of the present invention will be described below with reference to FIG.
The electric double layer capacitor F of the seventh embodiment of the present invention shown in FIG. 7 separates the positive electrode current collector 47, the negative electrode current collector 46, the positive electrode 9, the negative electrode 8, the positive electrode 9 and the negative electrode 8. Separator 10, an electrolyte solution (not shown), a container lid 12 </ b> F having a storage space for storing the positive electrode 9, the negative electrode 8, the separator 10, and the electrolyte solution, and a container 1 </ b> F including a container bottom 11 </ b> F. Charging / discharging is possible through the external terminals 73 and 63 that are electrically connected to the current collector 47 and the negative electrode current collector 46.

In the electric double layer capacitor F, the positive electrode current collector 47 and the external terminal 73 are electrically connected via a via 51 passing through a through hole formed in the container bottom 11F. In the present embodiment, the negative electrode current collector 46 formed along the storage space of the container lid 12F and adhered to the inner surface of the container lid 12F by the adhesive layer 43, and the external terminal 63 include the seal ring 3. And it is set as the structure electrically connected through the via 52 which passes along the through-hole formed in the container bottom part 11F. Further, in the electric double layer capacitor F, the positive electrode current collector 47 is provided on the container bottom 11F, and the protective layer 18F made of the same material as that of each of the above embodiments is provided thereon, whereby the positive electrode current collector is provided. 47 and the positive electrode 9 are joined. Further, although the detailed illustration in FIG. 6 is omitted in the electric double layer capacitor F of the present embodiment, the positive electrode current collector 47 is protected on the positive electrode current collector 47 made of tungsten or the like as described above. An aluminum layer is provided.
Note that the via 51 and the via 52 can also be formed of a tungsten material, like the current collectors.

  According to the electric double layer capacitor F, since the configuration in which the protective layer 18F having the above configuration is provided is employed, as in the above embodiments, even when the product is continuously exposed to a high temperature atmosphere. In addition, the adhesion force between each of the positive electrode current collector 47, the protective layer 18F, and the positive electrode 9 is increased, and peeling between the positive electrode 9 and the positive electrode current collector 47 does not occur, and an increase in contact resistance can be suppressed. . Accordingly, it is possible to realize the electric double layer capacitor F that can keep the internal resistance low, have high charge / discharge efficiency, and have excellent heat resistance and electrical characteristics.

  Next, an Example and a comparative example are shown and this invention is demonstrated further more concretely. The scope of the present invention is not limited by this example, and the electrochemical cell and the method for producing the same according to the present invention can be implemented with appropriate modifications without departing from the scope of the present invention. It is.

[Example 1]
In Example 1, first, an electric double layer capacitor having a rectangular shape in plan view as shown in FIG. 1 was produced as an electrochemical cell.
At this time, a ceramic body made of alumina was prepared as the base container (container), the outer shape in plan view was 5 × 3 mm, and the thickness from the bottom of the container to the top of the lid was 1 mm.
Further, by printing a tungsten material on the container bottom 11 and the container wall 12 made of ceramic, the negative electrode current collector 6 including the external terminals 60 and the positive electrode current collector 7 including the external terminals 70 are formed, and then sintered. I concluded.
Next, the container wall 12 and the seal ring 3 made of Kovar were joined with the brazing material 5. Further, the exposed portions of these metals were nickel-plated and then gold-plated.

  Next, as an electrode, graphite and polytetrafluoroethylene were mixed with commercial activated carbon in a ratio of 9: 1: 1 and rolled to obtain an activated carbon sheet having a thickness of 0.2 mm. The positive electrode 9 and the negative electrode 8 were punched into a square shape in a plan view of 1.5 mm.

Next, in preparing the protective layer, a paste made of a heat-fired product of polyamic acid and a mixture of fine particles of carbon and graphite was prepared. First, as the binder, a commercially available binder made of a polyimide precursor mixed solution containing thermosetting polyimide that is a fired product of polyamic acid was prepared. Moreover, commercially available carbon black was prepared as carbon. Commercial graphite was also prepared as graphite fine particles.
And after mixing carbon black and graphite on the conditions shown in following Table 1 using the mortar made from agate, a binder is added to this mixture by the compounding ratio shown to Experimental example 1-7 of following Table 1 At the same time, a commercially available solvent was added and sufficiently kneaded in a time of at least 5 minutes, and further, defoaming was performed using a planetary stirring defoamer to prepare a paste.

