JP2008041421A - Secondary battery - Google Patents

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JP2008041421A
JP2008041421A JP2006214085A JP2006214085A JP2008041421A JP 2008041421 A JP2008041421 A JP 2008041421A JP 2006214085 A JP2006214085 A JP 2006214085A JP 2006214085 A JP2006214085 A JP 2006214085A JP 2008041421 A JP2008041421 A JP 2008041421A
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secondary battery
electrode
negative electrode
positive electrode
sulfuric acid
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Yasuyuki Nukina
康之 貫名
Shinichi Nakajima
信市 中島
Taketoshi Sato
武年 佐藤
Tomotaka Nobue
等隆 信江
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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    • 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
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a secondary battery with high economic efficiency. <P>SOLUTION: The secondary battery is provided with a battery part 12 including a positive electrode 2, a negative electrode 1, and a diaphragm 3 provided between the positive electrode 2 and negative electrode 1, and the same sulfuric acid solutions are filled between the positive electrode 2 and diaphragm 3 and between the negative electrode 1 and diaphragm 3 of the battery part 12, respectively. Thereby, the sulfuric acid solution as an electrolyte solution can be varied in valency greatly without solubility limitation, has large energy density, is inexpensive, and provides high economic efficiency. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、電力エネルギーを貯留する二次電池に関するものである。   The present invention relates to a secondary battery that stores electric power energy.

二次電池の一つにレドックスフロー電池がある。レドックスフロー電池とは、鉄の２価と３価の陽イオンのように複数のイオン価をもち、異なる酸化還元状態をとる、所謂レドックスイオンの溶液を電解質溶液として、貯留槽から流通型電解槽に送り込んで使用するものを言う。レドックスイオンとしては鉄、クロム、バナジウム、チタンなどが検討され、そのうちバナジウムでは大型の装置が実用化された。通常、多くの二次電池の電極活物質が固体で電池内に封入されるのに対し、レドックスフロー電池の電極活物質は液体である電解質溶液である。   One of the secondary batteries is a redox flow battery. A redox flow battery is a so-called redox ion solution having a plurality of ionic valences, such as iron divalent and trivalent cations, and taking different oxidation-reduction states, as an electrolytic solution from a storage tank to a flow-through electrolytic tank. Say what you use. As redox ions, iron, chromium, vanadium, titanium, and the like have been studied. Among them, a large apparatus has been put to practical use in vanadium. Usually, the electrode active material of many secondary batteries is solid and enclosed in the battery, whereas the electrode active material of a redox flow battery is a liquid electrolyte solution.

従来から知られているオールバナジウムレドックスフロー電池（例えば、特許文献１参照）を図３に例示した。   A conventionally known albanadium redox flow battery (see, for example, Patent Document 1) is illustrated in FIG.

これは、図のように、正極３０と負極３１は、等しい電荷の授受を行うものである。従って、充電時、正極３０側の電解質溶液ではバナジウムは４価から５価となり、これと同時に負極３１側の電解質溶液ではバナジウムは３価から２価となる。また、放電時、正極３０側の電解質溶液ではバナジウムは５価から４価となり、これと同時に負極３１側の電解質溶液ではバナジウムは２価から３価となる。さらに、正極３０側と負極３１側の電解質溶液はイオン交換膜３２で仕切られ、両側の電解質溶液が混合して、価数が中和されて電力が失われることを防止している。また、貯留槽３３、３４、ポンプ３６、３７を設けており、貯留槽３３、３４を大きく設定して巨大な電力を蓄えることができ、単純な構成ゆえにサイクル寿命が長くまた保守管理が容易であるなどの優れた特長がある。
特開平６−１８８００５号公報 As shown in the figure, the positive electrode 30 and the negative electrode 31 transfer and receive equal charges. Therefore, at the time of charging, vanadium is changed from tetravalent to pentavalent in the electrolyte solution on the positive electrode 30 side, and at the same time, vanadium is changed from trivalent to divalent in the electrolyte solution on the negative electrode 31 side. Further, at the time of discharge, vanadium becomes pentavalent to tetravalent in the electrolyte solution on the positive electrode 30 side, and at the same time, vanadium becomes divalent to trivalent in the electrolyte solution on the negative electrode 31 side. Further, the electrolyte solution on the positive electrode 30 side and the negative electrode 31 side is partitioned by an ion exchange membrane 32, and the electrolyte solutions on both sides are mixed to prevent the valence from being neutralized and the loss of power. In addition, the storage tanks 33 and 34 and the pumps 36 and 37 are provided, and the storage tanks 33 and 34 can be set large to store a huge amount of electric power. Because of the simple configuration, the cycle life is long and maintenance management is easy. There are excellent features such as.
JP-A-6-188005

