WO2017203921A1 - Vanadium redox secondary battery and method for producing vanadium redox secondary battery - Google Patents

Vanadium redox secondary battery and method for producing vanadium redox secondary battery Download PDF

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WO2017203921A1
WO2017203921A1 PCT/JP2017/016315 JP2017016315W WO2017203921A1 WO 2017203921 A1 WO2017203921 A1 WO 2017203921A1 JP 2017016315 W JP2017016315 W JP 2017016315W WO 2017203921 A1 WO2017203921 A1 WO 2017203921A1
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vanadium
secondary battery
electrode
diaphragm
vanadium redox
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French (fr)
Japanese (ja)
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吉田　茂樹
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ブラザー工業株式会社
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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 vanadium redox secondary battery according to the present invention includes a vanadium ion whose oxidation number changes between pentavalent and tetravalent or an ion containing vanadium whose oxidation number changes between pentavalent and tetravalent by an oxidation-reduction reaction.
  • a vanadium redox secondary battery 1 (hereinafter referred to as battery 1) includes an outer bag 2 and a positive electrode terminal 3 protruding from a part of the peripheral edge of the outer bag 2. And a negative electrode terminal 4, a positive electrode material 5, and a negative electrode material 6.
  • the positive electrode terminal 3 and the negative electrode terminal 4 protrude from a part of the peripheral edge portion of the outer bag 2 in a state where the base end side is covered with the sealing materials 30 and 40.
  • the battery 1 alone or a combination of the battery 1 and another battery 1 may be accommodated in a case (not shown).
  • the half 22 is electrolyte impermeable.
  • the half 22 is preferably composed of a laminate sheet containing a synthetic resin layer and a metal layer.
  • the material for the synthetic resin layer include polypropylene, polyethylene, polyamide such as nylon 6, nylon 66, and the like.
  • the material for the metal layer include aluminum, aluminum alloy, copper, copper alloy, iron, stainless steel, titanium, and titanium alloy.
  • the thickness of the half body 22 is not particularly limited, but is preferably 15 to 250 ⁇ m. When the thickness is 15 to 250 ⁇ m, the battery has sufficient strength and the volume energy density of the battery is improved.
  • vanadium ions whose oxidation number changes between divalent and trivalent or ions containing vanadium whose oxidation number changes between divalent and trivalent due to oxidation-reduction reaction are applied to the protective layer 62.
  • a precipitate containing a solid compound containing the contained vanadium solid salt as a negative electrode active material is supported.
  • contact between the positive electrode 5 and the negative electrode 6 due to passage of pentavalent vanadium ions and divalent vanadium ions through the diaphragm 7 is suppressed, that is, cross contamination of active material ions is prevented. Since it is suppressed, a long life and long-time voltage maintenance can be realized, and since proton conductivity is high, it is considered that use at a high input / output density is realized.
  • the thickness of the diaphragm 7 is preferably 50 ⁇ m or less, more preferably 25 ⁇ m or less, and even more preferably 10 ⁇ m or less. When the thickness is 50 ⁇ m or less, the charge energy density and the discharge energy density when the current density is increased are good.
  • V 2 (SO 4 ) 3 as a trivalent vanadium compound, VOSO 4 as a tetravalent vanadium compound, and a hinder are mixed in a carbon material, and mixed powder is obtained by mixing with a stirrer.
  • the composition of the carbon material, active material, and binder is determined according to the required capacity, drying conditions, external environment (temperature, humidity), and the like.
  • the electrode material is selectively used for the electrode material 5 and the electrode material 6.
  • a water retention film 55 is provided on the electrode 50 of the electrode material 5.
  • the current collector of the electrode material 5 is fixed to the half body 22 of the outer bag 2 and the current collector of the electrode material 6 of the electrode material 6 is fixed to the half body 21 by hot pressing or the like.
  • the volume resistivity at 1 kHz measured in 0.5 M sulfuric acid of the diaphragm 7 is 280 ⁇ ⁇ cm or more, and the sheet resistance is 3 ⁇ ⁇ cm. Since it is 2 or less, it has a good energy density when it is input / output at a high current density, that is, it can realize a high input / output, has a long life, and can maintain a voltage for a long time. And since it has the water retention film
  • Comparative Example 3 A battery of Comparative Example 3 was produced in the same manner as in Example 1 except that an anion exchange membrane (“ion exchange membrane M”, manufactured by FuMA-Tech) was used as the diaphragm. The thickness and the like of the ion exchange membrane of Comparative Example 3 are shown in No. 1 of Table 1. 7 shows.
  • Step 1 of Table 2 after CC charging to 1.45 V at 8 mA, CC discharging to 0.8 V at 8 mA was taken as one cycle, and 20 cycles of charging / discharging were performed.
  • step 2 after charging CC to 1.45 V at 8 mA, charging and discharging for one cycle was performed in which CC discharging was performed to 0.8 V at 16 mA. Thereafter, charge and discharge were performed in the same manner.
  • the “capacity maintenance ratio” in Table 1 was obtained by (discharge current capacity at 40th cycle) / (discharge current capacity at 20th cycle).
  • the “@ 20 mA / cm 2 ” of “Discharge energy density” in Table 1 can be taken out when CC discharge is performed at 8 mA to 1.45 V and then CC discharge is performed at 125 mA to 0.8 V in Step 5.
  • Energy (Wh) divided by (L) by electrode volume. 125 (mA) /6.25 20 (mA / cm 2 ), and the discharge energy density extracted when a current was passed at a current density of 20 mA / cm 2 was obtained.
  • FIG. 3 is a graph showing the relationship between the volume resistivity of the ion exchange membrane 7 of the example and the ion exchange membrane of the comparative example and the voltage maintenance rate.
  • the horizontal axis represents volume resistivity [ ⁇ ⁇ cm], and the vertical axis represents voltage maintenance ratio [%]. From FIG. 3, it can be seen that the batteries 1 of Examples 1 to 4 in which the volume resistivity of the ion exchange membrane is 280 ⁇ ⁇ cm or more and the batteries of Comparative Example 1 have a voltage maintenance rate of 92% or more and are good. .
  • the voltage maintenance rate is 97% or more, which is more preferable.
  • FIG. 4 is a graph showing the relationship between the volume resistivity of the ion exchange membrane 7 of the example and the ion exchange membrane of the comparative example and the capacity retention rate.
  • the horizontal axis represents volume resistivity [ ⁇ ⁇ cm], and the vertical axis represents capacity retention rate [%].
  • the batteries 1 of Examples 1 to 4 in which the volume resistivity of the ion exchange membrane is 280 ⁇ ⁇ cm or more and the batteries of Comparative Example 1 have a capacity retention rate of 65% or more. It turns out that it is improving more.
  • the voltage maintenance rate is preferably 86% or more, and when the volume resistivity is 1500 ⁇ ⁇ cm or more, the voltage maintenance rate is 89% or more, more preferable.
  • the capacity retention rate of Comparative Example 4 is high. This is because the discharge current capacity has already greatly decreased due to the deterioration of the battery at the 20th cycle, and the discharge current capacity at the 40th cycle. Since it has not changed, the capacity retention rate is apparently high.
  • FIG. 7 is a graph showing the relationship between the sheet resistance value of the ion exchange membrane 7 of the example and the ion exchange membrane of the comparative example and the discharge energy density.
  • the horizontal axis represents the sheet resistance [ ⁇ ⁇ cm 2 ], and the vertical axis represents the discharge energy density [Wh / L].
  • 2.56mA / cm 2, 10mA / cm 2, 20mA / cm 2 by applying a current at a current density of each shows the result of obtaining discharge energy density could be extracted when fully been charged. As the current density increases, the discharge energy density that can be extracted decreases.
  • FIG. 8 is a graph showing the relationship between the thickness of the ion exchange membrane 7 of the example and the energy density.
  • the horizontal axis is the thickness [ ⁇ m]
  • the vertical axis is the energy density [Wh / L].
  • ⁇ is charging energy density @ 10 mA / cm 2
  • ⁇ is discharging energy density @ 10 mA / cm 2 . From FIG. 8, it can be seen that the batteries 1 of Examples 1 to 4 have a high charge energy density and discharge energy density when a current is passed at a high current density of 10 mA / cm 2 .
  • the discharge energy density becomes higher when the current density is increased.
  • the Coulomb efficiency when charging and discharging are repeated becomes better, and the discharge energy density becomes higher when the current density is increased.

Abstract

Provided are: a vanadium redox secondary battery that has an excellent energy density when inputting/outputting at a high current density, has a long life, and can maintain voltage for a long time; and a method for producing said vanadium redox secondary battery. This battery 1 comprises: a positive electrode material 5 including a positive-electrode active material that includes vanadium ions having an oxidation number changing between pentavalence and tetravalence, or vanadium-containing ions having an oxidation number changing between pentavalence and tetravalence, by an oxidation-reduction reaction; a negative electrode material 6 including a negative-electrode active material that includes vanadium ions having an oxidation number changing between divalence and trivalence, or vanadium-containing ions having an oxidation number changing between divalence and trivalence, by an oxidation-reduction reaction; and a diaphragm 7 that partitions the electrode materials and that lets hydrogen ions pass through. The diaphragm 7 has a volume resistivity of 280 Ω·cm or higher at 1 kHz as measured in a 0.5 M sulfuric acid.

Description

バナジウムレドックス二次電池、及びバナジウムレドックス二次電池の製造方法Vanadium redox secondary battery and method for manufacturing vanadium redox secondary battery
　本発明は、活物質として、バナジウムイオン又はバナジウムを含むイオンを含有し、活物質による酸化還元反応を利用して充放電を行うバナジウムレドックス二次電池、及びバナジウムレドックス二次電池の製造方法に関する。 The present invention relates to a vanadium redox secondary battery that contains vanadium ions or vanadium-containing ions as an active material and performs charge / discharge using an oxidation-reduction reaction by the active material, and a method for manufacturing a vanadium redox secondary battery.
　二次電池は、デジタル家電製品、電気自動車、ハイブリッド自動車及び太陽光発電設備等に広く用いられている。この電池として、リチウムイオン二次電池、バナジウムレドックス二次電池（特許文献１）等が挙げられる。バナジウムレドックス二次電池は、２組の酸化還元対を利用して、イオンの価数変化によって充放電を行う。活物質としては、バナジウムイオン又はバナジウムを含むイオンが用いられる。 Secondary batteries are widely used in digital home appliances, electric vehicles, hybrid vehicles, solar power generation facilities, and the like. Examples of the battery include a lithium ion secondary battery and a vanadium redox secondary battery (Patent Document 1). The vanadium redox secondary battery performs charge and discharge by changing the valence of ions using two sets of redox pairs. As the active material, vanadium ions or ions containing vanadium are used.
　バナジウムレドックス二次電池は、活物質及び水系電解液を有する電極と、電極に対向する銅等の導電体（集電体）とを備える電極材を、極性が異なる電極材が隔膜、例えばイオン交換膜を介して対向する状態で複数並設し、外装袋に収容することにより構成される。このバナジウムレドックス二次電池は、さらにケースに収容されることもある。 A vanadium redox secondary battery is composed of an electrode material comprising an electrode having an active material and an aqueous electrolyte and a conductor (current collector) such as copper facing the electrode. A plurality are arranged side by side in a state of being opposed to each other through a membrane, and are housed in an exterior bag. The vanadium redox secondary battery may be further accommodated in a case.
