JP2009200302A - Method of manufacturing electricity storage device, and electricity storage device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enhance the productivity and quality of an electricity storage device. <P>SOLUTION: An electricity storage device 10 has positive electrodes 13 and negative electrodes 14 which are alternately laminated. Each of the positive electrodes 13 has a positive electrode collector 20 having through-holes 20a. The positive electrode collector 20 is coated with a positive electrode mixed material layer 21 containing active carbon. Each of the negative electrodes 14 has a negative electrode collector 23 having through-holes 23a. The negative electrode collector 23 is coated with a negative electrode mixed material layer 24 containing a polyacenic semiconductor (PAS). A lithium electrode 16 is disposed so as to face the outermost negative electrode 14. The lithium electrode 16 has a lithium electrode collector 26 joined to the negative electrode collector 23. Metal lithium foil 27 is press-bonded to the lithium electrode collector 26. The electricity storage device 10 of such a structure is injected with an electrolytic solution, and the electricity storage device 10 is maintained in a temperature environment from 40°C to 70°C. Thus, lithium ions are doped from the metal lithium foil 27 into the negative electrode 14 in the temperature environment from 40°C to 70°C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for manufacturing an electricity storage device in which at least one of a positive electrode and a negative electrode is doped with lithium ions, and a technique effective when applied to the electricity storage device.

Examples of power storage devices mounted on electric vehicles and hybrid vehicles include lithium ion capacitors and lithium ion secondary batteries. In addition, it has been proposed to previously dope lithium ions into the negative electrodes of these electricity storage devices (see, for example, Patent Document 1). By doping lithium ions into the negative electrode, cell voltage, cell capacity, and capacitance can be improved, and the energy density of the electricity storage device can be increased. When the negative electrode is doped with lithium ions, a method in which the negative electrode and metallic lithium are brought into electrochemical contact is employed.
JP 2007-67285 A

  However, a long doping time is required for doping lithium ions into the negative electrode. This long doping time has been a factor of reducing the productivity of the electricity storage device and increasing the cost of the electricity storage device. Therefore, it is desired to improve the productivity of the electricity storage device by reducing the doping time.

  Further, when the lithium ion doped in the negative electrode is decreased, the cell voltage, the cell capacity, and the electrostatic capacity are decreased although the doping time is shortened. Thus, reducing the doping amount of lithium ions becomes a factor of reducing the energy density of the electricity storage device. On the other hand, when the amount of lithium ions doped in the negative electrode increases, not only does the doping time become longer, but an unnecessarily thick film or the like is formed on the electrode surface. As described above, increasing the doping amount of lithium ions causes deterioration of the electricity storage device, such as increasing the internal resistance of the electricity storage device. That is, in order to improve the quality of the electricity storage device, it is necessary to appropriately set the amount of lithium ions doped into the negative electrode.

  An object of the present invention is to improve the productivity and quality of an electricity storage device.

  The method for manufacturing an electricity storage device of the present invention includes a positive electrode including a positive electrode current collector in which a through hole is formed, a negative electrode including a negative electrode current collector in which a through hole is formed, and the stacked positive electrode and the negative electrode. A method for manufacturing an electricity storage device having an ion supply source connected to at least one of them, wherein a doping step of doping at least one of the positive electrode and the negative electrode with lithium ions from the ion supply source is provided. , In a temperature environment of 40 ° C. or higher and 70 ° C. or lower.

  The method for manufacturing an electricity storage device according to the present invention is characterized in that lithium ions of 70% or more and 120% or less of the maximum negative electrode charge capacity are released from the ion supply source.

In the method for manufacturing an electricity storage device of the present invention, the electricity storage device is a material in which the positive electrode active material is capable of doping and undoping lithium ions and / or anions, and the negative electrode active material is capable of doping and undoping lithium ions. Lithium in which the negative electrode and / or the positive electrode is doped with lithium ions so that the positive electrode potential after the positive electrode and the negative electrode are short-circuited is 2.0 V (vs. Li / Li ⁺ ) or less. It is an ion capacitor.

  In the method for producing an electricity storage device of the present invention, the negative electrode has a polyacene skeleton structure that is a heat-treated product of an aromatic condensation polymer and has a hydrogen atom / carbon atom ratio of 0.05 to 0.50. It contains polyacene-based organic semiconductor, graphite, or non-graphitizable carbon.

  The electricity storage device of the present invention includes at least one of a positive electrode including a positive electrode current collector formed with a through hole, a negative electrode including a negative electrode current collector formed with a through hole, and the positive electrode and the negative electrode stacked. An ion supply source connected to one side and emitting lithium ions, and at least one of the positive electrode and the negative electrode is doped with lithium ions from the ion supply source in a temperature environment of 40 ° C. or higher and 70 ° C. or lower It is characterized by making it.

  The electricity storage device of the present invention is characterized in that lithium ions of 70% or more and 120% or less of the maximum negative electrode charge capacity are released from the ion supply source.

In the electricity storage device of the present invention, the electricity storage device is a material in which the positive electrode active material is capable of doping and dedoping lithium ions and / or anions, and the negative electrode active material is a material in which lithium ions can be doped and dedope, A lithium ion capacitor in which lithium ions are doped to the negative electrode and / or the positive electrode so that the positive electrode potential after short-circuiting the positive electrode and the negative electrode is 2.0 V (vs. Li / Li ⁺ ) or less. It is characterized by being.

  In the electricity storage device of the present invention, the negative electrode has a polyacene-based skeleton structure that is a heat-treated product of an aromatic condensation polymer and has a hydrogen atom / carbon atom ratio of 0.05 to 0.50. An organic semiconductor, graphite, or non-graphitizable carbon is included.

  In the present invention, at least one of the positive electrode and the negative electrode is doped with lithium ions from an ion supply source in a temperature environment of 40 ° C. or higher and 70 ° C. or lower. Thereby, since the doping rate can be increased, the productivity of the electricity storage device can be improved. In addition, since the deterioration of the electricity storage device in the doping process can be prevented, the quality of the electricity storage device can be improved.

  FIG. 1 is a perspective view showing an electricity storage device 10 according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing the internal structure of the electricity storage device 10 along the line AA in FIG. As shown in FIGS. 1 and 2, the laminate film 11 constitutes an outer container of the electricity storage device 10. An electrode laminate unit 12 is accommodated in the laminate film 11. The electrode stacking unit 12 includes positive electrodes 13 and negative electrodes 14 that are alternately stacked. A separator 15 is provided between the positive electrode 13 and the negative electrode 14. A lithium electrode 16 is disposed on the outermost part of the electrode laminate unit 12 so as to face the negative electrode 14. A separator 15 is provided between the negative electrode 14 and the lithium electrode 16. The electrode laminate unit 12 and the lithium electrode 16 constitute a triode laminate unit 17. An electrolyte solution is injected into the laminate film 11. This electrolytic solution is composed of an aprotic organic solvent containing a lithium salt.

