JP5317687B2 - Winding type power storage - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wound-type accumulator which is simplified in the layout of lithium ion supply sources and shortened in time spent on injecting a nonprotonic organic solvent electrolytic solution and on predoping, so as to allow quick completion of assembly and obtain high productivity. <P>SOLUTION: The wound-type accumulator is provided with: a cylindrical wound electrode unit which has cathode and anode strips and is configured by winding from one end in an electrode stack body comprised of a stack of the cathode and anode with a separator disposed therebetween; and an electrolytic solution. In this wound-type accumulator, the anode and/or cathode is doped with lithium ions and/or anions by means of electrochemical contact of the anode and/or cathode with a lithium ion supply source. At the cathode, a cathode gap section is formed, and at least one lithium ion supply source is arranged at the cathode gap section or at a position opposing the cathode gap section at the anode, in a state not contacting the cathode. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a high-capacity wound-type storage power source with high energy density and high output density.

In recent years, a battery using a carbon material such as graphite for the negative electrode and a lithium-containing metal oxide such as LiCoO _{2 for} the positive electrode has been proposed. This battery is a so-called rocking chair type battery in which lithium ions are supplied from the lithium-containing metal oxide of the positive electrode to the negative electrode by charging after the battery is assembled, and lithium ions are returned from the negative electrode to the positive electrode in the discharge. This is called a lithium ion secondary battery and is distinguished from a lithium battery using lithium metal because only lithium ions are involved in charging and discharging without using metallic lithium. This battery is characterized by high voltage, high capacity, and high safety.

  In addition, while environmental issues are being highlighted, development of a clean energy storage system using solar power generation or wind power generation, and a power source for an electric vehicle or a hybrid electric vehicle that replaces a gasoline vehicle are being actively conducted. Furthermore, recently, in-vehicle devices and equipment such as power windows and IT-related equipment have become more sophisticated and functional, and new power sources are being demanded in terms of energy density and output density.

  In recent years, a power storage device called a hybrid capacitor, which combines the power storage principles of a lithium ion secondary battery and an electric double layer capacitor, has been attracting attention as a power storage device for such applications that require high energy density and high output characteristics. . As one of them, a lithium ion can be occluded and desorbed in advance by occlusion and support (hereinafter sometimes referred to as doping) of lithium ions by a chemical method or an electrochemical method to lower the negative electrode potential. An organic electrolyte capacitor using a carbon material that can significantly increase the energy density as a negative electrode has been proposed (see, for example, Patent Document 1).

  Although this type of organic electrolyte capacitor is expected to have high performance, there are problems in that it takes a very long time when lithium ions are doped in advance on the negative electrode and that lithium ions are uniformly supported on the entire negative electrode. In particular, it has been considered difficult to put into practical use in a large-sized high-capacity cell such as a cylindrical battery in which electrodes are wound or a square battery in which a plurality of electrodes are stacked.

  As a method for solving such a problem, a positive electrode current collector and a negative electrode current collector (hereinafter, both are also referred to as “electrode current collector”) each have a hole penetrating the front and back surfaces, and the negative electrode active material is There has been proposed an organic electrolyte battery capable of reversibly supporting lithium ions and having lithium ions supported on the negative electrode by electrochemical contact with the negative electrode or lithium metal disposed opposite to the positive electrode (for example, a patent) Reference 2). That is, in Patent Document 2, as an example of the organic electrolyte battery, lithium metal is pasted on the outermost negative electrode current collector of a wound body (electrode winding unit) obtained by winding a positive electrode and a negative electrode through a separator. Alternatively, a cylindrical wound lithium ion battery in which a cylindrical lithium metal is disposed at the center of the wound body and the lithium metal and the negative electrode are short-circuited to dope lithium ions into the negative electrode is disclosed. .

In the wound lithium ion battery, since the electrode current collector is provided with a hole penetrating the front and back surfaces, the lithium metal can be placed on either the outer periphery or the center of the wound body. The ions move between the electrodes through the through hole without being blocked by the electrode current collector, so that the lithium ions are electrochemically applied not only to the negative electrode near the lithium metal but also to the negative electrode far from the lithium metal. It can be supported.
Patent Document 3 discloses a method in which lithium metal is disposed in the outer peripheral portion and the central portion of a wound body in a lithium ion capacitor, and a large amount of lithium ions is doped in a shorter time than conventional.

Japanese Patent Laid-Open No. 8-1007048 Japanese Patent No. 3485935 JP 2007-67105 A

  As described above, the negative electrode in which lithium ions are doped in advance into a carbon material that can occlude and desorb lithium ions has a lower potential than the active carbon used in the electric double layer capacitor. In addition, since the withstand voltage of the cell is improved and the capacity of the negative electrode is much larger than that of the activated carbon, the organic electrolyte capacitor (lithium ion capacitor) provided with the negative electrode has a high energy density.

  However, as shown in the wound type lithium ion battery, when lithium metal is disposed on the outer peripheral portion and the central portion of the electrode winding unit, there is a problem that the penetration of the electrolytic solution is slow. This is presumably because the electrolytic solution cannot diffuse because lithium metal covers the surface of the electrode winding unit. Further, since it takes time for the electrolyte to penetrate, a long time is required to uniformly dope lithium ions into all the negative electrodes of the electrode winding unit. In particular, when a large-sized wound lithium ion battery is manufactured, the required time for doping is increased to, for example, about 30 days by increasing the number of times of winding, and the productivity is extremely low.

  Furthermore, the assembling method shown in Patent Document 3 in which lithium metal is arranged at the outer peripheral portion and the central portion is obtained by winding the positive electrode and the negative electrode through a separator to produce an electrode winding unit, and then forming metal at the outer peripheral portion and the central portion. Since lithium is disposed, the assembly process becomes complicated, and the productivity is not always satisfactory.

  The present invention has been made based on the above circumstances, and its purpose is to simplify the arrangement of the lithium ion supply source, the time for injecting the aprotic organic solvent electrolyte solution, and the negative electrode and / or Alternatively, a lithium ion storage power source capable of shortening the doping time of lithium ions (hereinafter also referred to as “pre-doping”) to the positive electrode and thus completing assembly in a short time and obtaining high productivity can be obtained. It is to provide.

In the wound storage power source of the present invention, an electrode layer containing a positive electrode active material capable of reversibly supporting lithium ions and / or anions is formed on at least one surface of a current collector having holes penetrating the front and back surfaces. And a negative electrode in which an electrode layer containing a negative electrode active material capable of reversibly carrying lithium ions is formed on at least one surface of a current collector having holes penetrating the front and back surfaces, A cylindrical electrode winding unit in which an electrode stack formed by stacking a positive electrode and the negative electrode via a separator is wound from one end thereof, and
Comprising an electrolyte comprising an aprotic organic solvent electrolyte solution of a lithium salt,
A wound-type storage power source in which lithium ions and / or anions are doped into the negative electrode and / or positive electrode by electrochemical contact between the negative electrode and / or the positive electrode and a lithium ion supply source,
A gap is formed between the positive electrodes,
The gap, or, in a position facing the gap portion in the negative electrode, wherein at least one of the lithium ion supply source is provided in a state not in contact with the positive electrode.

  In the wound-type storage power source of the present invention, it is preferable that a lithium ion supply source is provided on the inner peripheral surface and / or the outer peripheral surface of the electrode winding unit.

  In the wound-type storage power source of the present invention, it is preferable that the lithium ion supply source is disposed so as not to contact the positive electrode and the negative electrode via a separator.

  Moreover, in the wound-type storage power source of the present invention, it is preferable that the lithium ion supply source is pressure-bonded or stacked on the lithium electrode current collector.

  In the wound storage battery of the present invention, it is preferable that the lithium electrode current collector on which the lithium ion supply source is crimped or stacked is made of a porous foil.

In the wound type accumulator of the present invention, the lithium ion supply source provided at a position corresponding to the gap portion or the gap portion in the negative electrode is such that the wound body to be covered by the lithium ion supply source is a negative electrode. It is preferable that the electrode winding unit is configured by being inserted and wound after being covered with the outermost peripheral portion.

  In the wound storage power source of the present invention, after the wound body around which the lithium ion supply source constituting the inner peripheral surface of the electrode winding unit is wound is covered with the negative electrode, the positive electrode is inserted. It is preferable that the electrode winding unit is configured by being rotated.

  Moreover, in the wound-type storage power source of the present invention, the lithium ion supply source constituting the outer peripheral surface of the electrode winding unit is such that the wound body to be covered by the lithium ion supply source is covered at the outermost periphery of the negative electrode It is preferable that the electrode winding unit is configured by being inserted and wound later.

Moreover, in the wound-type storage power source of the present invention, it is preferable that the positive electrode has a plurality of positive electrode pieces, and each positive electrode piece is disposed with the gap portion therebetween.

  In the wound-type storage power source of the present invention, it is preferable that the negative electrode overlaps at least a part of the positive electrode.

  The wound storage power source of the present invention is preferably a lithium ion capacitor or a lithium ion secondary battery.

According to the wound-type storage power source of the present invention, the electrode winding unit has a lithium ion supply source arranged at a position corresponding to the gap portion (positive electrode gap portion) formed between the positive electrodes or the gap portion in the negative electrode. Since the electrode stack is formed and obtained by winding, the electrode winding unit can be easily assembled, and therefore the assembly can be completed in a short time and the positive electrode gap portion can be completed. Alternatively, since the lithium ion supply source is arranged in the gap between the negative electrodes, the pre-doping time can be shortened and high productivity can be obtained.
In the case where a lithium ion supply source is arranged between the positive electrode and the negative electrode arranged opposite to each other, the speed of pre-doping can be increased, but the distance between the positive electrode and the negative electrode is partially different from others. When the lithium metal remains between the positive electrode and the negative electrode, or when a lithium ion supply source is laminated on the lithium electrode current collector , the lithium metal is deposited on the lithium electrode current collector. Sometimes.

  According to the wound-type storage power source manufactured in this way, since the pre-doping can be speeded up and uniformed, the internal resistance is reduced even if the assembly is completed in a short time. Thus, high performance is obtained and high durability is obtained.

  Hereinafter, embodiments of the present invention will be described in detail in an example in which a wound-type storage power source is applied to a lithium ion capacitor (LIC).