　従来のバナジウムレドックス電池においては、高入出力密度（高入出力化）を実現できるイオン交換膜を選択した場合、高寿命（良好なサイクル特性）、及び長時間の電圧維持の実現が困難であった。一方、高寿命及び長時間の電圧維持を実現できるイオン交換膜を選択した場合、高入出力化が困難であるという問題があった。従って、バナジウムレドックス二次電池において、高寿命であり、電圧を長時間維持できることと、高入出力密度での使用が可能であることとの両立が求められている。 In a conventional vanadium redox battery, when an ion exchange membrane capable of realizing a high input / output density (high input / output) is selected, it is difficult to realize a long life (good cycle characteristics) and a long-time voltage maintenance. It was. On the other hand, when an ion exchange membrane capable of realizing a long life and maintaining a voltage for a long time is selected, there is a problem that it is difficult to increase the input / output. Therefore, in a vanadium redox secondary battery, it is required to have both a long life and being able to maintain a voltage for a long time and being able to be used at a high input / output density.
特開２０１４－２３５８３３号公報JP 2014-235833 A
　本発明は、斯かる事情に鑑みてなされたものであり、高電流密度で入出力した場合に良好なエネルギー密度を有し、高寿命であり、電圧を長時間維持することができるバナジウムレドックス二次電池、及びバナジウムレドックス二次電池の製造方法を提供することを目的とする。 The present invention has been made in view of such circumstances, and has a good energy density when input / output is performed at a high current density, has a long life, and can maintain a voltage for a long time. An object of the present invention is to provide a secondary battery and a method for producing a vanadium redox secondary battery.
　本発明に係るバナジウムレドックス二次電池は、酸化還元反応によって、５価及び４価の間で酸化数が変化するバナジウムイオン、又は５価及び４価の間で酸化数が変化するバナジウムを含むイオンを含有する正極活物質を含む正の電極材と、酸化還元反応によって、２価及び３価の間で酸化数が変化するバナジウムイオン、又は２価及び３価の間で酸化数が変化するバナジウムを含むイオンを含有する負極活物質を含む負の電極材と、両電極材を区画するプロトン伝導性の隔膜とを有し、前記隔膜は、０．５Ｍ硫酸中で測定した１ｋＨｚにおける体積抵抗率が２８０Ω・ｃｍ以上であり、かつ、面積抵抗値が３Ω・ｃｍ2 以下であることを特徴とする。 The vanadium redox secondary battery according to the present invention includes a vanadium ion whose oxidation number changes between pentavalent and tetravalent or an ion containing vanadium whose oxidation number changes between pentavalent and tetravalent by an oxidation-reduction reaction. A positive electrode material containing a positive electrode active material containing vanadium and a vanadium ion whose oxidation number changes between divalent and trivalent by a redox reaction, or vanadium whose oxidation number changes between divalent and trivalent A negative electrode material containing a negative electrode active material containing ions containing protons, and a proton-conductive diaphragm separating both electrode materials, the diaphragm being volume resistivity at 1 kHz measured in 0.5 M sulfuric acid Is 280 Ω · cm or more, and the sheet resistance is 3 Ω · cm 2 or less.
　本発明に係るバナジウムレドックス二次電池の製造方法は、３価のバナジウム化合物と、４価のバナジウム化合物と、炭素材料と、バインダとを混合して混合物を得、該混合物に水系電解液を配合して、混練物を得、該混練物を成形して電極を得、集電体に該電極を配置して電極材を得、一対の前記電極材間に、０．５Ｍ硫酸中で測定した１ｋＨｚにおける体積抵抗率が２８０Ω・ｃｍ以上であり、かつ、面積抵抗値が３Ω・ｃｍ2 以下であるプロトン伝導性の隔膜を介在させた状態で電池を組み立てることを特徴とする。 The manufacturing method of the vanadium redox secondary battery which concerns on this invention mixes a trivalent vanadium compound, a tetravalent vanadium compound, a carbon material, and a binder, obtains a mixture, and mix | blends aqueous electrolyte solution with this mixture Then, a kneaded product was obtained, the kneaded product was molded to obtain an electrode, the electrode was arranged on a current collector to obtain an electrode material, and measurement was performed in 0.5 M sulfuric acid between the pair of electrode materials. The battery is assembled in a state where a proton conductive diaphragm having a volume resistivity at 1 kHz of 280 Ω · cm or more and an area resistance value of 3 Ω · cm 2 or less is interposed.
　本発明によれば、隔膜は、０．５Ｍ硫酸中で測定した１ｋＨｚにおける体積抵抗率が２８０Ω・ｃｍ以上であり、かつ、面積抵抗値が、３Ω・ｃｍ2 以下であるので、バナジウムレドックス二次電池は、高電流密度で入出力した場合に良好なエネルギー密度を有し、即ち高入出力化を実現できるとともに、高寿命であり、かつ電圧を長時間維持することができる。 According to the present invention, the diaphragm has a volume resistivity at 1 kHz measured in 0.5 M sulfuric acid of 280 Ω · cm or more and an area resistance value of 3 Ω · cm 2 or less, so that the vanadium redox secondary The battery has a good energy density when input / output is performed at a high current density, that is, it can realize high input / output, has a long life, and can maintain a voltage for a long time.
本発明の実施の形態１に係るバナジウムレドックス二次電池１を示す模式的平面図である。1 is a schematic plan view showing a vanadium redox secondary battery 1 according to Embodiment 1 of the present invention. 図１のII－II線模式的断面図である。FIG. 2 is a schematic cross-sectional view taken along the line II-II in FIG. 実施例及び比較例のイオン交換膜の体積抵抗率と、電圧維持率との関係を示すグラフである。It is a graph which shows the relationship between the volume resistivity of the ion exchange membrane of an Example and a comparative example, and a voltage maintenance factor. 実施例及び比較例のイオン交換膜の体積抵抗率と、容量維持率との関係を示すグラフである。It is a graph which shows the relationship between the volume resistivity of the ion exchange membrane of an Example and a comparative example, and a capacity | capacitance maintenance factor. 実施例及び比較例のイオン交換膜の体積抵抗率と、４０サイクル目の放電電流容量との関係を示すグラフである。It is a graph which shows the relationship between the volume resistivity of the ion exchange membrane of an Example and a comparative example, and the discharge current capacity of the 40th cycle. 実施例及び比較例のイオン交換膜の面積抵抗値と、２０サイクル目のクーロン効率との関係を示すグラフである。It is a graph which shows the relationship between the area resistance value of the ion exchange membrane of an Example and a comparative example, and the Coulomb efficiency of 20th cycle. 実施例及び比較例のイオン交換膜の面積抵抗値と、放電エネルギー密度との関係を示すグラフである。It is a graph which shows the relationship between the sheet resistance value of the ion exchange membrane of an Example and a comparative example, and discharge energy density. 実施例のイオン交換膜の厚みと、エネルギー密度との関係を示すグラフである。It is a graph which shows the relationship between the thickness of the ion exchange membrane of an Example, and an energy density.
　以下、本発明をその実施の形態を示す図面に基づいて詳述する。
１．バナジウムレドックス二次電池
　図１及び図２に示すように、バナジウムレドックス二次電池１（以下、電池１という）は、外装袋２と、外装袋２の周縁部の一部から突出した正極端子３及び負極端子４と、正極の電極材５と、負極の電極材６とを備える。正極端子３，負極端子４は、基端部側がシール材３０，４０に覆われた状態で、外装袋２の周縁部の一部から突出している。この電池１単体、又は該電池１と他の電池１とを組み合わせてケース（不図示）に収容してもよい。 Hereinafter, the present invention will be described in detail with reference to the drawings illustrating embodiments thereof.
1. Vanadium Redox Secondary Battery As shown in FIGS. 1 and 2, a vanadium redox secondary battery 1 (hereinafter referred to as battery 1) includes an outer bag 2 and a positive electrode terminal 3 protruding from a part of the peripheral edge of the outer bag 2. And a negative electrode terminal 4, a positive electrode material 5, and a negative electrode material 6. The positive electrode terminal 3 and the negative electrode terminal 4 protrude from a part of the peripheral edge portion of the outer bag 2 in a state where the base end side is covered with the sealing materials 30 and 40. The battery 1 alone or a combination of the battery 1 and another battery 1 may be accommodated in a case (not shown).
　電極材５は、電極５０、導電体５１、保護層５２、シーラント５４、及び保水膜５５を備える。
　導電体５１は角型平板状をなし、前記外装袋２の、図２における下側の半体２２の上面に配されており、導電体５１の上面は保護層５２により覆われている。保護層５２の上面の周縁部の内側には、活物質、導電助剤としての炭素材料、バインダ、及び水系電解液を有する角型平板状の電極５０が設けられている。 The electrode material 5 includes an electrode 50, a conductor 51, a protective layer 52, a sealant 54, and a water retention film 55.
The conductor 51 has a rectangular flat plate shape and is disposed on the upper surface of the lower half 22 in FIG. 2 of the outer bag 2, and the upper surface of the conductor 51 is covered with a protective layer 52. Inside the peripheral edge of the upper surface of the protective layer 52, a square plate electrode 50 having an active material, a carbon material as a conductive additive, a binder, and an aqueous electrolyte is provided.
　電極５０上には、電極５０より平面面積が大きい保水膜５５が設けられており、保水膜５５上には、保水膜５５より平面面積が大きいプロトン伝導性の隔膜７が設けられている。
　なお、保水膜５５は電極６０に設けてもよく、電池１には備えないことにしてもよい。　シーラント５４は縁部を有する枠状をなし、前記周縁部及び半体２２に接着されており、半体２２及び保護層５２とにより導電体５１を封止する。 A water retention film 55 having a larger planar area than the electrode 50 is provided on the electrode 50, and a proton conductive diaphragm 7 having a larger planar area than the water retention film 55 is provided on the water retention film 55.
The water retention film 55 may be provided on the electrode 60 and may not be provided in the battery 1. The sealant 54 has a frame shape having an edge portion, and is bonded to the peripheral edge portion and the half body 22. The conductor 51 is sealed by the half body 22 and the protective layer 52.
　以下、電極材５の各部、及び外装袋２の半体２２について詳述する。
　半体２２は電解液非透過性である。半体２２は、合成樹脂層及び金属層を含有するラミネートシートからなるのが好ましい。
　合成樹脂層の材料としては、ポリプロピレン、ポリエチレン、ナイロン６，ナイロン６６等のポリアミド等が挙げられる。金属層の材料としては、アルミニウム、アルミニウム合金、銅、銅合金、鉄、ステンレス、チタン、チタン合金等が挙げられる。
　半体２２の厚みは特に限定されないが、１５～２５０μｍであるのが好ましい。厚みが１５～２５０μｍである場合、十分な強度を有するとともに、電池の体積エネルギー密度が向上する。 Hereinafter, each part of the electrode material 5 and the half body 22 of the exterior bag 2 will be described in detail.
The half 22 is electrolyte impermeable. The half 22 is preferably composed of a laminate sheet containing a synthetic resin layer and a metal layer.
Examples of the material for the synthetic resin layer include polypropylene, polyethylene, polyamide such as nylon 6, nylon 66, and the like. Examples of the material for the metal layer include aluminum, aluminum alloy, copper, copper alloy, iron, stainless steel, titanium, and titanium alloy.
The thickness of the half body 22 is not particularly limited, but is preferably 15 to 250 μm. When the thickness is 15 to 250 μm, the battery has sufficient strength and the volume energy density of the battery is improved.
　導電体５１の平面面積は半体２２の平面面積より小さい。
　導電体５１は、銅、アルミニウム、ニッケル等の金属箔からなるのが好ましい。厚みは、５～１００μｍであるのが好ましい。厚みが１００μｍ以下である場合、電池の体積エネルギー密度、重量エネルギー密度が向上する。
　導電体５１は、周縁部の一部から突出したタブ（不図示）を有し、タブの先端部は正極端子３に接続されている。 The planar area of the conductor 51 is smaller than the planar area of the half body 22.
