JP2015219984A - Electrical device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrical device capable of preventing temperature rise due to generation of hydrogen gas from being caused by inhibiting hydrogen gas generated from a power generation element constituting a battery from being reacted with oxygen.SOLUTION: An electrical device 10 includes: a first exterior member 21 which forms a sealed first closed space 51; a bipolar type secondary battery 100 which is constituted by stacking each of a plurality of positive electrodes 112, negative electrodes 113, and electrolyte layers 114 interposed between the positive electrode and the negative electrode and which includes a power generation element 110 arranged in a first closed space; and a hydrogen adsorption part 60 which absorbs hydrogen gas generated from the power generation element.

Description

  The present invention relates to an electrical device comprising a power generating element.

  Electric devices that can be charged and discharged, such as batteries, are widely used in various fields. The battery includes various compounds as its constituent materials. When charging / discharging or the like is repeatedly performed during use of the battery, the constituent material may cause a chemical reaction to generate various gases. Further, when the temperature rises due to the generation of gas and warming the battery, there arises a problem that the cycle characteristics of the battery and the charge / discharge characteristics are degraded.

  For example, in the battery described in Patent Document 1, attention is paid to the problem that when the electrolyte is decomposed as the battery temperature rises due to an internal short circuit or the like, the cycle characteristics and charge / discharge characteristics are degraded. Thus, a flame retardant is included in the electrolyte. By including a flame retardant in the electrolyte, decomposition of the electrolyte due to temperature rise is suppressed, and deterioration of cycle characteristics and charge / discharge characteristics are prevented from occurring.

JP 2001-338682 A

  However, although the conventional battery described in Patent Document 1 can suppress the decomposition of the electrolyte, it is not configured to recover the gas when the gas is generated. There are various types of gases that are generated with the use of a battery. If hydrogen gas is generated, the battery can reach a relatively high temperature due to the thermal energy generated by the reaction between hydrogen gas and oxygen. There is a possibility of being warmed. Conventional batteries have no measures to prevent the temperature rise of the battery due to the generation of hydrogen gas, so when the hydrogen gas is generated, the temperature rise cannot be suppressed, and the cycle characteristics There is a problem that it is not possible to sufficiently suppress the deterioration of the battery and the charge / discharge characteristics.

  Accordingly, the present invention provides an electric device that can suppress the hydrogen gas generated from the power generation element constituting the battery from reacting with oxygen and prevent the temperature rise caused by the generation of the hydrogen gas. With the goal.

  The electrical device of the present invention is configured by laminating a plurality of exterior bodies that form a sealed closed space, and a positive electrode, a negative electrode, and an electrolyte layer interposed between the positive electrode and the negative electrode, and is disposed in the closed space. A battery including a power generation element. Furthermore, it has a hydrogen adsorption part that adsorbs hydrogen gas generated from the power generation element.

  According to the electric device of the present invention, it is possible to suppress the occurrence of temperature increase due to the reaction between hydrogen gas and oxygen by adsorbing the hydrogen gas generated from the power generation element by the hydrogen adsorption unit. Therefore, it is possible to suitably prevent the deterioration of the cycle characteristics and the charge / discharge characteristics due to the generation of hydrogen gas.

It is an outline perspective view of an assembled battery with which an electric device concerning a 1st embodiment of the present invention is provided. It is an outline perspective view of the battery module concerning a 1st embodiment. It is a disassembled perspective view which shows the internal structure of the battery module which concerns on 1st Embodiment. It is a top view of the bipolar battery which concerns on 1st Embodiment. It is sectional drawing of the bipolar battery which follows the 3B-3B line | wire shown to FIG. 3A. It is a figure for demonstrating the effect | action of the electric device which concerns on 1st Embodiment, Comprising: It is a fragmentary sectional view which simplifies and shows the cross section which follows the 4A-4A line | wire shown in FIG. It is a figure for demonstrating the effect | action of the electric device which concerns on 1st Embodiment, Comprising: It is a fragmentary sectional view which shows a mode that gas is discharged | emitted outside the 3rd exterior member. It is a fragmentary sectional view which simplifies and shows the internal structure of the battery module with which the electric device which concerns on 2nd Embodiment is provided. It is a fragmentary sectional view which simplifies and shows the internal structure of the battery module with which the electric device which concerns on 2nd Embodiment is provided. It is a fragmentary sectional view which simplifies and shows the internal structure of the battery module with which the electric device which concerns on 3rd Embodiment is provided. It is a fragmentary sectional view showing signs that hydrogen adsorption substance is emitted from the 1st exterior member with which an electric device concerning a 3rd embodiment is provided. It is a fragmentary sectional view for demonstrating the effect | action of the electric device which concerns on 4th Embodiment. It is a fragmentary sectional view for explaining an operation of an electric device concerning a 5th embodiment. It is a figure which expands and shows the broken-line part 8B part shown to FIG. 8A. It is a fragmentary sectional view for demonstrating the effect | action of the electric device which concerns on 6th Embodiment.

  Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may differ from the actual ratios.

<First Embodiment>
1 to 3 are diagrams for explaining the configuration of the electrical device according to the first embodiment, and FIGS. 4A and 4B are diagrams for explaining the operation of the electrical device according to the first embodiment.

  Referring to FIGS. 1, 2A, 2B, and 3B, an electric device 10 according to the present embodiment includes a battery 100 including a power generation element 110 that can charge and discharge electricity, and a plurality of batteries 100 (100A). To 100B), a battery module 200 including a stacked body 210, a battery pack 300 configured by electrically connecting a plurality of battery modules 200, a power generation element 110, a stacked body 210, and a battery pack 300. Exterior bodies 20 (first exterior member 21, second exterior member 22) that form a closed space 50 (first closed space 51, second closed space 52, third closed space 53) around each of them A third exterior member 23). Furthermore, the electric device 10 includes a hydrogen adsorption unit 60 that adsorbs gas generated from the power generation element 110 as the electric device 10 is used. The hydrogen adsorbing unit 60 makes it possible to prevent the temperature of the electric device 10 from rising due to the generation of hydrogen gas by adsorbing hydrogen gas. Hereinafter, the electric device 10 will be described in detail.

  First, with reference to FIG. 3A and FIG. 3B, the battery 100 which is a component of the electric device 10 is demonstrated.

  In the description of the embodiment, a lithium ion secondary battery using a bipolar electrode will be described as an example of the battery 100. However, the battery to which the present invention is applied is not particularly limited as long as it can contain a substance capable of generating a chemical reaction capable of generating hydrogen gas as described later. For example, a lithium ion secondary battery using a stacked electrode A polymer lithium battery or the like may also be used. Hereinafter, the battery 100 will be described as a bipolar battery 100.

  As shown in FIGS. 3A and 3B, the bipolar battery 100 includes a power generation element 110 in which a charge / discharge reaction proceeds. In addition, the bipolar battery 100 includes a first exterior member 21 that seals the power generation element 110 and forms a first closed space 51 around the power generation element 110.

  Bipolar battery 100 includes a plurality of current collectors 111, a positive electrode 112 electrically coupled to one surface of current collector 111, and a negative electrode 113 electrically coupled to the other surface of current collector 111. The bipolar electrode is provided.

  The positive electrode 112, the electrolyte layer 114, and the negative electrode 113 form a unit cell 115. The unit cells 115 arranged adjacent to each other have a structure in which a positive electrode 112 and a negative electrode 113 are stacked with a current collector 111 interposed therebetween. Each unit cell 115 is electrically connected in series via a current collector 111. A power generation element 110 is configured by stacking a plurality of unit cells 115.

  Each of the current collectors 111a and 111b located in the outermost layer forms either the positive electrode 112 or the negative electrode 113 only on one side. Current collector plates 118b and 119b are provided outside the current collectors 111a and 111b. The respective end portions of the current collector plates 118b and 119b extend to the outside of the first exterior member 21. The extended portions of the current collector plates 118b and 119b constitute a negative electrode tab 118 and a positive electrode tab 119 (see FIG. 3A). A sealing member 120 for insulating between adjacent current collectors 111 is provided on the outer peripheral portion of the unit cell 115.

  Below, an example of the constituent material of each part of the bipolar battery 100 will be described.

