WO2013172221A1 - Procédé permettant de fabriquer un dispositif de stockage d'électricité et dispositif de stockage d'électricité obtenu à l'aide dudit procédé - Google Patents

Procédé permettant de fabriquer un dispositif de stockage d'électricité et dispositif de stockage d'électricité obtenu à l'aide dudit procédé Download PDF

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WO2013172221A1
WO2013172221A1 PCT/JP2013/062883 JP2013062883W WO2013172221A1 WO 2013172221 A1 WO2013172221 A1 WO 2013172221A1 JP 2013062883 W JP2013062883 W JP 2013062883W WO 2013172221 A1 WO2013172221 A1 WO 2013172221A1
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storage device
positive electrode
electricity storage
negative electrode
state
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PCT/JP2013/062883
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English (en)
Japanese (ja)
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弘義 武
大谷　彰
阿部　正男
植谷　慶裕
由姫 加治佐
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日東電工株式会社
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Priority to CN201380014715.6A priority Critical patent/CN104247140A/zh
Publication of WO2013172221A1 publication Critical patent/WO2013172221A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for producing an electricity storage device and an electricity storage device obtained by the method, and more particularly, to produce a novel electricity storage device having sufficient battery performance without the complicated work of pre-doping electrodes with lithium ions.
  • the present invention relates to a method and an electricity storage device obtained thereby.
  • the electrode of the electricity storage device contains an active material having a function capable of inserting and removing ions.
  • the insertion / desorption of ions of the active material is also referred to as so-called doping / dedoping (or sometimes referred to as “doping / dedoping”), and the doping / dedoping amount per certain molecular structure is called a doping rate.
  • doping rate the doping rate, the higher the capacity of the battery.
  • Electrochemically it is possible to increase the capacity of a battery by using a material having a large amount of ion insertion / desorption as an electrode. More specifically, lithium secondary batteries, which are attracting attention as power storage devices, use a graphite-based negative electrode that can insert and desorb lithium ions, and about one lithium ion is inserted per six carbon atoms. -Desorption and high capacity have been achieved.
  • lithium secondary batteries a lithium-containing transition metal oxide such as lithium manganate or lithium cobaltate is used for the positive electrode, and a carbon material capable of inserting and removing lithium ions is used for the negative electrode.
  • Lithium secondary batteries that face each other in an electrolytic solution have a high energy density, and thus are widely used as power storage devices for the electronic devices described above.
  • the lithium secondary battery is a secondary battery that obtains electric energy by an electrochemical reaction, and has a drawback that the output density is low because the speed of the electrochemical reaction is low. Furthermore, since the internal resistance of the secondary battery is high, rapid discharge is difficult and rapid charge is also difficult. Moreover, since an electrode and electrolyte solution deteriorate by the electrochemical reaction accompanying charging / discharging, generally a lifetime, ie, a cycling characteristic, is not good.
  • a lithium secondary battery using a conductive polymer such as polyaniline having a dopant as a positive electrode active material is also known (see Patent Document 1).
  • a secondary battery having a conductive polymer as a positive electrode active material is an anion transfer type in which an anion is doped into the conductive polymer during charging and the anion is dedoped from the polymer during discharging. Therefore, when a carbon material that can insert and desorb lithium ions is used as the negative electrode active material, a cation-moving rocking chair type secondary battery in which cations move between both electrodes during charge and discharge cannot be configured.
  • the rocking chair type secondary battery has the advantage that the amount of the electrolyte is small, but the secondary battery having the conductive polymer as the positive electrode active material cannot do so, and contributes to the miniaturization of the electricity storage device. Can not.
  • a cation migration type secondary battery has also been proposed.
  • a positive electrode is formed using a conductive polymer having a polymer anion such as polyvinyl sulfonic acid as a dopant, and lithium metal is used for the negative electrode (see Patent Document 2).
  • JP-A-3-129679 Japanese Patent Laid-Open No. 1-132052
  • the secondary battery is still not sufficient in performance. That is, the capacity density and energy density are lower than those of a lithium secondary battery using a lithium-containing transition metal oxide such as lithium manganate or lithium cobaltate for the positive electrode.
  • an electric double layer capacitor called a lithium ion capacitor using activated carbon as a positive electrode and carbon pre-doped (pre-doped) with a lithium ion as a negative electrode can charge and discharge with a large current because ionic molecules store electric charge. Has become.