The conductor 51 is preferably made of a metal foil such as copper, aluminum, or nickel. The thickness is preferably 5 to 100 μm. When the thickness is 100 μm or less, the volume energy density and weight energy density of the battery are improved.
The conductor 51 has a tab (not shown) protruding from a part of the peripheral edge, and the tip of the tab is connected to the positive electrode terminal 3.
　保護層５２は、導電体５１の一面に、グラファイトシートを例えば導電性の接着シートを介し設けてなる。保護層５２の厚みは１～１００μｍであるのが好ましい。この場合、電極５０と導電体５１との電気伝導性の低下を抑制でき、電池の内部抵抗を小さくすることができる。
　なお、保護層５２の材質はグラファイトシートには限定されない。保護層５２は導電性かつ電解液非透過性であればよく、導電性フィルム、シート状の導電性ゴムを用いることにしてもよい。また、導電体５１の一面に黒鉛でコーティングすることにより、保護層５２を形成することにしてもよい。また、水系電解液が酸性又はアルカリ性ではなく、導電体５１が腐食等される虞がない場合は、保護層５２を備えていなくてもよい。 The protective layer 52 is formed by providing a graphite sheet on one surface of the conductor 51 with, for example, a conductive adhesive sheet. The thickness of the protective layer 52 is preferably 1 to 100 μm. In this case, a decrease in electrical conductivity between the electrode 50 and the conductor 51 can be suppressed, and the internal resistance of the battery can be reduced.
The material of the protective layer 52 is not limited to the graphite sheet. The protective layer 52 may be conductive and non-permeable to electrolyte solution, and a conductive film or a sheet-like conductive rubber may be used. Alternatively, the protective layer 52 may be formed by coating one surface of the conductor 51 with graphite. Further, when the aqueous electrolyte is not acidic or alkaline and there is no possibility that the conductor 51 is corroded, the protective layer 52 may not be provided.
　なお、本実施の形態において、以後、符号を付さずに単に「集電体」と記載するときは、「導電体５１（又は６１）及び保護層５２（又は６２）」、又は「導電体５１（又は６１）単体」、を意味する。 In the present embodiment, hereinafter, when “collector” is simply described without reference, “conductor 51 (or 61) and protective layer 52 (or 62)” or “conductor” 51 (or 61) simple substance ”.
　電極５０は、上述したように保護層５２の上面の周縁部の内側に、即ち保護層５２の上面の周縁部以外の部分に設けられている。
　電極５０においては、保護層５２に、酸化還元反応によって、５価及び４価の間で酸化数が変化するバナジウムイオン、又は５価及び４価の間で酸化数が変化するバナジウムを含むイオンを含有するバナジウム固体塩を正極活物質として含有する固体状の化合物を含む析出物が担持されている。 As described above, the electrode 50 is provided inside the peripheral edge of the upper surface of the protective layer 52, that is, at a portion other than the peripheral edge of the upper surface of the protective layer 52.
In the electrode 50, vanadium ions whose oxidation number changes between pentavalent and tetravalent or ions containing vanadium whose oxidation number changes between pentavalent and tetravalent by oxidation-reduction reaction are applied to the protective layer 52. A precipitate containing a solid compound containing the contained vanadium solid salt as a positive electrode active material is supported.
　５価及び４価の間で酸化数が変化する前記バナジウムを含むイオンとしては、ＶＯ2+（IV）、ＶＯ2 +（V ）が例示される。
　正極用の活物質であるバナジウム化合物としては、酸化硫酸バナジウム（IV）（ＶＯＳＯ4 ・ｎＨ2 Ｏ）、酸化硫酸バナジウム（V）（（ＶＯ2 ）2 ＳＯ4 ・ｎＨ2 Ｏ）を挙げることができる。中でも、ＶＯＳＯ4 ・ｎＨ2 Ｏが好ましい。なお、ｎは０から５の整数を示す。 The ion containing pentavalent and tetravalent the vanadium oxidation number changes between, VO 2+ (IV), VO 2 + (V) are exemplified.
Examples of the vanadium compound which is an active material for the positive electrode include vanadium oxide (IV) (VOSO 4 · nH 2 O) and vanadium oxide (V) ((VO 2 ) 2 SO 4 · nH 2 O). it can. Of these, VOSO 4 · nH 2 O is preferable. N represents an integer of 0 to 5.
　バインダとしては、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）、及びフッ化ビニリデンとヘキサフルオロプロピレンとの共重合体（ＰＶＤＦ／ＨＦＰ）等が挙げられる。 Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and a copolymer of vinylidene fluoride and hexafluoropropylene (PVDF / HFP).
　炭素材料としては、アセチレンブラック，ケッチェンブラック（登録商標）等のカーボンブラック、及びグラファイト等が挙げられる。炭素材料は１種又は２種以上を用いることができる。 Examples of the carbon material include carbon black such as acetylene black and ketjen black (registered trademark), and graphite. The carbon material can use 1 type (s) or 2 or more types.
　電極５０に含まれる水系電解液は、硫酸水溶液であるのが好ましい。硫酸水溶液として、例えば濃度が９０質量％未満の硫酸を用いることができる。電解液は、電池のＳＯＣを０～１００％まで取り得るのに過不足のない量である。電解液の量は、例えばバナジウム化合物１００ｇに対して、２Ｍ（ｍｏｌ／Ｌ）の硫酸７０ｍＬである。 The aqueous electrolyte contained in the electrode 50 is preferably an aqueous sulfuric acid solution. As the sulfuric acid aqueous solution, for example, sulfuric acid having a concentration of less than 90% by mass can be used. The amount of the electrolyte is not excessive or deficient so that the SOC of the battery can be taken from 0 to 100%. The amount of the electrolytic solution is, for example, 70 mL of 2M (mol / L) sulfuric acid with respect to 100 g of the vanadium compound.
　電極５０上に設けられる保水膜５５は電解液透過性である。保水膜５５は多孔質材料からなるのが好ましい。この場合、保水性が良好である。
　保水膜５５として、具体的には、多孔質ガラスセパレータ、多孔質ＰＴＦＥセパレータ、及びカーボンペーパー等が挙げられる。 The water retention film 55 provided on the electrode 50 is electrolyte permeable. The water retaining film 55 is preferably made of a porous material. In this case, water retention is good.
Specific examples of the water retention film 55 include a porous glass separator, a porous PTFE separator, and carbon paper.
　保水膜５５の厚みは５０μｍ以上１３５μｍ以下であることが好ましい。保水膜５５の厚みが５０μｍ以上１３５μｍ以下である場合、隔膜７の水分低下に伴う抵抗値の上昇が抑制されるともに、電極占有率が低下してエネルギー密度が下がることがなく、充放電性能が良好である。 The thickness of the water retaining film 55 is preferably 50 μm or more and 135 μm or less. When the thickness of the water retaining film 55 is not less than 50 μm and not more than 135 μm, an increase in the resistance value due to a decrease in the moisture content of the diaphragm 7 is suppressed, and the electrode occupancy rate does not decrease and the energy density does not decrease. It is good.
　保水膜５５には水、又は水溶液を含浸させる。水溶液にはバナジウム、又は硫黄を含むことができる。特にバナジウムを含む水溶液を含浸させる場合、電池１の理論的な容量を増加させることができる。 The water retaining film 55 is impregnated with water or an aqueous solution. The aqueous solution can contain vanadium or sulfur. In particular, when the aqueous solution containing vanadium is impregnated, the theoretical capacity of the battery 1 can be increased.
　保水膜５５中のバナジウム元素濃度は５mol ／Ｌ以下であることが好ましい。この場合、電池１の充放電性能が良好である。 The vanadium element concentration in the water retaining film 55 is preferably 5 mol / L or less. In this case, the charge / discharge performance of the battery 1 is good.
　シーラント５４は上述したように枠状をなし、角筒状の枠本体の上端部に、内側に張り出した内側縁部５４ａを備え、枠本体の下端部に、外側に張り出した外側縁部５４ｂを備える。即ち、シーラント５４は平面視で、内側縁部５４ａ（電極５０の外側部分）の外側に、外側縁部５４ｂが位置するように構成されている。 The sealant 54 has a frame shape as described above, and includes an inner edge portion 54a projecting inwardly at the upper end portion of the rectangular tube-shaped frame body, and an outer edge portion 54b projecting outwardly at the lower end portion of the frame body. Prepare. That is, the sealant 54 is configured such that the outer edge portion 54b is positioned outside the inner edge portion 54a (the outer portion of the electrode 50) in plan view.
　シーラント５４の内側縁部５４ａは保護層５２の上面の周縁部に接着されており、内側縁部５４ａの内側面の上部は、保水膜５５の側面に接着されている。
　外側縁部５４ｂは半体２２の導電体５１側の面の、導電体５１の外側に接着されている。これにより、導電体５１及び保護層５２は、半体２２とシーラント５４とに挟着されている。即ち、半体２２、保護層５２、及びシーラント５４により、導電体５１は封止された状態で、導電体５１は半体２２に固定されている。なお、導電体５１の側面はシーラント５４に接着されていてもよく、接着されていなくてもよい。 The inner edge portion 54 a of the sealant 54 is bonded to the peripheral edge portion of the upper surface of the protective layer 52, and the upper portion of the inner side surface of the inner edge portion 54 a is bonded to the side surface of the water retention film 55.
The outer edge portion 54 b is bonded to the outer surface of the conductor 51 on the surface of the half body 22 on the conductor 51 side. Thereby, the conductor 51 and the protective layer 52 are sandwiched between the half body 22 and the sealant 54. That is, the conductor 51 is fixed to the half body 22 in a state where the conductor 51 is sealed by the half body 22, the protective layer 52, and the sealant 54. In addition, the side surface of the conductor 51 may be bonded to the sealant 54, or may not be bonded.
　シーラント５４の材料としては、例えばポリプロピレン又はポリエチレン等が挙げられる。ポロプロピレン又はポリエチレン等を用いることにより、熱溶着で容易に導電体５１を封止することが可能となる。 Examples of the material of the sealant 54 include polypropylene or polyethylene. By using polypropylene or polyethylene, the conductor 51 can be easily sealed by heat welding.
　電極材６は電極材５と同様の構成を有し、電極６０、導電体６１、保護層６２、及びシーラント６４を備える。導電体６１は角型平板状をなし、外装袋１の半体２１の図２における下面に配されており、導電体６１の下面は保護層６２により覆われている。保護層６２の下面の周縁部の内側には、活物質及び電解液を有する角型平板状の電極６０が設けられている。シーラント６４は枠状をなし、角筒状の枠本体の下端部に、内側に張り出した内側縁部６４ａを備え、枠本体の上端部に、外側に張り出した外側縁部６４ｂを備える。内側縁部６４ａは前記周縁部に接着され、外側縁部６４ｂは半体２１に接着され、シーラント６４は半体２１及び保護層６２とにより導電体６１を封止する。
　電極材６の導電体６１は、周縁部の一部から突出したタブ（不図示）を有し、タブの先端部は負極端子４に接続されている。
　電極材６の導電体６１、保護層６２、及びシーラント６４は電極材５と同様の材料を用いてなる。 The electrode material 6 has the same configuration as the electrode material 5, and includes an electrode 60, a conductor 61, a protective layer 62, and a sealant 64. The conductor 61 has a rectangular flat plate shape, and is disposed on the lower surface in FIG. 2 of the half body 21 of the outer bag 1, and the lower surface of the conductor 61 is covered with a protective layer 62. A rectangular flat plate-like electrode 60 having an active material and an electrolytic solution is provided inside the peripheral edge of the lower surface of the protective layer 62. The sealant 64 has a frame shape, and includes an inner edge portion 64a projecting inward at the lower end portion of the rectangular tube-shaped frame body, and an outer edge portion 64b projecting outward at the upper end portion of the frame body. The inner edge portion 64 a is bonded to the peripheral edge portion, the outer edge portion 64 b is bonded to the half body 21, and the sealant 64 seals the conductor 61 with the half body 21 and the protective layer 62.