<First Embodiment>
FIG. 1 is an explanatory cross-sectional view schematically showing an example of the configuration of a wound lithium ion capacitor (hereinafter also referred to as “winding LIC”) according to the present invention, and FIG. It is sectional drawing for description which shows typically the state of the cross section of the electrode stacked body which solved the winding state of the electrode winding unit of a rotary LIC.
In the wound type lithium ion capacitor of this example (hereinafter also referred to as “winding type LIC”), a strip-like positive electrode 11 having a positive electrode gap portion 11S and a strip-like negative electrode 12 having a negative electrode gap portion 12S are interposed via a separator. Specifically, a cylindrical electrode winding unit 10 configured by winding an electrode stack 10A in which the negative electrode 12, the separator 13A, and the positive electrode 11 are stacked in this order on the separator 13B is wound from one end thereof. This is housed in a cylindrical outer container 20 and filled with an electrolyte solution made of an aprotic organic solvent electrolyte solution of lithium salt.
Each of the inner peripheral surface and the outer peripheral surface of the electrode winding unit 10 is constituted by lithium ion supply sources 16A and 16B, and the lithium ion is not in contact with the positive electrode 11 in the positive electrode gap 11S of the positive electrode 11. A supply source 16C is provided. The lithium ion supply sources 16A to 16C are preferably arranged so as not to contact the negative electrode 12 via the separators 13A and 13B.
In such a wound LIC, the negative electrode 12 and the lithium ion supply sources 16A to 16C are short-circuited, and by electrochemical contact between the negative electrode 12 and / or the positive electrode 11 and the lithium ion supply sources 16A to 16C . The negative electrode 12 and / or the positive electrode 11 are doped with lithium ions and / or anions.
In the present invention, the “positive electrode” means that a current flows out during discharging, the electrode into which current flows during charging, and the “negative electrode” refers to a current flowing during discharging, and during charging. It means the pole where the current flows out.

As shown in FIG. 3, the specific structure of the positive electrode 11 includes a plurality of positive electrode pieces (two in FIGS. 1 to 3) 111 and 112, and the positive electrode pieces 111 and 112 are mutually connected to the positive electrode. It arrange | positions through the gap | interval part 11S.
The specific structure of the negative electrode 12 includes a plurality of negative electrode pieces (two in FIG. 1 and FIG. 2) 121 and 122, similar to the positive electrode 11, and the negative electrode pieces 121 and 122 are mutually connected to the negative electrode gap. It arranges via part 12S.

In the electrode winding unit 10 in which the positive electrode 11, the negative electrode 12, and the lithium ion supply sources 16 </ b> A to 16 </ b> C are stacked and wound on the separators 13 </ b> A and 13 </ b> B, the positive electrode 11 is superimposed on the negative electrode 12 over the entire length. Is preferred. In the present invention, the state in which the negative electrode and the positive electrode are superimposed refers to a state in which the negative electrode and the positive electrode are stacked without any other elements than the separator.
Specifically, in the electrode winding unit 10, the positive electrode 111 is inserted and wound after the wound body in which the lithium ion supply source 16 </ b> A constituting the inner peripheral surface is wound is covered with the negative electrode 121. It is preferable to be configured. In addition, the outer peripheral surface of a pair of electrode pairs (for example, a portion surrounded by a chain line Z in FIG. 1) composed of the opposing positive electrode portion (111) and negative electrode portion (121) is the negative electrode portion (121) of the electrode pair portion. A winding body is configured by being covered with the surplus portion (121α) of the winding body, and the outer peripheral surface of the winding body is covered with the lithium ion supply source 16C related to the positive electrode gap portion 11S. It is preferable that the electrode is covered with the electrode pair portion. Further, the lithium ion supply source 16B constituting the outer peripheral surface is inserted and wound after the wound body to be covered is covered by the outermost peripheral portion of the negative electrode, thereby forming an electrode winding unit. preferable.
By adopting such a configuration, high durability can be obtained for the wound LIC. In addition, when it is made to oppose without interposing a negative electrode between a lithium ion supply source and a positive electrode, pre dope becomes inadequate and lithium metal remains, or a lithium ion supply source is placed on a lithium electrode current collector. Depending on the charge / discharge conditions, dendritic lithium metal called dendrite may be deposited on the lithium electrode current collector and cause a short circuit.

  Although FIG. 1 shows a configuration in which one lithium ion source 16C is arranged between two electrode pair portions, the electrode pair portions are not limited to two sets. You may be comprised by the electrode pair part of 3 or more sets. In such a case, the lithium ion supply source is arranged in at least one of the electrode pair portions.

Lithium ion supply sources 16A and 16B constituting the inner and outer peripheral surfaces of the electrode winding unit 10, and a lithium ion supply source 16C inserted into a gap formed on the outer peripheral surface of the wound body by the electrode pair portion. Are preferably formed with intermittent portions S (see FIG. 4) having no lithium ion supply sources 16A to 16C, respectively. The “occupation ratio” is preferably 10 to 70%, more preferably 15 to 50%, and particularly preferably 20 to 30%.
Each of the lithium ion supply sources 16 </ b> A to 16 </ b> C is configured such that plate-like lithium ion supply source pieces are arranged in parallel via the intermittent portion S.

When the lithium electrode non-occupancy in the lithium ion supply sources 16A to 16C is less than 10% of each circumferential surface, it takes time for the aprotic organic solvent electrolyte solution to permeate and shortens the injection time. I can't. On the other hand, when the lithium electrode non-occupancy ratio in the lithium ion supply sources 16A to 16C exceeds 70% of each circumferential surface, the lithium ions that donate lithium ions and / or anions to the positive electrode and / or the negative electrode are provided. Since the area of the supply source is small, it takes time to complete the pre-doping, and the pre-doping time cannot be shortened.
When the lithium electrode non-occupancy in the lithium ion supply sources 16A to 16C is 20 to 30% of each circumferential surface, both the reduction of the penetration time of the aprotic organic solvent electrolyte solution and the reduction of the pre-doping time Can be achieved.
In addition, the gaps are preferably formed uniformly distributed over the entire area. For example, instead of using a single lithium ion supply source having a large area, it is preferable to separately arrange a plurality of small area lithium ion supply sources to form a predetermined gap portion. Thereby, the distribution channel of the aprotic organic solvent electrolyte solution can be secured widely. In addition, it is more preferable to use one lithium ion supply source having a large area that is made porous by punching or the like because a predetermined gap portion can be obtained by one lithium ion supply source.

  As shown in FIG. 5, such an electrode winding unit 10 is formed by winding the electrode stack 10 </ b> A from the outside from the viewpoint of improving the assembly workability of the wound LIC. It is preferable that the outer container 20 is housed in a state of being fixed at 25. In FIG. 5, 17 is a positive terminal electrically connected to the positive electrode, and 18 is a negative terminal electrically connected to the negative electrode. In FIG. 5, these are extended in the opposite direction with respect to the electrode winding unit 10, but may be extended in the same direction.

[Method of winding electrode stack]
In the assembly process of the electrode winding unit 10 as described above, in the insertion of the lithium ion supply source 16B constituting the outer peripheral surface, the lithium ion supply source 16B is previously pressure-bonded to the separator 13A as shown in FIG. It is preferable that the winding is performed from the viewpoint of shortening the assembly time. Further, as shown in FIGS. 7 and 8, a lithium electrode current collector 26a (26b) is pressure-bonded on the lithium ion supply source 16B so as to be in close contact with the lithium ion supply source 16B pressed on the separator 13A. By rotating, the lithium ion supply source 16B can be electrically connected to the negative electrode 12, and both can be short-circuited.
Further, in the assembly process of the electrode winding unit 10, the insertion of the lithium ion supply source 16A constituting the inner peripheral surface is the same as the insertion of the lithium ion supply source 16B constituting the outer peripheral surface, as shown in FIG. The lithium ion supply source 16A is preferably wound in a state in which the lithium ion supply source 16A is preliminarily pressure-bonded to the separator 13A, and, as shown in FIG. By crimping and winding the lithium electrode current collector 26c on the lithium ion supply source 16A, the lithium ion supply source 16A can be electrically connected to the negative electrode 12 and both can be short-circuited.
Further, in the assembly process of the electrode winding unit 10, the insertion of the lithium ion supply source 16C disposed in the positive electrode gap portion 11S is the same as the insertion of the lithium ion supply sources 16A and 16B constituting the inner peripheral surface and the outer peripheral surface. In addition, it is preferable to wind the lithium ion supply source 16C in a state in which the lithium ion supply source 16C is preliminarily pressure-bonded to the separator 13A, and on the lithium ion supply source 16C so as to be in close contact with the lithium ion supply source 16C pressure-bonded to the separator 13A. By crimping and winding the lithium electrode current collector, the lithium ion supply source 16C can be electrically connected to the negative electrode 12 and both can be short-circuited.

Specifically, in such an electrode winding unit 10, first, the negative electrode gap portion 12S , the negative electrode piece 121, the negative electrode gap portion 12S, and the negative electrode piece 122 are arranged on the first separator 13B from one end to the other end. On the first strip formed in this order and the second separator 13A, the lithium ion supply source 16A, the positive electrode piece 111, the lithium ion supply source 16C, and the positive electrode piece that are the innermost peripheral surface of the electrode winding unit 10 112 and the lithium ion supply source 16B which becomes the outermost peripheral surface of the electrode winding unit 10 produce a second strip formed in this order from one end to the other end. In the first strip and the second strip, when the gaps between the positive electrode 11 and the negative electrode 12 and the length and arrangement position of the electrode pieces are wound, the positive electrode piece faces the negative electrode piece only through the separator. In addition, the lithium ion supply source is also set based on the thickness of each constituent member so that the negative electrode piece is opposed to the negative electrode piece only through the separator, and the inner peripheral surface and the outer peripheral surface are configured by the lithium ion supply source. .
And this 1st strip | belt material and a 2nd strip | belt material are piled up, and this electrode stacking body 10A is wound by the core rod from the one end (one end of lithium ion supply source 16A), The electrode winding unit 10 Is obtained.

  The electrode winding unit 10 configured in this manner is housed in the outer container 20 together with the aprotic organic solvent electrolyte solution, and left in this state for a predetermined time (for example, 10 days), whereby the lithium ion supply sources 16A to 16A- Since 16C and the negative electrode 12 are short-circuited, the negative electrode 12 is previously doped with lithium ions.

