JP6284198B2 - Method for manufacturing power storage device - Google Patents

Description

  The present invention relates to a method for manufacturing an electricity storage device, and more particularly, to a method for manufacturing an electricity storage device that has a simplified manufacturing process and has low cost and excellent long-term stability.

  2. Description of the Related Art Conventionally, small batteries have been developed in order to reduce the size and weight of general electric devices using batteries such as notebook computers and mobile phones. In order to reduce the size and weight of general electric devices such as various portable devices, it is essential that the energy density of the battery as a power source is high (high capacity). In addition to small batteries, large batteries can also be developed as power storage devices for automobiles installed in electric vehicles and hybrid vehicles, or as storage batteries for power storage combined with new energy systems such as solar cells and wind power generation. Progressing. Such a large battery is required to have higher energy density and higher output density.

Research and development of power storage devices such as lithium ion secondary batteries and electric double layer capacitors have been actively conducted to meet the above requirements. Specifically, for example, Patent Document 1 discloses a carbonaceous material having a layered structure, in which a plurality of amorphous portions are dispersed on the (002) plane, and the average area of the amorphous portions is 1. Carbonaceous materials that are greater than or equal to ⁵ nm ² are described. Patent Document 1 discloses that, when this carbonaceous material is used for a positive electrode of a power storage device (a negative electrode is graphite), the capacity of the power storage device can be increased.

  Patent Document 2 discloses a positive electrode mainly including a carbonaceous material into which anions are inserted / desorbed, a negative electrode including a carbonaceous material into which metallic lithium or lithium ions can be inserted / extracted, and a lithium salt in a non-aqueous solvent. When a non-aqueous electrolyte secondary battery composed of at least a non-aqueous electrolyte formed by dissolving lithium is represented by 5.3 to 5.6 V when the end-of-charge voltage of the positive electrode is expressed using metallic lithium as a reference electrode Describes a method for charging a non-aqueous electrolyte secondary battery that is charged to a predetermined voltage. Patent Document 2 discloses that the capacity of the non-aqueous electrolyte secondary battery can be increased.

Japanese Published Patent Publication “Japanese Patent Laid-Open No. 2010-254637 (Publication Date: November 11, 2010)” Japanese Patent Publication “Patent No. 4569126 (issue date: October 27, 2010)”

  However, in order to manufacture the power storage device described in Patent Document 1, first, in order to produce a positive electrode, a cell for electrode production is separately assembled, for example, charged and discharged at least once at 2.25 to 3.5 V. After the pretreatment (charge / discharge) is performed to produce the positive electrode, it is necessary to disassemble the cell, take out the positive electrode, and assemble a cell for a power storage device using the obtained positive electrode and negative electrode. Similarly, in order to manufacture the nonaqueous electrolyte secondary battery (power storage device) described in Patent Document 2, first, a cell for electrode preparation is separately assembled in order to manufacture a positive electrode, for example, 5.3 to 5 A positive electrode was prepared by performing a pre-treatment of charging and discharging at least once at 6 V (based on metallic lithium), then the cell was disassembled and the positive electrode was taken out, and the non-aqueous electrolyte secondary solution was obtained using the obtained positive electrode and negative electrode. It is necessary to assemble a battery cell. Further, in both of the above production methods, the negative electrode is also assembled by separately assembling the cell for electrode preparation, preliminarily preliminarily storing lithium ions (lithium pre-doping), and then disassembling the cell to prepare the negative electrode Need to take out.

  In other words, in the conventional method for manufacturing a power storage device, before assembling the cell for the power storage device, in order to produce the positive electrode and the negative electrode, the cells for electrode preparation are separately assembled and pre-processed. Since it is necessary to disassemble and take out the positive electrode and the negative electrode, the manufacturing process is complicated and the productivity is poor. In addition, in order to popularize power storage devices as power sources for general electric devices such as various portable devices, or electric vehicles and hybrid vehicles, the battery market is expected to greatly expand. Although it is important to plan, the conventional power storage device has a problem that it is difficult to reduce the cost because the manufacturing process is complicated. Therefore, a low-cost power storage device with a simplified manufacturing process, that is, a method for manufacturing a power storage device is desired.

  The present invention has been made in view of the above problems, and a main object thereof is to provide a method for manufacturing a low-cost power storage device with a simplified manufacturing process.

  As a result of intensive investigations to achieve the above object, the inventors of the present invention have found that in a method for manufacturing an electricity storage device, a laminate formed by laminating a positive electrode and a negative electrode through a separator in a cell for an electricity storage device, and lithium An ion storage source is placed and a storage device cell manufacturing step for injecting a non-aqueous electrolyte is performed to manufacture the storage device cell, and then charge and discharge between the positive electrode and the lithium ion supply source. It is possible to perform a charging / discharging process, an electrochemical contact between the negative electrode and the lithium ion supply source, and an occlusion process for occluding lithium ions in the negative electrode, that is, after producing a cell for an electricity storage device, The present inventors have found that the treatment (charging / discharging) of the positive electrode and the negative electrode can be performed, and have completed the present invention.

  That is, the method for manufacturing an electricity storage device according to the present invention includes a positive electrode containing a carbonaceous material having a layered structure capable of inserting and releasing anions formed on a positive electrode current collector having a through hole as a positive electrode active material, One or more materials selected from the group consisting of a carbonaceous material, a metal material that occludes lithium, and an alloy material, which are formed on a negative electrode current collector having a through hole and have a layered structure capable of inserting and extracting lithium ions A negative electrode containing a negative electrode active material and a non-aqueous electrolyte containing a lithium salt, wherein the positive electrode and the negative electrode are laminated via a separator in a cell for an electric storage device The laminated body and the lithium ion supply source are disposed, and the cell manufacturing process for the electricity storage device in which the non-aqueous electrolyte is injected, and charging and discharging are performed between the positive electrode and the lithium ion supply source. A discharge step, performed electrochemical contact between the negative electrode and the lithium ion source is characterized by comprising a storage step of occluding lithium ions in the negative electrode, the.

  According to the method for manufacturing an electricity storage device according to the present invention, the charge / discharge step and the occlusion step can be performed after producing the cell for the electricity storage device. That is, after the storage device cell is manufactured, the positive electrode and the negative electrode can be processed (charge / discharge). Therefore, it is possible to simplify the manufacturing process as compared with the conventional method for manufacturing an electricity storage device in which cells for electrode preparation are separately assembled and pre-processed (charge / discharge) to produce a positive electrode and a negative electrode. it can. Moreover, since it is not necessary to assemble the cell for electrode preparation separately, the cost concerning this operation | work etc. can be reduced. Therefore, according to the method for manufacturing an electricity storage device according to the present invention, it is possible to produce an electricity storage device with a simplified manufacturing process at low cost (excellent productivity) and excellent long-term stability. .

