WO2007040114A1 - Électrode pour une batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux - Google Patents

Électrode pour une batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2007040114A1
WO2007040114A1 PCT/JP2006/319149 JP2006319149W WO2007040114A1 WO 2007040114 A1 WO2007040114 A1 WO 2007040114A1 JP 2006319149 W JP2006319149 W JP 2006319149W WO 2007040114 A1 WO2007040114 A1 WO 2007040114A1
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WO
WIPO (PCT)
Prior art keywords
electrode
secondary battery
electrolyte secondary
nonaqueous electrolyte
working electrode
Prior art date
Application number
PCT/JP2006/319149
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English (en)
Japanese (ja)
Inventor
Kumiko Kanai
Masaharu Itaya
Takao Inoue
Masahisa Fujimoto
Original Assignee
Sanyo Electric Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sanyo Electric Co., Ltd. filed Critical Sanyo Electric Co., Ltd.
Publication of WO2007040114A1 publication Critical patent/WO2007040114A1/fr

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Classifications

    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Definitions

  • the present invention relates to an electrode for a nonaqueous electrolyte secondary battery and a nonaqueous electrolyte secondary battery using the same.
  • non-aqueous electrolyte secondary batteries that use non-aqueous electrolytes as secondary batteries with high energy density, such as charging and discharging by moving lithium ions between a positive electrode and a negative electrode, are available. Many are used.
  • a lithium transition metal composite having a layered structure such as lithium nickelate (LiNiO) or lithium cobaltate (LiCoO) is generally used as a positive electrode.
  • An oxide is used, and a carbon material capable of inserting and extracting lithium, a lithium metal, a lithium alloy, or the like is used as the negative electrode (see, for example, Patent Document 1).
  • an electrolyte such as lithium tetrafluoroborate (LiBF) or lithium hexafluorophosphate (LiPF) in an organic solvent such as ethylene carbonate or jetyl carbonate.
  • LiBF lithium tetrafluoroborate
  • LiPF lithium hexafluorophosphate
  • the negative electrode of this nonaqueous electrolyte secondary battery is formed of a metal containing sodium. Sodium is abundant in seawater, and the cost can be reduced by using sodium.
  • Patent Document 1 Japanese Patent Laid-Open No. 2003-151549
  • An object of the present invention is to provide a nonaqueous electrolyte secondary battery electrode capable of inserting and extracting sodium ions and a nonaqueous electrolyte secondary battery using the same. Means for solving the problem
  • An electrode for a non-aqueous electrolyte secondary battery can occlude and release sodium ions, and contains bismuth as a single component or main component.
  • sodium ions are sufficiently occluded and released by containing bismuth as a single component or a main component. Moreover, low cost can be achieved by using resource-rich sodium and inexpensive bismuth.
  • the electrode for the nonaqueous electrolyte secondary battery may further include a current collector made of metal, and the bismuth may be formed on the current collector. In this case, bismuth can be easily formed on the current collector.
  • a nonaqueous electrolyte secondary battery includes a negative electrode that also serves as an electrode for a nonaqueous electrolyte secondary battery, a positive electrode, and a nonaqueous electrolyte containing sodium ions.
  • a negative electrode that also serves as an electrode for a nonaqueous electrolyte secondary battery, a positive electrode, and a nonaqueous electrolyte containing sodium ions.
  • Is capable of occluding and releasing sodium ions contains a bismuth as a single component or main component, and a current collector made of metal and a negative electrode mixture containing bismuth coated on the current collector.
  • the negative electrode mixture contains 10% by weight or more of carbon as a conductive agent with respect to the negative electrode mixture.
  • non-aqueous electrolyte secondary battery sodium ions can be occluded and released, and by using a negative electrode comprising a non-aqueous electrolyte secondary battery electrode containing bismuth as a single component or main component.
  • reversible charging / discharging can be performed, and the low cost of the nonaqueous electrolyte secondary battery can be achieved.
  • the negative electrode mixture contains carbon
  • conductivity in the negative electrode is improved and non-aqueous is added.
  • the permeability of the electrolyte to the negative electrode is improved.
  • the negative electrode mixture contains 10% by weight or more of carbon with respect to the negative electrode mixture, the charge / discharge characteristics are improved.
  • the carbon may include carbon black.
  • the conductivity in the negative electrode is further improved and the permeability of the nonaqueous electrolyte to the negative electrode is further improved.