〔electrode〕
The positive electrode 11 and the negative electrode 12 (hereinafter, both are also referred to as “electrodes”) are each formed by forming an electrode layer on at least one surface of a strip-shaped current collector, and both have substantially the same structure. Therefore, the following description will be made with reference to the same drawing.
FIG. 11 is an explanatory plan view showing an electrode in the electrode winding unit in a developed state, and FIG. 12 is an explanatory view showing an AA cross section of the electrode shown in FIG. 11 in an enlarged manner.
In this example, the negative electrode 12 (positive electrode 11) is formed on one surface (upper surface in FIG. 12) of a strip-shaped negative electrode current collector 12a (positive electrode current collector 11a) via a base layer 12c (11c). An electrode layer 12b (11b) containing a substance is formed, and a negative electrode terminal 18 (positive electrode terminal 17) is stitched or cold, for example, on the other surface of the negative electrode current collector 12a (positive electrode current collector 11a). Fixed and connected by welding.
When the electrode layer 12b or the electrode layer 11b formed on both surfaces of the negative electrode current collector 12a or the positive electrode current collector 11a is used as the electrode, the electrode layer 12b or the electrode layer 11b is partially made of the negative electrode current collector. The negative electrode terminal 18 or the positive electrode terminal 17 can be connected to the negative electrode current collector 12a or the positive electrode current collector 11a by peeling from the body 12a or the positive electrode current collector 11a .
Here, the negative electrode terminal 18 and the positive electrode terminal 17 may be drawn separately from both ends of the electrode winding unit 10 or may be drawn from one end portion. Further, it is sufficient that one negative electrode terminal 18 and one positive electrode terminal 17 are provided, but it is preferable that a plurality of each of the negative electrode terminal 18 and the positive electrode terminal 17 is provided because internal resistance is reduced.

The positive electrode current collector 11a and the negative electrode current collector 12a (hereinafter also referred to as “electrode current collector”) are made of a porous material having holes P penetrating the front and back surfaces. Examples of the form include expanded metal, punching metal, metal net, foam, or porous foil having through holes formed by etching.
The shape of the hole P of the electrode current collector can be set to a circular shape, a rectangular shape, or any other appropriate shape. Moreover, it is preferable that the thickness of an electrode electrical power collector is 20-50 micrometers from a viewpoint of intensity | strength and weight reduction.
The porosity of the electrode current collector is usually 10 to 79%, preferably 20 to 60%. Here, the porosity is calculated by [1− (mass of electrode current collector / true specific gravity of electrode current collector) / (apparent volume of electrode current collector)] × 100.
As the material of the electrode current collector, various materials generally used for applications such as organic electrolyte batteries can be used. Specific examples of the material of the negative electrode current collector 12a include stainless steel, copper, and nickel. Examples of the material of the positive electrode current collector 11a include aluminum and stainless steel.
By using such a porous material as an electrode current collector, even if the lithium ion supply sources 16A to 16C are arranged on the inner and outer peripheral surfaces of the electrode winding unit 10 and the positive electrode gap portion 11S, Lithium ions can be doped into the negative electrode 12 and / or the positive electrode 11 because the lithium ion sources 16A to 16C freely move between the electrodes through the holes P of the electrode current collector.

In the present invention, at least some of the holes P in the electrode current collector are closed with a conductive material that does not easily drop off. In this state, the electrode layers 11a and 12b are formed on one surface of the electrode current collector. Preferably, it is possible to improve the productivity of the electrode, and to prevent or suppress a decrease in the reliability of the storage power source caused by the electrode layers 11b and 12b dropping from the electrode current collector. be able to.
Further, by reducing the thickness of the electrode (total thickness of the electrode current collector and the electrode layer), a higher output density can be obtained.
In addition, the shape and number of holes P in the electrode current collector are such that lithium ions in the electrolyte described later can move between the front and back of the electrode without being blocked by the current collector, and depending on the conductive material. It can set suitably so that it may block easily.

The electrode layer 12b in the negative electrode 12 contains a negative electrode active material capable of reversibly carrying lithium ions.
The negative electrode active material constituting the electrode layer 12b is, for example, a heat-treated product of graphite, non-graphitizable carbon, and aromatic condensation polymer, and the hydrogen atom / carbon atom number ratio (hereinafter referred to as “H / C”). ) Is a polyacene-based organic semiconductor (hereinafter referred to as “PAS”)) having a polyacene-based skeleton structure of 0.50 to 0.05, among which PAS has a high capacity. It is more preferable at the point obtained. For example, if a PAS having H / C of about 0.2 carries 400 mAh / g of lithium ions (discharges) and then discharges, a capacitance of 650 F / g or more is obtained, and a lithium of 500 mAh / g or more is obtained. When ions are supported (charged), a capacitance of 750 F / g or more is obtained. From this, it is understood that PAS has a very large capacitance.

  In the present invention, when an anode active material having an amorphous structure such as PAS is used, the potential decreases as the amount of lithium ions to be carried increases, so that the withstand voltage (charge voltage) of the obtained storage power source is reduced. Since the voltage rise rate (discharge curve slope) during discharge increases, the amount of lithium ions is appropriately set within the range of lithium ion storage capacity of the active material, depending on the required operating voltage of the storage power source. It is preferable to do.

  Since PAS has an amorphous structure, it does not undergo structural changes such as swelling / shrinkage due to the insertion / desorption of lithium ions, so it has excellent cycle characteristics. Since it has an isotropic molecular structure (higher order structure), it has excellent characteristics for rapid charge and rapid discharge, and is therefore suitable as a negative electrode active material.

  The aromatic condensation polymer that is a precursor of PAS is a condensate of an aromatic hydrocarbon compound and aldehydes. As the aromatic hydrocarbon compound, for example, phenols such as phenol, cresol and xylenol can be suitably used. Examples thereof include methylene / bisphenols, hydroxy / biphenyls, hydroxynaphthalenes and the like represented by the following formula. Of these, phenols, and particularly phenols, are suitable for practical use.

(In the formula, x and y are each independently an integer of 0 to 2.)

In addition, the aromatic condensation polymer includes a modified fragrance in which a part of an aromatic hydrocarbon compound having a phenolic hydroxyl group is substituted with an aromatic hydrocarbon compound having no phenolic hydroxyl group, such as xylene, toluene, aniline, etc. A group condensation polymer such as a condensate of phenol, xylene and formaldehyde can also be used. Furthermore, a modified aromatic polymer substituted with melamine or urea can be used, and a furan resin is also suitable.

PAS is used as an insoluble and infusible substrate, and the insoluble and infusible substrate can also be produced, for example, from the aromatic condensation polymer as follows. That is, by gradually heating the aromatic condensation polymer to a temperature of 400 to 800 ° C. in a non-oxidizing atmosphere (including vacuum), H / C is preferably 0.5 to 0.05, preferably Can obtain an insoluble and infusible substrate of 0.35 to 0.10.
However, the method for producing an insoluble and infusible substrate is not limited to this. For example, in the method described in JP-B-3-24024, H / C is in the above range, and 600 m ² / g. It is also possible to obtain an insoluble and infusible substrate having a specific surface area by the above BET method.

  In the insoluble infusible substrate, according to X-ray diffraction (CuKα), the position of the main peak is represented by 2θ and is not more than 24 °, and in addition to the main peak, the position is 41 to 46 °. There are other broad peaks in between. That is, the insoluble infusible substrate has a polyacene skeleton structure in which an aromatic polycyclic structure is appropriately developed, has an amorphous structure, and can be stably doped with lithium ions. It is suitable as a negative electrode active material for a storage power source.

  In the present invention, the negative electrode active material preferably has a pore diameter of 3 nm or more and a pore volume of 0.10 mL / g or more, and the upper limit of the pore diameter is not limited, but is usually in the range of 3 to 50 nm. is there. Moreover, although it does not specifically limit about the range of pore volume, Usually, it is 0.10-0.5 mL / g, Preferably it is 0.15-0.5 mL / g.

In the wound LIC according to the present invention, the electrode layer 12b in the negative electrode 12 is formed on the negative electrode current collector 12a using a material containing a negative electrode active material such as the above carbon material or PAS. The method is not specified and a known method can be used. Specifically, a negative electrode active material powder, a binder and, if necessary, a slurry in which conductive powder is dispersed in an aqueous medium or an organic solvent are prepared, and this slurry is applied to the surface of the negative electrode current collector 12a. The electrode layer 12b can be formed by drying or by previously forming the slurry into a sheet shape and attaching the resulting molded body to the surface of the negative electrode current collector 12a.
Here, examples of the binder used for preparing the slurry include rubber-based binders such as SBR, synthetic fluorine-based resins such as polytetrafluoroethylene and polyvinylidene fluoride, and thermoplastic resins such as polypropylene and polyethylene. Among these, a fluorine-based resin is preferable as the binder, and a fluorine-based resin having a fluorine atom / carbon atom ratio (hereinafter referred to as “F / C”) of 0.75 or more and less than 1.5 is used. It is preferable that a fluororesin having an F / C of 0.75 or more and less than 1.3 is more preferable.
Although the usage-amount of a binder changes with kinds, electrode shape, etc. of a negative electrode active material, it is 1-20 mass% with respect to a negative electrode active material, Preferably it is 2-10 mass%.
Moreover, as an electroconductive material used as needed, acetylene black, a graphite, a metal powder etc. are mentioned, for example. The amount of the conductive material used varies depending on the electric conductivity of the negative electrode active material, the electrode shape, and the like, but it is preferably used at a ratio of 2 to 40% by mass with respect to the negative electrode active material.

When the electrode layer 12b is formed by applying the slurry to the negative electrode current collector 12a, an underlying layer 12c of a conductive material is formed on the coated surface of the negative electrode current collector 12a as shown in FIG. It is preferable to do. When the slurry is directly applied to the surface of the negative electrode current collector 12a, the negative electrode current collector 12a is a porous material, so that the slurry leaks from the hole P of the negative electrode current collector 12a, or the negative electrode current collector Since the surface of 12a is not smooth, it may be difficult to form the electrode layer 12b having a uniform thickness. Then, by forming the base layer 12c on the surface of the negative electrode current collector 12a, the hole P is blocked by the base layer 12c and a smooth coating surface is formed, so that the slurry can be easily applied, The electrode layer 12b having a uniform thickness can be formed.
In the illustrated example, the electrode layer 12b is formed on only one surface of the negative electrode current collector 12a. However, when the electrode layer 12b is formed on both surfaces of the negative electrode current collector 12a, for example, The negative electrode terminal can be connected to the uncoated region by intermittently applying the slurry on either side to form an uncoated region on the negative electrode current collector 12a.