It is a schematic sectional drawing which shows an example of a structure of the electrical storage device manufactured by the manufacturing method of the electrical storage device which concerns on this invention.

  An embodiment of the present invention will be described in detail below. All of the academic and patent literature described in this specification are hereby incorporated by reference. In the present specification, unless otherwise specified, “A to B” representing a numerical range means “A or more and B or less”.

<A. Power storage device>
An electricity storage device according to the present invention includes a positive electrode containing a carbonaceous material having a layered structure capable of inserting and releasing anions formed on a positive electrode current collector having a through hole as a positive electrode active material, and a negative electrode having a through hole One or more materials selected from the group consisting of a carbonaceous material, a metal material that occludes lithium, and an alloy material having a layered structure capable of inserting and releasing lithium ions formed on a current collector are used as a negative electrode active material It is an electrical storage device which has the negative electrode containing and the non-aqueous electrolyte containing lithium salt. The power storage device further includes a separator that separates the positive electrode and the negative electrode, an electrode portion, an exterior member, and the like. Hereinafter, these various components will be described.

<1. Positive electrode>
<1-1. Carbonaceous material contained in positive electrode>
The carbonaceous material as a positive electrode active material included in the positive electrode is a carbonaceous material having a layered structure capable of inserting and releasing anions, and a carbonaceous material satisfying any of the following (i) and (ii): preferable.
(i) A carbonaceous material in which a plurality of amorphous portions are dispersed on the (002) plane, and the average area of the amorphous portions is 1.5 nm ² or more, or
(ii) A plurality of amorphous portions are dispersed in the (002) plane, and the total area of the amorphous portions in the (002) plane is the amorphous portion and crystal in the (002) plane. The carbonaceous material whose ratio with respect to the sum total of the area of a mass part is 30% or more.

  For example, in the carbonaceous material (i), a plurality of amorphous portions having an appropriate area are dispersed on the (002) plane of the carbonaceous material having a layered structure. Can be increased. Moreover, these amorphous parts remain after discharge. Therefore, when this carbonaceous material is used as an electrode of an electricity storage device, electrolyte ions are preferentially and easily inserted into and desorbed from the amorphous part of the carbonaceous material. The amount of desorption can be increased, and the discharge capacity of the electricity storage device can be improved.

  In the case of the carbonaceous material (ii), a plurality of amorphous portions having an appropriate ratio are dispersed on the (002) plane of the carbonaceous material having a layered structure, and the area ratio is 30% or more. Therefore, the anion insertion and desorption sites of the electrolyte can be increased. And this amorphous part remains after discharge. Therefore, when this carbonaceous material is used as an electrode of an electricity storage device, the anion of the electrolyte is preferentially and easily inserted into and desorbed from the amorphous part of the carbonaceous material. The amount of desorption can be increased, and the discharge capacity of the electricity storage device can be improved.

  Graphite (commercially available) is preferable as the carbonaceous material satisfying either of the above (i) and (ii). Graphite has a layered structure on the (002) plane. Here, the “(002) plane” refers to a carbon 002 plane (plane parallel to the graphite layer) measured by X-ray diffraction.

  The carbonaceous material having a layered structure included in the positive electrode is preferably graphite, but is not limited to graphite, and is a carbonaceous material having a layered structure that satisfies any of the above (i) and (ii). Any material can be suitably used. For example, the carbonaceous material described in JP 2010-254537 A can be used as the carbonaceous material. In the present invention, as the carbonaceous material included in the positive electrode, it is not necessary to use a carbonaceous material that has been subjected to a charge / discharge treatment in advance before producing a cell for an electricity storage device.

<1-2. Method for producing positive electrode>
The positive electrode can be formed by applying the carbonaceous material on a positive electrode current collector having a through hole. Specifically, the positive electrode can be formed by applying the carbonaceous material to a surface (one side or both sides) facing the negative electrode in an electrode plate as a positive electrode current collector and covering the surface.

  As the electrode plate, an aluminum plate having a through-hole penetrating the front and back surfaces is preferable, and specifically, a porous aluminum foil (commercially available) having a thickness of 10 to 40 μm and an aperture ratio of 20 to 40% is more preferable. The positive electrode current collector is not limited to an aluminum plate, and any metal plate that can be used as a positive electrode plate of a lithium ion battery and that has a through-hole penetrating the front and back surfaces can be suitably used.

  As a method for coating the surface of the electrode plate with the carbonaceous material, for example, a dispersion (slurry) is prepared by dispersing a carbonaceous material and, if necessary, a conductive additive in a solvent in which a binder is dissolved. A method of applying the dispersion liquid to the surface of the electrode plate using a coating machine such as a doctor blade (horizontal coating machine and vertical coating machine) and then drying (volatilizing) the solvent is preferable. In addition, as a method of coat | covering the surface of an electrode plate with the said carbonaceous material, not only the said method but a well-known method can be employ | adopted suitably. Further, the thickness of the carbonaceous material after drying, that is, the thickness (single side) of the positive electrode may be appropriately set according to the size (area) of the positive electrode, but is preferably 30 to 150 μm, preferably 50 to 50 μm. 90 μm is more preferable.

  As the binder, a mixture of carboxymethyl cellulose and SBR rubber, polyvinylidene fluoride, polyamideimide, polyimide, polytetrafluoroethylene, and the like are preferable, and polyvinylidene fluoride is more preferable. The amount of the binder contained in the positive electrode is preferably 1 to 20% by weight.

  As the solvent, N, N-dimethylformamide, N-methyl-2-pyrrolidone, water and the like are preferable, and N-methyl-2-pyrrolidone is more preferable.

<2. Negative electrode>
<2-1. Materials such as carbonaceous materials included in the negative electrode>
The carbonaceous material as the negative electrode active material included in the negative electrode is a carbonaceous material having a layered structure that can insert and desorb lithium ions. The carbonaceous material included in the negative electrode is preferably graphite, non-graphitizable carbon, natural graphite, artificial graphite, non-graphitizable carbon, graphitizable carbon, low-temperature calcined carbon, activated carbon, etc., graphite, non-graphitizable carbon or artificial graphite Is more preferable.