[Current collector]
Each current collector 111 (the same applies to current collectors 111a and 111b) is made of a predetermined conductive material. The material forming the current collector 111 is not particularly limited as long as it has conductivity. For example, a metal or a conductive polymer can be used. Examples of the metal material include aluminum, nickel, iron, stainless steel, titanium, and copper. In addition to these, a clad material of nickel and aluminum, a clad material of copper and aluminum, or a plating material combining these metals may be used. Further, it may be a foil-shaped member in which aluminum is coated on the metal surface. For example, it is preferable to use a stainless steel foil as a current collector from the viewpoint of corrosion resistance, ease of production, economy, and the like. In addition, there is no restriction | limiting in particular about the thickness dimension, external dimension, etc. of the electrical power collector 111, As long as the function as the electrical power collector 111 is not impaired, it can change suitably.

[Positive electrode and negative electrode]
Each of the positive electrode 112 and the negative electrode 113 includes an active material and an additive. Note that the positive electrode active material included in the positive electrode 112 forms a positive electrode active material layer, and the negative electrode active material included in the negative electrode 113 forms a negative electrode active material layer.

Examples of the positive electrode active material used for the positive electrode 112 include LiMn ₂ O ₄ , LiCoO ₂ , LiNiO ₂ , Li (Ni—Co—Mn) O _2, and a part of these transition metals substituted with other elements. Examples thereof include lithium-transition metal composite oxides, lithium-transition metal phosphate compounds, lithium-transition metal sulfate compounds, and two or more positive electrode active materials thereof. Preferably, among the positive electrode active materials described above, a lithium-transition metal composite oxide is used as the positive electrode active material.

Examples of the negative electrode active material used for the negative electrode 113 include carbon materials such as graphite, soft carbon, and hard carbon, lithium-transition metal composite oxides (for example, Li ₄ Ti ₅ O ₁₂ ), metal materials, and lithium. -Metal alloy materials and the like. Moreover, as a negative electrode material based on the advantage of higher density, for example, a negative electrode active material using silicon, silicon oxide, tin, or the like can be used.

  The positive electrode 112 and the negative electrode 113 can contain, for example, a binder, a conductive additive, an electrolyte salt (lithium salt), an ion conductive polymer, and the like as additives.

  A conductive support agent is an additive blended in order to improve the conductivity of the positive electrode active material layer or the negative electrode active material layer. As a conductive support agent, carbon materials, such as carbon black, such as acetylene black, a graphite, and a vapor growth carbon fiber, etc. are mentioned, for example. When each of the active material layers includes a conductive additive, an electronic network inside the active material layer is effectively formed, so that the output characteristics of the battery can be improved.

  Examples of the binder include thermoplastic resins such as polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), polytetrafluoroethylene (PTFE), polyvinyl acetate, acrylic resin, and liquid silicone rubber (LSR), polyimide, and epoxy. Examples thereof include thermosetting resins such as resins, polyurethane resins, and urea resins, and rubber-based materials such as styrene-butadiene rubber (SBR).

Examples of the electrolyte salt include LiPF ₆ , LiN (SO ₂ C ₂ F ₅ ), LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiCF ₃ SO _{3 and the} like.

  Examples of the ion conductive polymer include polyethylene oxide (PEO) -based and polypropylene oxide (PPO) -based polymers.

  The compounding ratio of each component contained in the positive electrode active material and the negative electrode active material is not particularly limited. The blending ratio can be adjusted by appropriately referring to known knowledge about the battery. The thickness dimension of the positive electrode 112 and the negative electrode 113 (thickness dimension including each active material layer) is not particularly limited, and can be adjusted by appropriately referring to conventionally known knowledge about the battery.

[Electrolyte layer]
The electrolyte layer 114 functions as a spatial partition between the positive electrode 112 and the negative electrode 113. The electrolyte layer 114 has a function of holding an electrolyte that is a lithium ion moving medium between the positive and negative electrodes during charge and discharge.

  There is no restriction | limiting in particular in the electrolyte which comprises the electrolyte layer 114, Polymer electrolytes, such as a liquid electrolyte and a polymer gel electrolyte and a polymer solid electrolyte, can be used suitably.