  • the present invention has been made in order to solve the above-described problems in power storage devices such as conventional lithium secondary batteries and electric double layer capacitors, and requires a complicated operation of pre-doping electrodes with lithium ions.
  • a method for producing a novel electricity storage device having sufficient battery performance and an electricity storage device obtained thereby are provided.
  • the present invention relates to a method of manufacturing an electricity storage device having an electrolyte layer and a positive electrode and a negative electrode provided to face each other with the electrolyte layer interposed therebetween, the step of forming a positive electrode by the following a to c, and the formation of a negative electrode by the following d
  • the manufacturing method of an electrical storage device provided with a process be a 1st summary.
  • a. The process of making following (X) into a reduction
  • b. The process of compensating the anion of the following (Y) with a counter ion.
  • a step of forming a negative electrode using the following (Z) in an undoped state (X) A positive electrode active material in a doped state whose conductivity is changed by insertion / extraction of ions (hereinafter also referred to as “positive electrode active material”). (Y) Anionic material. (Z) A negative electrode active material capable of inserting / extracting ions (hereinafter also referred to as “negative electrode active material”).
  • the second gist of the present invention is an electricity storage device obtained by the method for producing an electricity storage device.
  • the present inventors have made extensive studies in order to obtain a novel power storage device that can be manufactured without complicated operations and has a high capacity density and a high energy density.
  • the rocking chair type energy storage device mechanism which is a cation transfer type that requires less electrolyte
  • the reserve type energy storage device mechanism which is an anion transfer type that has excellent output characteristics. Further research centered on and conducted various experiments.
  • the inventors of the present invention can manufacture a power storage device that can easily and quickly be manufactured while eliminating the complicated work of pre-doping lithium ions on a negative electrode such as carbon, and can obtain a power storage device having sufficient battery characteristics. I found a way.
  • the present invention is a method for producing an electricity storage device having an electrolyte layer and a positive electrode and a negative electrode provided to face each other with the electrolyte layer interposed therebetween, and a method for producing an electricity storage device having the above steps a to d. .
  • this production method an electricity storage device having sufficient battery performance can be obtained, and a complicated operation of pre-doping lithium ions into a negative electrode such as carbon can be omitted, so that an electricity storage device can be produced easily and quickly. become.
  • a high-performance power storage device having a higher capacity density can be obtained when the power storage device is obtained by the method for manufacturing the power storage device.
  • the positive electrode is an electricity storage device including at least the above (X) and (Y), the negative electrode includes the above (Z), and the positive electrode (X) is in a reduction-dedoped state and is fixed in the positive electrode
  • the capacity density is further improved.
  • the method for producing an electricity storage device of the present invention is, as described above, a method for producing an electricity storage device having an electrolyte layer and a positive electrode and a negative electrode provided facing each other with the electrolyte layer interposed therebetween. And a step of forming a negative electrode by the following d.
  • a. The process of making following (X) into a reduction
  • b. The process of compensating the anion of the following (Y) with a counter ion.
  • c. A step of forming a positive electrode using at least the reduced and doped (X) obtained from a and the compensated (Y) obtained from b.
  • d A step of forming a negative electrode using the following (Z) in an undoped state.
  • (X) A positive electrode active material in a doped state in which conductivity is changed by insertion / extraction of ions.
  • Y) Anionic material.
  • Z) A negative electrode active material capable of inserting / extract
  • the electrical storage device obtained by the said manufacturing method is an electrical storage device which has the electrolyte layer 3, and the positive electrode 2 and the negative electrode 4 which were provided facing on both sides of this, as shown in FIG. (X) and (Y), the negative electrode 4 is an electricity storage device including the above (Z), and (X) of the positive electrode 2 is in a reduction-dedoped state, and is fixed in the positive electrode 2
  • the anion of (Y) is compensated by a counter ion, and (Z) of the negative electrode 4 is undoped.
  • (X) to (Z) will be described in the following order.
  • FIG. 1 shows that the positive electrode 2 and the electrolyte layer 3 contain ion (gray color part).
  • (X) is a positive electrode active material in a doped state in which the conductivity is changed by ion insertion / extraction, for example, polyacetylene, polypyrrole, polyaniline, polythiophene, polyfuran, polyselenophene, polyisothianaphthene, polyphenylene sulfide Conductive polymer materials such as polyphenylene oxide, polyazulene and poly (3,4-ethylenedioxythiophene), and carbon materials such as polyacene, graphite, carbon nanotubes, carbon nanofibers and graphene. In particular, polyaniline or polyaniline derivatives having a large electrochemical capacity are preferably used. Usually, the conductive polymer-based material is in a doped state.