  The carbonaceous material having a layered structure included in the negative electrode is not limited to the carbonaceous material exemplified above, but may be any carbonaceous material having a layered structure and capable of inserting and releasing lithium ions. It can be used suitably. For example, as the carbonaceous material, a carbonaceous material described in JP2009-260187A can be used. In the present invention, as the carbonaceous material included in the negative electrode, it is not necessary to use a carbonaceous material that has been subjected to a lithium ion occlusion treatment (lithium pre-doping) in advance before producing a cell for an electricity storage device.

  Moreover, it can replace with a carbonaceous material and can also use the metal material or alloy material which occludes lithium. That is, the negative electrode active material included in the negative electrode includes one or more materials selected from the group consisting of carbonaceous materials, metal materials that occlude lithium, and alloy materials.

  Examples of the metal material that occludes lithium include silicon, tin, germanium, lead, antimony, aluminum, indium, zinc, and bismuth. Examples of the alloy material that occludes lithium include silicon alloys and tin alloys. Examples of the silicon alloy include an alloy containing at least one different element selected from the group consisting of iron, cobalt, antimony, bismuth, lead, nickel, copper, zinc, germanium, indium, tin, and titanium. . Examples of the tin alloy include an alloy in which at least one different element selected from the group consisting of nickel, magnesium, iron, copper, and titanium is contained in tin.

  Hereinafter, for convenience, “carbonaceous material” will be described as “one or more materials selected from the group consisting of a carbonaceous material, a metal material that occludes lithium, and an alloy material”.

<2-2. Method for producing negative electrode>
The negative electrode can be formed by applying the carbonaceous material on a negative electrode current collector having a through hole. Specifically, a negative electrode can be formed by applying the carbonaceous material to a surface (one side or both sides) facing the positive electrode in an electrode plate as a negative electrode current collector and covering the surface.

  As the electrode plate, a copper plate having a through-hole penetrating the front and back surfaces is preferable, and specifically, a porous copper foil (commercially available) having a thickness of 10 to 40 μm and an aperture ratio of 20 to 40% is more preferable. The negative electrode current collector is not limited to a copper plate, and any metal plate having a through-hole penetrating the front and back surfaces that can be used as a negative electrode plate for a lithium ion battery can be suitably used.

  As a method for coating the surface of the electrode plate with the carbonaceous material, for example, a dispersion (slurry) is prepared by dispersing a carbonaceous material and, if necessary, a conductive additive in a solvent in which a binder is dissolved. A method of applying the dispersion liquid to the surface of the electrode plate using a coating machine such as a doctor blade (horizontal coating machine or vertical coating machine) and then drying (volatilizing) the solvent is preferable. In addition, as a method of coat | covering the surface of an electrode plate with the said carbonaceous material, not only the said method but a well-known method can be employ | adopted suitably. Further, the thickness of the carbonaceous material after drying, that is, the thickness (single side) of the negative electrode may be appropriately set according to the size (area) of the negative electrode, but is preferably 30 to 150 μm, preferably 50 to 50 μm. 90 μm is more preferable.

  As the binder, a mixture of carboxymethyl cellulose and SBR rubber, polyvinylidene fluoride, polyamideimide, polyimide, polytetrafluoroethylene, and the like are preferable, and polyvinylidene fluoride is more preferable. The amount of the binder contained in the negative electrode is preferably 1 to 20% by weight.

  As the solvent, N, N-dimethylformamide, N-methyl-2-pyrrolidone, water and the like are preferable, and N-methyl-2-pyrrolidone is more preferable.

<3. Non-aqueous electrolyte>
The non-aqueous electrolyte contains a lithium salt as an electrolyte. That is, the non-aqueous electrolyte is an organic electrolyte containing a lithium salt as an electrolyte (solute) dissolved in an organic solvent. The non-aqueous electrolyte may contain an electrolyte other than the lithium salt as necessary.

Examples of the lithium salt include LiPF ₆ , LiBF ₄ , LiCIO ₄ , LiN (CF ₃ SO ₂ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ , LiCF ₃ SO ₃ , LiC (SO ₂ CF ₃ ) ₃ , LiAsF. ₆ and one or more salts selected from the group consisting of LiSbF ₆ are preferred, and LiPF ₆ is more preferred. The concentration of the lithium salt (electrolyte concentration) in the nonaqueous electrolytic solution is preferably higher, and specifically, 0.5 to 5.0 mol / L (0.5 to 5.0 M) is preferable. 0.0 to 1.5 mol / L is more preferable.

  As the organic solvent, ethylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, sulfolane, dimethoxyethane and the like are preferable. These organic solvents may be used as a single solvent or as a mixed solvent of two or more. As the mixed solvent, a mixed solvent of ethylene carbonate and dimethyl carbonate is preferable, and a mixed solvent obtained by mixing ethylene carbonate and dimethyl carbonate at a weight ratio of 1: 1 is more preferable.

  In addition, as the lithium salt and the organic solvent, known lithium salts and organic solvents other than the exemplified compounds can also be used (a compound other than the exemplified compounds is not limited).

<4. Other configurations>
In the electricity storage device, the separator separating the positive electrode and the negative electrode is preferably a porous film made of a cellulose-based polymer or a polyolefin-based polymer such as polyethylene, and more preferably a porous film made of a cellulose-based polymer.

  As an electrode part that is an external extraction electrode for leading the positive electrode and the negative electrode to the outside in the electricity storage device, a known electrode part can be used.

  As an exterior member constituting a cell (cell for power storage device) in the power storage device, a laminate film made of aluminum is preferable. Therefore, the cell of the electricity storage device is preferably a laminate sheath made of aluminum.

  In addition, as the separator and the exterior member, known separators and exterior members other than the exemplified substances can be used (a substance other than the exemplified substances is not limited).

  Then, the electricity storage device according to the present invention is disposed adjacent to a laminate formed by laminating the positive electrode and the negative electrode via a separator in a cell for an electricity storage device having an exterior made of an exterior member at the time of production. And a lithium ion supply source. That is, in the electricity storage device according to the present invention, metallic lithium is disposed in the electricity storage device cell at the time of production. The lithium ion supply source is a metal foil such as a copper foil (commercially available product) or a nickel foil to which metallic lithium is bonded or bonded. The lithium ion supply source has an electrode portion that is an external extraction electrode that leads out the metal lithium electrode made of the metal foil to the outside. The lithium ion supply source is disposed in the electricity storage device cell so as not to be in direct contact with the positive electrode and the negative electrode. Note that at least one lithium ion supply source may be disposed in one stacked body in the power storage device cell, but two or more lithium ion supply sources may be disposed so as to sandwich the stacked body. Moreover, the metal lithium of the lithium ion supply source is all lithium ions when the power storage device is used, and does not exist in the metal state.