  The thickness of the negative electrode layer 2b in the negative electrode 12 is designed in balance with the thickness of the electrode layer 11b in the positive electrode 11 so as to ensure a sufficient energy density for the obtained wound LIC. From the viewpoint of output density, energy density, industrial productivity, and the like, when formed on one surface of the negative electrode current collector 12a, it is usually 15 to 100 μm, preferably 20 to 80 μm.

The electrode layer 11b in the positive electrode 11 contains a positive electrode active material capable of reversibly carrying lithium ions and / or anions such as tetrafluoroborate.
The positive electrode active material constituting the electrode layer 11b is, for example, a heat-treated product of activated carbon, conductive polymer, aromatic condensation polymer, and has a polyacene skeleton structure with H / C of 0.05 to 0.50. PAS or the like can be used.
The electrode layer 11b in the positive electrode 11 can be formed by the same method as the electrode layer 12b in the negative electrode 12.

In the wound LIC according to the present invention, the potential of the positive electrode 11 and the negative electrode 12 after the positive electrode 11 and the negative electrode 12 are short-circuited is preferably 2.0 V or less.
In conventional electric double layer capacitors, generally the same type (mainly activated carbon) of the same type is used as the active material in the positive electrode and the negative electrode. This active material has a potential of about 3 V when the capacitor is assembled. When the capacitor is charged, an anion forms an electric double layer on the surface of the positive electrode, thereby increasing the potential of the positive electrode. On the other hand, the cation forms an electric double layer on the surface of the negative electrode, thereby lowering the potential of the negative electrode. Conversely, during discharge, anions are released from the positive electrode and cations are released from the negative electrode into the electrolyte, respectively, so that the potential drops or rises, and finally the potential becomes about 3V. Thus, since the normal carbon material has a potential of about 3 V, the organic electrolyte capacitor in which the carbon material is used for both the positive electrode and the negative electrode has the positive electrode and the negative electrode after the positive electrode and the negative electrode are short-circuited. Each of the potentials is about 3V.

On the other hand, in the wound LIC according to the present invention, the potential of the positive electrode after the positive electrode 11 and the negative electrode 12 are short-circuited as described above is 2.0 V (Li / Li ⁺ , the same shall apply hereinafter) or less. It is preferable. That is, in the wound LIC according to the present invention, a positive electrode active material that can reversibly carry lithium ions and / or anions is used, while an active material that can reversibly carry lithium ions as a negative electrode active material. It is preferable to carry lithium ions on the negative electrode 12 and / or the positive electrode 11 in advance so that the potential of the positive electrode and the negative electrode becomes 2.0 V or less after the positive electrode 11 and the negative electrode 12 are short-circuited using a substance.

In addition, in this invention, the electric potential of the positive electrode after short-circuiting a positive electrode and a negative electrode is 2.0V or less means the electric potential of the positive electrode calculated | required by either of the following two methods (A) or (B). The case where it becomes 2.0V or less.
(A) After being doped with lithium ions, the positive electrode terminal and the negative electrode terminal were allowed to stand for 12 hours or longer in a state where the positive electrode terminal and the negative electrode terminal were directly bonded to each other, then the short circuit was released and the positive electrode measured within 0.5 to 1.5 hours Potential.
(B) After discharging at constant current to 0 V over 12 hours with a charge / discharge tester, leaving the positive electrode terminal and the negative electrode terminal connected with a conducting wire for 12 hours or more, then releasing the short circuit, 0.5 ~ Positive electrode potential measured within 1.5 hours.

  In the present invention, the positive electrode potential of 2.0 V or less after the positive electrode and the negative electrode are short-circuited is not limited to immediately after the lithium ions are doped, and is repeatedly charged, discharged or charged / discharged. In other words, the positive electrode potential after short-circuiting is 2.0 V or less.

In the present invention, the fact that the potential of the positive electrode becomes 2.0 V or less after the positive electrode and the negative electrode are short-circuited will be described in more detail.
As described above, activated carbon and carbon materials usually have a potential of about 3 V (Li / Li ⁺ ), and when a capacitor is formed using activated carbon for both the positive electrode and the negative electrode as an active material, any potential is used. Therefore, even if the positive electrode and the negative electrode are short-circuited, the potential of the positive electrode does not change and remains at about 3V. The same applies to so-called hybrid capacitors using activated carbon as the positive electrode active material and carbon materials such as graphite and non-graphitizable carbon used in lithium ion secondary batteries as the negative electrode active material. Since the potential is also about 3V, even if the positive electrode and the negative electrode are short-circuited, the potential of the positive electrode does not change and remains at about 3V. Therefore, although depending on the mass balance of the positive electrode and the negative electrode, since the potential of the negative electrode transitions to around 0 V when charged, the charge voltage can be increased, and thus a capacitor having a high voltage and a high energy density can be obtained. . In general, the upper limit of the charging voltage is determined to be a voltage at which the electrolyte does not decompose due to an increase in the positive electrode potential. Therefore, when the positive electrode potential is set as the upper limit, the charging voltage is increased by a value that decreases the negative electrode potential. Can be increased.

However, in the above-described hybrid capacitor in which the positive electrode potential is about 3 V at the time of short circuit, when the upper limit potential of the positive electrode is 4.0 V, for example, the positive electrode potential at the time of discharge is up to 3.0 V, The change is about 1.0 V, and the capacity of the positive electrode cannot be fully utilized. Furthermore, when lithium ions are inserted (charged) and desorbed (discharged) into the negative electrode, the initial charge / discharge efficiency is often low, and it is known that there are lithium ions that cannot be desorbed during discharge. . This has been explained that the surface of the negative electrode is consumed for the decomposition of the electrolyte solution or trapped in the structural defect portion of the carbon material, but in this case, compared to the charge / discharge efficiency of the positive electrode When the charge / discharge efficiency of the negative electrode is lowered and the positive electrode and the negative electrode are short-circuited after repeated charge / discharge, the positive electrode potential becomes higher than 3V and the utilization capacity further decreases. In other words, the positive electrode can be discharged from 4.0 V to 2.0 V. However, when the positive electrode can only be discharged from 4.0 V to 3.0 V, or only half of the available capacity is used. Although it is possible to obtain a high voltage, it is difficult to obtain a high capacity.
Therefore, in order to obtain not only a high voltage and a high energy density as a capacitor, but also a high capacity and a high energy density, it is necessary to improve the utilization capacity of the positive electrode.

  If the potential of the positive electrode after a short circuit between the positive electrode and the negative electrode is lower than 3.0 V, the use capacity increases and the capacity increases accordingly. In order to set the potential of the positive electrode to 2.0 V or less after a short circuit between the positive electrode and the negative electrode, not only the amount charged by charging / discharging of the capacitor but also lithium ions from a lithium ion supply source such as lithium metal to the negative electrode separately. It is preferable to charge. By supplying lithium ions from other than the positive electrode and the negative electrode, when the positive electrode and the negative electrode are short-circuited, the positive electrode, the negative electrode, and the lithium metal are in an equilibrium potential, so both the positive electrode potential and the negative electrode potential are 3.0 V. It becomes as follows. Also, the equilibrium potential decreases as the amount of lithium metal constituting the lithium ion supply source increases. If the negative electrode active material and the positive electrode active material change, the equilibrium potential also changes. Therefore, the negative electrode in consideration of the characteristics of the negative electrode active material and the positive electrode active material so that the positive electrode potential after the short circuit between the positive electrode and the negative electrode is 2.0 V or less. It is necessary to adjust the amount of lithium ions to be supported.

  In the wound LIC according to the present invention, as described above, the potential of the positive electrode 11 after the positive electrode 11 and the negative electrode 12 are short-circuited is 2.0 V or less. That is, lithium ions are supplied to the positive electrode 11 and / or the negative electrode 12 from other than the negative electrode 12. The supply of lithium ions may be either one or both of the negative electrode 12 and the positive electrode 11. For example, when activated carbon is used as the positive electrode active material, the amount of lithium ions supported increases and the potential of the positive electrode decreases. Since problems such as irreversible consumption of lithium ions and a decrease in the capacity of the capacitor may occur, the amount of lithium ions supplied to the negative electrode and the positive electrode needs to be appropriately controlled so as not to cause problems. In any case, since the lithium ions previously supplied to the positive electrode and / or the negative electrode are supplied to the negative electrode by charging the cell, the potential of the negative electrode is lowered.

Further, when the potential of the positive electrode 11 after the positive electrode 11 and the negative electrode 12 are short-circuited is higher than 2.0 V, it is obtained because the amount of lithium ions supplied to the positive electrode 11 and / or the negative electrode 12 is small. The energy density of the wound LIC is small. As the supply amount of lithium ions increases, the potential of the positive electrode after the positive electrode and the negative electrode are short-circuited becomes lower and the energy density is improved. In order to obtain a high energy density, 2.0 V or less is preferable, and in order to obtain a higher energy density, 1.0 V (Li / Li ⁺ ) or less is preferable. When the positive electrode 11 and the negative electrode 12 are short-circuited, the potential of the positive electrode is lowered. In other words, the amount of lithium ions supplied to the negative electrode 12 is increased by charging the wound LIC. As the electrostatic capacity of the negative electrode 12 increases and the potential change amount of the negative electrode 12 decreases, as a result, the potential change amount of the positive electrode 11 increases and the electrostatic capacity and capacity of the wound LIC increase. High energy density can be obtained.

  Further, when the potential of the positive electrode 11 is less than 0.1 V, although depending on the positive electrode active material, problems such as gas generation and irreversible consumption of lithium ions occur. It becomes difficult. Moreover, when the electric potential of the positive electrode 11 becomes too low, it means that the mass of the negative electrode active material is excessive, and conversely, the energy density decreases. Therefore, generally, the potential of the positive electrode 11 is 0.1 V or higher, preferably 0.3 V or higher.

In the present invention, the capacitance and the capacitance are defined as follows. The capacitance of the capacitor indicates the slope of the discharge curve of the capacitor, the unit is F (farad), and the capacitance per unit mass of the capacitor is the capacitance of the capacitor based on the mass of the positive electrode active material and the negative electrode active material. It is the value divided by the total mass of the substance, the unit is F / g, the capacitance of the positive electrode indicates the slope of the discharge curve of the positive electrode, the unit is F, and the capacitance per unit mass of the positive electrode , The capacitance of the positive electrode divided by the mass of the positive electrode active material, the unit is F / g, the capacitance of the negative electrode indicates the slope of the discharge curve of the negative electrode, the unit is F, the unit mass of the negative electrode The hit capacitance is a value obtained by dividing the capacitance of the negative electrode by the mass of the negative electrode active material, and the unit is F / g.