  • polyaniline derivative examples include at least a substituent such as an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, and an alkoxyalkyl group at positions other than the 4-position of the aniline.
  • a substituent such as an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, and an alkoxyalkyl group at positions other than the 4-position of the aniline.
  • a substituent such as an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, and an alkoxyalkyl group at positions other than the 4-position of the aniline.
  • o-substituted anilines such as o-methylaniline, o-ethylaniline, o-phenylaniline, o-methoxyaniline, o-ethoxyaniline, m-methylaniline, m-ethylaniline, m-methoxyaniline, m M-substituted anilines such as -ethoxyaniline and m-phenylaniline are preferably used. These may be used alone or in combination of two or more.
  • the production method of the present invention includes a step of bringing the above (X) into a reduced dedope state.
  • a step of bringing the above (X) into a reduced dedope state In order to obtain this reductive de-doping state, (i) a method obtained by passing the above (X) into a de-doped state and a reducing step, and (ii) direct reductive desorption of (X) above.
  • a method obtained by passing the above (X) into a de-doped state and a reducing step In order to obtain this reductive de-doping state, (i) a method obtained by passing the above (X) into a de-doped state and a reducing step, and (ii) direct reductive desorption of (X) above.
  • doping step There are two methods that can be obtained through the doping step. Hereinafter, it demonstrates in order.
  • the method (i) includes a step of bringing (X) into a dedope state, and this dedope state is obtained by neutralizing a dopant contained in (X).
  • (X) in a dedope state is obtained by stirring in a solution for neutralizing the dopant (X) and then washing and filtering.
  • a method of neutralizing by stirring in an aqueous sodium hydroxide solution can be mentioned.
  • the method (i) there is a step of changing the undoped (X) to a reduced dedope state.
  • the reductive dedope state is obtained by reducing (X) in the dedope state.
  • stirring in a solution for reducing (X) in the dedope state, followed by washing and filtering yields (X) in the reduced dedope state.
  • a method of reducing polyaniline in a dedoped state by stirring in an aqueous methanol solution of phenylhydrazine can be mentioned.
  • the method (ii) is a method in which reductive dedope is obtained by passing the step (X) directly into a reductive dedope state. For example, by stirring in a reducing agent solution for reducing polypyrrole and then washing and filtering, polypyrrole in a reduced and dedoped state can be obtained.
  • the positive electrode is comprised from the material containing (X) of this reduction
  • examples of the anionic material (Y) include a polymer anion, an anion compound having a relatively large molecular weight, and an anion compound having a low solubility in an electrolytic solution. More specifically, a compound having a carboxyl group in the molecule is preferably used, and in particular, a polycarboxylic acid that is a polymer is more preferably used because it can also serve as a binder.
  • polycarboxylic acid examples include polyacrylic acid, polymethacrylic acid, polyvinylbenzoic acid, polyallylbenzoic acid, polymethallylbenzoic acid, polymaleic acid, polyfumaric acid, polyglutamic acid, and polyaspartic acid.
  • Methacrylic acid is particularly preferably used. These may be used alone or in combination of two or more.
  • the polymer when a polymer such as the above polycarboxylic acid is used, the polymer has a function as a binder and also functions as a dopant. It seems that it is also related to the improvement of the characteristics of the electricity storage device according to the invention.
  • the production method of the present invention includes a step of compensating the anion of the anionic material (Y) with a counter ion (becomes electrically neutral).
  • a counter ion becomes electrically neutral.
  • Examples thereof include those in which the carboxylic acid of a compound having a carboxyl group in the molecule is made into a lithium type.
  • the exchange rate for the lithium type is preferably 100%, but the exchange rate may be low depending on the situation, and is preferably 40% to 100%.
  • the anionic material (Y) is usually in the range of 1 to 100 parts by weight, preferably 2 to 70 parts by weight, and most preferably 5 to 40 parts by weight with respect to 100 parts by weight of the positive electrode active material (X). Used in If the amount of the anionic material (Y) relative to (X) is too small, it tends to be impossible to obtain an electricity storage device having excellent energy density, while the amount of the anionic material (Y) relative to (X) is large. Even if it is too much, there is a tendency that an energy storage device having a high energy density cannot be obtained.
  • the positive electrode according to the production method of the present invention is formed as follows.
  • the anionic material (Y) is dissolved in water to form an aqueous solution, and the positive electrode active material (X) and, if necessary, a conductive assistant such as conductive carbon black or vinylidene fluoride.