  The weight of the metallic lithium is preferably 50 to 90% by weight, preferably 60 to 80% by weight, based on the maximum weight (theoretical weight) of lithium ions that can be occluded by the carbonaceous material as the negative electrode active material. Is more preferable, and it is still more preferable that it is 70 weight%.

  Further, an electrochemical contact is performed between the negative electrode and the lithium ion supply source, and the negative electrode that occludes lithium ions can be used as a lithium ion supply source for the positive electrode.

<5. Configuration of power storage device>
A power storage device manufactured by the method for manufacturing a power storage device according to the present invention (a power storage device manufactured by a cell manufacturing process for a power storage device) will be described below with reference to FIG. FIG. 1 is a schematic cross-sectional view showing an example of the configuration of an electricity storage device manufactured by the method for manufacturing an electricity storage device according to the present invention. In the following description, the case where the electricity storage device has a laminated body in which five layers including a positive electrode and a negative electrode are laminated is taken as an example.

  As shown in FIG. 1, an electricity storage device (an electricity storage device manufactured by an electricity storage device cell manufacturing process) 10 according to the present invention includes a separator 3 in an electricity storage device cell 8 whose exterior is constituted by an exterior member 7. And a laminated body 6 in which the positive electrode 1 and the negative electrode 2 are laminated, and a lithium ion supply source 5 made of a metal foil provided with the metallic lithium 4 are arranged, and a nonaqueous electrolytic solution 9 is injected. ing. The storage device cell 8 is sealed. The non-aqueous electrolyte 9 is also injected into the laminate 6.

  The laminated body 6 is configured by laminating five layers of the positive electrode 1 and the negative electrode 2 through the separator 3 so that the outermost layer becomes the negative electrode 2. Therefore, the positive electrode 1 is configured by applying a carbonaceous material on both surfaces of the electrode plate. On the other hand, the negative electrode 2 located inside is configured by applying a carbonaceous material on both sides of the electrode plate, and the negative electrode 2 positioned on the outermost layer is configured by applying a carbonaceous material on one side of the electrode plate. . In addition, the positive electrode 1 and the negative electrode 2 in the laminated body 6 should just be laminated | stacked two or more layers in total, Preferably the three or more layers should just be laminated | stacked, More preferably, the five or more layers should just be laminated | stacked. When three or more layers are stacked, the outermost layer of the stacked body 6 is preferably the negative electrode 2.

  Further, the separator 3 is inserted between the laminated body 6 and the lithium ion supply source 5, between the laminated body 6 and the exterior member 7, and between the lithium ion supply source 5 and the exterior member 7 so as not to contact each other. . That is, by inserting the separator 3, the exterior member 7, the positive electrode 1, the negative electrode 2, and the lithium ion supply source 5 are not in contact with each other.

<B. Manufacturing method of power storage device>
A method for manufacturing an electricity storage device according to the present invention includes a positive electrode 1 including a carbonaceous material having a layered structure that can insert and desorb anions formed on a positive electrode current collector having a through hole as a positive electrode active material, A negative electrode 2 formed on a negative electrode current collector having holes and having a layered structure capable of inserting and releasing lithium ions as a negative electrode active material; and a non-aqueous electrolyte 9 containing a lithium salt. A laminated body 6 in which the positive electrode 1 and the negative electrode 2 are laminated via a separator 3 and a lithium ion supply source 5 in an exterior member 7 to be a storage device cell 8. And a storage device cell manufacturing step for injecting the non-aqueous electrolyte 9, a charge / discharge step for charging / discharging between the positive electrode 1 and the lithium ion supply source 5, and the negative electrode 2 and the lithium ion supply source 5. When Perform electrochemical contact between, the method comprising a storage step of occluding lithium ions in the negative electrode 2, a.

  The order in which the occlusion step and the charge / discharge step are performed is not particularly limited, and the charge / discharge step may be performed after the occlusion step, or the occlusion step may be performed after the charge / discharge step. .

  In addition, when performing the said charging / discharging process after the said occlusion process, an electrochemical contact is made between the negative electrode 2 and the lithium ion supply source 5 by the said occlusion process, and the negative electrode 2 which occluded lithium ion is made into lithium ion. It is preferable to perform charge / discharge between the positive electrode 1 and the negative electrode 2 that occludes lithium ions in the subsequent charge / discharge step, which functions as a supply source. Thereby, since the positive electrode 1 performs charging / discharging separately with the negative electrode 2 which adjoins via the separator 3, the uniformity of the increase amount of the anion insertion and desorption site of the positive electrode 1 can be improved. Moreover, when performing the said occlusion process after the said charging / discharging process, it charges / discharges between the lithium ion supply source 5 and the positive electrode 1 at the said charging / discharging process, and the negative electrode 2 and a lithium ion supply source at the said occlusion process. Electrochemical contact with 5 is performed, and the negative electrode 2 is made to occlude lithium ions.

  Hereinafter, for convenience of explanation, each of the steps will be described by taking as an example a case where the occlusion step is performed after the charge / discharge step.

<6. Cell manufacturing process for power storage device>
First, according to the above method, a positive electrode 1 containing a carbonaceous material having a layered structure capable of inserting and releasing anions formed on a positive electrode current collector having a through hole as a positive electrode active material is manufactured. A negative electrode 2 containing a carbonaceous material formed on the negative electrode current collector and having a layered structure capable of inserting and releasing lithium ions as a negative electrode active material is produced. And the laminated body 6 is produced by laminating | stacking the positive electrode 1 and the negative electrode 2 through the separator 3. FIG. Further, the lithium ion supply source 5 made of a non-aqueous electrolyte 9 or a metal foil provided with the metal lithium 4 is prepared (or prepared). Furthermore, electrode portions are attached to the positive electrode 1, the negative electrode 2, and the lithium ion supply source 5. The production method of the laminated body 6 and the production method of the non-aqueous electrolyte 9 are not particularly limited, and a known production method can be adopted.

  Next, as shown in FIG. 1, the laminated body 6 and the lithium ion supply source 5 are disposed via the separator 3 in the exterior member 7 that becomes the power storage device cell 8, and the non-aqueous electrolyte 9 is added. inject. Then, the electricity storage device cell 8, that is, the electricity storage device 10, is manufactured by sealing the electricity storage device cell 8 by sealing the exterior member 7 (cell storage device manufacturing step).