  FIG. 3 is a cross-sectional view showing a partially enlarged internal structure of the electricity storage device 10. As shown in FIG. 3, the positive electrode 13 has a positive electrode current collector 20 having a large number of through holes 20a. A positive electrode mixture layer 21 is coated on the positive electrode current collector 20. Further, the positive electrode current collector is provided with a terminal welded portion 20b extending in a convex shape. The plurality of terminal welds 20b are joined to each other in a stacked state. Furthermore, the positive electrode terminal 22 is joined to the terminal welding part 20b joined mutually. Similarly, the negative electrode 14 has a negative electrode current collector 23 having a large number of through holes 23a. The negative electrode current collector 23 is coated with a negative electrode mixture layer 24. Further, the negative electrode current collector 23 is provided with a terminal welding portion 23b extending in a convex shape. The plurality of terminal welds 23b are joined to each other in a stacked state. Furthermore, the negative electrode terminal 25 is joined to the terminal welding part 23b joined together.

  The positive electrode mixture layer 21 includes activated carbon as a positive electrode active material. This activated carbon can be reversibly doped and dedoped with lithium ions and anions. Further, the negative electrode mixture layer 24 includes a polyacene organic semiconductor (PAS) as a negative electrode active material. This PAS can be reversibly doped / undoped with lithium ions. Thus, by using activated carbon as the positive electrode active material and adopting PAS as the negative electrode active material, the electricity storage device 10 functions as a lithium ion capacitor. In the present invention, doping (doping) means occlusion, support, adsorption, insertion, and the like. That is, dope means a state in which lithium ions and the like enter the positive electrode active material and the negative electrode active material. De-doping (de-doping) means release, desorption and the like. That is, dedoping means a state in which lithium ions and the like are emitted from the positive electrode active material and the negative electrode active material.

  As described above, the lithium electrode 16 is incorporated in the electricity storage device 10. The lithium electrode 16 has a lithium electrode current collector 26 joined to the negative electrode current collector 23. A lithium metal foil 27 as an ion supply source is pressure-bonded to the lithium electrode current collector 26. Therefore, the metal lithium foil 27 and the negative electrode mixture layer 24 are connected via the lithium electrode current collector 26 and the negative electrode current collector 23. In this way, the negative electrode 14 and the lithium electrode 16 are electrically connected. Therefore, by injecting the electrolytic solution into the laminate film 11, lithium ions are doped from the lithium electrode 16 to the negative electrode 14 (hereinafter referred to as pre-doping).

  Thus, the negative electrode potential can be lowered by pre-doping lithium ions into the negative electrode 14. Thereby, the cell voltage of the electricity storage device 10 can be increased. In addition, the positive electrode 13 can be deeply discharged by lowering the negative electrode potential, and the cell capacity (discharge capacity) of the electricity storage device 10 can be increased. Furthermore, it becomes possible to increase the electrostatic capacity of the negative electrode 14 by pre-doping the negative electrode 14 with lithium ions. Thereby, the electrostatic capacity of the electricity storage device 10 can be increased. Thus, since the cell voltage, cell capacity, and electrostatic capacity of the electricity storage device 10 can be increased, the energy density of the electricity storage device 10 can be improved. Further, through holes 20 a and 23 a are formed in the positive electrode current collector 20 and the negative electrode current collector 23. For this reason, the lithium ions released from the lithium electrode 16 can be moved in the stacking direction. This makes it possible to smoothly pre-dope lithium ions for all the negative electrodes 14 to be laminated.

  Subsequently, the content of lithium ion pre-doping on the negative electrode 14 will be described in detail. As described above, a lithium ion doping process for the negative electrode 14 is started by injecting an electrolyte into the laminate film 11 and sealing the laminate film 11. This doping process is performed in a state where the electricity storage device 10 is held in a temperature environment of 40 ° C. or higher and 70 ° C. or lower. As described above, by performing the doping process in a temperature environment of 40 ° C. or higher and 70 ° C. or lower, the doping time can be shortened while maintaining the quality of the electricity storage device 10.

  That is, by performing the doping step in a temperature environment of 40 ° C. or higher, the lithium ion pre-doping rate can be increased. As a result, the doping time can be shortened, and the manufacturing cost of the electricity storage device 10 can be reduced. Moreover, since the implementation temperature of the doping process is suppressed to 70 ° C. or less, irreversible consumption of lithium ions can be suppressed. Thereby, the cell capacity of the electricity storage device 10 can be ensured. Furthermore, deterioration of the laminate film 11 can be avoided by suppressing the temperature for performing the doping step to 70 ° C. or lower. Thereby, the quality of the electricity storage device 10 can be ensured. In order to further shorten the doping time, it is preferable to perform the doping process in a temperature environment of 50 ° C. or higher. In order to further improve the quality of the electricity storage device 10, it is preferable to perform the doping step in a temperature environment of 60 ° C. or less.

  In such a temperature environment, when the temperature of the doping process is lower than 40 ° C., a long doping time is required although it depends on the number of stacked positive electrodes 13 and negative electrodes 14. Therefore, the productivity of the electricity storage device 10 is lowered, and the manufacturing cost of the electricity storage device 10 is increased. Moreover, when the implementation temperature of a doping process exceeds 70 degreeC, a lithium ion will be consumed irreversibly. Therefore, there is a risk of causing a decrease in discharge capacity and an increase in DC resistance. In order to solve these problems, when manufacturing the electricity storage device 10 of the present invention, the doping process is performed in a temperature environment of 40 ° C. or higher and 70 ° C. or lower. In order to further shorten the doping time and further prevent deterioration of the electricity storage device 10, it is preferable to perform the doping step in a temperature environment of 50 ° C. or more and 60 ° C. or less.

  By the way, when the implementation temperature of the doping step is set to 40 ° C. or higher, not only the pre-doping rate is increased, but also the amount of lithium ions doped into the negative electrode 14 can be increased. Therefore, the metal lithium foil 27 incorporated in the electricity storage device 10 is set to an amount capable of releasing lithium ions of 70% or more and 120% or less of the negative electrode maximum charge capacity. That is, when the negative electrode maximum charge capacity under a predetermined condition is Ca and the amount of lithium ions released from the metal lithium foil 27 (hereinafter referred to as pre-doping amount) is Cb, Ca × 0.7 ≦ Cb ≦ Ca × 1 The amount of the metallic lithium foil 27 is set so that the relationship of.