  Further, the capacitance of the capacitor is the difference between the discharge start voltage and the discharge end voltage of the capacitor, that is, the product of the voltage change amount and the capacitance of the capacitor. The unit is C (coulomb), but 1C is 1 Since this is the amount of charge when a current of 1 A flows per second, in this specification, it is converted and displayed as mAh. The capacity of the positive electrode is the product of the difference between the potential of the positive electrode at the start of discharge and the potential of the positive electrode at the end of discharge (amount of change in positive electrode potential) and the capacitance of the positive electrode, and the unit is C or mAh. The capacity is a product of the difference between the potential of the negative electrode at the start of discharge and the potential of the negative electrode at the end of discharge (amount of change in negative electrode potential) and the capacitance of the negative electrode, and the unit is C or mAh. The capacity of the capacitor matches the capacity of the positive electrode and the capacity of the negative electrode.

In the wound LIC according to the present invention, the capacitance per unit mass of the negative electrode active material is three times or more than the capacitance per unit mass of the positive electrode active material, and the mass of the positive electrode active material is the negative electrode active material. The mass of the negative electrode is preferably larger than the mass of the material. For example, by appropriately controlling the lithium ion filling amount (pre-doping amount) into the negative electrode in consideration of the capacitance of the positive electrode, The electric capacity can be set to 3 times or more the electrostatic capacity per unit mass of the positive electrode active material, and the mass of the positive electrode active material can be larger than the mass of the negative electrode active material. Thereby, a capacitor having a higher voltage and a higher capacity than the conventional electric double layer capacitor can be obtained.
Further, when a negative electrode active material having a capacitance per unit mass larger than the capacitance per unit mass of the positive electrode active material is used, the mass of the negative electrode active material is reduced without changing the potential change amount of the negative electrode. Therefore, the filling amount of the positive electrode active material is increased, and the capacitance and capacity of the wound LIC can be increased.
The mass of the positive electrode active material is preferably larger than the mass of the negative electrode active material, but more preferably 1.1 to 10 times the mass of the negative electrode active material. When the mass of the positive electrode active material is less than 1.1 times the mass of the negative electrode active material, the capacity difference becomes small, which is not preferable. On the other hand, when the mass of the positive electrode active material exceeds 10 times the mass of the negative electrode active material, the capacity may be reduced, and the thickness difference between the positive electrode 11 and the negative electrode 12 becomes too large. This is not preferable in the configuration of the rotary LIC.

[Separator]
As the first separator 13A and the second separator 13B, it is possible to use a porous body that has durability against an electrolytic solution, a positive electrode active material, or a negative electrode active material and has continuous air holes, and has low electrical conductivity.
As materials of the first separator 13A and the second separator 13B, cellulose (paper), polyethylene, polypropylene, and other known materials can be used. Among these, cellulose (paper) is preferable in terms of durability and economy.
Although the thickness of 13 A of 1st separators and the 2nd separator 13B is not specifically limited, About 20-50 micrometers is preferable normally.

[Lithium ion source]
The lithium ion supply sources 16A to 16C are preferably pressure-bonded or stacked on a metal lithium electrode current collector. In such a configuration, the lithium electrode current collector can be electrically connected to, for example, the negative electrode terminal 18 through the lithium electrode terminal by providing a lithium electrode terminal.
As this lithium electrode current collector, one having a porous structure similar to that of the electrode current collector is used so that the lithium metal constituting the lithium ion supply sources 16A to 16C can be pressure-bonded easily and lithium ions can pass if necessary. It is preferable. Moreover, it is preferable to use what does not react with lithium ion supply sources, such as stainless steel, as a material of a lithium electrode electrical power collector.
Further, when a conductive porous material such as a stainless mesh is used as the lithium electrode current collector, at least a part of lithium metal constituting the lithium ion supply sources 16A to 16C, particularly 80% by mass or more, is a lithium electrode current collector. It is preferable that the gap is formed between the electrodes due to the disappearance of the lithium metal even after the lithium ions are supported on the negative electrode 12, and the reliability of the obtained wound LIC is preferable. Sex can be maintained more reliably.
The lithium electrode current collector preferably has a thickness of about 10 to 200 μm.
In addition, the thickness of the lithium metal to be pressure-bonded to the lithium electrode current collector is appropriately determined in consideration of the amount of lithium ions supported in advance on the negative electrode 12, but is usually preferably about 50 to 300 μm.

  The amount of lithium metal that constitutes the lithium ion supply sources 16A to 16C is such that the lithium ion is doped so that the potential of the positive electrode 11 after the positive electrode 11 and the negative electrode 12 are short-circuited is 2.0 V or less. It is preferable to set the inner peripheral surface so that, for example, lithium ions are doped to the negative electrode 12 in a balanced manner and rapidly from both the outer peripheral surface and the inner peripheral surface of the electrode winding unit 10 as much as possible. The amount of lithium metal constituting the lithium ion source 16A according to the above, the amount of lithium metal constituting the lithium ion source 16C relating to the electrode gap portion, and the amount of lithium metal constituting the lithium ion source 16B relating to the outer peripheral surface It is preferable to distribute.

  The material of the negative electrode terminal 18 and the positive electrode terminal 17 is not particularly limited as long as it has conductivity, and various materials can be used, but the same material as that of the negative electrode current collector 12a and the positive electrode current collector 11a, respectively. A thing is preferable from points, such as connectivity and expansibility.

The material of the tape 25 is not particularly limited as long as it has durability against the electrolytic solution and does not adversely affect the obtained wound LIC, but the material of the first separator 13A and the second separator 13B is not limited. The same material is preferred.
Further, the tape 25 having a thickness of about 50 to 100 μm and a width of about 5 to 10 mm is preferable because the electrode winding unit 10 can be stably fixed and workability is improved.
In addition, the number of tapes 25 and the positions fixed by the tapes 25 are appropriately determined mainly depending on the dimensions of the electrode winding unit 10. Usually, when the number of the tapes 25 is 2 to 3, the electrode winding unit is used. 10 can be stably fixed.

As a material of the core rod 19, a metal material such as stainless steel, copper, or nickel, or a resin having high resistance to electrolyte such as polypropylene or polyphenylene sulfide can be used.
Further, the diameter of the core rod 19 can be appropriately set according to the diameter of the inner periphery of the electrode winding unit 10. The core rod 19 is used in the manufacturing process of the electrode winding unit 10. In the completed electrode winding unit 10, the core rod 19 may be left as it is. Thus, the electrode winding unit may not have a core rod.

The material of the outer container 20 is not particularly limited, and various materials generally used for batteries or capacitors can be used. For example, a metal material such as iron or aluminum, a plastic material, or a composite material obtained by laminating them is used. The outer container 20 may be a film type using a laminate film of aluminum and a polymer material such as nylon and polypropylene from the viewpoint of reducing the size and weight of the wound LIC. preferable.
The shape of the outer container 20 is not particularly limited and can be appropriately selected depending on the application, such as a cylindrical shape or a rectangular shape. However, when a cylindrical electrode winding unit is accommodated, a cylindrical shape is flattened. When a cylindrical electrode winding unit body is accommodated, a rectangular type is preferable.

As the electrolytic solution filled in the outer container 20, an aprotic organic solvent electrolyte solution of lithium salt is used.
As the lithium salt constituting the electrolyte, any lithium salt can be used as long as it is capable of transporting lithium ions, does not cause electrolysis even under high voltage, and lithium ions can exist stably. Specific examples thereof include LiClO ₄ , Examples include LiAsF ₆ , LiBF ₄ , LiPF ₆ , and Li (C ₂ F ₅ SO ₂ ) ₂ N.
Specific examples of the aprotic organic solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, methylene chloride, sulfolane and the like. These aprotic organic solvents can be used alone or in admixture of two or more.
The electrolytic solution is prepared by mixing the above electrolyte and solvent in a sufficiently dehydrated state, but the concentration of the electrolyte in the electrolytic solution is at least 0.1 in order to reduce the internal resistance due to the electrolytic solution. It is preferably at least mol / L, more preferably from 0.5 to 1.5 mol / L.

  According to the above wound-type storage power source, the electrode winding unit 10 is obtained by winding the lithium ion supply source 16C in the positive electrode gap portion 11S to form the electrode stack 10A and winding it. Therefore, the electrode winding unit 10 can be easily assembled. Therefore, the assembly can be completed in a short time, and the lithium ion supply source 16C is arranged in the positive electrode gap portion 11S. Therefore, the pre-doping time can be shortened, and high productivity can be obtained.

  According to the wound-type storage power source manufactured in this way, since the pre-doping can be speeded up and uniformed, the internal resistance is reduced even if the assembly is completed in a short time. Thus, high performance is obtained and high durability is obtained.

As mentioned above, although the example of the embodiment was demonstrated about the winding type | mold storage power supply of this invention, this invention is not limited to said embodiment, A various change can be added.
Further, as a reference example, for example, the positive electrode is, as shown in FIG. 13, showing a wound-type electric storage source having a positive electrode gap portion including a plurality of slits 31T. In such a positive electrode 31, the lithium ion supply source 36C which concerns on a positive electrode gap | interval part is arrange | positioned in the state which is not in contact with the positive electrode 31 in the said slit 31T, and an electrode winding unit is comprised by winding with a negative electrode. .

  Further, for example, the negative electrode is not limited to a negative electrode having a plurality of negative electrode pieces, and a negative electrode 42 having a negative electrode gap portion as shown in FIGS. 14 and 15 may be used.