  The cell manufacturing process for an electricity storage device is performed in a dry atmosphere or an inert gas atmosphere having a dew point of −35 ° C. or lower, more preferably −60 ° C. or lower, as in a known method for manufacturing an electricity storage device.

<7. Charge / Discharge Process>
Subsequently, charging / discharging is performed between the electrode part of the positive electrode 1 and the electrode part of the lithium ion supply source 5 in the electricity storage device 10 produced in the electricity production device cell production process (charge / discharge process). That is, at least one charge / discharge cycle is performed in which charging is performed by passing a constant current between the positive electrode 1 and the lithium ion supply source 5 and then discharging is performed.

Charging is performed at a constant current of, for example, a current density of 1.85 mA / cm ² until the voltage reaches a predetermined voltage. Here, as for the predetermined voltage (positive electrode potential) at the time of charge, it is more preferable that the charge voltage is 5.0 V or more and 6.0 V or less with respect to metallic lithium. The charge / discharge cycle may be performed at least once, but may be performed a plurality of times. When a charging current is passed between the positive electrode 1 and the lithium ion supply source 5, cations in the non-aqueous electrolyte 9 are adsorbed on the metal lithium 4 of the lithium ion supply source 5, and the anions are carbonaceous materials having a positive electrode layer structure ( For example, it is inserted between graphite layers). After charging until a predetermined voltage is reached, this time, discharging is performed until the voltage reaches 3.0 V with reference to metallic lithium. In addition, the specific conditions of a charging / discharging cycle are not specifically limited.

  By the above method, a positive electrode that has been subjected to charge / discharge treatment (pre-treatment), that is, a positive electrode used for the electric storage device, is produced in the electric storage device cell 8.

  Thereby, the amorphous part can be formed in the carbonaceous material having a layered structure, and anion insertion and desorption sites can be increased. Further, even after discharge, the amorphous part remains. Therefore, the anion of the electrolyte is preferentially and easily inserted into and desorbed from the amorphous part of the carbonaceous material, so that the amount of insertion and desorption in the carbonaceous material can be increased, and the discharge capacity of the electricity storage device can be increased. Can be improved. This is presumed to be related to, for example, the presence / absence of formation of an amorphous part in graphite and the expansion of the interlayer distance, and the amount of insertion and desorption. That is, it can be said that the amorphous part increases and the interlayer distance increases, and as a result, the anion is easily inserted and extracted preferentially with respect to the amorphous part, and the amount of stored electricity increases.

<8. Occlusion process>
Subsequently, electrochemical contact is made between the electrode portion of the negative electrode 2 and the electrode portion of the lithium ion supply source 5 in the power storage device 10 manufactured in the power storage device cell manufacturing step, and lithium ions are occluded in the negative electrode 2. (Occlusion process) Here, the potential of the negative electrode 2 by electrochemical contact is more preferably 0.01 V or more and 0.1 V or less with respect to metallic lithium. That is, by short-circuiting the electrode part of the negative electrode 2 and the electrode part of the lithium ion supply source 5 through an external circuit (or passing a current), the carbonaceous material having the layered structure of the negative electrode 2 and the metal lithium 4 are electrochemically produced. To react. In addition, the specific occlusion conditions in the occlusion process are not particularly limited.

  By the above method, the negative electrode by which lithium pre dope process (pre-processing) was made in the cell 8 for electrical storage devices, ie, the negative electrode used for an electrical storage device, is produced.

  The weight of the lithium metal occluded in the carbonaceous material of the negative electrode 2 is preferably 50 to 90% by weight with respect to the maximum weight (theoretical weight) of lithium ions that can be occluded by the carbonaceous material. More preferably, it is 70% by weight. If it is in this range, since the capacity of the negative electrode 2 is not too small compared with the capacity of the electricity storage device 10, a sufficient amount of lithium ions can be occluded in the negative electrode 2. Moreover, since the weight of the electrical storage device 10 can be prevented from increasing by suppressing the increase in the weight of the negative electrode 2, the capacity density of the electrical storage device 10 does not decrease. In addition, since the amount of lithium ions occluded in the negative electrode 2 is an appropriate amount, the capacity density of the electricity storage device 10 can be maintained, and a decrease in capacity due to float charging can also be prevented.

<9. Other processes>
In the method for manufacturing an electricity storage device according to the present invention, it is more preferable to perform an exchange step of exchanging at least a part of the non-aqueous electrolyte 9 in the electricity storage device cell 8 between the charge / discharge step and the occlusion step. .

  Thereby, it is possible to supplement the amount of anion (irreversible capacity) which decreases by adhering (trapping) to the positive electrode during the charge / discharge process, that is, maintaining the concentration of the electrolyte in the non-aqueous electrolyte. In addition, an electricity storage device having excellent long-term characteristics can be manufactured.

<10. Modification>
When the charge / discharge process is performed after the occlusion process, the above <7. Charging / discharging process> and <8. The order of performing the occlusion process> is changed, and <8. Subsequent to <Occlusion process><7. Charging / discharging process> may be performed. Also when performing both processes in this order, it is more preferable to perform the replacement process which replaces at least one part of the nonaqueous electrolyte 9 in the electrical storage device cell 8 between the said occlusion process and charging / discharging process.

<11. Maximum charge / discharge voltage>
The power storage device manufactured by the manufacturing method according to the present invention is charged / discharged such that the upper limit voltage of the operating voltage range (charge / discharge voltage) of the power storage device is 5.0 V or higher and 6.0 V or lower. Is preferred.

  In the electricity storage device cell (electric storage device) having the above-described configuration, charge / discharge is performed so that the upper limit voltage is 5.0 V or more and 6.0 V or less, thereby allowing the electric storage to be larger than that of a known electricity storage device such as a lithium ion battery. Capacitance can be generated. For example, according to the electricity storage device of the present invention, compared to conventional EDLC (charge / discharge voltage range of about 0V to 2.7V) and lithium ion capacitor (charge / discharge voltage range of about 2.2V to 3.8V), As compared with the conventional high capacity type lithium ion battery (charge / discharge voltage range of about 2.5 V to 4.2 V), it has an effect that it is superior in either or both of capacity density and output density.