A paste was prepared in the same manner as described above except that the mixing ratio of the solvent in the paste was changed under the conditions shown in Experimental Examples 2 and 8 to 10 in Table 2 below.
Moreover, it is the same as the above except that the blending ratio of graphite in the whole paste and the blending ratio of graphite in the mixture of carbon and graphite were changed under the conditions shown in Experimental Examples 11 to 17 shown in Table 3 below. A paste was prepared.
Further, except that the average particle size (D50), particle size D90, specific surface area (BET), and oil absorption of graphite contained in the paste were changed under the conditions shown in Experimental Examples 18 to 27 shown in Table 4 below. A paste was prepared in the same manner as described above.

  And after apply | coating each paste obtained in the said procedure on the positive electrode collector 7 and the container bottom part 11, the positive electrode 9 was arrange | positioned and it was hardened in nitrogen stream at the heating temperature of 250 degreeC after that. The thickness of the protective layer 18A after curing was about 10 μm.

  Next, a plate material obtained by nickel plating on 0.1 mm thick Kovar was punched into a size of 4.5 × 2.5 mm in a plan view, and the lid 4 was produced. The lid 4 is nickel-plated on the front and back surfaces, but has no nickel plating on the side surfaces. Furthermore, after applying a general-purpose conductive adhesive in this field on the lid 4 and installing the negative electrode 8 thereon, it is cured in a nitrogen stream (inert gas atmosphere) at a heating temperature of 250 ° C. Thus, the negative electrode 8 was bonded to the lid 4 by forming the adhesive layer 13.

Next, a separator made of glass fiber is placed on the positive electrode 9 as the separator 10, and then an electrolytic solution in which 1 mol / L of (C ₂ H ₅ ) ₄ NBF ₄ is dissolved in propylene carbonate (PC) is used as a container. 2 μL was injected into 1A.
Next, the lid 4 is placed on the seal ring 3, and arbitrary two points on the lid 4 are temporarily fixed by spot resistance welding, and then the lid 4 is entirely attached using a resistance seam welding apparatus having two roller electrodes. The circumference was welded in a nitrogen atmosphere to produce the electric double layer capacitor of this example.

  And regarding the electric double layer capacitor of Experimental Examples 1-7 produced by changing the blending ratio of the binder (solid content) under the above conditions, a heat treatment corresponding to reflow soldering was performed under the conditions shown in the graph of FIG. After a total of 10 times, the internal resistance value was measured, and the result is shown in the graph of FIG. At this time, the internal resistance value was measured at an alternating current of 1 KHz by using the R function using an LCR meter. As detailed heat treatment conditions at this time, as shown in FIG. 8 (b), at a temperature measured on the upper surface of the product (electric double layer capacitor) main body, a time of 217 ° C. or more: 80 seconds or less, 250 ° C. or more Time: 20 seconds or less, peak temperature: 260 ° C.

  In addition, regarding the electric double layer capacitors of Experimental Examples 2 and 8 to 10 manufactured by changing the mixing ratio of the solvent in the paste under the above conditions, heat treatment corresponding to reflow soldering was performed 10 times in the same manner as described above. Thereafter, the internal resistance value was measured, and the result is shown in the graph of FIG.

  In addition, the electric double layer capacitors of Experimental Examples 11 to 17 manufactured by changing the blending ratio of graphite in the entire paste and the blending ratio of graphite in the mixture of carbon and graphite under the above-described conditions were also the same as described above. The internal resistance value after performing a total of 10 heat treatments corresponding to reflow soldering was measured, and the results are shown in the graphs of FIGS.

  Further, regarding the electric double layer capacitors of Experimental Examples 18 to 27 manufactured by changing the average particle size (D50), particle size (D90), specific surface area (BET), and oil absorption of graphite contained in the paste under the above conditions. In the same manner as described above, the internal resistance value after performing a total of 10 heat treatments corresponding to reflow soldering was measured, and the results are shown in the graphs of FIGS.

  As shown in Table 1 and FIG. 8 (a), an electric double layer capacitor is formed by forming a protective layer using a paste having a blending ratio of the binder (solid content) defined in the claims of the present invention. Is produced, even after reflow soldering that is continuously exposed to a high temperature environment, it shows a generally low internal resistance value, especially when the binder compounding ratio is increased to 40 wt%, It can be seen that the internal resistance after reflow is suppressed.