  • a binder and disperse well to prepare a paste.
  • the water is evaporated to form a composite having a layer of a mixture of the X component and the Y component (conducting aid and binder as required) on the current collector.
  • a sheet electrode can be obtained.
  • the anionic material (Y) is fixed in the positive electrode because it is arranged as a layer of a mixture with the X component.
  • the positive electrode is made of a composite composed of at least (X) and (Y), and is preferably formed into a porous sheet.
  • the thickness of the positive electrode is preferably 1 to 500 ⁇ m, more preferably 10 to 300 ⁇ m.
  • the thickness of the positive electrode is obtained by measuring the positive electrode using a dial gauge (manufactured by Ozaki Mfg. Co., Ltd.), which is a flat plate with a tip shape of 5 mm in diameter, and obtaining the average of 10 measurement values with respect to the electrode surface.
  • a dial gauge manufactured by Ozaki Mfg. Co., Ltd.
  • the thickness of the composite is measured in the same manner as described above, the average of the measured values is obtained, and the thickness of the current collector is subtracted.
  • the thickness of the positive electrode can be obtained.
  • the electrolyte layer according to the production method of the present invention is composed of an electrolyte.
  • a sheet formed by impregnating a separator with an electrolytic solution or a sheet formed of a solid electrolyte is preferably used.
  • the sheet made of the solid electrolyte itself also serves as a separator.
  • the electrolyte is composed of a solute and, if necessary, a solvent and various additives.
  • solutes include metal ions such as lithium ions and appropriate counter ions, sulfonate ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphate ions, hexafluoroarsenic ions, bis ions.
  • metal ions such as lithium ions and appropriate counter ions
  • sulfonate ions such as lithium ions and appropriate counter ions
  • perchlorate ions such as sulfonate ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphate ions, hexafluoroarsenic ions, bis ions.
  • electrolyte examples include LiCF 3 SO 3 , LiClO 4 , LiBF 4 , LiPF 6 , LiAsF 6 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiCl. Etc.
  • the solvent used as necessary for example, at least one non-aqueous solvent such as carbonates, nitriles, amides, ethers, that is, an organic solvent is used.
  • an organic solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, acetonitrile, propionitrile, N, N′-dimethylacetamide, N-methyl-2- Examples include pyrrolidone, dimethoxyethane, diethoxyethane, and ⁇ -butyrolactone. These may be used alone or in combination of two or more. In addition, what melt
  • the separator can be used in various modes.
  • the separator it is possible to prevent an electrical short circuit between the positive electrode and the negative electrode that are arranged to face each other across the separator.
  • the separator is electrochemically stable, has a large ion permeability, and has a certain level. Any insulating porous sheet having mechanical strength may be used. Therefore, as the material of the separator, for example, a porous film made of a resin such as paper, nonwoven fabric, polypropylene, polyethylene, or polyimide is preferably used. These may be used alone or in combination of two or more.
  • the negative electrode in the electricity storage device according to the present invention is formed using a negative electrode active material (Z) that can insert and desorb ions.
  • a negative electrode active material (Z) a carbon material, a transition metal oxide, silicon, tin or the like from which lithium ions can be inserted / extracted during oxidation / reduction is preferably used.
  • “use” means not only the case where only the forming material is used, but also the case where the forming material is used in combination with another forming material. Is used at less than 50% by weight of the forming material.
  • the thickness of the negative electrode preferably conforms to the thickness of the positive electrode.
  • the battery is preferably assembled in a glove box under an inert gas atmosphere such as ultra-high purity argon gas.
  • metal foils and meshes such as nickel, aluminum, stainless steel, and copper are appropriately used as current collectors of positive electrode 2 and negative electrode 4 (1, 5 in FIG. 1).
  • the current collectors 1 and 5 are connected to positive and negative current extraction connection terminals (tab electrodes, not shown) using a spot welder.
  • the positive electrode 2 and the current collector 1 are vacuum-dried. Thereafter, an undoped hard carbon electrode is pressed against the stainless steel mesh in a ⁇ 100 ° C. glove box to produce a composite of the negative electrode 4 and the current collector 5.
  • a separator (not shown) is sandwiched between the positive electrode 2 and the negative electrode 4, and the positive electrode 2 and the negative electrode 4 are correctly opposed to each other in a heat-sealed laminate cell. Also, adjust the position of the separator to avoid short circuit.