The conductor 61 of the electrode material 6 has a tab (not shown) protruding from a part of the peripheral edge, and the tip of the tab is connected to the negative electrode terminal 4.
The conductor 61, the protective layer 62, and the sealant 64 of the electrode material 6 are formed using the same materials as the electrode material 5.
　電極６０においては、保護層６２に、酸化還元反応によって、２価及び３価の間で酸化数が変化するバナジウムイオン、又は２価及び３価の間で酸化数が変化するバナジウムを含むイオンを含有するバナジウム固体塩を負極活物質として含有する固体状の化合物を含む析出物が担持されている。 In the electrode 60, vanadium ions whose oxidation number changes between divalent and trivalent or ions containing vanadium whose oxidation number changes between divalent and trivalent due to oxidation-reduction reaction are applied to the protective layer 62. A precipitate containing a solid compound containing the contained vanadium solid salt as a negative electrode active material is supported.
　２価及び３価の間で酸化数が変化する前記バナジウムイオンとしては、Ｖ2+（II）、Ｖ3+（III ）が例示される。
　負極用の活物質であるバナジウム化合物としては、硫酸バナジウム（II）（ＶＳＯ4 ・ｎＨ2 Ｏ）、硫酸バナジウム（III ）（Ｖ2 （ＳＯ4 ）3 ・ｎＨ2 Ｏ）が挙げられる。中でも、Ｖ2 （ＳＯ4 ）3 ・ｎＨ2 Ｏが好ましい。なお、ｎは０から１０の整数を示す。 Examples of the vanadium ion whose oxidation number changes between divalent and trivalent include V 2+ (II) and V 3+ (III).
Examples of the vanadium compound that is an active material for the negative electrode include vanadium sulfate (II) (VSO 4 · nH 2 O) and vanadium sulfate (III) (V 2 (SO 4 ) 3 · nH 2 O). Among these, V 2 (SO 4 ) 3 · nH 2 O is preferable. N represents an integer of 0 to 10.
　隔膜７は保水膜５５を覆い、シーラント５４の内側縁部５４ａの上面に接着されている。
　隔膜７は水素イオン（プロトン）を通過させることができる。すなわち、隔膜７は、プロトン伝導性を有している。また、隔膜７は、硫酸イオンを通過させることができる。隔膜７はイオン交換膜であるのが好ましい。
　本実施の形態に係る電池１は保水膜５５を有し、保水膜５５が隔膜７に水分を供給することができ、隔膜７のイオン移動に関する抵抗の増加を抑制することができる。 The diaphragm 7 covers the water retention film 55 and is bonded to the upper surface of the inner edge portion 54 a of the sealant 54.
The diaphragm 7 can pass hydrogen ions (protons). That is, the diaphragm 7 has proton conductivity. Further, the diaphragm 7 can pass sulfate ions. The diaphragm 7 is preferably an ion exchange membrane.
The battery 1 according to the present embodiment has a water retention film 55, and the water retention film 55 can supply moisture to the diaphragm 7, and an increase in resistance related to ion movement of the diaphragm 7 can be suppressed.
　隔膜７の、０．５Ｍ硫酸中で測定した１ｋＨｚにおける体積抵抗率は２８０Ω・ｃｍ以上であり、かつ、面積抵抗値が３Ω・ｃｍ2 以下である。
　この場合、電圧を長時間維持することができ、充放電を繰り返したときの放電電流容量が高く、クーロン効率及び容量維持率が良好であり、サイクル特性が良好である。そして、高電流密度で入出力した場合に良好なエネルギー密度を有し、高入出力密度での使用が可能である。
　本実施の形態においては、正の電極５及び負の電極６間で、５価のバナジウムイオン及び２価のバナジウムイオンの隔膜７の通過による接触が抑制され、即ち活物質イオンのクロスコンタミネーションが抑制されているので、高寿命及び長時間の電圧維持が実現でき、かつ、プロトン伝導度が高いので、高入出力密度での使用が実現されると考えられる。 The volume resistivity of the diaphragm 7 at 1 kHz measured in 0.5 M sulfuric acid is 280 Ω · cm or more and the sheet resistance is 3 Ω · cm 2 or less.
In this case, the voltage can be maintained for a long time, the discharge current capacity when charging / discharging is repeated is high, the coulomb efficiency and the capacity maintenance ratio are good, and the cycle characteristics are good. And when it inputs / outputs with a high current density, it has a favorable energy density and can be used with a high input / output density.
In the present embodiment, contact between the positive electrode 5 and the negative electrode 6 due to passage of pentavalent vanadium ions and divalent vanadium ions through the diaphragm 7 is suppressed, that is, cross contamination of active material ions is prevented. Since it is suppressed, a long life and long-time voltage maintenance can be realized, and since proton conductivity is high, it is considered that use at a high input / output density is realized.
　前記体積抵抗率は６００Ω・ｃｍ以上であるのが好ましく、１５００Ω・ｃｍ以上であるのがより好ましい。この場合、長時間の電圧維持率、並びに充放電を繰り返した場合の放電電流容量及び容量維持率がより良好になる。
　前記体積抵抗率は１００００Ω・ｃｍ以下であるのが好ましい。体積抵抗率が１００００Ω・ｃｍを超えた場合、仮に隔膜７の厚みを薄くしたとしても抵抗値が高くなりすぎてしまい、高入出力密度を得るのが困難となる。 The volume resistivity is preferably 600 Ω · cm or more, and more preferably 1500 Ω · cm or more. In this case, the voltage maintenance rate for a long time, and the discharge current capacity and the capacity maintenance rate when charging and discharging are repeated become better.
The volume resistivity is preferably 10,000 Ω · cm or less. When the volume resistivity exceeds 10,000 Ω · cm, even if the thickness of the diaphragm 7 is reduced, the resistance value becomes too high, and it becomes difficult to obtain a high input / output density.
　０．５Ｍ硫酸中で測定した１ｋＨｚにおける面積抵抗値の上限は２Ω・ｃｍ2 であるのが好ましく、１Ω・ｃｍ2 であるのがより好ましい。この場合、電流密度を高くした場合の放電エネルギー密度がより高くなる。
　面積抵抗値の下限は０．１５Ω・ｃｍ2 であるのが好ましい。この場合、充放電を繰り返した場合のクーロン効率がより良好になり、電流密度を高くした場合の放電エネルギー密度がより高くなる。 The upper limit of the sheet resistance value at 1 kHz measured in 0.5 M sulfuric acid is preferably 2 Ω · cm 2 , and more preferably 1 Ω · cm 2 . In this case, the discharge energy density when the current density is increased becomes higher.
The lower limit of the sheet resistance value is preferably 0.15 Ω · cm 2 . In this case, the Coulomb efficiency when charging and discharging are repeated becomes better, and the discharge energy density becomes higher when the current density is increased.
　隔膜７の厚みは５０μｍ以下であるのが好ましく、２５μｍ以下であるのがより好ましく、１０μｍ以下であるのがさらに好ましい。厚みは５０μｍ以下である場合、電流密度を高くした場合の充電エネルギー密度及び放電エネルギー密度が良好である。 The thickness of the diaphragm 7 is preferably 50 μm or less, more preferably 25 μm or less, and even more preferably 10 μm or less. When the thickness is 50 μm or less, the charge energy density and the discharge energy density when the current density is increased are good.
　隔膜７は陰イオン交換膜であるのが好ましい。
　この場合、低い膜抵抗値を維持しつつ、イオン選択性が良好である。 The diaphragm 7 is preferably an anion exchange membrane.
In this case, the ion selectivity is good while maintaining a low membrane resistance value.
　以上のように構成された電池１の電極材５の電極５０と電極材６の電極６０との間において、下記式(1)及び(2)の反応が生じる。
正極：ＶＯＸ2 ・ｎＨ2 Ｏ（ｓ）⇔ＶＯ2 Ｘ・（ｎ－１）Ｈ2 Ｏ（ｓ）＋ＨＸ＋Ｈ+ ＋ｅ- 　…（１）
負極：ＶＸ3 ・ｎＨ2 Ｏ（ｓ）＋Ｈ+ ＋ｅ- ⇔ＶＸ2 ・ｎＨ2 Ｏ（ｓ）＋ＨＸ　…（２）
　式中、Ｘは１価の陰イオンを表す。Ｘがｍ価の陰イオンである場合、結合係数（１／ｍ）が考慮される。ｎは種々の値をとり得る。 Reactions of the following formulas (1) and (2) occur between the electrode 50 of the electrode material 5 and the electrode 60 of the electrode material 6 of the battery 1 configured as described above.
Positive electrode: VOX 2 · nH 2 O (s) ⇔VO 2 X · (n−1) H 2 O (s) + HX + H + + e − (1)
Negative electrode: VX 3 · nH 2 O (s) + H + + e − ⇔VX 2 · nH 2 O (s) + HX (2)
In the formula, X represents a monovalent anion. When X is an m-valent anion, the coupling coefficient (1 / m) is considered. n can take various values.
　前記式（１）及び（２）の反応を利用してバナジウム固体塩電池１を用いたバナジウム固体塩電池の充放電が行われる。このとき、正極端子３，負極端子４を介して、外部の負荷又は充電器等との間で充放電が行われる。式（１）及び（２）の反応において隔膜７を介して、電極５０，６０間でプロトンが移動する。 The charge and discharge of the vanadium solid salt battery using the vanadium solid salt battery 1 is performed using the reactions of the above formulas (1) and (2). At this time, charging / discharging is performed with an external load or a charger via the positive terminal 3 and the negative terminal 4. In the reaction of the formulas (1) and (2), protons move between the electrodes 50 and 60 through the diaphragm 7.
　なお、電極材５のバナジウム化合物としてＶＯＳＯ4 ・ｎＨ2 Ｏを用い、電極材６のバナジウム化合物としてＶ2 （ＳＯ4 ）3 ・ｎＨ2 Ｏを用いた場合の各物質の反応を以下に示す。
正極：２ＶＯＳＯ4 ・ｎＨ2 Ｏ（ｓ）⇔（ＶＯ2 ）2 ＳＯ4 ・（ｎ－２）Ｈ2 Ｏ（ｓ）＋Ｈ2 ＳＯ4 ＋２Ｈ+ ＋２ｅ- 　…（３）
負極：Ｖ2 （ＳＯ4 ）3 ・ｎＨ2 Ｏ（ｓ）＋２Ｈ+ ＋２ｅ- ⇔２ＶＳＯ4 ・ｎＨ2 Ｏ（ｓ）＋Ｈ2 ＳＯ4 　…（４） The reaction of each material when VOSO 4 · nH 2 O is used as the vanadium compound of the electrode material 5 and V 2 (SO 4 ) 3 · nH 2 O is used as the vanadium compound of the electrode material 6 is shown below.