Here, the negative electrode maximum charge capacity Ca [mAh / g] is a value obtained by dividing the charge capacity of the negative electrode 14 measured under a predetermined condition by the weight of the negative electrode active material. The pre-doping amount Cb [mAh / g] is a value obtained by dividing the amount of lithium ions released from the metal lithium foil 27 by the weight of the negative electrode active material. When measuring the negative electrode maximum charge capacity Ca, a test cell is prepared in which metallic lithium is incorporated as a counter electrode and a reference electrode, and the negative electrode 14 is incorporated as a working electrode. Subsequently, the negative electrode 14 serving as the working electrode is charged (current density 1 mA / cm ² , temperature environment 20 ± 5 ° C.) by potential control based on the reference electrode of the test cell. This charging process is continued for 12 hours even after the negative electrode potential reaches 0V. Next, the charge capacity of the negative electrode 14 when this charging process is performed is measured. A value obtained by dividing the measured charge capacity of the negative electrode 14 by the weight of the negative electrode active material in the negative electrode 14 is defined as the negative electrode maximum charge capacity Ca.

  Thus, by setting the amount of the metal lithium foil 27 incorporated in the electricity storage device 10 to 70% or more of the negative electrode maximum charge capacity Ca, the negative electrode 14 can be sufficiently doped with lithium ions. . Thereby, the cell voltage, cell capacity, and electrostatic capacity of the electricity storage device 10 can be sufficiently secured, and the quality of the electricity storage device 10 can be improved. Further, by setting the amount of the metal lithium foil 27 incorporated in the electricity storage device 10 to 120% or less of the negative electrode maximum charge capacity Ca, it is possible to avoid excessive lithium ion doping to the negative electrode 14. Thereby, since deterioration of the negative electrode 14 can be prevented, the durability of the electricity storage device 10 can be improved.

  When the amount of the metal lithium foil 27 incorporated in the electricity storage device 10 is less than 70% of the negative electrode maximum charge capacity Ca with respect to the set amount of the metal lithium foil 27, lithium doped in the negative electrode 14 There are too few ions. Such an insufficient amount of lithium ion doping is not preferable because the discharge capacity of the negative electrode 14 is reduced and the cell capacity of the electricity storage device 10 is reduced. In addition, when the amount of lithium ions to be doped decreases, the negative electrode potential and the positive electrode potential during charging increase, which is not preferable because the durability of the electricity storage device 10 decreases. On the other hand, when the amount of the metal lithium foil 27 incorporated in the electricity storage device 10 exceeds 120% of the negative electrode maximum charge capacity Ca, the lithium ions doped in the negative electrode 14 become excessive. Thus, when the doping amount of lithium ions becomes excessive, the metal lithium foil 27 remains in the electricity storage device 10 after pre-doping or metal lithium is deposited from the negative electrode 14, which is not preferable. Further, excessive doping of lithium ions with respect to the negative electrode 14 is not preferable because a film is formed on the surface of the negative electrode to increase resistance.

Further, from the viewpoint of increasing the capacity of the electricity storage device 10, the metal lithium foil 27 has a positive electrode potential of 2.0 V (vs. Li / Li ⁺ ) or less after the positive electrode 13 and the negative electrode 14 are short-circuited. The amount is set. In the present invention, the positive electrode potential after the positive electrode 13 and the negative electrode 14 are short-circuited is 2.0 V (vs. Li / Li ⁺ ) or less, which is determined by the following method (A) or (B) A case where the potential is 2.0 V or less.

In the method (A), after pre-doping with lithium ions, the electricity storage device 10 is allowed to stand for 12 hours or more in a state where the positive electrode terminal 22 and the negative electrode terminal 25 are directly coupled to each other with a conductive wire. And after cancellation | release of the short circuit state of the positive electrode terminal 22 and the negative electrode terminal 25, a positive electrode electric potential is measured within 0.5 to 1.5 hours. The positive electrode potential measured at this time is the positive electrode potential obtained by the method (A). In the method (B), the electricity storage device 10 is discharged at a constant current to 0 V over 12 hours using a charge / discharge tester. Thereafter, the power storage device 10 is left for 12 hours or longer in a state where the positive electrode terminal 22 and the negative electrode terminal 25 are coupled with each other with a conductive wire. And after cancellation | release of the short circuit state of the positive electrode terminal 22 and the negative electrode terminal 25, a positive electrode electric potential is measured within 0.5 to 1.5 hours. The positive electrode potential measured at this time is the positive electrode potential obtained by the method (B). That is, in the present invention, the positive electrode potential after the positive electrode 13 and the negative electrode 14 are short-circuited is 2.0 V (vs. Li / Li ⁺ ) or less, as determined by the method (A) or (B) described above. This refers to the case where the positive electrode potential is 2.0 V (vs. Li / Li ⁺ ) or less.

In the present invention, the fact that the positive electrode potential after the positive electrode 13 and the negative electrode 14 are short-circuited is 2.0 V (vs. Li / Li ⁺ ) or less is determined only in the state immediately after the lithium ions are pre-doped. It is not a thing. For example, the positive electrode potential after the positive electrode 13 and the negative electrode 14 are short-circuited in any state, such as the charged state, discharged state, or repeated charge / discharge state of the electricity storage device 10, is 2.0 V (vs. Li / Li ⁺ ) or less.

As described above, by setting the incorporation amount of the metal lithium foil 27 so that the positive electrode potential after the positive electrode 13 and the negative electrode 14 are short-circuited is 2.0 V (vs. Li / Li ⁺ ) or less, the positive electrode A region where the potential is 3 V or less can be used. That is, when the conventional electric double layer capacitor is discharged, if the positive electrode potential decreases to about 3V, the negative electrode potential increases to about 3V. Therefore, the discharge of the conventional electric double layer capacitor ends when the positive electrode potential drops to about 3V. On the other hand, the electricity storage device 10 is configured to continue discharging to a region where the positive electrode potential is 2 V or less by adjusting the doping amount of lithium ions with respect to the negative electrode 14. Thus, the region where the positive electrode potential is 3 V or less can be used, and the capacity of the electricity storage device 10 can be increased. In the region where the positive electrode potential is higher than 3 V, the potential changes due to anion doping / dedoping with respect to the positive electrode 13. Further, in the region where the positive electrode potential is 3 V or less, the potential changes due to the doping and dedoping of lithium ions with respect to the positive electrode 13.