  • the power storage device of the present invention is formed into various shapes such as a film type, a sheet type, a square type, a cylindrical type, and a button type in addition to the laminate cell.
  • the positive electrode size of the electricity storage device is preferably 1 to 300 mm on one side in the case of a laminate cell, particularly preferably 10 to 50 mm, and the electrode size of the negative electrode is 1 to 400 mm. It is preferably 10 to 60 mm.
  • the electrode size of the negative electrode is preferably slightly larger than the positive electrode size.
  • a negative electrode that does not require lithium pre-doping treatment can be used, and a high-performance electricity storage device that is excellent in capacity density per active material weight and capacity density per cathode volume can be easily produced.
  • the anionic material (Y) that is a polymer is used as a binder, but this binder itself functions as a dopant, and a rocking chair type mechanism exists in part. It is assumed. That is, although not yet clarified accurately, a rocking chair type mechanism in which cations such as lithium ions move from the negative electrode to the positive electrode during discharging and cations move from the positive electrode to the negative electrode during charging. Is assumed to exist.
  • the reaction mixture containing the produced reaction product was further stirred for 100 minutes while cooling. Then, using a Buchner funnel and a suction bottle, the obtained solid was No. No. 2 (manufactured by ADVANTEC) was suction filtered with a filter paper to obtain a powder. This powder was stirred and washed in a 2 mol / L tetrafluoroboric acid aqueous solution using a magnetic stirrer. Subsequently, it was stirred and washed several times with acetone, and this was filtered under reduced pressure.
  • conductive polyaniline having tetrafluoroboric acid as a dopant
  • the conductive polyaniline was a bright green powder.
  • anionic material (Y) Using polyacrylic acid (Wako Pure Chemical Industries, Ltd., weight average molecular weight 25,000) as an anionic material (Y) compensated for anion with counter ion, adding carboxylic acid equivalent lithium hydroxide in aqueous solution, A uniform and viscous polyacrylic acid aqueous solution having a concentration of 4.4% by weight was prepared.
  • negative electrode active material (Z) capable of inserting and removing ions As the negative electrode active material (Z), hard carbon (Bellfine LN-0010, manufactured by Air Water Co., Ltd.) was prepared.
  • FIG. 1 ⁇ Process of making conductive polyaniline powder into dedope state>
  • the conductive polyaniline powder in a doped state obtained as described above is placed in a 2 mol / L aqueous sodium hydroxide solution, stirred for 30 minutes in a 3 L separable flask, and the tetrafluoroboric acid as a dopant is removed by a neutralization reaction. Doped.
  • the dedoped polyaniline was washed with water until the filtrate became neutral, then stirred and washed in acetone, and filtered under reduced pressure using a Buchner funnel and a suction bottle to obtain a dedoped polyaniline powder on No. 2 filter paper. . This was vacuum-dried at room temperature for 10 hours to obtain a brown undoped polyaniline powder.
  • the positive electrode the polyaniline sheet electrode obtained above is used, and as the negative electrode, a hard carbon electrode not pre-doped with lithium ions is used.
  • the separator non-woven fabric TF40-50 (porosity: 55%) purchased from Hosen Co., Ltd. was used, and these electrodes and separator were placed in a vacuum dryer at 100 ° C. for 5 hours before cell assembly. Vacuum dried.
  • an ethylene carbonate / dimethyl carbonate solution manufactured by Kishida Chemical Co., Ltd.
  • lithium tetrafluoroborate LiBF 4
  • the assembly of a laminate cell, which is an electricity storage device (lithium secondary battery), using the prepared material is shown below.
  • the battery was assembled in a glove box under an ultrahigh purity argon gas atmosphere (dew point in the glove box: ⁇ 100 ° C.).
  • the electrode size of the positive electrode for the laminate cell is 27 mm ⁇ 27 mm, the negative electrode size is 29 mm ⁇ 29 mm, which is slightly larger than the positive electrode size.
  • a nickel metal foil having a thickness of 50 ⁇ m was connected by a spot welder.
  • an aluminum metal foil having a thickness of 50 ⁇ m was connected to the aluminum foil of the positive electrode current collector with a spot welder.
  • the positive electrode composite, the hard carbon as the negative electrode, the stainless mesh, and the separator are placed in a glove box with a dew point of ⁇ 100 ° C., and the hard carbon electrode is pressed against the stainless steel mesh of the current collector in the glove box. And a current collector composite.