Positive electrode: 2VOSO 4 · nH 2 O (s) ⇔ (VO 2 ) 2 SO 4 · (n−2) H 2 O (s) + H 2 SO 4 + 2H + + 2e − (3)
Negative electrode: V 2 (SO 4 ) 3 · nH 2 O (s) + 2H + + 2e − ⇔2VSO 4 · nH 2 O (s) + H 2 SO 4 (4)
２．バナジウムレドックス二次電池の製造方法
　以下、本発明の電池１の製造方法について説明する。
　ここで、正極の電極材５と負極の電極材６とを各別に作製するのではなく、単一の電極材を作製した後、正極側及び負極側のいずれに用いるかを使い分けし、電池１の組立後の通電によって、正極の電極材５及び負極の電極材６を形成する場合について説明する。 2. Method for Manufacturing Vanadium Redox Secondary Battery Hereinafter, a method for manufacturing the battery 1 of the present invention will be described.
Here, the positive electrode material 5 and the negative electrode material 6 are not manufactured separately, but after a single electrode material is manufactured, the battery 1 is used depending on whether it is used for the positive electrode side or the negative electrode side. A case where the positive electrode material 5 and the negative electrode material 6 are formed by energization after assembly will be described.
　まず、炭素材料に、３価のバナジウム化合物としてのＶ2 （ＳＯ4 ）3 、４価のバナジウム化合物としてのＶＯＳＯ4 、及びハインダを配合し、攪拌機により混合することにより混合粉を得る。炭素材料、活物質、及びバインダの組成は、要求される容量、乾燥条件、及び外部環境（気温、湿度）等に応じて決定する。 First, V 2 (SO 4 ) 3 as a trivalent vanadium compound, VOSO 4 as a tetravalent vanadium compound, and a hinder are mixed in a carbon material, and mixed powder is obtained by mixing with a stirrer. The composition of the carbon material, active material, and binder is determined according to the required capacity, drying conditions, external environment (temperature, humidity), and the like.
　次に、前記混合粉に水系電解液を配合し、プラネタリーミキサ等を用いて混練することにより、混錬物を得る。 Next, a kneaded product is obtained by blending an aqueous electrolyte into the mixed powder and kneading it using a planetary mixer or the like.
　前記混錬物はロールプレス等により圧延成形され、電極形状に打ち抜かれて集電体に配置される。ここで、集電体としては、上述の「導電体５１（又は６１）単体」、及び「導電体５１（又は６１）及び保護層５２（又は６２）」等が挙げられる。 The kneaded material is rolled and formed by a roll press or the like, punched into an electrode shape, and placed on a current collector. Here, examples of the current collector include the above-mentioned “conductor 51 (or 61) alone”, “conductor 51 (or 61) and protective layer 52 (or 62)”, and the like.
　上述したように、電極材を電極材５用，電極材６用に使い分ける。電極材５の電極５０上には保水膜５５を設ける。外装袋２の半体２２に電極材５の集電体を、半体２１に電極材６の電極材の集電体を熱プレス等により固着する。 As described above, the electrode material is selectively used for the electrode material 5 and the electrode material 6. A water retention film 55 is provided on the electrode 50 of the electrode material 5. The current collector of the electrode material 5 is fixed to the half body 22 of the outer bag 2 and the current collector of the electrode material 6 of the electrode material 6 is fixed to the half body 21 by hot pressing or the like.
　以上のように集電体が固定された半体２１，２２を内側が対向するように合わせ、半体２１，２２の周縁部の一部から正極端子３及び負極端子４が突出する状態で、周縁部を圧接し、接着することにより外装袋２が形成され、電池１が得られる。なお、半体２１，２２は最初から一体化されていてもよい。 As described above, the halves 21 and 22 to which the current collector is fixed are aligned so that the inside faces each other, and the positive electrode terminal 3 and the negative electrode terminal 4 protrude from a part of the peripheral edge of the halves 21 and 22. The outer bag 2 is formed by press-contacting and bonding the peripheral edge portion, and the battery 1 is obtained. The halves 21 and 22 may be integrated from the beginning.
　電池の組み立て後の通電により、正極の電極材５のバナジウム化合物の価数が４価、負極の電極材６のバナジウム化合物の価数が３価になる。 By energization after the battery is assembled, the valence of the vanadium compound of the positive electrode material 5 becomes tetravalent and the valence of the vanadium compound of the negative electrode material 6 becomes trivalent.
　以上のように構成された本実施の形態に係る電池１は、隔膜７の０．５Ｍ硫酸中で測定した１ｋＨｚにおける体積抵抗率は２８０Ω・ｃｍ以上であり、かつ、面積抵抗値が３Ω・ｃｍ2 以下であるので、高電流密度で入出力した場合に良好なエネルギー密度を有し、即ち高入出力化を実現できるとともに、高寿命であり、かつ電圧を長時間維持することができる。
　そして、負極の電極５０との間に保水膜５５を有するので、隔膜７の厚みを薄くした場合に、隔膜７の保水量が向上する。
　また、本実施の形態においては、導電体５１は、シーラント５４、保護層５２、及び半体２２により封止され、電極５０は保水膜５５及び隔膜７と、シーラント５４ａとにより包囲されているので、電極５０に含まれる酸性電解液が導電体５１に接触することがなく、導電体５１の腐食が防止されている。同様に、導電体６１は、シーラント６４、保護層６２、及び半体２１により封止され、電極６０は隔膜７と、シーラント６４ａとにより包囲されているので、電極６０に含まれる酸性電解液が導電体６１と反応することがなく、導電体６１の腐食が防止されている。 In the battery 1 according to this embodiment configured as described above, the volume resistivity at 1 kHz measured in 0.5 M sulfuric acid of the diaphragm 7 is 280 Ω · cm or more, and the sheet resistance is 3 Ω · cm. Since it is 2 or less, it has a good energy density when it is input / output at a high current density, that is, it can realize a high input / output, has a long life, and can maintain a voltage for a long time.
And since it has the water retention film | membrane 55 between the electrodes 50 of a negative electrode, when the thickness of the diaphragm 7 is made thin, the water retention amount of the diaphragm 7 improves.
In the present embodiment, the conductor 51 is sealed by the sealant 54, the protective layer 52, and the half body 22, and the electrode 50 is surrounded by the water retention film 55, the diaphragm 7, and the sealant 54a. The acidic electrolyte contained in the electrode 50 does not come into contact with the conductor 51, and corrosion of the conductor 51 is prevented. Similarly, since the conductor 61 is sealed by the sealant 64, the protective layer 62, and the half body 21, and the electrode 60 is surrounded by the diaphragm 7 and the sealant 64a, the acidic electrolyte contained in the electrode 60 is It does not react with the conductor 61, and corrosion of the conductor 61 is prevented.
　以下、本発明の実施例を具体的に説明するが、本発明はこの実施例に限定されるものではない。 Hereinafter, examples of the present invention will be described in detail, but the present invention is not limited to these examples.
１．電池の製造
［実施例１］
　炭素材料としてのカーボンブラック（「ケッチェンブラック（登録商標）」、株式会社ライオン製）２．９３ｇに、３価のバナジウム化合物としてのＶ2 （ＳＯ4 ）3 ・ｎＨ2 Ｏ（自社製）を２．８９ｇ、４価のバナジウム化合物としてのＶＯＳＯ4 ・ｎＨ2 Ｏ（新興化学株式会社製）を２．５ｇ、バインダとしてのＰＴＦＥ（「６－Ｊ」、三井デュポンフロロケミカル株式会社製）を０．０８ｇ配合して、上述の混合粉を得た。
　次に、この混合粉２．０ｇに１Ｍ硫酸０．７３ｍＬを配合して混練し、上述の混錬物を得た。該混練物をロールプレス等により圧延成形し、打ち抜いて電極を得た。
　銅箔からなる導電体にグラファイトシートを接着して集電体を得た。
　該集電体に前記電極を配置して電極材を作製した。
　保水膜５５として、２７ｍｍ角のガラスセパレータ（「ＴＧＰ００８Ｆ」、日本板硝子株式会社製）に、４価のバナジウム１Ｍと硫酸２Ｍとの溶液を８０μＬ含浸させたものを用いた。
　隔膜７として、陰イオン交換膜（「ＶＸ－１０」、ＦｕＭＡ－Ｔｅｃｈ社製）を用い、上述にようにして、実施例１の電池１を作製した。 1. Production of battery [Example 1]
Carbon black (“Ketjen Black (registered trademark)”, manufactured by Lion Corporation) as a carbon material 2.93 g of V 2 (SO 4 ) 3 · nH 2 O (made in-house) as a trivalent vanadium compound 2.89 g, 2.5 g of VOSO 4 · nH 2 O (made by Shinsei Chemical Co., Ltd.) as a tetravalent vanadium compound, and 0 PTFE (“6-J”, made by Mitsui DuPont Fluoro Chemical Co., Ltd.) as a binder 0.08 g was mixed to obtain the above-mentioned mixed powder.
Next, 0.73 mL of 1M sulfuric acid was added to 2.0 g of the mixed powder and kneaded to obtain the above kneaded product. The kneaded product was roll-formed by a roll press or the like and punched to obtain an electrode.
A graphite sheet was bonded to a conductor made of copper foil to obtain a current collector.
The electrode was arranged on the current collector to produce an electrode material.
As the water retaining film 55, a 27 mm square glass separator ("TGP008F" manufactured by Nippon Sheet Glass Co., Ltd.) impregnated with 80 μL of a solution of tetravalent vanadium 1M and sulfuric acid 2M was used.
Using an anion exchange membrane (“VX-10”, manufactured by FuMA-Tech) as the diaphragm 7, the battery 1 of Example 1 was produced as described above.
　下記の表１のＮｏ．１が実施例１に相当する。実施例１のイオン交換膜７の厚み［μｍ］、面積抵抗値［Ω・ｃｍ2 ］、体積抵抗率［Ω・ｃｍ］を表１に示す。
　イオン交換膜７の抵抗は、ＡＧＣエンジニアリング株式会社のイオン交換膜抵抗測定器を用いて測定した。
　抵抗の測定条件は、以下の通りである。
　電解液：０．５Ｍ硫酸
　周波数：１ｋＨｚ No. in Table 1 below. 1 corresponds to Example 1. Table 1 shows the thickness [μm], sheet resistance [Ω · cm 2 ], and volume resistivity [Ω · cm] of the ion exchange membrane 7 of Example 1.
The resistance of the ion exchange membrane 7 was measured using an ion exchange membrane resistance measuring instrument manufactured by AGC Engineering Co., Ltd.
The resistance measurement conditions are as follows.
Electrolyte: 0.5M sulfuric acid Frequency: 1kHz
　後述する実施例２～４が表１のＮｏ．２～４に相当し、比較例１～４が表１のＮｏ．５～８に相当する。 Examples 2 to 4 described later are Nos. In Table 1. No. 2 in Table 1 corresponds to Comparative Examples 1 to 4. Corresponds to 5-8.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
［実施例２］
　隔膜７として、陰イオン交換膜（「ＶＸ－０５」、ＦｕＭＡ－Ｔｅｃｈ社製）を用いたこと以外は実施例１と同様にして、実施例２の電池１を作製した。実施例２のイオン交換膜７の厚み等を表１のＮｏ．２に示す。 [Example 2]
A battery 1 of Example 2 was fabricated in the same manner as Example 1 except that an anion exchange membrane (“VX-05”, manufactured by FuMA-Tech) was used as the diaphragm 7. The thickness and the like of the ion exchange membrane 7 of Example 2 are set as No. 1 in Table 1. It is shown in 2.