しかしながら、前記従来の構成では、バナジウムなどの電極活物質の溶解度制限があるためにエネルギー密度が低く大きな貯留槽３３、３４を要し、また電極反応が遅いために電池部３５も大きくなり、さらに電解質のバナジウムは高価であり、決して十分な経済性を持つものではなかった。   However, in the conventional configuration, the solubility of the electrode active material such as vanadium is limited, so that the energy density is low and the large storage tanks 33 and 34 are required. Further, the electrode reaction is slow, and the battery unit 35 is also large. The electrolyte vanadium was expensive and never economically sufficient.

本発明は、前記従来の課題を解決するもので、高い経済性を持つことができる二次電池を提供することを目的とする。   The present invention solves the above-described conventional problems, and an object thereof is to provide a secondary battery that can have high economic efficiency.

前記従来の課題を解決するために、本発明の二次電池は、正極および負極と、正極、負極の間に設けた隔膜とを有する電池部を備え、この電池部の正極と隔膜の間、負極と隔膜の間にそれぞれ同一の硫酸溶液を充填したものである。   In order to solve the conventional problems, the secondary battery of the present invention includes a battery unit having a positive electrode and a negative electrode, and a diaphragm provided between the positive electrode and the negative electrode, and between the positive electrode and the diaphragm of the battery unit, The same sulfuric acid solution is filled between the negative electrode and the diaphragm.

これによって、電解質溶液としての硫酸溶液は溶解度の制限がなく価数変化が大きくとれ、エネルギー密度の大きい、安価なものであり、高い経済性を持つことができる。   As a result, the sulfuric acid solution as the electrolyte solution is not limited in solubility, can have a large valence change, has a large energy density, is inexpensive, and can be highly economical.

本発明の二次電池は、電解質溶液として硫酸溶液を用い高い経済性を持つものである。   The secondary battery of the present invention uses a sulfuric acid solution as an electrolyte solution and has high economic efficiency.

第１の発明は、正極および負極と、正極、負極の間に設けた隔膜とを有する電池部を備え、この電池部の正極と隔膜の間、負極と隔膜の間にそれぞれ同一の硫酸溶液を充填した二次電池とすることにより、電解質溶液としての硫酸溶液は溶解度の制限がなく価数変化が大きくとれ、エネルギー密度の大きい、安価なものであり、高い経済性を持つことができる。   1st invention is equipped with the battery part which has a positive electrode and a negative electrode, and the diaphragm provided between the positive electrode and the negative electrode, and the same sulfuric acid solution is respectively provided between the positive electrode and the diaphragm of this battery part, and between the negative electrode and the diaphragm. By using a filled secondary battery, the sulfuric acid solution as the electrolyte solution has no limitation on solubility, can have a large valence change, has a high energy density, is inexpensive, and can be highly economical.

第２の発明は、特に、第１の発明において、電池部の外に貯留槽を設け、送液装置を用いて貯留槽と電池部の間で硫酸溶液を循環することにより、外部の蓄電容量を含めて大きな蓄電容量を実現することができる。   In particular, according to a second invention, in the first invention, an external storage capacity is provided by providing a storage tank outside the battery unit and circulating a sulfuric acid solution between the storage tank and the battery unit using a liquid feeding device. In addition, a large storage capacity can be realized.

第３の発明は、特に、第１の発明において、隔膜を陽イオン交換膜としたことにより、導電性を確保してイオン移動を容易にし、電極反応を促進することができる。   In the third invention, in particular, by using a cation exchange membrane as the diaphragm in the first invention, it is possible to ensure conductivity, facilitate ion movement, and promote an electrode reaction.

第４の発明は、特に、第１または第２の発明において、正極、負極を多孔質炭素電極とし、硫酸溶液を多孔質炭素電極内の間隙内に存在させることにより、硫酸溶液と電極との接触面積を大きくとり、反応面積を拡大して電極反応を促進することができる。   In particular, according to the fourth invention, in the first or second invention, the positive electrode and the negative electrode are made of porous carbon electrodes, and the sulfuric acid solution is present in the gaps in the porous carbon electrode. The electrode reaction can be promoted by increasing the contact area and expanding the reaction area.