  In general, the charge / discharge capacity of an electricity storage device decreases as the value of the upper limit voltage of the charge / discharge voltage decreases. However, in the electricity storage device according to the present invention, since the upper limit voltage of the operating voltage range (charge / discharge voltage) is 5.0 V or more and 6.0 V or less, sufficient charge / discharge capacity can be obtained. In addition, when the upper limit voltage exceeds 6.0 V, decomposition of the electrolytic solution may proceed and characteristics may deteriorate. Moreover, the lower limit voltage of the operating voltage range (charge / discharge voltage) of the electricity storage device may be around 3 V, and is not particularly limited.

  The power storage device manufactured by the manufacturing method according to the present invention is a high-capacity storage battery having an upper limit voltage of an operating voltage range (charge / discharge voltage) as high as 5.0 V or higher and 6.0 V or lower. Therefore, a power storage device manufactured by the manufacturing method or a power storage device including the power storage device is mounted on a general electric device such as a laptop computer or a mobile device such as a mobile phone, an electric vehicle, or a hybrid vehicle. It can be widely used in various fields such as a power storage device for automobiles or a storage battery for power storage combined with a new energy system such as a solar battery or wind power generation.

Moreover, the following invention is also included in the manufacturing method of the electrical storage device which concerns on this invention.
1. A positive electrode current collector having a hole penetrating the front and back surfaces is used as a positive electrode active material, and a negative electrode active material is a carbonaceous material in which cations are inserted and released between layers. The positive electrode and the negative electrode formed on the electrode body and the negative electrode current collector have a cell structure in which three or more layers are alternately stacked via a separator, and a lithium ion supply source is disposed opposite to the cell structure. In a non-aqueous electrolyte secondary battery including a non-aqueous electrolyte in which salt is dissolved, first, a step of charging / discharging between a lithium source and a positive electrode, and then electrochemical contact between the lithium source and the negative electrode And a step of previously inserting lithium ions as cations into the negative electrode. A method for producing a non-aqueous electrolyte secondary battery.
2. Between the step of charging / discharging between the lithium source and the positive electrode, and then the step of electrochemically contacting the lithium source and the negative electrode and inserting lithium ions as cations in advance into the negative electrode It is more preferable to include a step of replacing the non-aqueous electrolyte solution in which is dissolved.
3. A positive electrode current collector having a hole penetrating the front and back surfaces is used as a positive electrode active material, and a negative electrode active material is a carbonaceous material in which cations are inserted and released between layers. The positive electrode and the negative electrode formed on the electrode body and the negative electrode current collector have a cell structure in which three or more layers are alternately stacked via a separator, and a lithium ion supply source is disposed opposite to the cell structure. In a non-aqueous electrolyte secondary battery including a non-aqueous electrolyte solution in which a salt is dissolved, first, electrochemical contact is performed between a lithium supply source and a negative electrode, lithium ions are previously inserted into the negative electrode as cations, and then lithium The manufacturing method of the nonaqueous electrolyte secondary battery characterized by including the process of charging / discharging between a supply source and a positive electrode.
4). Between the step of electrochemical contact between the lithium supply source and the negative electrode to insert lithium ions as cations in advance into the negative electrode, and the subsequent step of charging / discharging between the lithium supply source and the positive electrode It is more preferable to include a step of replacing the non-aqueous electrolyte solution in which is dissolved.
5. It is more preferable that the charge / discharge between the lithium supply source and the positive electrode be 5.0 to 6.0 V based on metallic lithium.
6). More preferably, the potential of the negative electrode due to electrochemical contact between the lithium supply source and the negative electrode is 0.01 to 0.1 V with respect to metallic lithium.
7). A non-aqueous electrolyte secondary battery manufactured by the method for manufacturing a non-aqueous electrolyte secondary battery having an upper limit voltage of 5.0 to 6.0 V in the operating voltage range of the battery.

  The present invention is not limited to the configurations described above, and various modifications can be made within the scope described in the specification, and implementations obtained by appropriately combining technical means disclosed in different embodiments. The form is also included in the technical scope of the present invention. Moreover, all the literatures described in this specification are used as reference.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited only to the Example which concerns.

[Example 1]
An electricity storage device 10 having the configuration shown in FIG. 1 was produced. That is, the electricity storage device according to this example was manufactured by the following manufacturing method.

<Preparation of positive electrode 1>
After dissolving polyvinylidene fluoride as a binder in N-methyl-2-pyrrolidone as a solvent, graphite (KS6: manufactured by Timcal) was dispersed as a positive electrode active material in the obtained solution to obtain a slurry (dispersion). . This slurry was applied to the front and back surfaces of a porous aluminum foil (commercial product; thickness: 20 μm, opening ratio: 30%) as a positive electrode current collector using a doctor blade, and dried to produce positive electrode 1. The thickness of the coated slurry after drying, that is, the thickness (one side) of the positive electrode 1 was 80 μm. Further, the weight ratio of graphite to polyvinylidene fluoride (graphite: polyvinylidene fluoride) was 90:10.

<Preparation of negative electrode 2>
After dissolving polyvinylidene fluoride as a binder in N-methyl-2-pyrrolidone as a solvent, artificial graphite (commercial product; graphite) was dispersed as a negative electrode active material in the obtained solution to obtain a slurry (dispersion). . This slurry was applied to the front and back surfaces or one surface of a porous copper foil (commercial product; thickness: 15 μm, opening ratio: 20%) as a negative electrode current collector using a doctor blade, and dried to prepare a negative electrode 2. The thickness of the coated slurry after drying, that is, the thickness (one side) of the negative electrode 2 was 90 μm. The weight ratio of artificial graphite to polyvinylidene fluoride (artificial graphite: polyvinyl fluoride) was 90:10.

<Production of electricity storage device 10>
In a mixed solvent obtained by mixing ethylene carbonate and dimethyl carbonate at a weight ratio of 1: 1, lithium hexafluorophosphate (LiPF ₆ ), which is an electrolyte (lithium salt), has a concentration (electrolyte concentration) of 1.5 mol / A nonaqueous electrolytic solution 9 was prepared by dissolving to L (1.5 M).

  And the electrical storage device 10 was produced in the dry atmosphere. That is, a laminate 6 was produced by laminating five layers of the produced positive electrode 1 and negative electrode 2 through the separator 3 with the outermost layer being the negative electrode 2. Further, a lithium ion supply source (commercially available product) 5 made of a copper foil provided with metallic lithium 4 was laminated on the laminate 6 with the separator 3 interposed therebetween. The weight of metallic lithium was set to an amount of 70% by weight with respect to the maximum weight (theoretical weight) of lithium ions that can be occluded by the negative electrode 2. And the electrode part was attached to the positive electrode 1, the negative electrode 2, and the lithium ion supply source 5, respectively.