［実施例３］
　隔膜７として、陰イオン交換膜（「イオン交換膜Ｉ」、ＦｕＭＡ－Ｔｅｃｈ社製）を用いたこと以外は実施例１と同様にして、実施例３の電池１を作製した。実施例３のイオン交換膜７の厚み等を表１のＮｏ．３に示す。 [Example 3]
A battery 1 of Example 3 was fabricated in the same manner as in Example 1 except that an anion exchange membrane (“Ion Exchange Membrane I”, manufactured by FuMA-Tech) was used as the diaphragm 7. The thickness and the like of the ion exchange membrane 7 of Example 3 are shown in No. 1 of Table 1. 3 shows.
［実施例４］
　隔膜７として、陰イオン交換膜（「イオン交換膜Ｊ」、ＦｕＭＡ－Ｔｅｃｈ社製）を用いたこと以外は実施例１と同様にして、実施例４の電池１を作製した。実施例４のイオン交換膜７の厚み等を表１のＮｏ．４に示す。 [Example 4]
A battery 1 of Example 4 was produced in the same manner as in Example 1 except that an anion exchange membrane (“ion exchange membrane J”, manufactured by FuMA-Tech) was used as the diaphragm 7. The thickness and the like of the ion exchange membrane 7 of Example 4 are set as No. 1 in Table 1. 4 shows.
［比較例１］
　隔膜として、陰イオン交換膜（「イオン交換膜Ｋ」、ＦｕＭＡ－Ｔｅｃｈ社製）を用いたこと以外は実施例１と同様にして、比較例１の電池を作製した。比較例１のイオン交換膜の厚み等を表１のＮｏ．５に示す。 [Comparative Example 1]
A battery of Comparative Example 1 was produced in the same manner as in Example 1 except that an anion exchange membrane (“ion exchange membrane K”, manufactured by FuMA-Tech) was used as the diaphragm. The thickness and the like of the ion exchange membrane of Comparative Example 1 are shown in No. 1 of Table 1. As shown in FIG.
［比較例２］
　隔膜として、陰イオン交換膜（「イオン交換膜Ｌ」、ＦｕＭＡ－Ｔｅｃｈ社製）を用いたこと以外は実施例１と同様にして、比較例２の電池を作製した。比較例２のイオン交換膜の厚み等を表１のＮｏ．６に示す。 [Comparative Example 2]
A battery of Comparative Example 2 was produced in the same manner as in Example 1 except that an anion exchange membrane (“ion exchange membrane L”, manufactured by FuMA-Tech) was used as the diaphragm. The thickness and the like of the ion exchange membrane of Comparative Example 2 are shown in No. 1 of Table 1. It is shown in FIG.
［比較例３］
　隔膜として、陰イオン交換膜（「イオン交換膜Ｍ」、ＦｕＭＡ－Ｔｅｃｈ社製）を用いたこと以外は実施例１と同様にして、比較例３の電池を作製した。比較例３のイオン交換膜の厚み等を表１のＮｏ．７に示す。 [Comparative Example 3]
A battery of Comparative Example 3 was produced in the same manner as in Example 1 except that an anion exchange membrane (“ion exchange membrane M”, manufactured by FuMA-Tech) was used as the diaphragm. The thickness and the like of the ion exchange membrane of Comparative Example 3 are shown in No. 1 of Table 1. 7 shows.
［比較例４］
　隔膜として、陰イオン交換膜（「ＦＳ－１０４０」、ＦｕＭＡ－Ｔｅｃｈ社製）を用いたこと以外は実施例１と同様にして、比較例４の電池を作製した。比較例４のイオン交換膜の厚み等を表１のＮｏ．８に示す。 [Comparative Example 4]
A battery of Comparative Example 4 was produced in the same manner as in Example 1 except that an anion exchange membrane (“FS-1040”, manufactured by FuMA-Tech) was used as the diaphragm. The thickness and the like of the ion exchange membrane of Comparative Example 4 are shown in No. 1 of Table 1. It is shown in FIG.
２．電池の性能評価
　上述の各実施例の電池１、及び各比較例の電池について、性能を評価した。充放電条件を下記の表２に示す。 2. Battery Performance Evaluation The performance of the battery 1 of each of the above examples and the battery of each comparative example was evaluated. The charge / discharge conditions are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２のステップ１においては、８ｍＡで１．４５ＶまでＣＣ充電した後、８ｍＡで０．８ＶまでＣＣ放電を行うことを１サイクルとし、２０サイクルの充放電を実施した。ステップ２においては、８ｍＡで１．４５ＶまでＣＣ充電した後、１６ｍＡで０．８ＶまでＣＣ放電を行う１サイクルの充放電を実施した。以下、同様にして充放電を行った。 In Step 1 of Table 2, after CC charging to 1.45 V at 8 mA, CC discharging to 0.8 V at 8 mA was taken as one cycle, and 20 cycles of charging / discharging were performed. In step 2, after charging CC to 1.45 V at 8 mA, charging and discharging for one cycle was performed in which CC discharging was performed to 0.8 V at 16 mA. Thereafter, charge and discharge were performed in the same manner.
　各実施例及び比較例の電池性能の評価結果を上記表１に示す。
　表１の「２０サイクル目」の項目の「放電電流容量」は、表２のステップ１の２０サイクル目を実施したときの放電電流容量、「Ｃ効率」は２０サイクル目の充電時のクーロン量に対する放電時のクーロン量の比率である。
　表１の「４０サイクル目」の項目の「放電電流容量」は、表２のステップ１６の２０サイクル目（全体としては５４サイクル目に相当する）を実施したときの放電電流容量、「Ｃ効率」は前記２０サイクル目の充電時のクーロン量に対する放電時のクーロン量の比率である。 The evaluation results of the battery performance of each example and comparative example are shown in Table 1 above.
“Discharge current capacity” in the item of “20th cycle” in Table 1 is the discharge current capacity when the 20th cycle in Step 1 of Table 2 is performed, and “C efficiency” is the amount of coulomb at the time of charging in the 20th cycle. It is the ratio of the amount of coulomb at the time of discharge to
“Discharge current capacity” in the item of “40th cycle” in Table 1 is the discharge current capacity when the 20th cycle of Step 16 in Table 2 (corresponding to the 54th cycle as a whole) is performed, “C efficiency” "Is the ratio of the coulomb amount during discharging to the coulomb amount during charging in the 20th cycle.
　表１の「容量維持率」は、（４０サイクル目の放電電流容量）／（２０サイクル目の放電電流容量）により求めた。 The “capacity maintenance ratio” in Table 1 was obtained by (discharge current capacity at 40th cycle) / (discharge current capacity at 20th cycle).
　表１の「放電エネルギー密度」の「＠２．５６ｍＡ／ｃｍ2 」は、上述したようにステップ２において、８ｍＡで１．４５ＶまでＣＣ充電した後、１６ｍＡで０．８ＶまでＣＣ放電を行った際に取り出せたエネルギー（Ｗｈ）を電極体積で（Ｌ）で除することにより求めた。電極の面積が６．２５ｃｍ2 であるので、１６（ｍＡ）／６．２５＝２．５６（ｍＡ／ｃｍ2 ）であり、電流密度２．５６（ｍＡ／ｃｍ2 ）で電流を流したときに取り出せた放電エネルギー密度を求めたことになる。
　表１の「放電エネルギー密度」の「＠１０ｍＡ／ｃｍ2 」は、同様に、ステップ４において、８ｍＡで１．４５ＶまでＣＣ充電した後、６３ｍＡで０．８ＶまでＣＣ放電を行った際に取り出せたエネルギー（Ｗｈ）を電極体積で（Ｌ）で除することにより求めた。６３（ｍＡ）／６．２５＝１０（ｍＡ／ｃｍ2 ）であり、電流密度１０ｍＡ／ｃｍ2 で電流を流したときに取り出せた放電エネルギー密度を求めたことになる。
　表１の「放電エネルギー密度」の「＠２０ｍＡ／ｃｍ2 」は、同様に、ステップ５において、８ｍＡで１．４５ＶまでＣＣ充電した後、１２５ｍＡで０．８ＶまでＣＣ放電を行った際に取り出せたエネルギー（Ｗｈ）を電極体積で（Ｌ）で除することにより求めた。１２５（ｍＡ）／６．２５＝２０（ｍＡ／ｃｍ2 ）であり、電流密度２０ｍＡ／ｃｍ2 で電流を流したときに取り出せた放電エネルギー密度を求めたことになる。 As described above, “@ 2.56 mA / cm 2 ” of “Discharge energy density” in Table 1 was CC charged to 1.45 V at 8 mA in Step 2 and then CC discharged to 0.8 V at 16 mA. It calculated | required by remove | dividing the energy (Wh) taken out in that case by (L) by electrode volume. Since the area of the electrode is 6.25 cm 2 , 16 (mA) /6.25=2.56 (mA / cm 2 ), and a current is passed at a current density of 2.56 (mA / cm 2 ). The discharge energy density that can be taken out is obtained.
Similarly, “@ 10 mA / cm 2 ” of “Discharge energy density” in Table 1 can be taken out when CC discharge is performed at 8 mA to 1.45 V and then CC discharge is performed at 63 mA to 0.8 V in Step 4. Energy (Wh) divided by (L) by electrode volume. It is 63 (mA) /6.25=10 (mA / cm 2 ), and the discharge energy density that can be taken out when a current is passed at a current density of 10 mA / cm 2 is obtained.
Similarly, the “@ 20 mA / cm 2 ” of “Discharge energy density” in Table 1 can be taken out when CC discharge is performed at 8 mA to 1.45 V and then CC discharge is performed at 125 mA to 0.8 V in Step 5. Energy (Wh) divided by (L) by electrode volume. 125 (mA) /6.25=20 (mA / cm 2 ), and the discharge energy density extracted when a current was passed at a current density of 20 mA / cm 2 was obtained.
　表１の「充電エネルギー密度」の「＠１０ｍＡ／ｃｍ2 」は、同様に、ステップ１１において、６３ｍＡで１．４５ＶまでＣＣ充電した後、８ｍＡで０．８ＶまでＣＣ放電を行った際に取り出せたエネルギー（Ｗｈ）を電極体積で（Ｌ）で除することにより求めた。６３（ｍＡ）／６．２５＝１０（ｍＡ／ｃｍ2 ）であり、電流密度１０ｍＡ／ｃｍ2 で電流を流して充電した後、２．５６ｍＡ／ｃｍ2 で放電したときに取り出せた放電エネルギー密度を求めたことになる。 Similarly, “@ 10 mA / cm 2 ” of “Charge energy density” in Table 1 can be taken out when CC discharge is performed at 63 mA to 1.45 V and then CC discharge is performed at 8 mA to 0.8 V in Step 11. Energy (Wh) divided by (L) by electrode volume. 63 (mA) /6.25=10 (mA / cm 2 ), and after charging with a current density of 10 mA / cm 2 , the discharge energy density extracted when discharging at 2.56 mA / cm 2 I asked for.
　表１の「８０ｈでの電圧維持率」は、ステップ１５において、８ｍＡで１．４５ＶまでＣＣ充電した後、８０時間放置した際の開回路電圧をモニタリングして求めた。その後、８ｍＡで０．８ＶまでのＣＣ放電を行った。 The “voltage maintenance rate at 80 h” in Table 1 was obtained by monitoring the open circuit voltage when CC was charged to 1.45 V at 8 mA in step 15 and left for 80 hours. Then, CC discharge to 0.8V was performed at 8 mA.