  Furthermore, from the viewpoint of increasing the capacity of the electricity storage device 10, the electrostatic capacity per unit weight of the negative electrode active material is set to three times or more the electrostatic capacity per unit weight of the positive electrode active material. Thus, since the electrostatic capacitance per unit weight of the negative electrode active material is set larger than that of the positive electrode active material, the negative electrode active material can be reduced while suppressing the amount of change in the negative electrode potential during charge / discharge. In the electricity storage device 10, the filling amount of the positive electrode active material is increased while the filling amount of the negative electrode active material is decreased so that the weight of the positive electrode active material is larger than the weight of the negative electrode active material. Thereby, it is possible to increase the electrostatic capacity and the cell capacity of the electricity storage device 10 while suppressing the enlargement of the electricity storage device 10.

  Hereinafter, the components of the electricity storage device described above will be described in detail in the following order. [A] positive electrode, [B] negative electrode, [C] positive electrode current collector and negative electrode current collector, [D] lithium electrode, [E] separator, [F] electrolyte, [G] exterior container.

[A] Positive Electrode The positive electrode has a positive electrode current collector and a positive electrode mixture layer integrated therewith. When the electric storage device functions as a lithium ion capacitor, it is possible to employ a material capable of reversibly doping and dedoping lithium ions and / or anions as the positive electrode active material contained in the positive electrode mixture layer. . That is, there is no particular limitation as long as it is a substance capable of reversibly doping and dedoping at least one of lithium ions and anions. For example, activated carbon, transition metal oxide, conductive polymer, polyacene-based material, or the like can be used.

For example, the activated carbon is preferably formed from activated carbon particles having an alkali activation treatment and a specific surface area of 600 m ² / g or more. As a raw material for the activated carbon, phenol resin, petroleum pitch, petroleum coke, coconut shell, coal-based coke and the like are used. Phenol resin and coal-based coke are preferable because the specific surface area can be increased. The alkali activator used in the alkali activation treatment of these activated carbons is preferably a metal lithium ion salt or hydroxide such as lithium, sodium or potassium. Of these, potassium hydroxide is preferred. Examples of the alkali activation method include a method in which a carbide and an activator are mixed and then heated in an inert gas stream. Further, there is a method in which an activation agent is supported on the raw material of activated carbon in advance and then heated to perform carbonization and activation processes. Furthermore, after activating carbide by a gas activation method such as water vapor, a method of surface treatment with an alkali activating agent is also included. The activated carbon that has been subjected to such alkali activation treatment is pulverized using a known pulverizer such as a ball mill. As the particle size of the activated carbon, a wide range of commonly used materials can be used. For example, D50 is 2 μm or more, preferably 2 to 50 μm, and most preferably 2 to 20 μm. Further, activated carbon having an average pore diameter of preferably 10 nm or less and a specific surface area of preferably 600 to 3000 m ² / g is suitable. Of these, 800 m ² / g or more, and particularly it is preferable that a 1300~2500m ² / g.

In addition, when the power storage device functions as a lithium ion secondary battery, the positive electrode active material contained in the positive electrode mixture layer can be reversibly doped or dedoped with a conductive polymer such as polyanine or lithium ions. It is possible to adopt a substance. For example, vanadium pentoxide (V ₂ O ₅ ) or lithium cobaltate (LiCoO ₂ ) can be used as the positive electrode active material. In addition, Li _X M _Y O _Z such as Li _X CoO ₂ , Li _X NiO ₂ , Li _X MnO ₂ , and Li _X FeO ₂ (x, y, z are positive numbers, M is a metal, two or more types It is also possible to use lithium-containing metal oxides that can be represented by the general formula (1), transition metal oxides such as cobalt, manganese, vanadium, titanium, nickel, or sulfides. In particular, when a high voltage is required, it is preferable to use a lithium-containing oxide having a potential of 4 V or higher with respect to metallic lithium. For example, lithium-containing cobalt oxide, lithium-containing nickel oxide, or lithium-containing cobalt-nickel composite oxide is particularly suitable.

  The positive electrode active material such as activated carbon described above is formed into a powder form, a granular form, a short fiber form, or the like. This positive electrode active material is mixed with a binder to form a slurry. Then, the positive electrode active material layer is formed on the positive electrode current collector by applying the slurry containing the positive electrode active material to the positive electrode current collector and drying the slurry. As the binder to be mixed with the positive electrode active material, for example, a rubber-based binder such as SBR, a fluorine-containing resin such as polytetrafluoroethylene or polyvinylidene fluoride, or a thermoplastic resin such as polypropylene, polyethylene, or polyacrylate is used. be able to. Moreover, you may make it add electrically conductive materials, such as acetylene black, a graphite, and a metal powder, with respect to a positive mix layer.

[B] Negative Electrode The negative electrode has a negative electrode current collector and a negative electrode mixture layer integrated therewith. The negative electrode active material contained in the negative electrode mixture layer is not particularly limited as long as it can reversibly dope and dedope lithium ions. For example, graphite, various carbon materials, polyacene materials, tin oxide, silicon oxide, and the like can be used. Graphite (graphite) and hard carbon (non-graphitizable carbon) are preferable as the negative electrode active material because they can increase the capacity. In addition, a polyacene organic semiconductor (PAS), which is a heat-treated product of an aromatic condensation polymer, is suitable as a negative electrode active material because the capacity can be increased. This PAS has a polyacene skeleton structure. The hydrogen atom / carbon atom number ratio (H / C) of the PAS is preferably in the range of 0.05 to 0.50. When H / C of PAS exceeds 0.50, the aromatic polycyclic structure is not sufficiently developed, so that lithium ions are not doped and undoped smoothly, and the charge / discharge efficiency of the electricity storage device May decrease. When the H / C of PAS is less than 0.05, the capacity of the electricity storage device may be reduced.