  • the positive electrode may contain a sodium-containing oxide!
  • sodium ions are more likely to be occluded and released from the positive electrode as compared to electrodes containing other than oxides (such as sulfides, fluorides, and chlorides). Thereby, charge / discharge characteristics are improved.
  • the nonaqueous electrolyte may include sodium hexafluorophosphate. In this case, safety is improved.
  • the nonaqueous electrolyte is selected from the group consisting of cyclic carbonates, chain carbonates, esters, cyclic ethers, chain ethers, nitriles and amides. One or more types may be included. In this case, low cost can be achieved and safety can be improved.
  • the electrode for a non-aqueous electrolyte secondary battery contains bismuth as a single component or main component, so that sodium ions are sufficiently occluded and stored in the electrode for the non-aqueous electrolyte secondary battery. Released.
  • low cost can be achieved by using resource-rich sodium and inexpensive bismuth.
  • FIG. 1 is a schematic explanatory view of a test cell for an electrode for a nonaqueous electrolyte secondary battery according to the present embodiment.
  • FIG. 2 is a two-phase phase diagram of sodium and bismuth.
  • FIG. 3 is a graph showing the charge / discharge characteristics of the electrode for a nonaqueous electrolyte secondary battery in Example 1.
  • the non-aqueous electrolyte secondary battery according to the present embodiment is generally called a sodium secondary battery because sodium ions are used.
  • the nonaqueous electrolyte secondary battery according to the present embodiment includes a working electrode, a counter electrode, and a nonaqueous electrolyte.
  • a slurry as an electrode mixture is prepared by adding and kneading the mixture so that the weight ratio thereof becomes, for example, 85: 10: 5.
  • the specific surface area of the acetylene black is, for example, 92 m 2 Zg, and the primary particle diameter is about 35 nm.
  • Acetylene black is a kind of high-purity carbon black with excellent conductivity.
  • the prepared slurry is applied onto the copper foil of the current collector by the doctor blade method, then dried in vacuum, and rolled with a rolling roller to form an active material layer. Then, the copper foil on which the active material layer is formed is cut into a size of, for example, 2 cm ⁇ 2 cm, and a working electrode tab is attached to complete a nonaqueous electrolyte secondary battery electrode.
  • non-aqueous electrolyte an electrolyte salt dissolved in a non-aqueous solvent can be used.
  • non-aqueous solvent examples include cyclic carbonates, chain carbonates, esters, cyclic ethers, chain ethers, nitriles, amides and the like, which are usually used as non-aqueous solvents for batteries. Combination power.
  • Examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, butylene carbonate and the like, and those in which some or all of these hydrogen groups are fluorinated can be used.
  • ethylene carbonate, propylene carbonate, butylene carbonate and the like and those in which some or all of these hydrogen groups are fluorinated can be used.
  • Trifluoropropylene carbonate, fluorethyl carbonate and the like Trifluoropropylene carbonate, fluorethyl carbonate and the like.
  • chain carbonic acid ester examples include dimethyl carbonate, ethyl methyl carbonate, dimethylol carbonate, methino lepropino carbonate, ethyl propyl carbonate, methyl isopropyl carbonate, and the like. Some or all It is also possible to use those that have been fluorinated.
  • esters include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and ⁇ -petit-mouth rataton.
  • Cyclic ethers include 1,3 dioxolane, 4-methyl-1,3 dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, 1,2 butylene oxide, 1,4 dioxane, 1,3,5 trioxane, furan, Examples include 2-methylfuran, 1,8 cineole, and crown ether.
  • chain ethers examples include 1,2 dimethoxyethane, jetyl ether, dipropyl etherenole, diisopropino enotenole, dibutino enoate, dihexino ethenore, ethyl vinyl ether, butyl vinyl ether, Methyl phenyl ether, ethyl phenyl enoleate, butino leneno enoate, pentino leneno enoate, methoxytonolene, benzeno retino enotenole, diphenino enotenate, dipenzino reeenore, ⁇ dimethoxybenzene 1,2-diethoxyethane, 1,2-dibutoxetane, diethylene glycol dimethylol ether, diethylene glycol jetinole ether, diethylene glycol dibutyl ether, 1,1-dimethoxymethane,
  • nitriles include acetonitrile
  • examples of amides include dimethylformamide.
  • electrolyte salt examples include sodium hexafluorophosphate (NaPF) and sodium tetrafluoroborate.
  • Non-peroxide soluble in non-aqueous solvents such as NaBeTi
  • one of the above electrolyte salts may be used, or two or more may be used in combination.
  • sodium hexafluorophosphate (NaPF 4) as an electrolyte salt is mixed with a non-aqueous solvent in which ethylene carbonate and jetyl carbonate are mixed at a volume ratio of 50:50 as a non-aqueous electrolyte. Use the one added to the concentration of ImolZl.