  In addition, as shown in Table 2 and FIG. 9, when the protective layer is formed using a paste in which the blending ratio of the solvent in the paste is changed to produce an electric double layer capacitor, the solvent It turns out that the internal resistance after reflow is suppressed by making a compounding ratio 3.3 or less.

  Further, as shown in Table 3 and the results shown in FIGS. 10 and 11, a protective layer is formed using a paste in which the mixing ratio of graphite in the entire paste and the mixing ratio of graphite in the mixture of carbon and graphite are changed. In the case of producing an electric double layer capacitor, the internal resistance after reflow is suppressed particularly by setting the mixing ratio of graphite in the mixture of carbon and graphite within the range specified in the claims of the present invention. You can see that

Further, as shown in Table 4 and the results shown in FIGS. 12 and 14, a protective layer is formed using a paste in which the average particle size (D50) and particle size D90 of graphite contained in the paste is changed, and an electric double layer capacitor is formed. In the case of production, it can be seen that the internal resistance after reflowing is remarkably reduced by setting the particle size within the range specified by the claims of the present invention.
Further, as shown in Table 4 and FIG. 13, even when a protective layer is formed using a paste having a changed specific surface area (BET) of graphite to produce an electric double layer capacitor, the above ratio is particularly high. It turns out that the internal resistance after reflow is suppressed by making a surface area into the range prescribed | regulated by the claim of this invention.
Further, as shown in Table 4 and FIG. 15, when a protective layer is formed using a paste in which the oil absorption content in the paste is changed to produce an electric double layer capacitor, the oil absorption content is particularly reduced. In addition, it can be seen that the internal resistance after reflow is suppressed by setting it to approximately 150 (mL / 100 g) or less.

[Example 2]
In Example 2, the mixture of carbon and graphite fine particles contained in the paste was the same as in Example 1 except that the type of carbon, the average particle diameter, and the specific surface area were the conditions shown in Table 5 below. An electric double layer capacitor having a rectangular shape in plan view as shown in FIG. 1 was produced (Experimental Examples 28 to 36).
Then, for the obtained electric double layer capacitor, the internal resistance value after performing heat treatment corresponding to reflow soldering a total of 10 times was measured in the same manner as in Example 1, and the results are shown in Table 5 and FIG. , 17 graphs.

  As in the results shown in Table 5 and FIGS. 16 and 17, in particular, when carbon is used as carbon (Experimental Example 33), or when the average particle diameter of carbon and the specific surface area are limited to a predetermined value or less, It can be seen that the internal resistance after reflow is suppressed.

[Example 3]
In Example 3, a rectangular electric double layer capacitor as shown in FIG. 1 was produced and implemented in the same manner as in Examples 1 and 2 except that the paste was produced under the conditions shown in Table 6 below. In the same manner as in Example 2, the internal resistance value after performing heat treatment corresponding to reflow soldering a total of 10 times was measured, and the results are shown in Table 6 below (Experimental Examples 37 to 46 and Experimental Example 3). ). Here, Experimental Examples 37 to 39 in Table 6 below are comparative examples of the present invention using a binder that does not contain a fired product of polyamic acid such as polyimide.

  As shown in Table 6, the electric double layer capacitors of Experimental Examples 37 to 39 in which a paste was prepared using a binder not containing a fired product of polyamic acid and a protective layer was formed from this paste were reflow soldering. It can be seen that the internal resistance value increases as heat treatment corresponding to the pasting is repeated.

[Example 4]
In Example 4, the electric double layer capacitor produced in Experimental Example 1 of Example 1 above was used, heat treatment corresponding to reflow soldering was performed under the conditions shown in Table 7 below, and after initial heat treatment, the number of reflows However, the internal resistance in each state of 1 time, 5 times, and 10 times was measured by the same method as in Example 1, and the results are shown in the following Table 7 and the graph of FIG. 18 (Experimental Example 47).
Further, in Example 4, as a comparative example, an electric double layer capacitor was produced in the same manner as described above except that a paste was produced using a binder made of an epoxy resin, and the internal resistance in each state was obtained in the same manner as described above. Was measured, and the results are shown in the following Table 8 and the graph of FIG. 18 (Experimental Example 48).
Further, in Example 4, as a comparative example of the present invention, an electric double layer capacitor was prepared in the same manner as described above except that a paste was prepared using a binder made of a phenol resin, and each state was obtained by the same method as described above. The internal resistance was measured, and the results are shown in the following Table 9 and the graph of FIG. 18 (Experimental Example 49).