The liquid electrolyte has a form in which a lithium salt as a supporting salt is dissolved in an organic solvent as a plasticizer. Examples of the organic solvent used as the plasticizer include carbonates such as ethylene carbonate (EC), diethyl carbonate, and propylene carbonate (PC). Further, examples of the supporting salt (lithium salt) include compounds such as LiPF ₆ , LiN (SO ₂ C ₂ F ₅ ) ₂ , LiN (SO ₂ CF ₃ ) ₂ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiSO ₃ CF ₃ . Can be used as well.

  On the other hand, the polymer electrolyte is classified into a gel electrolyte containing an electrolytic solution and a polymer solid electrolyte containing no electrolytic solution.

  The gel electrolyte has a configuration in which the above liquid electrolyte is injected into a matrix polymer having lithium ion conductivity. Examples of the matrix polymer having lithium ion conductivity include polyethylene oxide (PEO), polypropylene oxide (PPO), and copolymers thereof. In such a matrix polymer, an electrolyte salt such as a lithium salt can be well dissolved.

  In addition, when an electrolyte layer is comprised from a liquid electrolyte or a gel electrolyte, you may use a separator for an electrolyte layer. Specific examples of the separator include a microporous film made of a polyolefin such as polyethylene or polypropylene, a hydrocarbon such as polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), glass fiber, or the like.

[First exterior member]
The first exterior member 21 can be constituted by a known exterior member such as a laminate sheet, for example. Further, in the bipolar battery 100, the first exterior member 21 has a substantially rectangular outer shape when viewed in plan as shown in FIG. A sealing portion 121 is formed to keep hermetic. The sealing part 121 can be comprised by heat-seal | fusing the outer peripheral edge part of the 1st exterior member 21, for example.

  The laminate sheet constituting the first exterior member 21 is composed of a layer composed of polyethylene (PE), ionomer, or ethylene vinyl acetate (EVA), or a metal foil such as Al foil or Ni foil, for example. A polymer-metal composite laminate sheet formed by laminating a plurality of layers composed of a layer and a layer composed of a resinous material such as polyethylene terephthalate (PET) or nylon can be used.

  Next, the battery module 200 that is a component of the electrical device 10 will be described.

  2A and 2B, the battery module 200 includes a cell unit 205 including a plurality of bipolar batteries 100 connected in series or in parallel.

  The cell unit 205 includes a stacked body 210 formed by stacking four bipolar batteries 100A to 100D (hereinafter referred to as first and second bipolar batteries). The number of bipolar batteries provided in one cell unit 205 is not particularly limited, and can be changed as appropriate.

  The battery module 200 can be used alone. For example, as will be described later, a plurality of battery modules 200 are connected in series and / or in parallel so as to correspond to a desired current, voltage, and capacity. A battery 300 can be formed (see FIG. 1).

  The second exterior member 22 seals the stacked body 210 and forms a second closed space 52 around it. The material and shape of the second exterior member 22 are not particularly limited. For example, the second exterior member 22 can be configured by a hard resin case or a metal case in consideration of securing strength and ease of manufacture. In the present embodiment, the second exterior member 22 is configured by a metal case including a lower case 22a having a substantially rectangular box shape and an upper case 22b forming a lid of the lower case 22a. The lower case 22a and the upper case 22b can be formed by processing a plate material such as a relatively thin steel plate or aluminum plate, for example.

  The outer peripheral edge of the upper case 22b is wound around the outer peripheral wall of the lower case 22a by caulking. The lower case 22a and the upper case 22b have a through hole 231 for inserting a through bolt (not shown). The through holes 231 are arranged at the four corners of the lower case 22a and the upper case 22b. The through bolt is a fastener used to hold a state where a plurality of battery modules are stacked and assembled as an assembled battery 300 as shown in FIG.

  The cell unit 205 includes a plurality of spacers 232 and 233 for supporting the stacked body 210. Each of the spacers 232 and 233 can be made of an electrically insulating resin material. The spacer 232 is disposed on the front side of the stacked body 210, and the spacer 233 is disposed on the back side of the stacked body 210. The through hole 234 formed in the spacer 233 is provided to allow a through bolt to be inserted in the same manner as the through hole 231 of the lower case 22a and the upper case 22b.

  A negative output terminal 221, a positive output terminal 222, and a voltage detection terminal 223 are arranged on the outer side of the lower case 22a.

  The positive electrode tab 119 (see FIG. 3A) provided in each of the first bipolar battery 100A and the second bipolar battery 100B is electrically connected to the positive electrode output terminal 222 via a bus bar (not shown).