  • FIG. 1 is a schematic explanatory diagram of a test cell using the nonaqueous electrolyte secondary battery electrode according to the present embodiment.
  • a lead is attached to the working electrode 1 and, at the same time, a lead is attached to the counter electrode 2 having a sodium metal force.
  • the counter electrode 2 made of sodium metal, for example, sodium cobaltate represented by NaCoO, Na
  • a counter electrode 2 containing as a single component or as a main component Use a counter electrode 2 containing as a single component or as a main component.
  • the separator 4 is inserted between the working electrode 1 and the counter electrode 2, and the working electrode 1, the counter electrode 2, and the reference electrode 3 made of, for example, sodium metal are disposed in the cell container 10. Then, the test cell is manufactured by injecting the nonaqueous electrolyte 5 into the cell container 10.
  • the electrode mixture of the working electrode 1 contains carbon
  • the conductivity of the working electrode 1 is improved and the permeability of the nonaqueous electrolyte 5 to the working electrode 1 is improved.
  • the electrode mixture of the working electrode 1 contains 10% by weight or more of carbon with respect to the electrode mixture
  • the charge / discharge characteristics are improved.
  • the conductivity of the working electrode 1 can be further improved by using carbon black as a kind of the carbon. This is because carbon black has a larger specific surface area than other carbons such as graphite, so the proportion of carbon black in the volume of the working electrode 1 increases.
  • the primary particle diameter of carbon black as a conductive agent added to working electrode 1 is preferably about 35 nm, and the specific surface area is preferably 90 m 2 / g or more. .
  • the flexibility of the working electrode 1 and the permeability of the nonaqueous electrolyte 5 to the working electrode 1 are improved. This improves the charge / discharge cycle characteristics of the nonaqueous electrolyte secondary battery.
  • the above-mentioned flexibility means so-called softness, and the working electrode 1 can be checked into various shapes by this flexibility.
  • FIG. 3 is a graph showing the charge / discharge characteristics of the electrode for the nonaqueous electrolyte secondary battery of Example 1.
  • the initial discharge capacity density per lg of the active material 1 of the working electrode 1 was about 361 mAh Zg, which proved that charge and discharge were performed satisfactorily. There was no significant decrease in the discharge capacity density over the course of the cycle. It is also estimated that sodium ions are adsorbed on the carbon black in the working electrode 1.
  • Example 2 the weight ratio of the electrode active material containing bismuth powder and the above binder to a solution obtained by dissolving the binder polyvinylidene fluoride in N-methyl-2-pyrrolidone is 95: 5.
  • a test cell of a nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that a slurry as an electrode mixture was produced by adding and kneading.
  • the initial charge capacity density per lg of the active material 1 of the working electrode 1 was about 217 mAh Zg, which proved that charge and discharge were performed satisfactorily.
  • Example 3 the weight of the electrode active material containing bismuth powder, the binder, and the acetylene black as the conductive agent in a solution in which polyvinylidene fluoride as a binder was dissolved in N-methyl-2-pyrrolidone.
  • a slurry as an electrode mixture was prepared by adding and kneading so that the ratio was 90: 5: 5.
  • the nonaqueous electrolyte secondary battery electrode and the nonaqueous electrolyte secondary battery according to the present invention can be used for various power sources such as a portable power source and an automotive power source.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une solution comprenant du polyfluorovinylidène en tant que liant dissous dans de la N-méthyl-2-pyrrolidone qui est chargée avec une matière active d’électrode contenant une poudre de bismuth (Bi), le liant et du noir d’acétylène formant agent conducteur dans un rapport pondéral de, par exemple, 85/10/5 et étant broyés ensemble afin d’obtenir ainsi une bouillie formant un mélange pour électrode. Le noir d’acétylène présente une surface spécifique de, par exemple, 92 m2/g et un diamètre particulaire principal d’environ 35 nm. Après cela, selon le procédé de la racle, une feuille de cuivre d’un collecteur électrique est revêtue avec la bouillie obtenue, séchée sous vide et aplatie en utilisant un rouleau d’aplatissement, formant de ce fait une couche de matière active. Une languette d’électrode de travail est fixée à celle-ci, finalisant ainsi une électrode de travail.
PCT/JP2006/319149 2005-09-30 2006-09-27 Électrode pour une batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux WO2007040114A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2005-285783 2005-09-30
JP2005285783 2005-09-30
JP2006-204675 2006-07-27
JP2006204675A JP2007123236A (ja) 2005-09-30 2006-07-27 非水電解質二次電池用電極および非水電解質二次電池