  The laminated body composed of the laminated body 6 and the lithium ion supply source 5 is accommodated (exterior) in an exterior member (laminate film made of aluminum) 7 with a separator 3 interposed therebetween, and the non-existing member 7 is not in the exterior member 7. A water electrolyte 9 was injected. Subsequently, an electricity storage device (an electricity storage device produced by an electricity storage device cell production step) 10 was produced by sealing the electricity storage device cell 8 by sealing the exterior member 7.

  A charge / discharge cycle was performed once between the positive electrode 1 and the lithium ion supply source 5 in the produced power storage device 10, charging with a constant current at a positive electrode potential of 5.3 V with respect to metallic lithium, and then discharging. .

  Thereafter, the negative electrode 2 and the lithium ion supply source 5 in the electricity storage device 10 were short-circuited through an external circuit, whereby the negative electrode 2 was made to occlude lithium ions.

  This produced the electrical storage device which concerns on Example 1. FIG.

[Example 2]
In the same manner as in Example 1, an electricity storage device (an electricity storage device produced by an electricity storage device cell production process) 10 was produced.

  Lithium ions were occluded in the negative electrode 2 by short-circuiting between the negative electrode 2 and the lithium ion supply source 5 in the produced electricity storage device 10 through an external circuit.

  Thereafter, between the positive electrode 1 and the lithium ion supply source 5 in the electricity storage device 10, charging and discharging were performed once by charging with a constant current flowing at a positive potential of 5.3 V based on metallic lithium, and then discharging. .

  This produced the electrical storage device which concerns on Example 2. FIG.

Example 3
In the same manner as in Example 1, an electricity storage device (an electricity storage device produced by an electricity storage device cell production process) 10 was produced.

  Thereafter, a constant current is passed between the positive electrode 1 in the electricity storage device 10 and the negative electrode 2 functioning as the lithium ion supply source 5 by occluding lithium ions in the occlusion process with a positive electrode potential of 5.3 V based on metallic lithium. The battery was charged and then discharged, and a charge / discharge cycle was performed once.

  Thereby, the electrical storage device which concerns on Example 3 was produced.

[Comparative Example 1]
<Preparation of positive electrode>
A positive electrode was produced in the same manner as in <Preparation of positive electrode 1> in Example 1. Next, pretreatment (charging / discharging) of the produced positive electrode was performed. That is, activated carbon having a specific surface area of 2000 m ² / g obtained by steam activation of petroleum coke, conductive carbon black, and polytetrafluoroethylene as a binder, 80% by weight of activated carbon, 10% by weight of conductive carbon black, And it mixed in the ratio of 10 weight% of polytetrafluoroethylene, knead | mixed and rolled using ethyl alcohol, and it shape | molded in the sheet-like molded object. The thickness of the molded product was 400 μm. This molded product was bonded to an aluminum foil using a conductive adhesive to produce a negative electrode for positive electrode treatment.

Further, 4-trifluoromethyl-1,3-dioxolan-2-one and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether “H (CF ₂ ) ₂ CH _By dissolving 100 parts by weight of an electrolyte salt (SBP-PF6; manufactured by Nihon Carterit Co., Ltd.) in 100 parts by weight of a mixed solvent obtained by mixing ₂ O (CF ₂ ) ₂ H ”at a weight ratio of 1: 1. A non-aqueous electrolyte was prepared.

  The produced positive electrode and the negative electrode for positive electrode treatment are made to face each other through a cellulose-based porous separator, and an electrode part is attached to the positive electrode and the negative electrode for positive electrode treatment, and is accommodated in an exterior member (a laminate film made of aluminum). ). Next, the non-aqueous electrolyte was injected into the exterior member. Then, the charge / discharge device was produced by sealing the charging / discharging cell by sealing an exterior member.

  Between the positive electrode and the negative electrode for positive electrode treatment in the produced charge / discharge device, a direct current was passed to charge from 0 V to 3.5 V, and then immediately discharged to 0 V. After the discharge, the charge / discharge device was disassembled and only the positive electrode was taken out.

<Production of negative electrode>
A negative electrode was prepared in the same manner as in <Preparation of negative electrode 2> in Example 1. Next, a pretreatment (lithium pre-doping) in which lithium ions were occluded in the negative electrode was performed in the same manner as in <Production of electricity storage device 10> in Example 1. That is, in a dry atmosphere, the manufactured negative electrode and a lithium ion supply source (commercially available product) made of copper foil provided with metallic lithium are opposed to each other through a cellulosic porous separator, and the negative electrode and lithium ion supply are provided. The electrode part was attached to the source and accommodated in the exterior member (laminated film made of aluminum). Subsequently, the same non-aqueous electrolyte solution as produced in Example 1 was injected into the exterior member. Subsequently, the occlusion processing device was fabricated by sealing the occlusion processing cell by sealing the exterior member. Thereafter, the negative electrode and the lithium ion supply source in the prepared device for occlusion treatment were short-circuited through an external circuit, whereby lithium ions were occluded in the negative electrode. After the occlusion treatment, the occlusion treatment device was disassembled and only the negative electrode was taken out.

<Production of electricity storage device>
An electricity storage device was produced in the same manner as in <Production of electricity storage device 10> of Example 1 using the positive electrode and the negative electrode that had been subjected to the pretreatment. That is, a laminate was produced by laminating five layers of the produced positive electrode and negative electrode through a separator in a dry atmosphere with the outermost layer being a negative electrode. And the electrode part was attached to the positive electrode and the negative electrode, respectively. The laminate is accommodated (exterior) in an exterior member (a laminate film made of aluminum) via a separator, and the same nonaqueous electrolyte solution as that prepared in Example 1 was injected into the exterior member. . Then, the electrical storage device was produced by sealing the cell for electrical storage devices by sealing an exterior member. Therefore, the charge / discharge treatment and the occlusion treatment were not performed when the electricity storage device was manufactured. This produced the (conventional) electrical storage device which concerns on the comparative example 1. FIG.

<Result>
<I. Productivity>
Example 1, in which the pretreatment (charging / discharging treatment and occlusion treatment) of the positive electrode and the negative electrode does not have to be performed before the production of the electricity storage device when the production time of the electricity storage device according to Comparative Example 1 is 100 (reference) The manufacturing time of the electricity storage device 10 according to Example 2 and Example 3 was 30. That is, the time required to manufacture the electricity storage device 10 according to Example 1, Example 2, and Example 3 was 30% of the time required to manufacture the electricity storage device according to Comparative Example 1.