第５の発明は、特に、第４の発明において、正極、負極の多孔質炭素電極を硫酸溶液中に加熱浸漬し、隔膜の陽イオン交換膜に圧着したことにより、多孔質炭素電極と陽イオン交換膜との間隙の導電性を確保してイオン移動を容易にし、電極反応を促進することができる。   In particular, in the fifth invention, the porous carbon electrode and the cation are obtained by heating and immersing the positive and negative porous carbon electrodes in a sulfuric acid solution and press-bonding them to the cation exchange membrane of the diaphragm. The conductivity of the gap with the exchange membrane can be ensured to facilitate ion movement and promote the electrode reaction.

第６の発明は、特に、第１、第４、第５のいずれか１つの発明において、正極に金を添着したことにより、電極反応を促進することができる。   In the sixth invention, in particular, in any one of the first, fourth, and fifth inventions, the electrode reaction can be promoted by adding gold to the positive electrode.

第７の発明は、特に、第１、第４、第５のいずれか１つの発明において、負極に銅、銀、白金、パラジウム、金のいずれかを添着したことにより、電極反応を促進することができる。   The seventh invention promotes the electrode reaction by attaching any of copper, silver, platinum, palladium, and gold to the negative electrode in any one of the first, fourth, and fifth inventions. Can do.

第８の発明は、特に、第１、第２、第４〜第６のいずれか１つの発明において、正極、負極の多孔質炭素電極に磁性体を添着したことにより、イオン移動を容易にし、電極反応を促進することができる。   In an eighth aspect of the invention, in particular, in any one of the first, second, and fourth to sixth aspects of the invention, by attaching a magnetic substance to the positive and negative porous carbon electrodes, ion migration is facilitated, The electrode reaction can be promoted.

以下、本発明の実施の形態について、図面を参照しながら説明する。なお、この実施の形態によって本発明が限定されるものではない。   Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the present invention is not limited to the embodiments.

（実施の形態１）
図１は、本発明の実施の形態１における二次電池を示すものである。 (Embodiment 1)
FIG. 1 shows a secondary battery according to Embodiment 1 of the present invention.

図に示すように、多孔質炭素材料であるカーボンフェルト製の負極１と正極２は、負極１と正極２間に設けた陽イオン交換膜製の隔膜３を挟んで対向し、電池部１２を構成する。負極１と正極２の多孔質炭素材料内の間隙は、初期状態において硫酸と水の混合溶液が充填され、硫酸溶液は循環路４、５で連通して、それぞれ負極側電解質タンク６と正極側電解質タンク７とに接続され、負極側ポンプ８と正極側ポンプ９とにより電池部１２の正極２と隔膜３の間、負極１と隔膜３の間にそれぞれ充填され、電極とタンクの間を循環する。なお、負極１と正極２にはそれぞれ集電体１０、１１を設けている。   As shown in the figure, a negative electrode 1 and a positive electrode 2 made of carbon felt, which are porous carbon materials, face each other with a diaphragm 3 made of a cation exchange membrane provided between the negative electrode 1 and the positive electrode 2, and the battery unit 12 is Constitute. The gap between the negative electrode 1 and the positive electrode 2 in the porous carbon material is filled with a mixed solution of sulfuric acid and water in the initial state, and the sulfuric acid solution is communicated with the circulation paths 4 and 5, respectively. It is connected to the electrolyte tank 7 and is filled between the positive electrode 2 and the diaphragm 3 of the battery unit 12 and between the negative electrode 1 and the diaphragm 3 by the negative electrode side pump 8 and the positive electrode side pump 9 and circulates between the electrode and the tank. To do. Note that current collectors 10 and 11 are provided on the negative electrode 1 and the positive electrode 2, respectively.

次に、二次電池の充放電時の動作について説明する。   Next, the operation during charging / discharging of the secondary battery will be described.

充電時には、負極１に負電位を、正極２に正電位を外部電源（図示せず）から印加する。これにより負極１の材質表面で、負極１から電子を与えて、（化１）に示す硫酸から亜硫酸の生成を行わせる。   During charging, a negative potential is applied to the negative electrode 1 and a positive potential is applied to the positive electrode 2 from an external power source (not shown). Thus, electrons are applied from the negative electrode 1 on the material surface of the negative electrode 1 to generate sulfurous acid from the sulfuric acid shown in (Chemical Formula 1).

正極２表面では、正極２が電子を受け取って（化２）に示す硫酸から過硫酸の生成を行わせる。   On the surface of the positive electrode 2, the positive electrode 2 receives electrons and generates persulfuric acid from the sulfuric acid shown in (Chemical Formula 2).

正極２で（化２）に従い生成する水素イオンは、隔膜３を越えて負極１側に移行し、（化１）の反応により消費される。   Hydrogen ions generated according to (Chemical Formula 2) at the positive electrode 2 move to the negative electrode 1 side beyond the diaphragm 3 and are consumed by the reaction of (Chemical Formula 1).