  The negative electrode active material such as PAS described above is formed into a powder form, a granular form, a short fiber form, or the like. This negative electrode active material is mixed with a binder to form a slurry. Then, the negative electrode active material layer is formed on the negative electrode current collector by applying the slurry containing the negative electrode active material to the negative electrode current collector and drying the slurry. Examples of the binder mixed with the negative electrode active material include fluorine-containing resins such as polytetrafluoroethylene and polyvinylidene fluoride, thermoplastic resins such as polypropylene, polyethylene, and polyacrylate, styrene butadiene rubber (SBR), and the like. These rubber-based binders can be used. Among these, it is preferable to use a fluorine-based binder. Examples of the fluorine-based binder include polyvinylidene fluoride, vinylidene fluoride-trifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, and propylene-tetrafluoroethylene copolymer. Moreover, you may make it add electroconductive materials, such as acetylene black, a graphite, and a metal powder, with respect to a negative electrode compound material layer suitably.

[C] Positive electrode current collector and negative electrode current collector As the positive electrode current collector and the negative electrode current collector, those having through holes penetrating the front and back surfaces are suitable. For example, an expanded metal, a punching metal, an etching foil, a net, a foam, etc. can be mentioned. The shape and number of through holes are not particularly limited. Any material can be set as long as it does not hinder the movement of anions and lithium ions. As materials for the positive electrode current collector and the negative electrode current collector, various materials generally proposed for batteries and capacitors can be used. For example, aluminum, stainless steel, or the like can be used as a material for the positive electrode current collector. Stainless steel, copper, nickel, or the like can be used as a material for the negative electrode current collector.

[D] Lithium Electrode As a material for the lithium electrode current collector, various materials generally proposed as current collectors for batteries and capacitors can be used. As these materials, stainless steel, copper, nickel and the like can be used. Moreover, you may use what is provided with the through-hole which penetrates front and back, such as an expanded metal, a punching metal, an etching foil, a net | network, and a foam, as a lithium electrode electrical power collector. Further, instead of the metal lithium foil attached to the lithium electrode current collector, a lithium-aluminum alloy capable of releasing lithium ions or the like may be used.

[E] Separator As the separator, it is possible to use a porous body that has durability against an electrolytic solution, a positive electrode active material, a negative electrode active material, and the like and has continuous air holes and has no electron conductivity. Usually, paper (cellulose), glass fiber, cloth made of polyethylene or polypropylene, nonwoven fabric or porous material is used. The thickness of the separator can be appropriately set in consideration of the amount of electrolytic solution retained, the strength of the separator, and the like. The separator is preferably thinner in order to reduce the internal resistance of the electricity storage device.

[F] Electrolytic Solution As the electrolytic solution, it is preferable to use an aprotic organic solvent containing a lithium salt from the viewpoint that electrolysis does not occur even at a high voltage and that lithium ions can exist stably. Examples of the aprotic organic solvent include solvents in which ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, methylene chloride, sulfolane and the like are used alone or in combination. Examples of the lithium _{salt, LiClO 4, LiAsF 6, LiBF} 4, LiPF 6, LIN (C 2 F 5 SO 2) 2 and the like. The electrolyte concentration in the electrolytic solution is preferably at least 0.1 mol / L or more in order to reduce the internal resistance due to the electrolytic solution. Furthermore, it is preferable to set it within the range of 0.5-1.5 mol / L.

Further, an ionic liquid (ionic liquid) may be used instead of the organic solvent. As the ionic liquid, combinations of various cationic species and anionic species have been proposed. Examples of the cationic species include N-methylN-propylpiperidinium (PP13), 1-ethyl 3-methylimidazolium (EMI), diethylmethyl 2-methoxyethylammonium (DEME), and the like. Examples of the anion species include bis (fluorosulfonyl) imide (FSI), bis (trifluoromethanesulfonyl) imide (TFSI), PF ₆ ⁻ , BF ₄ ^{− and the} like.

[G] Exterior Container As the exterior container, various materials generally used for batteries can be used. For example, a metal material such as iron or aluminum may be used. Moreover, you may use film materials, such as resin. Further, the shape of the outer container is not particularly limited. It can be appropriately selected depending on the application such as a cylindrical shape or a rectangular shape. From the viewpoint of reducing the size and weight of the electricity storage device, it is preferable to use a film-type exterior container using an aluminum laminate film. In general, a three-layer laminate film having a nylon film on the outside, an aluminum foil in the center, and an adhesive layer such as modified polypropylene on the inside is used.

  Hereinafter, based on an Example, this invention is demonstrated in detail.

(Example 1)
[Manufacture of negative electrode]
A phenol resin molded plate having a thickness of 0.5 mm is placed in a siliconite electric furnace filled with a nitrogen atmosphere. The phenol resin molded plate is heated to 500 ° C. at a rate of 50 ° C./hour. Subsequently, the phenol resin molded plate is heated to 700 ° C. at a rate of 10 ° C./hour. PAS was synthesized from the phenol resin molded plate by such heat treatment. This PAS plate was pulverized with a disk mill to obtain a PAS powder. The H / C ratio of this PAS powder was 0.19.

  Next, 86 parts by weight of the PAS powder, 6 parts by weight of acetylene black powder, 5 parts by weight of an acrylic resin binder, 3 parts by weight of carboxymethyl cellulose, and 200 parts by weight of water are mixed thoroughly to prepare a slurry for negative electrode. Obtained. The negative electrode slurry was evenly coated on both sides of a copper expanded metal having a thickness of 32 μm (porosity 50%) using a die coater. Then, the negative electrode slurry coated on the copper expanded metal was dried and pressed to obtain a negative electrode having a thickness of 86 μm.

[Measurement of maximum negative electrode charge capacity]
The negative electrode was cut into 1.5 cm × 2.0 cm to obtain a negative electrode for evaluation. A simulated cell was prepared by making metallic lithium (dimensions 1.5 cm × 2.0 cm, thickness 200 μm) face this negative electrode for evaluation. Between the negative electrode for evaluation and the lithium metal, a 50 μm thick polyethylene non-woven fabric was placed as a separator. Moreover, metallic lithium was used as a reference electrode of the simulated cell. Furthermore, a solution in which LiPF ₆ was dissolved in propylene carbonate at a concentration of 1.2 mol / L was used as the electrolyte solution of the simulated cell. Subsequently, the negative electrode for evaluation was charged (doped) with a charging current of 1 mA / cm ² . The charging for the negative electrode for evaluation was continued for 12 hours even after the negative electrode potential reached 0V. The charge capacity of the negative electrode for evaluation when this charge treatment was performed was measured, and this measured value was divided by the weight of the negative electrode active material contained in the negative electrode for evaluation. This confirmed that the negative electrode maximum charge capacity Ca was 756 mAh / g per unit weight of the negative electrode active material.