  • the glove box put a separator between this positive electrode and negative electrode, and set them in a laminate cell that is heat-sealed on three sides, so that the positive electrode and negative electrode face each other correctly and do not short-circuit.
  • the position of the separator was also adjusted, and a sealing agent was set on the positive electrode and negative electrode tab portions, and the tab electrode portion was heat-sealed leaving a little electrolyte solution inlet.
  • a predetermined amount of battery electrolyte is sucked with a micropipette, and a predetermined amount is injected from the electrolyte inlet of the laminate cell.
  • the electrolyte inlet at the top of the laminate cell is sealed by heat sealing, and the laminate cell As completed.
  • the characteristics of the lithium secondary battery assembled in this way were performed in a constant current / constant voltage charging / constant current discharging mode using a battery charging / discharging device (Hokuto Denko, SD8).
  • the end-of-charge voltage is 3.8 V.
  • constant voltage charging at 3.8 V is performed for 2 minutes, and then constant current discharge is performed until the end-of-discharge voltage is 2.0 V. went.
  • the charge / discharge current was 0.18 mA.
  • the weight energy density was 225 Wh / kg.
  • the method for producing an electricity storage device of the present invention can be suitably used as a method for producing an electricity storage device such as a lithium secondary battery.
  • the power storage device of the present invention can be used for the same applications as conventional secondary batteries.
  • portable electronic devices such as portable PCs, mobile phones, and personal digital assistants (PDAs), hybrid electric vehicles, Widely used in power sources for driving automobiles, fuel cell vehicles and the like.

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Abstract

Afin d'obtenir un nouveau dispositif de stockage d'électricité présentant une performance de batterie suffisante sans requérir un travail incommode de prédopage d'une électrode avec des ions lithium, la présente invention se rapporte à un procédé permettant de fabriquer un dispositif de stockage d'électricité qui comprend une couche d'électrolyte (3) et une électrode positive (2) ainsi qu'une électrode négative (4) qui se font face et prennent en sandwich la couche d'électrolyte (3). Le procédé comprend une étape au cours de laquelle l'électrode positive (2) est formée par les étapes a à c décrites ci-après et une étape au cours de laquelle l'électrode négative (4) est formée par l'étape d décrite ci-après. L'étape a est une étape au cours de laquelle le matériau (X), décrit ci-après, est mis dans un état dé-dopé réduit. L'étape b est une étape au cours de laquelle les anions dans le matériau (Y), décrit ci-après, sont compensés par des contre-ions. L'étape c est une étape au cours de laquelle l'électrode positive (2) est formée à l'aide d'au moins le matériau (X) dans un état dé-dopé réduit, obtenu au cours de l'étape b décrite ci-dessus. L'étape d est une étape au cours de laquelle l'électrode négative (4) est formée à l'aide du matériau (Z), décrit ci-après, dans un état non dopé. (X) est un matériau actif d'électrode positive dans un état dopé dont la conductivité change selon l'insertion et la désorption des ions. (Y) est un matériau anionique. (Z) est un matériau actif d'électrode négative qui permet l'insertion et la désorption des ions.
PCT/JP2013/062883 2012-05-14 2013-05-08 Procédé permettant de fabriquer un dispositif de stockage d'électricité et dispositif de stockage d'électricité obtenu à l'aide dudit procédé WO2013172221A1 (fr)

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JP2003168436A (ja) * 2001-11-29 2003-06-13 Denso Corp リチウム電池用正極およびリチウム電池
JP2003297362A (ja) * 2002-03-29 2003-10-17 Asahi Glass Co Ltd ハイブリッド型二次電源
JP2009245921A (ja) * 2008-03-13 2009-10-22 Denso Corp 二次電池用電極及びその製造方法並びにその電極を採用した二次電池
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JP2002329495A (ja) * 2001-05-01 2002-11-15 Matsushita Electric Ind Co Ltd リチウム二次電池とその製造方法
JP2003168436A (ja) * 2001-11-29 2003-06-13 Denso Corp リチウム電池用正極およびリチウム電池
JP2003297362A (ja) * 2002-03-29 2003-10-17 Asahi Glass Co Ltd ハイブリッド型二次電源
JP2009245921A (ja) * 2008-03-13 2009-10-22 Denso Corp 二次電池用電極及びその製造方法並びにその電極を採用した二次電池
WO2013002415A1 (fr) * 2011-06-29 2013-01-03 日東電工株式会社 Batterie rechargeable à électrolyte non aqueux et feuille d'électrode positive pour celle-ci

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