  The negative electrode tab 118 (see FIG. 3A) included in each of the first bipolar battery 100A and the second bipolar battery 100B is the positive electrode tab 119 included in each of the third bipolar battery 100C and the fourth bipolar battery 100D. In addition, the voltage detection terminal 223 is electrically connected via a bus bar (not shown).

  The negative electrode tab 118 provided in each of the third bipolar battery 100C and the fourth bipolar battery 100D is electrically connected to a bus bar (not shown).

  As described above, the electrode tabs 118 and 119 of the bipolar batteries 100A to 100D are connected to the positive electrode output terminal 222, the negative electrode output terminal 221 and the voltage detection terminal 223 via bus bars (not shown), respectively. 2 parallel 2 series electrical connection configuration is formed.

  The voltage detection terminal 223 is a terminal used to detect the voltages of the bipolar batteries 100 </ b> A to 100 </ b> D constituting the battery module 200. Specifically, with respect to the voltages of the first bipolar battery 100A and the second bipolar battery 100B, the positive output terminal 222 and the voltage detection terminal 223 are used, and the voltage between these terminals is measured. Can be detected. Further, the voltages of the third bipolar battery 100C and the fourth bipolar battery 100D are detected by measuring the voltage between these terminals using the negative output terminal 221 and the voltage detection terminal 223. Can do.

  Next, the assembled battery 300 that is a component of the electrical device 10 will be described.

  Referring to FIG. 1, an assembled battery 300 is formed by combining a plurality of battery modules 200 and serializing and / or paralleling the battery modules 200. In the illustrated example, the twelve battery modules 200 are accommodated in the third exterior member 23 in two groups, one set of four, and two groups, two sets. ing. The number of battery modules 200 provided in one assembled battery 300, the arrangement of the battery modules 300, and the like are not limited to the illustrated example, and can be changed as appropriate.

  The third exterior member 23 seals the assembled battery 300 and forms a third closed space 53 around it. Although the material of the 3rd exterior member 23 is not specifically limited, For example, considering the ensuring of intensity | strength and the ease of manufacture, it can comprise with hard resin or a metal. In the present embodiment, the third exterior member 23 is configured using stainless steel. Each battery module 200 may be mechanically fixed using a fastener such as a connecting plate or fixed by welding or the like so as not to be displaced in the third exterior member 23. .

  In each battery module 200 constituting the assembled battery 300, the negative electrode tab 118 and the positive electrode tab 119 are electrically connected to each other via a bus bar (not shown). The third exterior member 23 is provided with an external output negative terminal 321 and an external output positive terminal 322 that function as electrodes of the assembled battery 40 as a whole.

  The outer shape and volume of the third exterior member 23 are not particularly limited as long as a desired number of battery modules 200 can be accommodated. For example, as shown in FIGS. It can be configured to have a cross-sectional shape that is recessed in a concave shape and that both end portions 32 adjacent to the central portion 31 protrude in the height direction from the central portion 31. By forming in such a cross-sectional shape, the generated hydrogen gas can be temporarily retained on the upper surface 36 side of the third exterior member 23, so that the arrangement of the hydrogen adsorbing portion 60 will be described later. Depending on the position, the adsorption of hydrogen gas can be performed efficiently.

  The amount of air (oxygen amount) present in the third closed space 53 in which the assembled battery 300 is disposed is preferably as small as possible from the viewpoint of suppressing the generation of thermal energy due to the reaction with hydrogen gas. For example, the amount of air present in the third closed space 53 is preferably set to 10 L or less with respect to the assembled battery 300 having a power generation amount of 1 kWh.

  The third exterior member 23 has an assembled battery side gas exhaust unit 330 that exhausts the gas as the gas staying in the third closed space 53 formed by the third exterior member 23 increases. .

  As shown in FIG. 4A, the assembled battery side gas discharge unit 330 includes an exhaust pipe 331 arranged to communicate with the inside and outside of the third exterior member 23, and an exhaust valve 332 arranged inside the exhaust pipe 331. have. The exhaust pipe 331 is configured by a tubular member formed therein so that gas can flow therethrough.