[Production of positive electrode]
For positive electrode by thoroughly mixing 85 parts by weight of commercially available activated carbon powder having a specific surface area of 2000 m ² / g, 5 parts by weight of acetylene black powder, 6 parts by weight of acrylic resin binder, 4 parts by weight of carboxymethylcellulose, and 200 parts by weight of water. A slurry was obtained. Further, a non-aqueous carbon conductive paint was coated on both surfaces of an aluminum expanded metal having a thickness of 35 μm (porosity 50%) by a spray method. By drying the carbon-based conductive paint applied to the aluminum expanded metal, a positive electrode current collector on which a conductive layer was formed was obtained. The total thickness of the positive electrode current collector (the total thickness of the base material and the conductive layer) is 52 μm. The through hole of the positive electrode current collector was almost blocked by the conductive paint. Subsequently, the positive electrode slurry was uniformly coated on both surfaces of the positive electrode current collector using a roll coater. Then, the positive electrode slurry coated on the positive electrode current collector was dried and pressed to obtain a positive electrode having a thickness dimension of 129 μm.

[Production of electrode stacking unit]
Ten negative electrodes were cut to 6.0 cm × 7.5 cm (excluding terminal welds). Eleven positive electrodes were cut into 5.8 cm × 7.3 cm (excluding terminal welds). And the negative electrode and the positive electrode were laminated | stacked alternately so that the terminal-welded part of a negative electrode collector and a positive electrode collector might be on the opposite side, respectively. A separator made of a cellulose / rayon mixed nonwoven fabric having a thickness of 35 μm was disposed between the negative electrode and the positive electrode. A negative electrode was disposed on the outermost part of the electrode laminate unit. Subsequently, separators were placed at the uppermost and lowermost parts, and the four sides were taped. Thereafter, the terminal welded portion (11 sheets) of the positive electrode current collector was ultrasonically welded to the positive electrode terminal (width 50 mm, length 50 mm, thickness 0.2 mm) made of aluminum. Further, the terminal welded portion (12 sheets) of the negative electrode current collector was ultrasonically welded to a copper negative electrode terminal (width 50 mm, length 50 mm, thickness 0.2 mm). In this way, an electrode laminate unit was produced.

[Production of cells 1 to 4]
As the lithium electrode, a stainless steel net having a thickness of 80 μm and a metal lithium foil bonded thereto was used. One lithium electrode was arranged on the upper part of the electrode laminate unit so that this lithium electrode was opposed to the entire surface of the negative electrode provided on the outermost part, thereby producing a three-electrode laminate unit. The stainless steel terminal welded portion, which is a lithium electrode current collector, was resistance welded to the negative electrode terminal welded portion. The triode laminate unit was placed inside a laminate film that had been deep-drawn to 3.5 mm. Subsequently, the opening of the laminate film was covered with another laminate film, and the three sides were fused. And the electrolyte solution was vacuum-impregnated in the laminate film. This electrolytic solution is a solution in which LiPF ₆ is dissolved in propylene carbonate at a concentration of 1.2 mol / L. Thereafter, the remaining side of the laminated film that had been opened was fused. Thus, 10 lithium ion capacitor cells 1 to 4 were assembled.

  The cell 1 is provided with a metal lithium foil that releases 600 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 1 is 600 mAh / g. The cell 2 is provided with a metal lithium foil that releases 700 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 2 is 700 mAh / g. The cell 3 is provided with a metal lithium foil that releases 800 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 3 is 800 mAh / g. The cell 4 is provided with a metal lithium foil that releases 900 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 4 is 900 mAh / g.

[Initial evaluation of cells 1 to 4]
The assembled cells 1 to 4 were placed in a thermostat set at 40 ° C. Thereby, the doping process of the lithium ion with respect to the negative electrode was implemented at 40 degreeC. After a predetermined number of days of pre-doping, each cell was disassembled, and the number of days when metallic lithium disappeared was defined as the number of days of pre-doping. In addition, in order to investigate the pre dope days, six cells were used for each of the cells 1 to 4. Thus, it was confirmed that a predetermined amount of lithium ions was pre-doped on the negative electrode. Thereafter, the cell capacitance (initial cell capacitance) of each of the cells 1 to 4 was measured. Thereafter, the temperature of the thermostatic bath was set to 60 ° C., and a constant voltage of 3.8 V was applied to each of the cells 1 to 4 over 500 hours. After this high-temperature load test was performed, the cell capacitance (cell capacitance after 500 hours) of each of the cells 1 to 4 was measured. These results are shown in Table 1. Each data shown in Table 1 is an average value of 4 cells.

(Example 2)
10 cells each of cells 5 to 8 were assembled in the same manner as in Example 1 except that the doping step was performed in a thermostat set at 70 ° C. The cell 5 is provided with a metal lithium foil that releases 600 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 5 is 600 mAh / g. The cell 6 is provided with a metal lithium foil that releases 700 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 6 is 700 mAh / g. The cell 7 is provided with a metal lithium foil that releases 800 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 7 is 800 mAh / g. The cell 8 is provided with a metal lithium foil that releases 900 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 8 is 900 mAh / g.

  After carrying out the lithium ion doping step on the negative electrode at 70 ° C. over a predetermined number of pre-doping days, each cell 5 to 8 was decomposed, and the number of days when metallic lithium disappeared was defined as the pre-doping days. In addition, 6 cells were used for each of the cells 5 to 8 in order to examine the pre-doping days. Thus, it was confirmed that a predetermined amount of lithium ions was pre-doped on the negative electrode. Thereafter, the cell capacitance (initial cell capacitance) of each of the cells 5 to 8 was measured. Then, the temperature of the thermostat was set to 60 ° C., and a constant voltage of 3.8 V was applied to each of the cells 5 to 8 for 500 hours. After executing this high temperature load test, the cell capacitance (cell capacitance after 500 hours) of each of the cells 5 to 8 was measured. These results are shown in Table 2. Each data shown in Table 2 is an average value of 4 cells.

(Comparative Example 1)
4 cells each of cells 9 to 12 were assembled in the same manner as in Example 1 except that the doping step was performed in a thermostat set to 25 ° C. The cell 9 is provided with a metal lithium foil that releases 600 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 9 is 600 mAh / g. The cell 10 is provided with a metal lithium foil that releases 700 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 10 is 700 mAh / g. The cell 11 is provided with a metal lithium foil that releases 800 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 11 is 800 mAh / g. The cell 12 is provided with a metal lithium foil that releases 900 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 12 is 900 mAh / g.