放電時には、負極１と正極２の間に外部負荷（図示せず）を接続する。これにより負極１表面で、（化３）に示す亜硫酸から硫酸の生成を行わせ負極１が電子を受け取り初期状態となる。   At the time of discharging, an external load (not shown) is connected between the negative electrode 1 and the positive electrode 2. As a result, sulfuric acid is generated from the sulfurous acid shown in (Chemical Formula 3) on the surface of the negative electrode 1 so that the negative electrode 1 receives electrons and enters an initial state.

正極２表面では、（化４）に示す過硫酸から硫酸の生成を行わせ正極２から電子を与える。   On the surface of the positive electrode 2, sulfuric acid is generated from the persulfuric acid shown in (Chemical Formula 4) and electrons are given from the positive electrode 2.

負極１で（化３）に従い生成する水素イオンは、隔膜３を越えて正極２側に移行し、（化４）の反応により消費される。正極２、負極１で授受した電子は、外部の負荷回路を流れる。   Hydrogen ions generated in the negative electrode 1 according to (Chemical Formula 3) move to the positive electrode 2 side beyond the diaphragm 3 and are consumed by the reaction (Chemical Formula 4). Electrons exchanged at the positive electrode 2 and the negative electrode 1 flow through an external load circuit.

（化１）（化３）の平衡電位が１．５Ｖ付近にある。また、（化２）（化４）の平衡電位が０．１６Ｖ付近にあり、１．３Ｖ付近で動作する二次電池である。これはオールバナジウムレドックスフロー電池１．４７Ｖよりやや低い。   The equilibrium potential of (Chemical Formula 1) and (Chemical Formula 3) is around 1.5V. Further, the equilibrium potential of (Chemical Formula 2) and (Chemical Formula 4) is around 0.16V, and the secondary battery operates at around 1.3V. This is slightly lower than the Albana redox flow battery 1.47V.

本実施の形態の二次電池では、常態が液体である硫酸を用いるために溶解度の制限がない。バナジウムの溶解度制限があるオールバナジウムレドックスフロー電池に比較して、モル濃度で８倍程度の高濃度が取りえる。さらに、オールバナジウムレドックスフロー電池では、正極２側、負極１側のそれぞれでバナジウムは１価の変化であるが、本実施の形態の二次電池では、正極２側２価、負極１側２価の変化であり、２倍の価数変化がある。両者を合わせて１６倍程度、蓄電の電荷密度を高く取りえる。このため、起電力と電荷密度の積で定まるエネルギー密度は大きくとれ、同じ充電容量では小さく安価な二次電池ができる。さらに、硫黄はバナジウムに比べ地殻の存在量が遥かに多い元素であり、流通量も多く安価である。   In the secondary battery of this embodiment, there is no limitation on solubility because sulfuric acid, which is normally liquid, is used. Compared with an all vanadium redox flow battery in which the solubility of vanadium is limited, a high concentration of about 8 times in molar concentration can be obtained. Further, in the allavana redox flow battery, vanadium is a monovalent change on each of the positive electrode 2 side and the negative electrode 1 side, but in the secondary battery of this embodiment, the positive electrode 2 side divalent and the negative electrode 1 side divalent. There is a valence change of 2 times. The total charge density of the battery can be increased by about 16 times. For this reason, the energy density determined by the product of the electromotive force and the charge density can be increased, and a small and inexpensive secondary battery can be produced with the same charge capacity. Furthermore, sulfur is an element that has a much larger amount of crust than vanadium, and has a large circulation and is inexpensive.

このように、本実施の形態の二次電池は、高いエネルギー密度と経済性を得ることができるものである。   Thus, the secondary battery of this embodiment can obtain a high energy density and economy.

（実施の形態２）
次に、本発明の実施の形態２における二次電池について説明する。二次電池の構成については実施の形態１と同じであるのでその説明を省略する。 (Embodiment 2)
Next, the secondary battery according to Embodiment 2 of the present invention will be described. Since the configuration of the secondary battery is the same as that of Embodiment 1, the description thereof is omitted.

本実施の形態における二次電池の特徴は、電池部１２の外に負極側電解質タンク６、正極側電解質タンク７である貯留槽を設け、負極側ポンプ８、正極側ポンプ９である送液装置を用いて、貯留槽と電池部１２の間で硫酸溶液を循環するようにしたことである。   A feature of the secondary battery in the present embodiment is that a storage tank which is a negative electrode side electrolyte tank 6 and a positive electrode side electrolyte tank 7 is provided outside the battery unit 12, and a liquid feeding device which is a negative electrode side pump 8 and a positive electrode side pump 9. Is used to circulate the sulfuric acid solution between the storage tank and the battery unit 12.