As shown in FIG. 15, such an electrode winding unit 40 first has a first strip member 42Q in which a strip-shaped negative electrode 42 is disposed on a first separator 43B, and a second separator 43A. Positive electrode gap portion 41S in which lithium ion supply source 16A serving as the inner peripheral surface of electrode winding unit 40 is arranged, positive electrode piece 411, positive electrode gap portion 41S in which lithium ion supply source 16C is arranged, positive electrode piece 412 and electrodes A positive electrode gap portion 41S in which the lithium ion supply source 16B serving as the outermost peripheral surface of the winding unit 40 is disposed forms a second band member 41Q formed in this order from one end to the other end. In the first strip member 42Q and the second strip member 41Q, when the length and arrangement position of the positive electrode gap and the electrode piece are wound, the positive electrode piece opposes the negative electrode piece only through the separator, and lithium The ion supply source is also set on the basis of the thickness of each component so that the negative electrode piece is opposed to the negative electrode piece only through the separator, and the inner peripheral surface and the outer peripheral surface are configured by the lithium ion supply source.
Then, the first strip member 42Q and the second strip member 41Q are stacked, and this electrode stack 40A is wound around the core rod 19 from one end thereof (one end of the lithium ion supply source 16A) in the direction of the arrow in the figure. Thus, the electrode winding unit 40 is obtained.

  Further, for example, the electrode winding unit is not limited to a substantially cylindrical shape, and may be a flat cylindrical shape formed by winding an electrode stack on a plate-like body, for example.

<Second Embodiment>
In the wound LIC according to the second embodiment, as shown in FIGS. 16 and 17, the electrode winding unit 50 has a belt-like shape in which a belt-like positive electrode 51 having a positive electrode gap 51S and a negative electrode gap 52S. The negative electrode 52 is a cylinder formed by winding an electrode stack 50A, in which the negative electrode 52, the separator 53A, and the positive electrode 51 are stacked in this order on the separator 53B through the separator. The configuration is the same as that of the first embodiment except that the configuration is the same as that of the first embodiment. 16 and 17, the same reference numerals as those in the first embodiment denote the same components.

In the electrode winding unit 50 in which the positive electrode 51, the negative electrode 52, and the lithium ion supply sources 16A to 16C are stacked on the separators 53A and 53B and wound, the negative electrode 52 is overlapped with at least a part of the positive electrode 51. Preferably it is.
Specifically, the electrode winding unit 50 is configured such that the outer peripheral surface of a pair of electrode pairs composed of opposing positive electrode portions and negative electrode portions is covered with a negative electrode portion extended from the negative electrode portion of the electrode pair portions, and The outer peripheral surface of the wound body covered with the extended negative electrode portion may be covered with the lithium ion supply source 16C, and the outer peripheral surface may be covered with another electrode pair portion. preferable.
Further, the electrode winding unit 50 is configured by inserting and winding the positive electrode 511 after the wound body in which the lithium ion supply source 16A constituting the inner peripheral surface is wound is covered with the negative electrode 521. It is preferable.
By adopting such a configuration, high durability can be obtained for the wound LIC. In addition, when it is made to oppose without interposing a negative electrode between a lithium ion supply source and a positive electrode, pre dope becomes inadequate and lithium metal remains, or a lithium ion supply source is placed on a lithium electrode current collector. Depending on the charge / discharge conditions, dendritic lithium metal called dendrite may be deposited on the lithium electrode current collector and cause a short circuit.

In such an electrode winding unit 50, as shown in FIG. 18, first, on the first separator 53B, a lithium ion supply source 16A, a negative electrode piece 521, a lithium piece serving as an inner peripheral surface of the electrode winding unit 50 are formed. A first strip 52Q in which an ion supply source 16C, a negative electrode piece 522, and a lithium ion supply source 16B that is the outermost peripheral surface of the electrode winding unit 50 are formed in this order from one end to the other end, On the separator 53A, the second band member 51Q in which the positive electrode gap portion 51S, the positive electrode piece 511, the positive electrode gap portion 51S, and the positive electrode piece 512 are formed in this order from one end to the other end is manufactured. In the first strip member 52Q and the second strip member 51Q, the length of the gap between the positive electrode 51 and the negative electrode 52 and the length and arrangement position of the electrode pieces are turned into the negative electrode pieces only through the separator. The lithium ion supply source is also opposed to the negative electrode piece through only the separator, and is set based on the thickness of each component so that the inner peripheral surface and the outer peripheral surface are configured by the lithium ion supply source. ing.
Then, the first strip 52Q and the second strip 51Q are stacked, and the electrode stack 50A is wound around the core rod 19 from one end (one end of the lithium ion supply source 16A) in the direction of the arrow in the figure. Thus, the electrode winding unit 50 is obtained.

  In the electrode winding unit 50 of this example, the positive electrode 51, the negative electrode 52, and the separators 53A and 53B have the same configuration as the positive electrode 11, the negative electrode 12, and the separators 13A and 13B in the first embodiment.

  According to the wound type LIC having the electrode winding unit 50 as described above, the same effects as those of the wound type LIC of the first embodiment can be obtained.

  As mentioned above, although the example of the 2nd Embodiment was demonstrated about the winding type | mold storage power supply of this invention, this invention is not limited to said embodiment, A various change can be added. .

For example, the electrode winding unit is not limited to a configuration in which the negative electrode is composed of a plurality of negative electrode pieces and a lithium ion supply source is disposed in the gap portion, and has a negative electrode gap portion as shown in FIG. You may have the structure by which the lithium ion supply sources 16A-16C are arrange | positioned in the position facing the positive electrode gap | interval part 61S using the negative electrode 62 of the structure which is not carried out. In FIG. 19, the same reference numerals as those in the first embodiment denote the same components.

In such an electrode winding unit 60, first, the positive electrode gap portion 61S, the positive electrode piece 611, the positive electrode gap portion 61S, the positive electrode piece 612, and the positive electrode gap portion 61S are arranged from one end to the other end on the second separator 63A. The strip-shaped negative electrode 62 is disposed on the second strip member 61Q formed in this order and the first separator 63B, and the electrode winding unit is disposed on the negative electrode 62 at a position facing each of the positive electrode gaps 61S. The lithium ion supply source 16A, the lithium ion supply source 16C, and the lithium ion supply source 16B, which are the outermost peripheral surfaces of the electrode winding unit 60, are arranged so as not to face the positive electrode pieces 611 and 612 at all. The manufactured first strip member 62Q is produced. In the first strip member 62Q and the second strip member 61Q, the length and the arrangement position of the positive electrode gap portion and the electrode piece are opposed to the negative electrode piece through the separator alone when the length and the arrangement position of the positive electrode gap are wound. The ion supply source is also set on the basis of the thickness of each component so that the negative electrode piece is opposed to the negative electrode piece only through the separator, and the inner peripheral surface and the outer peripheral surface are configured by the lithium ion supply source.
The first strip 62Q and the second strip 61Q are stacked, and the electrode stack 60A is wound around the core rod 19 from one end (one end of the lithium ion supply source 16A) in the direction of the arrow in the figure. Thus, the electrode winding unit 60 is obtained.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

<Example 1>
[Negative electrode production example 1]
A 0.5 mm thick phenolic resin molded plate is placed in a siliconite electric furnace, heated to 500 ° C. at a rate of 50 ° C./hour in a nitrogen atmosphere, and further heated to 660 ° C. at a rate of 10 ° C./hour. The PAS was synthesized by heat treatment. The obtained plate-like PAS was pulverized with a disk mill to obtain a PAS powder. The H / C ratio of this PAS powder was 0.21.

Next, a negative electrode slurry was obtained by sufficiently mixing 100 parts by mass of the above PAS powder and a solution in which 10 parts by mass of polyvinylidene fluoride powder was dissolved in 80 parts by mass of N-methylpyrrolidone. This negative electrode slurry was intermittently applied to both surfaces of a negative electrode current collector made of copper expanded metal (manufactured by Nippon Metal Industry Co., Ltd.) having a thickness of 32 μm (porosity 50%) by a die coater, and the coating part length was 15.2 cm. After patterning the negative electrode layer so that the length of the uncoated part becomes 10 cm and pressing, the total thickness of the negative electrode (total of the negative electrode layer thickness and the negative electrode collector thickness on both sides) is 77 μm. A negative electrode [1] was obtained. Further, after the negative electrode layer was patterned so that the coated part length was 36.1 cm and the uncoated part length was 10 cm in the same manner, the thickness of the whole negative electrode (the thickness of the negative electrode layers on both sides) And the negative electrode current collector thickness) was 77 μm.
A prototype cell using the negative electrode [1] and the negative electrode [2] as working electrodes, lithium metal as a counter electrode and reference electrode, and a solution of LiPF ₆ dissolved in propylene carbonate at a concentration of 1 mol / L as an electrolytic solution is experimentally produced. Then, 400 mAh / g of lithium ion was charged with respect to the mass of the negative electrode active material, and the capacitances per unit mass of the negative electrode [1] and the negative electrode [2] were determined. Both were 661 F / g. .

[Production Example 1 of Positive Electrode]
A positive electrode slurry is obtained by dispersing 100 parts by mass of activated carbon powder having a specific surface area of 1950 m ² / g, 10 parts by mass of acetylene black, 7 parts by mass of an acrylic binder, and 4 parts by mass of carboxymethyl cellulose in water and mixing them well. It was.
On the other hand, a non-aqueous carbon-based conductive paint “EB-815” (manufactured by Nippon Atchison Co., Ltd.) is applied to both sides of an aluminum expanded metal (manufactured by Nippon Metal Industry Co., Ltd.) having a thickness of 35 μm (porosity 50%). The positive electrode current collector [1] was obtained by intermittently coating on both sides, patterning the conductive layer so that the coated part length was 13.2 cm, and the uncoated part length was 10 cm, and drying. The total thickness (the sum of the thickness of the aluminum expanded metal and the thickness of the conductive layer) was 52 μm, and the through hole in the coated part was almost blocked by the conductive paint. Further, the positive electrode slurry [1] is intermittently applied onto the conductive layers on both sides by a die coater, and the electrode layer of the positive electrode is patterned so that the coated part length is 13.2 cm and the uncoated part length is 10 cm. After the press treatment, a positive electrode [1] was obtained in which the total thickness of the positive electrode (the sum of the electrode layer thickness of both positive electrodes and the thickness of the positive electrode current collector [1]) was 212 μm. Furthermore, after patterning the electrode layer of the positive electrode so that the coated part length is 26.1 cm and the uncoated part is 10 cm in the same manner and pressing, the total thickness of the positive electrode (the electrode layer thickness of the positive electrode on both sides) A positive electrode [2] having a positive electrode current collector [1] (total thickness) of 212 μm was obtained.
A prototype cell using the positive electrode [1] and the positive electrode [2] as working electrodes, lithium metal as a counter electrode and a reference electrode, and a solution of LiPF ₆ dissolved in propylene carbonate at a concentration of 1 mol / L as an electrolyte is manufactured as a prototype. And when the electrostatic capacitance per unit mass of positive electrode [1] and positive electrode [2] was calculated | required from the discharge time between 3.5V-2.5V, all were 119F / g.