As in the results shown in Table 7 and FIG. 18, the electric double layer capacitor of Experimental Example 47 having a configuration in which a paste was produced under the conditions specified in the present invention and a protective layer was formed using the paste was subjected to the reflow process after the initial heat treatment. It can be seen that the internal resistance is suppressed at any time after 10 times.
On the other hand, as in the results shown in Tables 8 and 9 and FIG. 18, the electric double layer capacitors of Experimental Examples 48 and 49 having a configuration in which a paste was produced under conditions other than those of the present invention and a protective layer was formed using the paste. Although the internal resistance is reduced in the state after the initial heat treatment, the internal resistance value increases each time reflow is repeated. In particular, in Experimental Example 49, the positive electrode and the positive electrode current collector were recharged after 10 reflows. It was confirmed that peeling occurred.

[Example 5]
In Example 5, the electric double layer capacitor of Experimental Example 4 shown in Example 1 above was used as an example of the present invention, and after the initial heat treatment was performed in the same manner as described above, the number of reflows was once and five times. The internal resistance in each state 10 times was measured, and the results are shown in the graph of FIG. 19 (Experimental Example 50).
Further, in Example 5, as a comparative example, an electric double layer capacitor was prepared in the same manner as described above using a commercially available conductive paste mainly composed of a fluorine-based resin not including a fired product of polyamic acid. The internal resistance in each state was measured by this method, and the results are shown in the graphs of FIGS. 20 to 24 (Experimental Examples 51 and 52). Here, a commercial activated carbon electrode sheet (thickness = 0.23 mm) was used as the positive electrode in Experimental Example 52, and a commercial activated carbon electrode sheet (with an aluminum foil substrate; electrode thickness = 100 μm / Al thickness = 20 μm (preliminarily etched) was used.

  As shown in FIG. 19, in Experimental Example 50 in which an experiment was performed using the electric double layer capacitor of Experimental Example 4 in which a paste was produced under the conditions specified in the present invention, either after the initial heat treatment or after 10 reflows. In FIG. 5, it can be seen that there is almost no change in the internal resistance, and the increase in contact is suppressed.

  On the other hand, as in the results shown in the graphs of FIGS. 20 to 24, in the experimental examples 51 and 52 which are comparative examples, the internal resistance after the initial heat treatment is relatively low and stable, but the reflow is 5th to 10th. It became clear that the internal resistance value increased. Among these, when a phenol resin-based conductive paste is used for the paste, the internal resistance value has greatly increased when the reflow is performed for the fifth and subsequent times, and between the positive electrode and the positive electrode current collector. It can be seen that peeling occurs. In this comparative example, the conductive paste conventionally used in this field is used, and although it has durability in practical use, peeling of the electrode and increase in internal resistance may occur due to repeated reflow. It became clear.

  According to the electrochemical cell and the manufacturing method thereof of the present invention, the heat treatment corresponding to reflow soldering is repeatedly performed by optimizing the composition of the protective layer provided between the positive electrode and the positive electrode current collector. Even when exposed to the atmosphere, peeling does not occur between each of the current collector, the protective layer, and the electrode, and an increase in contact resistance and internal resistance can be prevented. As a result, productivity and yield are high, and in particular, in electric double layer capacitors mounted on energy harvesting equipment, such as electric double layer capacitors, where temperature change and humidity change are large and harsh environmental resistance is required, it is represented by heat resistance. A highly reliable electrochemical cell having excellent environmental resistance and electrical characteristics can be provided.

A, B, C, D, E, F, G ... Electric double layer capacitor (non-aqueous electrolyte battery: electrochemical cell)
1A, 1B, 1C, 1D, 1E, 1F, 1G ... base container (container),
11, 11C, 11D, 11E, 11F, 11G ... container bottom,
12, 12C, 12D, 12E, 12G ... container wall,
12F ... Container lid,
14 ... Spacer,
15 ... groove,
3 ... Seal ring,
4 ... lid,
5 ... brazing material,
6, 16, 26, 36, 46 ... negative electrode current collector,
60, 61, 62, 63 ... external terminal (negative electrode current collector),
7, 17, 27, 37, 47 ... positive electrode current collector,
70, 71, 72, 73 ... external terminal (positive electrode current collector),
60G ... external terminal (negative electrode side),
72G ... external terminal (positive electrode side),
8 ... negative electrode,
9: Positive electrode,
10 ... separator,
13, 43 ... adhesive layer,
18A, 18B, 18C, 18D, 18E, 18F, 18G ... protective layer (paste)