このように、二次電池の電池部１２の外に貯留槽を設け、送液装置を用いて、貯留槽と電池部の間で硫酸溶液を循環することにより、硫酸溶液の大きな蓄電容量が電池部１２の外に増設され、外部の蓄電容量を含めて大きな蓄電容量を実現することができる。   Thus, a storage tank is provided outside the battery unit 12 of the secondary battery, and the sulfuric acid solution is circulated between the storage tank and the battery unit using the liquid feeding device, so that a large storage capacity of the sulfuric acid solution can be obtained. It is added outside the unit 12, and a large storage capacity including an external storage capacity can be realized.

（実施の形態３）
次に、本発明の実施の形態３における二次電池について説明する。二次電池の構成については実施の形態１と同じであるのでその説明を省略する。 (Embodiment 3)
Next, the secondary battery according to Embodiment 3 of the present invention will be described. Since the configuration of the secondary battery is the same as that of Embodiment 1, the description thereof is omitted.

本実施の形態における二次電池の特徴は、隔膜３を陽イオン交換膜としたことである。   The feature of the secondary battery in the present embodiment is that the diaphragm 3 is a cation exchange membrane.

実施の形態１の（化１）〜（化４）に示すように、硫酸電解質の電極反応に従い、陽イオンである水素イオンが両極１、２間を往来する。陽イオン交換膜である隔膜３は、多孔質フィルムの隔膜に比して、陽イオンである水素イオンの透過性に優れる。硫酸溶液の電気抵抗は１００マイクロメートル厚みで、１平方センチメートル当たり約２オームとかなり大きな抵抗を持つ。多孔質フィルムの隔膜では、十分な間隙率を持つ膜であっても、多孔質フィルムに含まれる、硫酸溶液の抵抗になり、大きな抵抗になる。   As shown in (Chemical Formula 1) to (Chemical Formula 4) of the first embodiment, hydrogen ions that are cations travel between the two electrodes 1 and 2 in accordance with the electrode reaction of the sulfuric acid electrolyte. The diaphragm 3, which is a cation exchange membrane, is superior in permeability of hydrogen ions, which are cations, as compared to a porous film. The electrical resistance of the sulfuric acid solution is 100 micrometers thick and has a fairly large resistance of about 2 ohms per square centimeter. In the case of a porous film diaphragm, even a film having a sufficient porosity becomes the resistance of the sulfuric acid solution contained in the porous film, resulting in a large resistance.

このように、隔膜３を陽イオン交換膜としたことにより、１平方センチメートル当たり約０．２から１オームほどであり、導電性を確保してイオン移動を容易にし、電極反応を促進することができる。   Thus, by making the diaphragm 3 into a cation exchange membrane, it is about 0.2 to 1 ohm per 1 square centimeter, can ensure electroconductivity, facilitate ion movement, and can promote an electrode reaction. .

（実施の形態４）
次に、本発明の実施の形態４における二次電池について説明する。二次電池の構成については実施の形態１と同じであるのでその説明を省略する。 (Embodiment 4)
Next, a secondary battery according to Embodiment 4 of the present invention will be described. Since the configuration of the secondary battery is the same as that of Embodiment 1, the description thereof is omitted.

本実施の形態における二次電池の特徴は、正極２、負極１を多孔質炭素電極とし、硫酸溶液を多孔質炭素電極内の間隙内に存在させることである。   The feature of the secondary battery in the present embodiment is that the positive electrode 2 and the negative electrode 1 are porous carbon electrodes, and the sulfuric acid solution is present in the gaps in the porous carbon electrode.

このように、正極、負極を多孔質炭素電極とし、硫酸溶液を多孔質炭素電極内の間隙内に存在させることにより、板状の電極に比べて硫酸溶液と電極との接触面積を大きく取ることができる。このため電極反応面積が拡大して、電極反応を促進することができる。   Thus, by making the positive electrode and the negative electrode porous carbon electrodes and making the sulfuric acid solution exist in the gaps in the porous carbon electrode, the contact area between the sulfuric acid solution and the electrode can be made larger than that of the plate-like electrode. Can do. For this reason, an electrode reaction area can be expanded and an electrode reaction can be promoted.

（実施の形態５）
次に、本発明の実施の形態５における二次電池について説明する。二次電池の構成については実施の形態１と同じであるのでその説明を省略する。 (Embodiment 5)
Next, a secondary battery according to Embodiment 5 of the present invention will be described. Since the configuration of the secondary battery is the same as that of Embodiment 1, the description thereof is omitted.