　図３は、実施例のイオン交換膜７及び比較例のイオン交換膜の体積抵抗率と、前記電圧維持率との関係を示すグラフである。横軸は体積抵抗率［Ω・ｃｍ］、縦軸は電圧維持率［％］である。
　図３より、イオン交換膜の体積抵抗率が２８０Ω・ｃｍ以上である実施例１～４の電池１、及び比較例１の電池は電圧維持率が９２％以上であり、良好であることが分かる。体積抵抗率が６００Ω・ｃｍ以上である場合、電圧維持率が９７％以上であるので、より好ましい。 FIG. 3 is a graph showing the relationship between the volume resistivity of the ion exchange membrane 7 of the example and the ion exchange membrane of the comparative example and the voltage maintenance rate. The horizontal axis represents volume resistivity [Ω · cm], and the vertical axis represents voltage maintenance ratio [%].
From FIG. 3, it can be seen that the batteries 1 of Examples 1 to 4 in which the volume resistivity of the ion exchange membrane is 280 Ω · cm or more and the batteries of Comparative Example 1 have a voltage maintenance rate of 92% or more and are good. . When the volume resistivity is 600 Ω · cm or more, the voltage maintenance rate is 97% or more, which is more preferable.
　図４は、実施例のイオン交換膜７及び比較例のイオン交換膜の体積抵抗率と、前記容量維持率との関係を示すグラフである。横軸は体積抵抗率［Ω・ｃｍ］、縦軸は容量維持率［％］である。
　図４より、イオン交換膜の体積抵抗率が２８０Ω・ｃｍ以上である実施例１～４の電池１、及び比較例１の電池は、容量維持率が６５％以上であり、比較例２及び３より向上していることが分かる。体積抵抗率が６００Ω・ｃｍ以上である場合、電圧維持率が８６％以上であるので好ましく、体積抵抗率が１５００Ω・ｃｍ以上である場合、電圧維持率が８９％以上であるのでより好ましい。
　なお、図４において、比較例４の容量維持率は高くなっているが、これは、２０サイクル目で電池の劣化により放電電流容量が既に大きく低下しており、４０サイクル目で放電電流容量が変化していないため、見かけ上、容量維持率が高くなっている。 FIG. 4 is a graph showing the relationship between the volume resistivity of the ion exchange membrane 7 of the example and the ion exchange membrane of the comparative example and the capacity retention rate. The horizontal axis represents volume resistivity [Ω · cm], and the vertical axis represents capacity retention rate [%].
As shown in FIG. 4, the batteries 1 of Examples 1 to 4 in which the volume resistivity of the ion exchange membrane is 280 Ω · cm or more and the batteries of Comparative Example 1 have a capacity retention rate of 65% or more. It turns out that it is improving more. When the volume resistivity is 600 Ω · cm or more, the voltage maintenance rate is preferably 86% or more, and when the volume resistivity is 1500 Ω · cm or more, the voltage maintenance rate is 89% or more, more preferable.
In FIG. 4, the capacity retention rate of Comparative Example 4 is high. This is because the discharge current capacity has already greatly decreased due to the deterioration of the battery at the 20th cycle, and the discharge current capacity at the 40th cycle. Since it has not changed, the capacity retention rate is apparently high.
　図５は、実施例のイオン交換膜７及び比較例のイオン交換膜の体積抵抗率と、４０サイクル目の放電電流容量との関係を示すグラフである。横軸は体積抵抗率［Ω・ｃｍ］、縦軸は放電電流容量［ｍＡｈ］である。
　図５より、実施例１～４の電池１、及び比較例１の電池は、４０サイクル目の放電電流容量が２．０ｍＡｈを超えており、良好であることが分かる。上述の比較例４は、前記放電電流容量が２．０ｍＡｈであり、電池が劣化していることが分かる。 FIG. 5 is a graph showing the relationship between the volume resistivity of the ion exchange membrane 7 of the example and the ion exchange membrane of the comparative example and the discharge current capacity at the 40th cycle. The horizontal axis represents volume resistivity [Ω · cm], and the vertical axis represents discharge current capacity [mAh].
FIG. 5 shows that the batteries 1 of Examples 1 to 4 and the battery of Comparative Example 1 have good discharge current capacity at the 40th cycle exceeding 2.0 mAh. In Comparative Example 4 described above, the discharge current capacity is 2.0 mAh, and it can be seen that the battery is deteriorated.
　図６は、実施例のイオン交換膜７及び比較例のイオン交換膜の面積抵抗値と、２０サイクル目のクーロン効率との関係を示すグラフである。横軸は面積抵抗［Ω・ｃｍ2 ］、縦軸は２０サイクル目のクーロン効率［％］である。
　図６より、面積抵抗値が０．１５Ω・ｃｍ以上である実施例１～４、及び比較例１～３は、２０サイクル目のクーロン効率が９４％以上であり、良好であることが分かる。 FIG. 6 is a graph showing the relationship between the area resistance values of the ion exchange membrane 7 of the example and the ion exchange membrane of the comparative example and the Coulomb efficiency at the 20th cycle. The horizontal axis represents the sheet resistance [Ω · cm 2 ], and the vertical axis represents the Coulomb efficiency [%] at the 20th cycle.
From FIG. 6, it can be seen that Examples 1 to 4 and Comparative Examples 1 to 3 having a sheet resistance value of 0.15 Ω · cm or more have excellent Coulomb efficiency at the 20th cycle of 94% or more.
　図７は、実施例のイオン交換膜７及び比較例のイオン交換膜の面積抵抗値と、放電エネルギー密度との関係を示すグラフである。横軸は面積抵抗値［Ω・ｃｍ2 ］、縦軸は放電エネルギー密度［Ｗｈ／Ｌ］である。
　２．５６ｍＡ／ｃｍ2 、１０ｍＡ／ｃｍ2 、２０ｍＡ／ｃｍ2 夫々の電流密度で電流を流し、満充電したときに取り出せた放電エネルギー密度を求めた結果を示す。
　電流密度が高くなるのに従い、取り出せる放電エネルギー密度は小さくなる。
　比較例１の場合、２．５６ｍＡ／ｃｍ2 のとき、放電エネルギー密度は略２１Ｗｈ／Ｌであるが、１０ｍＡ／ｃｍ2 、及び２０ｍＡ／ｃｍ2 のとき、０である。
　図７より、面積抵抗値が３Ω・ｃｍ2 以下である場合、２０ｍＡ／ｃｍ2 のとき、放電エネルギー密度が０を超えることが分かる。
　面積抵抗値の上限値は２Ω・ｃｍ2 であるのが好ましく、１．７Ω・ｃｍ2 であるのがより好ましく、１．５Ω・ｃｍ2 であるのがさらに好ましく、面積抵抗値の下限値は０．１５であるのが好ましく、０．５であるのがより好ましい。 FIG. 7 is a graph showing the relationship between the sheet resistance value of the ion exchange membrane 7 of the example and the ion exchange membrane of the comparative example and the discharge energy density. The horizontal axis represents the sheet resistance [Ω · cm 2 ], and the vertical axis represents the discharge energy density [Wh / L].
2.56mA / cm 2, 10mA / cm 2, 20mA / cm 2 by applying a current at a current density of each shows the result of obtaining discharge energy density could be extracted when fully been charged.
As the current density increases, the discharge energy density that can be extracted decreases.
For Comparative Example 1, when the 2.56mA / cm 2, discharge energy density is substantially the 21Wh / L, 10mA / cm 2 , and when 20 mA / cm 2, is zero.
From FIG. 7, it can be seen that when the sheet resistance value is 3 Ω · cm 2 or less, the discharge energy density exceeds 0 at 20 mA / cm 2 .
Upper limit of the sheet resistivity is preferably a 2Ω · cm 2, more preferably from 1.7 ohm · cm 2, more preferably from 1.5Ω · cm 2, the lower limit of the sheet resistivity is It is preferably 0.15, and more preferably 0.5.
　図８は、実施例のイオン交換膜７の厚みと、エネルギー密度との関係を示すグラフである。横軸は厚み［μｍ］、縦軸はエネルギー密度［Ｗｈ／Ｌ］である。図８中、◇は充電エネルギー密度＠１０ｍＡ／ｃｍ2 、□は放電エネルギー密度＠１０ｍＡ／ｃｍ2 である。
　図８より、実施例１～４の電池１は、１０ｍＡ／ｃｍ2 という高電流密度で電流を流した場合の充電エネルギー密度及び放電エネルギー密度が高いことが分かる。 FIG. 8 is a graph showing the relationship between the thickness of the ion exchange membrane 7 of the example and the energy density. The horizontal axis is the thickness [μm], and the vertical axis is the energy density [Wh / L]. In FIG. 8, ◇ is charging energy density @ 10 mA / cm 2 , and □ is discharging energy density @ 10 mA / cm 2 .
From FIG. 8, it can be seen that the batteries 1 of Examples 1 to 4 have a high charge energy density and discharge energy density when a current is passed at a high current density of 10 mA / cm 2 .
　以上より、本実施の形態に係る電池１は、高電流密度で入出力した場合に良好なエネルギー密度を有し、即ち高入出力化を実現できるとともに、高寿命であり、かつ電圧を長時間維持することができることが確認された。 As described above, the battery 1 according to the present embodiment has a good energy density when input / output is performed at a high current density, that is, can achieve a high input / output, has a long life, and a voltage for a long time. It was confirmed that it can be maintained.
　以上のように、本発明に係るバナジウムレドックス電池は、酸化還元反応によって、５価及び４価の間で酸化数が変化するバナジウムイオン、又は５価及び４価の間で酸化数が変化するバナジウムを含むイオンを含有する正極活物質を含む正の電極材と、酸化還元反応によって、２価及び３価の間で酸化数が変化するバナジウムイオン、又は２価及び３価の間で酸化数が変化するバナジウムを含むイオンを含有する負極活物質を含む負の電極材と、両電極材を区画するプロトン伝導性の隔膜とを有し、前記隔膜は、０．５Ｍ硫酸中で測定した１ｋＨｚにおける体積抵抗率が２８０Ω・ｃｍ以上であり、かつ、面積抵抗値が３Ω・ｃｍ2 以下であることを特徴とする。 As described above, the vanadium redox battery according to the present invention has vanadium ions whose oxidation number changes between pentavalent and tetravalent or vanadium whose oxidation number changes between pentavalent and tetravalent by an oxidation-reduction reaction. A positive electrode material containing a positive electrode active material containing ions containing vanadium and a vanadium ion whose oxidation number changes between divalent and trivalent by an oxidation-reduction reaction, or an oxidation number between divalent and trivalent A negative electrode material containing a negative electrode active material containing ions containing changing vanadium, and a proton-conductive diaphragm separating both electrode materials, the diaphragm at 1 kHz measured in 0.5 M sulfuric acid The volume resistivity is 280 Ω · cm or more and the sheet resistance value is 3 Ω · cm 2 or less.
　本発明においては、電圧を長時間維持することができ、充放電を繰り返した場合の放電電流容量が高く、クーロン効率及び容量維持率が良好であり、サイクル特性が良好である。そして、高電流密度で入出力した場合に良好なエネルギー密度を有し、高入出力密度での使用（高入力化）が可能である。 In the present invention, the voltage can be maintained for a long time, the discharge current capacity when charging and discharging are repeated is high, the coulomb efficiency and the capacity maintenance ratio are good, and the cycle characteristics are good. And when it inputs / outputs at a high current density, it has a favorable energy density and can be used at a high input / output density (higher input).
　本発明に係るバナジウムレドックス電池は、前記体積抵抗率は、６００Ω・ｃｍ以上であることを特徴とする。 The vanadium redox battery according to the present invention is characterized in that the volume resistivity is 600 Ω · cm or more.
　本発明においては、電圧維持率、充放電を繰り返した場合の放電電流容量及び容量維持率がより良好になる。 In the present invention, the voltage maintenance ratio, the discharge current capacity and the capacity maintenance ratio when charging and discharging are repeated become better.