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3007204A1 (fr) * 2013-06-17 2014-12-19 Centre Nat Rech Scient Utilisation de nouveaux composes a titre de matiere active d'electrode negative dans une batterie sodium-ion.

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015198000A (ja) * 2014-04-01 2015-11-09 日本電気硝子株式会社 蓄電デバイス用負極活物質、蓄電デバイス用負極材料および蓄電デバイス
KR102282911B1 (ko) * 2019-10-14 2021-07-27 경상국립대학교산학협력단 이차 전지, 및 이를 제조하는 방법
KR102294471B1 (ko) * 2020-06-11 2021-08-25 연세대학교 산학협력단 이차전지용 음극활물질, 이의 제조방법 및 이를 포함하는 이차전지

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0364869A (ja) * 1989-07-31 1991-03-20 Showa Denko Kk 二次電池
JPH04286864A (ja) * 1991-03-15 1992-10-12 Hitachi Ltd 二次電池
JPH0815095B2 (ja) * 1985-04-19 1996-02-14 アライド・コ−ポレ−シヨン 新規な電池
JP2000012015A (ja) * 1998-06-10 2000-01-14 Jurgen Otto Besenhard 非水系二次電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0815095B2 (ja) * 1985-04-19 1996-02-14 アライド・コ−ポレ−シヨン 新規な電池
JPH0364869A (ja) * 1989-07-31 1991-03-20 Showa Denko Kk 二次電池
JPH04286864A (ja) * 1991-03-15 1992-10-12 Hitachi Ltd 二次電池
JP2000012015A (ja) * 1998-06-10 2000-01-14 Jurgen Otto Besenhard 非水系二次電池

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3007204A1 (fr) * 2013-06-17 2014-12-19 Centre Nat Rech Scient Utilisation de nouveaux composes a titre de matiere active d'electrode negative dans une batterie sodium-ion.
WO2014202887A1 (fr) * 2013-06-17 2014-12-24 Centre National De La Recherche Scientifique Utilisation de nouveaux composes a titre de matiere active d'electrode negative dans une batterie sodium ion
JP2016522557A (ja) * 2013-06-17 2016-07-28 サントレ ナティオナル ド ラ ルシェルシェ シアンティフィク ナトリウムイオン電池の負極活物質としての新規の化合物の使用
JP7015634B2 (ja) 2013-06-17 2022-02-03 サントレ ナティオナル ド ラ ルシェルシェ シアンティフィク ナトリウムイオン電池の負極活物質としての新規の化合物の使用

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