本実施の形態における二次電池の特徴は、正極２、負極１の多孔質炭素電極を予め硫酸溶液中に加熱浸漬し、圧搾して硫酸を切る。その後、正極２、負極１の間に隔膜３の陽イオン交換膜を挟み、プレス機にかけて圧着したことである。   A feature of the secondary battery in the present embodiment is that the porous carbon electrodes of the positive electrode 2 and the negative electrode 1 are preliminarily heated and immersed in a sulfuric acid solution, and pressed to cut off sulfuric acid. After that, the cation exchange membrane of the diaphragm 3 was sandwiched between the positive electrode 2 and the negative electrode 1 and was pressed by a press machine.

このように、加熱浸漬、圧着により、多孔質炭素電極と陽イオン交換膜との間隙の導電性を確保してイオン移動を容易にし、電極反応を促進することができる。   Thus, heat immersion and pressure bonding ensure the conductivity of the gap between the porous carbon electrode and the cation exchange membrane, facilitate ion movement, and promote the electrode reaction.

（実施の形態６）
次に、本発明の実施の形態６における二次電池について説明する。二次電池の構成については実施の形態１と同じであるのでその説明を省略する。 (Embodiment 6)
Next, a secondary battery according to Embodiment 6 of the present invention will be described. Since the configuration of the secondary battery is the same as that of Embodiment 1, the description thereof is omitted.

本実施の形態における二次電池の特徴は、多孔質炭素電極である正極２に金を添着したことである。   The feature of the secondary battery in the present embodiment is that gold is attached to the positive electrode 2 which is a porous carbon electrode.

金は充電時の（化４）の反応、放電時の（化５）の反応に対し触媒的に働き、電極反応を促進する。   Gold acts as a catalyst for the reaction of (Chemical Formula 4) at the time of charging and the reaction of (Chemical Formula 5) at the time of discharging, and promotes the electrode reaction.

さらに、金は酸素発生の過電圧が大きく、充電時の副反応である（化６）の水から酸素を発生する反応が実用的充電電圧では起きず、電力のロスが少ない。   Furthermore, gold has a large overvoltage for oxygen generation, and a reaction for generating oxygen from water (chemical formula 6), which is a side reaction at the time of charging, does not occur at a practical charging voltage, and power loss is small.

多孔質炭素電極への金の添着には、各種の方法が可能である。四塩化金アルコール溶液をカーボンフェルトに吸わせ、空気を絶って加熱する方法、四塩化金を吸わせたカーボンフェルトにアルカリ性のホルムアルデヒド溶液を加えて、金を析出させる方法、四塩化金から電気メッキをする方法などである。   Various methods can be used to attach gold to the porous carbon electrode. A method of sucking gold tetrachloride alcohol solution into carbon felt and heating it out of air, a method of depositing gold by adding alkaline formaldehyde solution to carbon felt sucked with gold tetrachloride, electroplating from gold tetrachloride It is a method to do.

このように、正極２に金を添着したことにより、電極反応を促進することができる。   Thus, the electrode reaction can be promoted by attaching gold to the positive electrode 2.

（実施の形態７）
次に、本発明の実施の形態７における二次電池について説明する。二次電池の構成については実施の形態１と同じであるのでその説明を省略する。 (Embodiment 7)
Next, the secondary battery according to Embodiment 7 of the present invention will be described. Since the configuration of the secondary battery is the same as that of Embodiment 1, the description thereof is omitted.

本実施の形態における二次電池の特徴は、多孔質炭素電極である負極１に銅、銀、白金、パラジウム、金のいずれかを添着したことである。   A feature of the secondary battery in the present embodiment is that any one of copper, silver, platinum, palladium, and gold is attached to the negative electrode 1 that is a porous carbon electrode.

銅、銀、白金、パラジウム、金は充電時の（化１）の反応、放電時の（化３）の反応に対し触媒的に働き、電極反応を促進する。さらに、銅、銀、白金、パラジウム、金は亜硫酸の存在する負極側では硫酸に溶解せず耐久性を有する。   Copper, silver, platinum, palladium, and gold act as a catalyst for the reaction of (Chemical Formula 1) during charging and the reaction of (Chemical Formula 3) during discharge to promote the electrode reaction. Further, copper, silver, platinum, palladium, and gold do not dissolve in sulfuric acid on the negative electrode side where sulfurous acid exists, and have durability.