　本発明に係るバナジウムレドックス電池は、前記面積抵抗値は、２Ω・ｃｍ2 以下であることを特徴とする。 The vanadium redox battery according to the present invention is characterized in that the sheet resistance value is 2 Ω · cm 2 or less.
　本発明においては、電流密度を高くした場合の放電エネルギー密度がより高くなる。 In the present invention, the discharge energy density becomes higher when the current density is increased.
　本発明に係るバナジウムレドックス電池は、前記面積抵抗値は、０．１５Ω・ｃｍ2 以上であることを特徴とする。 The vanadium redox battery according to the present invention is characterized in that the sheet resistance value is 0.15 Ω · cm 2 or more.
　本発明においては、充放電を繰り返した場合のクーロン効率がより良好になり、電流密度を高くした場合の放電エネルギー密度がより高くなる。 In the present invention, the Coulomb efficiency when charging and discharging are repeated becomes better, and the discharge energy density becomes higher when the current density is increased.
　本発明に係るバナジウムレドックス電池は、前記隔膜の厚みは、５０μｍ以下であることを特徴とする。 The vanadium redox battery according to the present invention is characterized in that the thickness of the diaphragm is 50 μm or less.
　本発明においては、電流密度を高くした場合の充電エネルギー密度及び放電エネルギー密度が良好である。 In the present invention, the charge energy density and the discharge energy density when the current density is increased are good.
　本発明に係るバナジウムレドックス電池は、前記隔膜は、陰イオン交換膜であることを特徴とする。 The vanadium redox battery according to the present invention is characterized in that the diaphragm is an anion exchange membrane.
　本発明においては、低い膜抵抗値を維持しつつ、イオン選択性が良好である。 In the present invention, the ion selectivity is good while maintaining a low membrane resistance value.
　本発明に係るバナジウムレドックス二次電池の製造方法は、３価のバナジウム化合物と、４価のバナジウム化合物と、炭素材料と、バインダとを混合して混合物を得、該混合物に水系電解液を配合して、混練物を得、該混練物を成形して電極を得、集電体に該電極を配置して電極材を得、一対の前記電極材間に、０．５Ｍ硫酸中で測定した１ｋＨｚにおける体積抵抗率が２８０Ω・ｃｍ以上であり、かつ、面積抵抗値が３Ω・ｃｍ2 以下であるプロトン伝導性の隔膜を介在させた状態で電池を組み立てることを特徴とする。 The manufacturing method of the vanadium redox secondary battery which concerns on this invention mixes a trivalent vanadium compound, a tetravalent vanadium compound, a carbon material, and a binder, obtains a mixture, and mix | blends aqueous electrolyte solution with this mixture Then, a kneaded product was obtained, the kneaded product was molded to obtain an electrode, the electrode was arranged on a current collector to obtain an electrode material, and measurement was performed in 0.5 M sulfuric acid between the pair of electrode materials. The battery is assembled in a state where a proton conductive diaphragm having a volume resistivity at 1 kHz of 280 Ω · cm or more and an area resistance value of 3 Ω · cm 2 or less is interposed.
　本発明においては、得られた電池は、高電流密度で入出力した場合に良好なエネルギー密度を有し、即ち高入出力化を実現できるとともに、高寿命であり、かつ電圧を長時間維持することができる。 In the present invention, the obtained battery has a good energy density when input / output is performed at a high current density, that is, can realize a high input / output, has a long life, and maintains a voltage for a long time. be able to.
　本発明は上述した実施の形態の内容に限定されるものではなく、請求項に示した範囲で種々の変更が可能である。即ち、請求項に示した範囲で適宜変更した技術的手段を組み合わせて得られる実施形態も本発明の技術的範囲に含まれる。
　例えば、バナジウムレドックス二次電池は、一対の電極材を備える場合に限定されず、複数対の電極材を備えることにしてもよい。
　また、シーラント５４、６４を備える場合に限定されない。 The present invention is not limited to the contents of the above-described embodiments, and various modifications can be made within the scope of the claims. That is, embodiments obtained by combining technical means appropriately changed within the scope of the claims are also included in the technical scope of the present invention.
For example, the vanadium redox secondary battery is not limited to the case of including a pair of electrode materials, and may include a plurality of pairs of electrode materials.
Moreover, it is not limited to the case where the sealants 54 and 64 are provided.
　１：バナジウムレドックス二次電池、２：外装袋、３：正極端子、４：負極端子、５，６：電極材、５０，６０：電極、５１，６１：導電体、５２，６２：保護層、５４，６４：シーラント、５５：保水膜、７：隔膜
 
  1: vanadium redox secondary battery, 2: exterior bag, 3: positive electrode terminal, 4: negative electrode terminal, 5, 6: electrode material, 50, 60: electrode, 51, 61: conductor, 52, 62: protective layer, 54, 64: Sealant, 55: Water-retaining film, 7: Diaphragm

Claims (7)

  1. 　酸化還元反応によって、５価及び４価の間で酸化数が変化するバナジウムイオン、又は５価及び４価の間で酸化数が変化するバナジウムを含むイオンを含有する正極活物質を含む正の電極材と、
    　酸化還元反応によって、２価及び３価の間で酸化数が変化するバナジウムイオン、又は２価及び３価の間で酸化数が変化するバナジウムを含むイオンを含有する負極活物質を含む負の電極材と、
    　両電極材を区画するプロトン伝導性の隔膜と
    　を有し、
    　前記隔膜は、
    　０．５Ｍ硫酸中で測定した１ｋＨｚにおける体積抵抗率が２８０Ω・ｃｍ以上であり、かつ、
    　面積抵抗値が３Ω・ｃｍ2 以下であることを特徴とするバナジウムレドックス二次電池。     Positive electrode comprising a positive electrode active material containing vanadium ions whose oxidation number changes between pentavalent and tetravalent or ions containing vanadium whose oxidation number changes between pentavalent and tetravalent by oxidation-reduction reaction Material,
    Negative electrode comprising a negative electrode active material containing vanadium ions whose oxidation number changes between divalent and trivalent by oxidation-reduction reaction, or ions containing vanadium whose oxidation number changes between divalent and trivalent Material,
    A proton-conducting diaphragm that partitions both electrode materials,
    The diaphragm is
    The volume resistivity at 1 kHz measured in 0.5 M sulfuric acid is 280 Ω · cm or more, and
    A vanadium redox secondary battery having a sheet resistance value of 3 Ω · cm 2 or less.
  2. 　前記体積抵抗率は、６００Ω・ｃｍ以上であることを特徴とする請求項１に記載のバナジウムレドックス二次電池。 The vanadium redox secondary battery according to claim 1, wherein the volume resistivity is 600 Ω · cm or more.
  3. 　前記面積抵抗値は、２Ω・ｃｍ2 以下であることを特徴とする請求項１又は２に記載のバナジウムレドックス二次電池。 The vanadium redox secondary battery according to claim 1, wherein the sheet resistance value is 2 Ω · cm 2 or less.
  4. 　前記面積抵抗値は、０．１５Ω・ｃｍ2 以上であることを特徴とする請求項１から３のいずれか１項に記載のバナジウムレドックス二次電池。 4. The vanadium redox secondary battery according to claim 1, wherein the sheet resistance value is 0.15 Ω · cm 2 or more. 5.
  5. 　前記隔膜の厚みは、５０μｍ以下であることを特徴とする請求項１から４のいずれか１項に記載のバナジウムレドックス二次電池。 The vanadium redox secondary battery according to any one of claims 1 to 4, wherein a thickness of the diaphragm is 50 µm or less.
  6. 　前記隔膜は、陰イオン交換膜であることを特徴とする請求項１から５のいずれか１項に記載のバナジウムレドックス二次電池。 The vanadium redox secondary battery according to any one of claims 1 to 5, wherein the diaphragm is an anion exchange membrane.
  7. 　３価のバナジウム化合物と、４価のバナジウム化合物と、炭素材料と、バインダとを混合して混合物を得、
    　該混合物に水系電解液を配合して、混練物を得、
    　該混練物を成形して電極を得、
    　集電体に該電極を配置して電極材を得、
    　一対の前記電極材間に、０．５Ｍ硫酸中で測定した１ｋＨｚにおける体積抵抗率が２８０Ω・ｃｍ以上であり、かつ、面積抵抗値が３Ω・ｃｍ2 以下であるプロトン伝導性の隔膜を介在させた状態で電池を組み立てることを特徴とするバナジウムレドックス二次電池の製造方法。
          Mixing a trivalent vanadium compound, a tetravalent vanadium compound, a carbon material, and a binder to obtain a mixture,
    An aqueous electrolyte solution is blended into the mixture to obtain a kneaded product,
    The kneaded product is molded to obtain an electrode,
    An electrode material is obtained by arranging the electrode on a current collector,
    A proton-conductive membrane having a volume resistivity at 1 kHz measured in 0.5 M sulfuric acid of 280 Ω · cm or more and an area resistance of 3 Ω · cm 2 or less is interposed between the pair of electrode materials. A method for producing a vanadium redox secondary battery, comprising assembling the battery in a wet state.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113782843A (en) * 2021-09-07 2021-12-10 北京阳光鸿志电气工程技术有限公司 Preparation method of solid vanadium battery and obtained solid vanadium battery

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10208767A (en) * 1996-11-22 1998-08-07 Tokuyama Corp Diaphragm for vanadium-based redox flow cell and manufacture thereof
JP2008027627A (en) * 2006-07-18 2008-02-07 Kansai Electric Power Co Inc:The Diaphragm for redox flow battery
JP2015069935A (en) * 2013-09-30 2015-04-13 株式会社 東北テクノアーチ Vanadium solid salt battery
WO2015119272A1 (en) * 2014-02-07 2015-08-13 東洋紡株式会社 Ion-exchange membrane for redox battery, complex, and redox battery
WO2016158217A1 (en) * 2015-03-31 2016-10-06 株式会社東北テクノアーチ Vanadium redox cell

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10208767A (en) * 1996-11-22 1998-08-07 Tokuyama Corp Diaphragm for vanadium-based redox flow cell and manufacture thereof
JP2008027627A (en) * 2006-07-18 2008-02-07 Kansai Electric Power Co Inc:The Diaphragm for redox flow battery
JP2015069935A (en) * 2013-09-30 2015-04-13 株式会社 東北テクノアーチ Vanadium solid salt battery
WO2015119272A1 (en) * 2014-02-07 2015-08-13 東洋紡株式会社 Ion-exchange membrane for redox battery, complex, and redox battery
WO2016158217A1 (en) * 2015-03-31 2016-10-06 株式会社東北テクノアーチ Vanadium redox cell

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DOKYOUNG KIM ET AL.: "Test of ionic exchange membrane for Vanadium redox flow battery", KIST EUROPE ANNUAL REPORT 2013 2013, 23 May 2016 (2016-05-23), pages 89, Retrieved from the Internet <URL:http://www.kist-europe.com/index.php/en/publication/ect-3?task=document.viewdoc&id=80> *
JIAWEI SUN ET AL.: "The transfer behavior of different ions across anion and cation exchange membranes under vanadium flow battery medium", JOURNAL OF POWER SOURCES, vol. 271, 20 December 2014 (2014-12-20), pages 1 - 7, XP029055203, DOI: doi:10.1016/j.jpowsour.2014.07.111 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113782843A (en) * 2021-09-07 2021-12-10 北京阳光鸿志电气工程技术有限公司 Preparation method of solid vanadium battery and obtained solid vanadium battery
CN113782843B (en) * 2021-09-07 2024-01-05 北京阳光鸿志电气工程技术有限公司 Preparation method of solid vanadium battery and obtained solid vanadium battery

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