  After the lithium ion doping step for the negative electrode was performed at 25 ° C. over a predetermined number of pre-doping days, each cell 9 to 12 was decomposed, and the number of days when metallic lithium disappeared was defined as the pre-doping days. In addition, six cells were used for each of the cells 9 to 12 in order to examine the pre-doping days. Thus, it was confirmed that a predetermined amount of lithium ions was pre-doped on the negative electrode. Thereafter, the cell capacitance (initial cell capacitance) of each of the cells 9 to 12 was measured. Thereafter, the temperature of the thermostatic bath was set to 60 ° C., and a constant voltage of 3.8 V was applied to each of the cells 9 to 12 over 500 hours. After performing this high temperature load test, the cell capacitance (cell capacitance after 500 hours) of each of the cells 9 to 12 was measured. These results are shown in Table 3. Each data shown in Table 3 is an average value of 4 cells.

(Comparative Example 2)
10 cells each of cells 13 to 16 were assembled in the same manner as in Example 1 except that the doping step was carried out in a thermostat set at 80 ° C. The cell 13 is provided with a metal lithium foil that releases 600 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 13 is 600 mAh / g. The cell 14 is provided with a metal lithium foil that releases 700 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 14 is 700 mAh / g. The cell 15 is provided with a metal lithium foil that releases 800 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 15 is 800 mAh / g. The cell 16 is provided with a metal lithium foil that releases 900 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 16 is 900 mAh / g.

  After the lithium ion doping step for the negative electrode was performed at 80 ° C. over a predetermined number of pre-doping days, each cell 13 to 16 was decomposed, and the number of days when metallic lithium disappeared was defined as the pre-doping days. In addition, six cells were used for each of the cells 13 to 16 in order to examine the pre-doping days. Thus, it was confirmed that a predetermined amount of lithium ions was pre-doped on the negative electrode. Thereafter, the cell capacitance (initial cell capacitance) of each of the cells 13 to 16 was measured. Then, the temperature of the thermostat was set to 60 ° C., and a constant voltage of 3.8 V was applied to each of the cells 13 to 16 over 500 hours. After this high temperature load test was performed, the cell capacitance (cell capacitance after 500 hours) of each of the cells 13 to 16 was measured. These results are shown in Table 4. Each data shown in Table 4 is an average value of 4 cells.

(Examination of Example 1, Example 2, Comparative Example 1 and Comparative Example 2)
As shown in Tables 1 to 3, when the cells 1 to 8 and the cells 9 to 12 are compared for each pre-doping amount Cb, the pre-doping days of the cells 1 to 8 are shortened compared to the pre-doping days of the cells 9 to 12. It was confirmed. That is, it was confirmed that the cells 1 to 8 had a higher pre-doping rate and higher productivity than the cells 9 to 12. It was also confirmed that there was no significant difference in cell capacitance after 500 hours between cells 1-8 and cells 9-12. That is, it was confirmed that the cells 1 to 8 did not deteriorate even when the pre-doping rate was increased. This is because the doping process was performed in the temperature environment of 40 ° C. or more and 70 ° C. or less for the cells 1 to 8, whereas the doping process was performed in the temperature environment lower than 40 ° C. for the cells 9 to 12. It is done.

  Moreover, as shown in Table 1, Table 2, and Table 4, when the cells 1 to 8 and the cells 13 to 16 are compared for each pre-doping amount Cb, the pre-doping days of the cells 13 to 16 are the pre-doping days of the cells 1 to 8. It was confirmed that it was shortened. However, for cells 13 to 16, it was confirmed that the cell capacitance significantly decreased after 500 hours, compared to cells 1 to 8. This is because the doping process was performed in a temperature environment of 40 ° C. or more and 70 ° C. or less for the cells 1 to 8, whereas the doping process was performed for the cells 13 to 16 in a temperature environment exceeding 70 ° C. It is done.

Example 3
10 cells each of cells 17 and 18 were assembled in the same manner as in Example 1 except that the amount of the metallic lithium foil incorporated was changed. The cell 17 is provided with a metal lithium foil that releases 500 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 17 is 500 mAh / g. The cell 18 is provided with a metal lithium foil that releases 1000 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 18 is 1000 mAh / g.

  The assembled cells 17 and 18 were placed in a thermostat set at 60 ° C. Thereby, the doping process of the lithium ion with respect to the negative electrode was implemented at 60 degreeC. After a predetermined number of days of pre-doping, each cell was disassembled, and the number of days when metallic lithium disappeared was defined as the number of days of pre-doping. In order to examine the number of days for pre-doping, six cells were used for each of the cells 17 and 18. Thus, it was confirmed that a predetermined amount of lithium ions was pre-doped on the negative electrode. Thereafter, the cell capacitance (initial cell capacitance) of each of the cells 17 and 18 was measured. Thereafter, the temperature of the thermostatic bath was set to 60 ° C., and a constant voltage of 3.8 V was applied to the cells 17 and 18 over 500 hours. After executing this high temperature load test, the cell capacitance of each of the cells 17 and 18 (cell capacitance after 500 hours) was measured. These results are shown in Table 5. Each data shown in Table 5 is an average value of 4 cells.

(Examination about Example 3)
In the cell 17, the doping process is performed at 60 ° C., and since few metal lithium foils are incorporated, the pre-doping can be completed in a short number of days. The amount of lithium ions released from the metal lithium foil is set to an amount that is less than 70% of the negative electrode maximum charge capacity Ca (Cb ≦ Ca × 0.7). Therefore, although the initial cell capacitance of the cell 17 is small, the cell capacitance after 500 hours tends to be high as with the cells 1 to 8. This is presumably because the amount of lithium ions pre-doped on the negative electrode is small, but there is no deterioration due to temperature.

  Further, in the cell 18, the doping process is performed at 60 ° C., although many metal lithium foils are incorporated. For this reason, it is possible to complete the pre-doping for the negative electrode in a significantly shorter number of days of pre-doping than normal pre-doping at room temperature. However, when the cell 18 was compared with the cells 1 to 4 of Example 1, the internal resistance tended to be slightly higher. This is considered because the amount of lithium ions released from the metal lithium foil exceeds 120% of the negative electrode maximum charge capacity Ca (Cb ≧ Ca × 1.2). When the amount of lithium ions greatly exceeds the allowable range of the negative electrode active material, the load on the negative electrode is increased, decomposition of the electrolyte occurs, and a film is formed on the negative electrode, which increases the resistance. . However, in the charging / discharging shown in the present example, the effect of the internal resistance is not generated, so that the cell capacitance was high after 500 hours.