カーボンフェルトへの銅、銀、白金、パラジウム、金の添着には、各種の方法が可能である。塩のアルコール溶液をカーボンフェルトに吸わせ、空気を絶って加熱する方法、塩を吸わせたカーボンフェルトにアルカリ性のホルムアルデヒド溶液を加えて、析出させる方法、塩から電気メッキをする方法などである。   Various methods can be used to attach copper, silver, platinum, palladium, and gold to the carbon felt. There are a method in which an alcohol solution of salt is sucked into a carbon felt and the air is cut off and heated, a method in which an alkaline formaldehyde solution is added to the carbon felt soaked in salt and deposited, and a method in which electroplating is performed from the salt.

このように、負極１に銅、銀、白金、パラジウム、金のいずれかを添着したことにより、電極反応を促進することができる。   Thus, the electrode reaction can be promoted by attaching any of copper, silver, platinum, palladium, and gold to the negative electrode 1.

（実施の形態８）
次に、本発明の実施の形態８における二次電池について説明する。二次電池の構成については実施の形態１と同じであるのでその説明を省略する。 (Embodiment 8)
Next, a secondary battery according to Embodiment 8 of the present invention will be described. Since the configuration of the secondary battery is the same as that of Embodiment 1, the description thereof is omitted.

本実施の形態における二次電池の特徴は、正極２、負極１の多孔質炭素電極に磁性体を添着したことである。   A feature of the secondary battery in the present embodiment is that a magnetic material is attached to the porous carbon electrodes of the positive electrode 2 and the negative electrode 1.

上記構成において、多孔質炭素電極中の電流の流れについて図２を用いて説明する。   In the above configuration, the flow of current in the porous carbon electrode will be described with reference to FIG.

図において、多孔質炭素電極中のカーボン繊維２１の周囲は硫酸溶液２２である。カーボン繊維２１中を電子の流れ２３が電流を運ぶ。この電子の流れ２３に対して相補的にカーボン繊維２１の表面付近の硫酸溶液２２中では、水素イオンの流れ２４が電流を運ぶ。この場合、電子の流れ２３と水素イオンの流れ２４を結びつけるものは、電流に対し右ネジ方向にできる磁場２５である。   In the figure, the sulfuric acid solution 22 surrounds the carbon fiber 21 in the porous carbon electrode. An electron flow 23 carries an electric current through the carbon fiber 21. In the sulfuric acid solution 22 near the surface of the carbon fiber 21 in a complementary manner to the electron flow 23, the hydrogen ion flow 24 carries an electric current. In this case, what connects the electron flow 23 and the hydrogen ion flow 24 is a magnetic field 25 that can be formed in a right-handed direction with respect to the current.

しかしながら、硫酸溶液２２は小さな負の透磁率をもち、相補的な電流を誘起する効果はない。これに対し、本実施の形態では、多孔質炭素電極に磁性体を添着することにより、カーボン繊維２１の周囲に大きな透磁率を持たせる。これにより、磁場２５は強くなり、大きな水素イオンの流れ２４を作り出すことができ、イオン移動が容易になり電極反応が促進される。   However, the sulfuric acid solution 22 has a small negative permeability and has no effect of inducing a complementary current. On the other hand, in the present embodiment, a magnetic material is attached to the porous carbon electrode to give a large magnetic permeability around the carbon fiber 21. As a result, the magnetic field 25 is strengthened, and a large flow 24 of hydrogen ions can be created, which facilitates ion movement and promotes the electrode reaction.

このように、正極２、負極１の多孔質炭素電極に磁性体を添着したことにより、イオン移動を容易にし、電極反応を促進することができ、電池部１２の小型化がはかれるものである。   Thus, by attaching a magnetic substance to the porous carbon electrodes of the positive electrode 2 and the negative electrode 1, ion migration can be facilitated and the electrode reaction can be promoted, and the battery unit 12 can be reduced in size.

以上のように、本発明にかかる二次電池は、電解質溶液として硫酸溶液を用い高い経済性を持つものであるので、各種の機器や装置に適用できるものである。   As described above, since the secondary battery according to the present invention uses a sulfuric acid solution as an electrolyte solution and has high economic efficiency, it can be applied to various devices and apparatuses.