[Production example 1 of electrode winding unit]
The negative electrode [1] having a thickness of 77 μm was cut into a width of 5.6 × length of 16.2 cm ² so as to include an uncoated portion at a position 10 mm from the end, and a nickel terminal was connected to the negative electrode current collector. It arrange | positioned on a coating part and connected to the negative electrode collector by ultrasonic welding. Also, the positive electrode [1] having a thickness of 212 μm was cut into a width of 5.4 × length of 14.2 cm ² so as to include an uncoated portion at a position 10 mm from the end, and the aluminum terminal was connected to the positive electrode current collector It arrange | positioned on the uncoated part of this and connected to the positive electrode electrical power collector by ultrasonic welding. In the same manner, the negative electrode [2] was cut into a width of 5.6 × 37.1 cm ² and a nickel terminal was placed on the uncoated portion of the negative electrode current collector. Connected by sonic welding, the positive electrode [2] was cut to a width of 5.4 × length of 27.1 cm ² , an aluminum terminal was placed on the uncoated part of the positive electrode current collector, Connected by ultrasonic welding.
A cellulose / rayon mixed nonwoven fabric having a thickness of 35 μm was used as the separator, and the positive electrode [1] and the positive electrode [2] were arranged in this order from the core rod (19) side to the separator (13A) according to FIG. (13B), in order of the lithium ion supply source [1], the negative electrode [1], the lithium ion supply source [2], the negative electrode [2], and the lithium ion supply source [3] from the core rod (19) side. An electrode stack was formed, and the electrode stack was wound from one end so that the positive and negative terminals were in opposite directions, and the outermost periphery was taped to produce an electrode winding unit [1]. . A total of three of these were produced.
In the electrode stack, as a lithium ion supply source [1] for the inner peripheral surface, a winding start portion has one lithium metal having a thickness of 60 μm × width 5.4 × length 1.1 cm ² and a gap portion. As a lithium ion source [2] related to the above, one lithium metal having a thickness of 60 μm × width 5.4 × length 3.1 cm ^{2 and} a lithium ion source [3] related to the outer peripheral surface as a thickness 120 μm × width 5.4 × 5.0 cm ² length of lithium metal was used, and this was pre-bonded to the separator, and on top of these lithium metals, a 7.4 cm wide copper expanded metal (lithium electrode current collector) ) Was cut into the same length as each lithium metal, placed, and pressed by pressing. For this reason, the lithium ion supply source could be inserted easily.
In this electrode winding unit [1], the lithium electrode non-occupancy ratio on the inner peripheral surface, the outer peripheral surface, and the outer peripheral surface of the wound body was all 0%.

[Cell Production Example 1]
The electrode winding unit [1] is inserted into an iron-nickel-plated outer can having an outer diameter of 18 mmφ and a height of 65 mm, and the negative electrode terminal and the outer can are resistance-welded at the bottom of the can, Grooving was performed. Subsequently, after attaching a polypropylene gasket to the upper part of the can, the positive electrode terminal and the positive electrode cap were resistance-welded.
When 8 g of a solution obtained by dissolving LiPF ₆ in a concentration of 1 mol / L was injected into propylene carbonate as an electrolytic solution and impregnated with vacuum, 4 minutes were required.
After that, three cylindrical lithium ion capacitor cells [1] were assembled by covering the outer can with a positive electrode cap.

[Initial evaluation of cell]
Regarding the lithium ion capacitor cell [1], after being assembled for 4 days after cell assembly, one cell was disassembled, and all of the lithium metal was completely lost. From this, it is judged that lithium ions for obtaining a capacitance of 660 F / g or more per unit mass of the negative electrode active material were precharged for 4 days after the cell assembly.

[Evaluation of cell characteristics]
The lithium ion capacitor cell [1] was charged with a constant current of 750 mA until the cell voltage reached 3.8 V, and then a constant current-constant voltage charge in which a constant voltage of 3.8 V was applied was performed for 0.5 hour. Next, the battery was discharged at a constant current of 750 mA until the cell voltage reached 2.2V. This cycle of 3.8V-2.2V was repeated, and the cell capacity, energy density, and internal resistance in the 10th discharge were evaluated. Evaluation is the average value of two cells. The results are shown in Table 1.

  In the production process of the lithium ion capacitor cell [1], it was confirmed that the electrode winding unit [1] including the lithium ion supply source can be obtained in a short time. This is presumably because the lithium ion supply source (lithium metal) was previously pressure-bonded to the separator. Further, it was confirmed that the lithium ion doping time was short, although the time required to complete the electrolyte injection was long. This is presumably because the lithium ion supply source (lithium metal) was disposed not only on the inner and outer peripheral surfaces but also on the gaps between the electrodes.

<Comparative Example 1>
[Negative electrode production example 2]
A negative electrode slurry was obtained in the same manner as in negative electrode production example 1, and this negative electrode slurry was formed on both sides of a negative electrode current collector made of copper expanded metal (manufactured by Nippon Metal Industry Co., Ltd.) having a thickness of 32 μm (porosity 50%). The negative electrode layer was pattern-molded so that the coated part length was 49.3 cm and the uncoated part length was 10 cm, and after pressing, the total thickness of the negative electrode (the negative electrode layers on both sides) A negative electrode [3] having a total thickness of 77 μm was obtained.

[Production Example 2 of Positive Electrode]
On the other hand, a non-aqueous carbon-based conductive paint “EB-815” (manufactured by Nippon Atchison Co., Ltd.) is applied to both sides of an aluminum expanded metal (manufactured by Nippon Metal Industry Co., Ltd.) having a thickness of 35 μm (porosity 50%). The positive electrode current collector [2] was obtained by intermittently coating on both sides, patterning the conductive layer so as to have a length of 46.3 cm and an uncoated portion length of 10 cm, and drying. The total thickness (the sum of the thickness of the aluminum expanded metal and the thickness of the conductive layer) was 52 μm, and the through hole in the coated part was almost blocked by the conductive paint. Further, the positive electrode slurry [1] obtained in the same manner as in the positive electrode production example 1 is intermittently applied onto the conductive layers on both sides by a die coater so that the coated part length is 46.3 cm and the uncoated part length is 10 cm. After the electrode layer of the positive electrode is formed into a pattern and pressed, the positive electrode [3] having a total thickness of the positive electrode (total of the electrode layer thickness of the positive electrodes on both sides and the thickness of the positive electrode current collector [2]) is 212 μm. Obtained.

[Production example 2 of electrode winding unit]
The negative electrode [3] having a thickness of 77 μm was cut into a width of 5.6 × length of 49.3 cm ² so as to include an uncoated portion at a position 10 mm from the end, and a nickel terminal was connected to the negative electrode current collector. It arrange | positioned on a coating part and connected to the negative electrode collector by ultrasonic welding. Further, the positive electrode [3] having a thickness of 212 μm was cut into a width of 5.4 × length of 46.3 cm ² so as to include an uncoated portion at a position 10 mm from the end, and the aluminum terminal was connected to the positive electrode current collector It arrange | positioned on the uncoated part of this and connected to the positive electrode electrical power collector by ultrasonic welding.
A cellulose / rayon mixed nonwoven fabric having a thickness of 35 μm was used as a separator, and an electrode stack was formed so as to be composed of a continuous strip of negative electrode and positive electrode without forming the positive electrode gap and negative electrode gap in FIG. The electrode stack was wound from one end so that the positive and negative terminals were in opposite directions, and the outermost periphery was taped to produce an electrode winding unit [2]. A total of three of these were produced.
In the electrode stack, as a lithium ion supply source related to the inner peripheral surface, one lithium metal having a thickness of 135 μm × width 5.4 × length 1.1 cm ^{2 at} the winding start portion and lithium related to the outer peripheral surface As an ion supply source, one piece of lithium metal having a thickness of 135 μm × width of 5.4 × length of 5.0 cm ² was preliminarily pressure-bonded to a separator, and further on the lithium metal, a width of 7.4 cm The copper expanded metal (lithium electrode current collector) was cut into the same length as each lithium metal, arranged, and pressed by pressing. For this reason, the lithium ion supply source could be inserted easily.
In the electrode winding unit [2], the lithium electrode non-occupancy ratio on the inner peripheral surface, the outer peripheral surface, and the outer peripheral surface of the wound body was 0%.

[Cell Production Example 2]
The electrode winding unit [2] is inserted into an iron-nickel plated outer can having an outer diameter of 18 mmφ and a height of 65 mm, and the negative electrode terminal and the outer can are resistance-welded at the bottom of the can, Grooving was performed. Subsequently, after attaching a polypropylene gasket to the upper part of the can, the positive electrode terminal and the positive electrode cap were resistance-welded.
When 9 g of a solution obtained by dissolving LiPF ₆ in a concentration of 1 mol / L was poured into propylene carbonate as an electrolytic solution and vacuum impregnation was performed, 4 minutes were required.
After that, three cylindrical lithium ion capacitor cells [2] were assembled by covering the outer can with a positive electrode cap.

[Initial evaluation of cell]
Regarding the lithium ion capacitor cell [2], after being left for 4 days after cell assembly, one cell was disassembled. As a result, about 30% of the lithium metal remained, and after leaving for another 3 days, the cell was disassembled and disappeared completely. It was. From this, it is judged that the lithium ion for obtaining the electrostatic capacity of 660 F / g or more per unit mass of the negative electrode active material was precharged for 7 days after the cell assembly.

[Evaluation of cell characteristics]
The lithium ion capacitor cell [2] was charged at a constant current of 750 mA until the cell voltage reached 3.8 V, and then a constant current-constant voltage charge for applying a constant voltage of 3.8 V was performed for 0.5 hour. Next, the battery was discharged at a constant current of 750 mA until the cell voltage reached 2.2V. This cycle of 3.8V-2.2V was repeated, and the cell capacity, energy density, and internal resistance in the 10th discharge were evaluated. Evaluation is the average value of two cells. The results are shown in Table 2.

  In the manufacturing process of the lithium ion capacitor cell [2], it was confirmed that the electrode winding unit [2] including the lithium ion supply source can be obtained in a short time. This is presumably because the lithium ion supply source (lithium metal) was previously pressure-bonded to the separator. However, it was confirmed that the time until the electrolyte injection was completed was long, and the lithium ion doping time was longer than that of the lithium ion capacitor cell [1] according to Example 1. This is presumably because the number of lithium ion supply sources (lithium metal) is less than that of the lithium ion capacitor cell [1] according to the first embodiment.