  Therefore, according to the method for manufacturing an electricity storage device according to the present invention in which the production process is simplified, it can be seen that the production time (tact time) of the electricity storage device can be greatly reduced. That is, it can be seen that the method for manufacturing an electricity storage device according to the present invention is excellent in productivity.

  In addition, according to the method for manufacturing an electricity storage device according to the present invention, it is not necessary to perform pretreatment (charge / discharge treatment and storage treatment) of the positive electrode and the negative electrode before producing the electricity storage device. That is, it is not necessary to produce a charge / discharge device for performing pretreatment (charge / discharge) of the positive electrode and an occlusion device for performing pretreatment (occlusion) of the negative electrode. Therefore, it is not necessary to prepare (or prepare) a negative electrode for positive electrode treatment, a non-aqueous electrolyte, a porous separator, an electrode part, an exterior member, and the like for producing the charge / discharge device and the occlusion device. Therefore, it can be seen that according to the method for manufacturing an electricity storage device according to the present invention in which the manufacturing process is simplified, the manufacturing cost (cost required for the material) of the electricity storage device can be significantly reduced. That is, the power storage device can be manufactured at a low cost.

  In addition, when manufacturing cost of the electricity storage device according to Comparative Example 1 is set to 100 (standard), it is not necessary to perform pretreatment (charge / discharge treatment and storage treatment) of the positive electrode and the negative electrode before producing the electricity storage device. The manufacturing cost of the electricity storage device 10 according to Example 1, Example 2 and Example 3 was 40.

<Ii. Performance>
A charge / discharge cycle test was performed on the electricity storage device 10 according to Example 1, Example 2, and Example 3 and the electricity storage device according to Comparative Example 1. The conditions of the charge / discharge cycle test were a constant temperature bath of 25 ° C., an operating voltage range of 3.0 to 5.3 V, a 2C-CC charge rate and a 0.5C-CC discharge rate.

  And about the electrical storage device 10 which concerns on the said Example 1, and the electrical storage device which concerns on the comparative example 1, a charge / discharge cycle test is performed 100 cycles and the capacity | capacitance change is measured by measuring the capacity | capacitance before a test and after a test (after 100 cycles). did. That is, the capacity change (decrease) after the test when the capacity before the test (initial capacity) was 100 (reference) was measured to evaluate the performance of both power storage devices. The results are shown in Table 1. The initial capacities of the power storage device 10 according to Example 1 and the power storage device according to Comparative Example 1 were the same.

  Similarly, with respect to the electricity storage device 10 according to Example 1, Example 2 and Example 3, and the electricity storage device according to Comparative Example 1, 500 charge / discharge cycle tests were performed before and after the test (after 500 cycles). The capacitance change was measured to measure the change in capacitance. That is, the capacity change (decrease) after the test when the capacity before the test (initial capacity) was 100 (reference) was measured to evaluate the performance of each power storage device. The results are shown in Table 2. Note that the initial capacities of the electricity storage device 10 according to Example 1, Example 2, and Example 3 and the electricity storage device according to Comparative Example 1 were the same.

  As is clear from the descriptions in Tables 1 and 2, the electricity storage device 10 according to Example 1, Example 2 and Example 3 has a capacity change (decrease) after the test as compared with the electricity storage device according to Comparative Example 1. It can be seen that it has excellent performance in long-term characteristics. That is, it turns out that the electrical storage device manufactured by the manufacturing method of the electrical storage device which concerns on this invention is excellent in long-term stability. In addition, in the electricity storage device according to Comparative Example 1, the cause of the large capacity change (decrease) after the test was that after the electrode was pretreated, the positive electrode and the negative electrode were taken out from the charge / discharge device and the storage device. Deterioration of electrode and nonaqueous electrolyte performance due to contact with oxygen remaining in the dry atmosphere when producing an electricity storage device, and foreign matter (for example, exterior) caused by disassembly of charge / discharge device and storage device It is conceivable that a piece of material or the like is mixed into the power storage device.

  According to the method for manufacturing an electricity storage device according to the present invention, it is possible to produce an electricity storage device having a simplified manufacturing process at low cost (excellent productivity) and excellent long-term stability. Therefore, a power storage device manufactured by the manufacturing method or a power storage device including the power storage device is mounted on a general electric device such as a laptop computer or a mobile device such as a mobile phone, an electric vehicle, or a hybrid vehicle. It can be widely used in various fields such as a power storage device for automobiles or a storage battery for power storage combined with a new energy system such as a solar battery or wind power generation.

DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Separator 4 Metal lithium 5 Lithium ion supply source 6 Laminated body 7 Exterior member 8 Cell for electrical storage devices 9 Non-aqueous electrolyte 10 Electrical storage device

Claims (3)

A positive electrode comprising a carbonaceous material formed on a positive electrode current collector having a through hole and having a layered structure capable of inserting and releasing anions as a positive electrode active material;
One or more materials selected from the group consisting of a carbonaceous material, a metal material that occludes lithium, and an alloy material, which are formed on a negative electrode current collector having a through hole and have a layered structure capable of inserting and extracting lithium ions A negative electrode containing as a negative electrode active material,
A non-aqueous electrolyte containing a lithium salt, and a method for producing an electricity storage device comprising:
In the electricity storage device cell, a laminated body formed by laminating the positive electrode and the negative electrode via a separator and a lithium ion supply source, and injecting the non-aqueous electrolyte solution, an electricity storage device cell manufacturing step,
A charge / discharge step of charging / discharging between the positive electrode and the lithium ion source;
An electrochemical process between the negative electrode and the lithium ion supply source, and occlusion of lithium ions in the negative electrode;
The charge / discharge step is performed after the occlusion step,
Lithium source in the charging and discharging process, Ri anode der occluding lithium ions by the storage step,
In the charging / discharging step, a charging voltage is set to 5.0 V or more and 6.0 V or less with respect to metallic lithium, and the method for manufacturing an electricity storage device.   The method for manufacturing an electricity storage device according to claim 1, further comprising an exchange step of exchanging at least a part of the nonaqueous electrolytic solution in the cell for the electricity storage device between the charge / discharge step and the occlusion step. 3. The method for manufacturing an electricity storage device according to claim 1, wherein, in the occlusion step, the potential of the negative electrode by electrochemical contact is set to 0.01 V or more and 0.1 V or less based on metallic lithium.

Images