本発明の実施の形態１〜８における二次電池の構成図Configuration diagram of secondary battery in Embodiments 1 to 8 of the present invention 本発明の実施の形態８における多孔質炭素電極中の電流流れの説明図Explanatory drawing of the electric current flow in the porous carbon electrode in Embodiment 8 of this invention 従来のオールバナジウムレドックスフロー電池の構成図Configuration of conventional albanadium redox flow battery

符号の説明Explanation of symbols

１ 負極
２ 正極
３ 隔膜
４、５ 循環路
６ 負極側電解質タンク（貯留槽）
７ 正極側電解質タンク（貯留槽）
８ 負極側ポンプ（送液装置）
９ 正極側ポンプ（送液装置）
１２ 電池部 DESCRIPTION OF SYMBOLS 1 Negative electrode 2 Positive electrode 3 Diaphragm 4, 5 Circulation path 6 Negative electrode side electrolyte tank (storage tank)
7 Positive electrolyte tank (storage tank)
8 Negative side pump (liquid feeding device)
9 Positive side pump (liquid feeding device)
12 Battery section

Claims (8)

正極および負極と、正極、負極の間に設けた隔膜とを有する電池部を備え、この電池部の正極と隔膜の間、負極と隔膜の間にそれぞれ同一の硫酸溶液を充填した二次電池。 A secondary battery comprising a battery part having a positive electrode and a negative electrode, and a diaphragm provided between the positive electrode and the negative electrode, and the same sulfuric acid solution filled between the positive electrode and the diaphragm of the battery part and between the negative electrode and the diaphragm. 電池部の外に貯留槽を設け、送液装置を用いて貯留槽と電池部の間で硫酸溶液を循環する請求項１に記載の二次電池。 The secondary battery according to claim 1, wherein a storage tank is provided outside the battery unit, and the sulfuric acid solution is circulated between the storage tank and the battery unit using a liquid feeding device. 隔膜を陽イオン交換膜とした請求項１に記載の二次電池。 The secondary battery according to claim 1, wherein the diaphragm is a cation exchange membrane. 正極、負極を多孔質炭素電極とし、硫酸溶液を多孔質炭素電極内の間隙内に存在させる請求項１または２に記載の二次電池。 The secondary battery according to claim 1, wherein the positive electrode and the negative electrode are porous carbon electrodes, and the sulfuric acid solution is present in a gap in the porous carbon electrode. 正極、負極の多孔質炭素電極を硫酸溶液中に加熱浸漬し、隔膜の陽イオン交換膜に圧着した請求項４に記載の二次電池。 The secondary battery according to claim 4, wherein the porous carbon electrodes of the positive electrode and the negative electrode are heated and immersed in a sulfuric acid solution and pressure-bonded to the cation exchange membrane of the diaphragm. 正極に金を添着した請求項１、４、５のいずれか１項に記載の二次電池。 The secondary battery according to claim 1, wherein gold is attached to the positive electrode. 負極に銅、銀、白金、パラジウム、金のいずれかを添着した請求項１、４、５のいずれか１項に記載の二次電池。 The secondary battery according to claim 1, wherein any of copper, silver, platinum, palladium, and gold is attached to the negative electrode. 正極、負極の多孔質炭素電極に磁性体を添着した請求項１、２、４〜６のいずれか１項に記載の二次電池。 7. The secondary battery according to claim 1, wherein a magnetic material is attached to the porous carbon electrodes of the positive electrode and the negative electrode.
JP2006214085A 2006-08-07 2006-08-07 Secondary battery Pending JP2008041421A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015176648A (en) * 2014-03-13 2015-10-05 旭化成イーマテリアルズ株式会社 Electrode layer with resin, electrode composite body with resin, and redox flow secondary battery
JP2017091617A (en) * 2015-11-02 2017-05-25 旭化成株式会社 Carbon felt, secondary battery, and method of producing carbon felt
KR101846363B1 (en) * 2016-10-24 2018-05-18 인천대학교 산학협력단 Preparation method of 3d graphene electrode for supercapacitor using spray discharge
CN117558957A (en) * 2024-01-11 2024-02-13 西南石油大学 Flow battery system for magnetically managing paramagnetic reaction ions and performance improvement method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015176648A (en) * 2014-03-13 2015-10-05 旭化成イーマテリアルズ株式会社 Electrode layer with resin, electrode composite body with resin, and redox flow secondary battery
JP2017091617A (en) * 2015-11-02 2017-05-25 旭化成株式会社 Carbon felt, secondary battery, and method of producing carbon felt
KR101846363B1 (en) * 2016-10-24 2018-05-18 인천대학교 산학협력단 Preparation method of 3d graphene electrode for supercapacitor using spray discharge
CN117558957A (en) * 2024-01-11 2024-02-13 西南石油大学 Flow battery system for magnetically managing paramagnetic reaction ions and performance improvement method
CN117558957B (en) * 2024-01-11 2024-03-15 西南石油大学 Flow battery system for magnetically managing paramagnetic reaction ions and performance improvement method

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