<Comparative example 2>
[Production Example 3 of Electrode Winding Unit]
In Production Example 2 of the electrode winding unit of Comparative Example 1, as a lithium ion supply source related to the inner peripheral surface, lithium metal having a thickness of 60 μm × width 5.4 × length 1.0 cm ² and lithium ions related to the outer peripheral surface As a supply source, lithium metal having a thickness of 140 μm × width 5.4 × length 5.0 cm ² is used, and between the first strip material related to the negative electrode of the electrode stack and the second strip material related to the positive electrode, As a lithium ion supply source for the intermediate part, the electrode plate was formed in the same manner except that lithium metal was stacked on the negative electrode, wound and wound, with a thickness of 60 μm × width 5.4 × length 3.1 cm ^2. A rotating unit [3] was produced. A total of three of these were produced.
In this electrode winding unit [3], the lithium electrode non-occupancy ratios on the inner peripheral surface, the outer peripheral surface, and the outer peripheral surface of the wound body were all 0%.

[Cell Production Example 3]
The electrode winding unit [3] is inserted into an iron-nickel-plated outer can with an outer diameter of 18 mmφ and a height of 65 mm, and the negative electrode terminal and the outer can are resistance-welded at the bottom of the can, Grooving was performed. Subsequently, after attaching a polypropylene gasket to the upper part of the can, the positive electrode terminal and the positive electrode cap were resistance-welded.
When 9 g of a solution obtained by dissolving LiPF ₆ in a concentration of 1 mol / L was poured into propylene carbonate as an electrolytic solution and vacuum impregnation was performed, 4 minutes were required.
Thereafter, three cylindrical lithium ion capacitor cells [3] were assembled by covering the outer can with a positive electrode cap.

[Initial evaluation of cell]
When the lithium ion capacitor cell [3] was allowed to stand for 4 days after cell assembly and decomposed by one cell, a trace of lithium metal remained in the gap, but almost disappeared. From this, it is determined that lithium ions for obtaining a capacitance of 660 F / g or more per unit mass of the negative electrode active material were precharged about 4 days after the cell assembly.

[Evaluation of cell characteristics]
The lithium ion capacitor cell [3] was charged at a constant current of 750 mA until the cell voltage reached 3.8 V, and then a constant current-constant voltage charge for applying a constant voltage of 3.8 V was performed for 0.5 hour. Next, the battery was discharged at a constant current of 750 mA until the cell voltage reached 2.2V. This cycle of 3.8V-2.2V was repeated, and the cell capacity, energy density, and internal resistance in the 10th discharge were evaluated. Evaluation is the average value of two cells. The results are shown in Table 3.

In the production process of the lithium ion capacitor cell [3], it was confirmed that the electrode winding unit [3] including the lithium ion supply source can be obtained in a short time. This is presumably because the lithium ion supply source (lithium metal) was previously pressure-bonded to the separator. Further, it was confirmed that the lithium ion doping time was as short as that of the lithium ion capacitor cell [1] according to Example 1, although the time required for completing the injection of the electrolytic solution was long. This is presumably because the number of lithium ion supply sources (lithium metal) is as large as the lithium ion capacitor cell [1] according to the first embodiment. However, it was confirmed that the internal resistance was high. This is presumed that the lithium metal placed in the middle part caused a problem on the negative electrode because the resistance at the location where the lithium metal and the negative electrode were in contact increased.
Furthermore, when one cell was disassembled by adding 100 more charge / discharge cycles, dendrites (dendritic lithium metal) were generated on the lithium electrode current collector in the middle, so that durability and safety were improved. There seems to be a problem.
Therefore, when lithium metal is disposed in the middle portion, it is considered necessary to divide the electrode so that the lithium metal and the positive electrode do not face each other as in the lithium ion capacitor cell [1] according to the first embodiment. It is done.

It is sectional drawing for description which shows typically an example of a structure of the winding type lithium ion capacitor which concerns on this invention. It is sectional drawing for description which shows typically the state of the cross section of the electrode laminated body which solved the winding state of the electrode winding unit of winding type | mold LIC of FIG. It is a top view for explanation showing typically an example of composition of a positive electrode. FIG. 2 is an explanatory perspective view showing an electrode winding unit in the wound LIC shown in FIG. 1. It is a front view for description which shows the electrode winding unit in the winding type | mold LIC shown in FIG. It is explanatory drawing which shows an example of the insertion method of the lithium ion supply source which concerns on an outer peripheral surface. It is explanatory drawing which shows an example of the insertion method of the lithium electrode electrical power collector which concerns on an outer peripheral surface. It is explanatory drawing which shows another example of the insertion method of the lithium electrode electrical power collector which concerns on an outer peripheral surface. It is explanatory drawing which shows an example of the insertion method of the lithium ion supply source which concerns on an internal peripheral surface. It is explanatory drawing which shows an example of the insertion method of the lithium electrode electrical power collector which concerns on an internal peripheral surface. It is an explanatory top view shown in the state where the electrode in the electrode winding unit was developed. It is explanatory drawing which expands and shows the AA cross section of the electrode shown in FIG. It is an explanatory top view which shows typically another example of a structure of a positive electrode. It is sectional drawing for description which shows typically another example of a structure of an electrode stack. It is sectional drawing for description which shows typically the method of obtaining the electrode winding unit of winding type | mold LIC of FIG. It is sectional drawing for description which shows typically another example of a structure of the winding type lithium ion capacitor which concerns on this invention. FIG. 17 is an explanatory cross-sectional view schematically showing a cross-sectional state of the electrode stack in which the wound state of the electrode winding unit of the wound LIC of FIG. 16 is solved. FIG. 17 is an explanatory sectional view schematically showing a method for obtaining the electrode winding unit of the wound LIC of FIG. 16. It is sectional drawing for description which shows typically the method of obtaining the winding type lithium ion capacitor by another structure.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Electrode winding unit 10A Electrode stack 11 Positive electrode 111,112 Positive electrode piece 11S Positive electrode gap part 11a Positive electrode collector 11b Electrode layer 11c Underlayer 12 Negative electrode 12S Negative electrode gap part 121,122 Negative electrode piece 121α Surplus part 12a Negative electrode collector 12b Electrode layer 12c Underlayer 13A, 13B Separator 16A-16C Lithium ion supply source 17 Positive electrode terminal 18 Negative electrode terminal 19 Core rod 20 Exterior container 25 Tape 26a-26c Lithium electrode current collector 30A Electrode stack 31 Positive electrode 31T Slit 36C Lithium ion Supply source 40 Electrode winding unit 40A Electrode stack body 41 Positive electrode 411, 412 Positive electrode piece 41S Positive electrode gap 41Q First strip material 42 Negative electrode 43A, 43B Separator 42Q Second strip material 50 Electrode winding unit 50A Electrode stack body 51 Positive electrode 511 , 512 Positive electrode piece 51S Positive electrode Gap 51Q Second band 52 Negative electrode 521, 522 Negative electrode piece 52S Negative electrode gap 52Q First band 53A, 53B Separator 60 Electrode winding unit 60A Electrode stack 61 Positive electrode 611, 612 Positive electrode piece 61S Positive electrode gap 61Q Second Strip 62 Negative electrode 62Q First strip 63A, 63B Separator P Hole
S intermittent part

Claims (12)

A positive electrode in which an electrode layer containing a positive electrode active material capable of reversibly supporting lithium ions and / or anions is formed on at least one surface of a current collector having holes penetrating the front and back surfaces, and penetrates the front and back surfaces. A negative electrode in which an electrode layer containing a negative electrode active material capable of reversibly supporting lithium ions is formed on at least one surface of a current collector having pores, and the positive electrode and the negative electrode are stacked via a separator. A cylindrical electrode winding unit constituted by an electrode stack formed by being wound from one end thereof, and
Comprising an electrolyte comprising an aprotic organic solvent electrolyte solution of a lithium salt,
A wound-type storage power source in which lithium ions and / or anions are doped into the negative electrode and / or positive electrode by electrochemical contact between the negative electrode and / or the positive electrode and a lithium ion supply source,
A gap is formed between the positive electrodes,
The gap, or, in a position facing the gap in the anode, wound-type electric storage source, characterized in that at least one of the lithium ion supply source is provided in a state not in contact with the positive electrode.   The wound-type storage power source according to claim 1, wherein a lithium ion supply source is provided on an inner peripheral surface and / or an outer peripheral surface of the electrode winding unit.   The wound-type storage power source according to claim 1 or 2, wherein the lithium ion supply source is disposed so as not to contact the positive electrode and the negative electrode via a separator.   The wound-type storage power source according to any one of claims 1 to 3, wherein the lithium ion supply source is crimped or stacked on a lithium electrode current collector.   The wound-type storage power source according to any one of claims 1 to 4, wherein the lithium electrode current collector on which the lithium ion supply source is crimped or stacked is made of a porous foil. The lithium ion supply source provided at a position corresponding to the gap portion or the gap portion in the negative electrode is inserted and wound after the winding body to be covered by the lithium ion supply source is covered by the outermost peripheral portion of the negative electrode. The wound-type storage power source according to claim 1, wherein an electrode winding unit is configured.   The electrode winding unit is configured by inserting and winding the positive electrode after the wound body in which the lithium ion supply source constituting the inner peripheral surface of the electrode winding unit is wound is covered with the negative electrode. The wound-type storage power source according to any one of claims 1 to 6, wherein:   The lithium ion supply source constituting the outer peripheral surface of the electrode winding unit is inserted and wound after the wound body to be covered by the lithium ion supply source is covered at the outermost periphery of the negative electrode, whereby the electrode winding unit The wound-type storage power source according to any one of claims 1 to 7, wherein The winding according to any one of claims 1 to 8, wherein the positive electrode has a plurality of positive electrode pieces, and each positive electrode piece is arranged with the gap portion therebetween. Type accumulator. The wound-type power storage device according to any one of claims 1 to 9 , wherein the negative electrode is overlapped with at least a part of the positive electrode . It is a lithium ion capacitor, The winding type | mold storage power supply in any one of Claims 1-10 characterized by the above-mentioned. It is a lithium ion secondary battery, The winding type | mold storage power supply in any one of Claims 1-11 characterized by the above-mentioned.

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