Claims (10)

A positive electrode current collector, a negative electrode current collector, a positive electrode, a negative electrode, a separator separating the positive electrode and the negative electrode, an electrolytic solution, and the positive electrode, the negative electrode, the separator, and the electrolytic solution are accommodated. An electrochemical cell comprising a base container and a lid for sealing the container and capable of being charged and discharged via each external terminal electrically connected to the positive electrode current collector and the negative electrode current collector. And
The container has a container bottom and a container wall,
The positive electrode and the negative electrode are arranged to face each other via the separator so that the positive electrode is arranged on the container bottom side, and the positive electrode current collector is arranged on the container bottom side of the positive electrode In addition, the negative electrode current collector is disposed on the negative electrode side,
Between the positive electrode, the positive electrode current collector, and the bottom of the container, a good-electricity protective layer comprising a heat-fired product of polyamic acid, a mixture of carbon having an average particle size of 23 to 36 nm, and fine particles of graphite. Is provided,
The electrochemical cell, wherein the positive electrode and the positive electrode current collector are electrically connected via the protective layer. A positive electrode current collector, a negative electrode current collector, a positive electrode, a negative electrode, a separator separating the positive electrode and the negative electrode, an electrolytic solution, and the positive electrode, the negative electrode, the separator, and the electrolytic solution are accommodated. An electrochemical cell comprising a base container and a lid for sealing the container and capable of being charged and discharged via each external terminal electrically connected to the positive electrode current collector and the negative electrode current collector. And
The container comprises a container bottom, a container wall, a spacer disposed between the container bottom and the container wall, and a groove through which the spacer penetrates.
The positive electrode current collector is formed between the container bottom and the spacer, and the surface exposed to the groove is a polyamic acid fired product, carbon having an average particle diameter of 23 to 36 nm , and An electrochemical cell, which is covered with a good-electricity protective layer comprising a mixture of graphite fine particles, and wherein the positive electrode and the positive electrode current collector are electrically connected via the protective layer.   3. The electrochemical cell according to claim 1, wherein the protective layer is a polyimide having a low linear expansion coefficient as a result of heating and baking the polyamic acid. 4.   The electrochemical cell according to any one of claims 1 to 3, wherein the protective layer includes at least one of carbon black, carbon fiber, and carbon nanotube. . 5. The protective layer according to claim 1, wherein a specific surface area of the graphite fine particles is 20 m ² / g or less, and an average particle size thereof is 10 μm or less. Electrochemical cell.   6. The protective layer according to claim 1, wherein a mixing ratio of the carbon and the graphite fine particles is in a range of 8:30 to 19:19 (5: 5). 2. The electrochemical cell according to item 1.   The component of the binder containing the heat-fired product of polyamic acid used at the time of formation of the protective layer has a solid content ratio of 40 wt% or more and less than 80 wt%. The electrochemical cell according to 1.   The electrochemical cell according to claim 1, wherein an aluminum layer for protecting the positive electrode current collector is provided on the positive electrode current collector. A method for producing an electrochemical cell according to any one of claims 1 to 8,
After forming the positive electrode on the positive electrode current collector formed on the container bottom in the container, forming the separator on the positive electrode, and then forming the negative electrode to be connected to the separator, An electrode arrangement step of connecting the positive electrode and the negative electrode through the separator, and further forming the negative electrode current collector on the negative electrode side in the container;
An injection step of injecting the electrolytic solution into the container;
A sealing step of covering and sealing the opening of the container with the lid by overlaying the lid on the negative electrode,
Furthermore, the electrode arrangement step is arranged between the positive electrode and the positive electrode current collector and the container bottom, or between the container bottom and the container wall, and the positive electrode and the positive electrode current collector. A good-electricity protective layer comprising a polyamic acid fired product, a mixture of carbon having an average particle size of 23 to 36 nm, and fine particles of graphite is formed in a groove portion that penetrates a spacer provided between the body and the body. A process for producing an electrochemical cell comprising the steps of: Forming a pre-Symbol protective layer, after mixing with a binder comprising a heat burned material of polyamic acid, and a mixture of carbon and graphite particles, diluted with the addition amount of less than 3 times the solid content of the solidified solvent Then, the paste is prepared, and then the paste is applied on the positive electrode current collector and the bottom of the container or on the positive electrode current collector exposed in the groove formed in the spacer. The method for producing an electrochemical cell according to claim 9, wherein the method is heated and cured.

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