  Thus, although the pre-doping days can be shortened by setting the temperature environment of the doping process to 40 ° C. or more and 70 ° C. or less, the amount of lithium ions released from the metal lithium foil is 70% or more and 120% of the negative electrode maximum charge capacity Ca. Setting to the following is more desirable in terms of capacitance and internal resistance. That is, when the maximum charge capacity of the negative electrode is Ca and the pre-doping amount from the metal lithium foil is Cb, the amount of the metal lithium foil is set so that the relationship of Ca × 0.7 ≦ Cb ≦ Ca × 1.2 is established. It is desirable to set.

  Moreover, when the positive electrode potential after short-circuiting the positive electrode and negative electrode of each cell after the measurement of the cells 1 to 18 was measured, it was about 0.95 V and was 2.0 V or less. Since the negative electrode and / or the positive electrode were previously doped with lithium ions so that the positive electrode potential after short-circuiting the positive electrode and the negative electrode was 2.0 V or less, the lithium ion capacitor cells of Examples 1 to 3 and Comparative Examples 1 and 2 In 1-18, it is thought that the high energy density was obtained.

(Comparative Example 3)
10 cells each of cells 19 to 22 were assembled in the same manner as in Example 1 except that no through hole was formed in the positive electrode current collector or the negative electrode current collector. The cell 19 is provided with a metal lithium foil that releases 600 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 19 is 600 mAh / g. The cell 20 is provided with a metal lithium foil that releases 700 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 20 is 700 mAh / g. The cell 21 is provided with a metal lithium foil that releases 800 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 21 is 800 mAh / g. The cell 22 is provided with a metal lithium foil that releases 900 mAh / g of lithium ions per unit weight of the negative electrode active material. That is, the pre-doping amount Cb of the cell 22 is 900 mAh / g.

  The assembled cells 19 to 22 were placed in a thermostat set at 40 ° C. Thereby, the doping process of the lithium ion with respect to the negative electrode was implemented at 40 degreeC. After the same number of days of pre-doping as in Example 1, the respective cells 19 to 22 were decomposed, and almost all of the lithium metal in all the cells 19 to 22 remained. This is thought to be because diffusion of lithium ions was blocked by these current collectors because no through holes were formed in the positive electrode current collector or the negative electrode current collector. That is, even if the temperature environment of the doping process is set to 40 ° C. or higher and 70 ° C. or lower, it is considered that pre-doping is not completed if the positive electrode current collector or the negative electrode current collector has no through holes.

  It goes without saying that the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the scope of the invention. For example, the present invention may be applied not only to a lithium ion capacitor that is an electricity storage device but also to a lithium ion secondary battery that is an electricity storage device. In addition, the present invention may be applied not only to a stacked power storage device but also to a wound power storage device.

  In the illustrated case, one lithium electrode is incorporated, but a plurality of lithium electrodes may be incorporated. Moreover, you may make it dope lithium ion with respect to a positive electrode by connecting a lithium electrode and a positive electrode. Furthermore, you may dope lithium ion with respect to both a positive electrode and a negative electrode by providing a lithium electrode with respect to each of a positive electrode and a negative electrode, or short-circuiting a positive electrode and a negative electrode during dope.

It is a perspective view which shows the electrical storage device which is one embodiment of this invention. It is sectional drawing which shows schematically the internal structure of an electrical storage device along the AA line of FIG. It is sectional drawing which expands and shows the internal structure of an electrical storage device partially.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Power storage device 13 Positive electrode 14 Negative electrode 20 Positive electrode collector 20a Through-hole 23 Negative electrode collector 23a Through-hole 27 Metal lithium foil (ion supply source)

Claims (8)

Ion supply connected to at least one of a positive electrode including a positive electrode current collector with a through hole, a negative electrode including a negative electrode current collector with a through hole, and the positive electrode and the negative electrode stacked A method of manufacturing an electricity storage device having a source,
A method of manufacturing an electricity storage device, wherein a doping step of doping at least one of the positive electrode and the negative electrode with lithium ions from the ion supply source is performed in a temperature environment of 40 ° C. or higher and 70 ° C. or lower. In the manufacturing method of the electrical storage device of Claim 1,
A method for producing an electricity storage device, wherein lithium ions of 70% or more and 120% or less of the maximum negative electrode charge capacity are released from the ion supply source. In the manufacturing method of the electrical storage device of Claim 1 or 2,
In the electricity storage device, the positive electrode active material is a material capable of doping / dedoping lithium ions and / or anions, the negative electrode active material is a material capable of doping / dedoping lithium ions, and the positive electrode and the negative electrode A lithium ion capacitor in which lithium ions are doped to the negative electrode and / or the positive electrode so that the positive electrode potential after being short-circuited is 2.0 V (vs. Li / Li ⁺ ) or less. Device manufacturing method. In the manufacturing method of the electrical storage device of any one of Claims 1-3,
A polyacene organic semiconductor having a polyacene skeleton structure which is a heat-treated product of an aromatic condensation polymer and has a hydrogen atom / carbon atom ratio of 0.05 or more and 0.50 or less, graphite, or A method for producing an electricity storage device, comprising non-graphitizable carbon. A positive electrode comprising a positive electrode current collector having a through-hole formed therein;
A negative electrode comprising a negative electrode current collector formed with a through hole;
An ion source that is connected to at least one of the positive electrode and the negative electrode to be stacked and emits lithium ions;
An electricity storage device, wherein at least one of the positive electrode and the negative electrode is doped with lithium ions from the ion supply source in a temperature environment of 40 ° C. or higher and 70 ° C. or lower. The electricity storage device according to claim 5, wherein
70. The lithium ion of 70% or more and 120% or less of the negative electrode maximum charge capacity is released from the ion supply source. The electricity storage device according to claim 5 or 6,
In the electricity storage device, the positive electrode active material is a material capable of doping / dedoping lithium ions and / or anions, the negative electrode active material is a material capable of doping / dedoping lithium ions, and the positive electrode and the negative electrode A lithium ion capacitor in which lithium ions are doped to the negative electrode and / or the positive electrode so that the positive electrode potential after being short-circuited is 2.0 V (vs. Li / Li ⁺ ) or less. device. In the electrical storage device of any one of Claims 5-7,
A polyacene organic semiconductor having a polyacene skeleton structure which is a heat-treated product of an aromatic condensation polymer and has a hydrogen atom / carbon atom ratio of 0.05 or more and 0.50 or less, graphite, or An electricity storage device comprising non-graphitizable carbon.

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