  The exhaust valve 332 operates to open when the volume of the gas staying in the third closed space 53 increases and the internal pressure of the third closed space 53 reaches a predetermined pressure. The set pressure when the exhaust valve 332 opens is not particularly limited, and can be set according to the volume of the third exterior member 23, the power generation capacity of the assembled battery 300, and the like. Moreover, the structure of each part of the assembled battery side gas discharge part 330 should just be comprised so that the gas stagnated in the 3rd closed space 53 can be discharged | emitted, for example, a part of 3rd exterior member 23 It is also possible to form by providing a flow rate adjusting valve capable of adjusting the gas discharge amount, or providing a known mechanical one-way valve or the like in the opening. Moreover, it is also possible to comprise so that the operation which opens a valve may be implemented according to the temperature in the 3rd closed space 53, for example. As the pressure increases, a temperature rise can also occur. Therefore, even when the valve is configured to open based on any physical quantity, the gas discharge function is not impaired.

  As shown in FIG. 4A, the hydrogen adsorption unit 60 is provided on the upper surface 36 side of the third exterior member 23 in the third closed space 53. Here, the upper surface 36 of the third exterior member 23 is a surface located on the opposite side to the bottom surface 37 on which each battery module 200 is placed when the assembled battery 300 is used. When each battery module 200 is arranged as shown in FIG. 4A, the surface located on the upper side of the third exterior member 23 becomes the upper surface 36. For example, from the state where the third exterior member 23 is illustrated. When rotating and using, the side surface 38 or the like can be the upper surface in relation to the surface on which the battery module 200 is placed.

  The hydrogen adsorption unit 60 can be configured in various modes using a substance having hydrogen adsorption properties (hydrogen adsorption substance). For example, a coating material containing a hydrogen-adsorbing substance is applied to the third exterior member 23, or the third exterior member 23 itself contains a hydrogen-adsorbing substance, or is configured to have hydrogen adsorption properties. It can be configured by attaching the member to the inner surface of the third exterior member 23 by sticking or fixing. Further, the hydrogen-adsorbing substance may be any of a solid, a liquid, a gel, or a combination thereof. In the present embodiment, the hydrogen adsorbing portion 60 is configured by a hydrogen adsorbing material (hydrogen adsorbent) applied to the inner surface of the third exterior member 23.

  As shown in FIG. 1, for example, the hydrogen adsorption unit 60 can extend in the depth direction of the third exterior member 23 so as to face the upper surface of the battery module 200 constituting the assembled battery 300. By arranging in this way, the hydrogen gas generated from each battery module 200 can be adsorbed efficiently.

The hydrogen adsorbing material used in the hydrogen adsorption unit 60 is not particularly limited as long as having a function of adsorbing and holding the hydrogen, for _{example, MnO 2, CuO, Ag 2} O, BaO 2, AgO, KMnO 4, AgMnO Metal oxides such as ₄ , organic peracid compounds such as hydrogen peroxide, ethylene oxide, and methyl ethyl ketone peroxide, hydrogen storage alloys, and the like can be used.

  Next, the operation of the hydrogen adsorption unit 60 will be described.

As described above, various compounds exist in the constituent materials of the bipolar battery 100. For example, LiPF ₆ as a supporting salt that can be included in the electrolyte layer 114, diethyl carbonate as a plasticizer for an electrolytic solution, and the like. In addition, PVDF which is a material of a binder constituting the negative electrode 113 is available. In these components, the following chemical reaction occurs, and hydrogen gas is generated.

<Thermal decomposition of LiPF ₆ and reaction with electrolyte>

Due to the heat generated during operation of the bipolar battery 100, a reaction shown in the formula (1) occurs. Subsequently, as shown in Formula (2), diethyl carbonate contained in the electrolyte layer 114 reacts with phosphorus pentafluoride generated in Formula (1), and C ₂ H ₅ OCOOPF ₄ , hydrogen fluoride, To produce ethylene gas. Further, as shown in the formula (3), further decomposition occurs in the C ₂ H ₅ OCOOPF ₄ generated in the formula (2). And the lithium ion occluded in the graphite (Gr) which comprises a negative electrode active material reacts with the hydrogen fluoride produced | generated by Formula (2), and generates hydrogen gas.

  <Thermal decomposition of PVDF>

  On the other hand, PVDF, which is a constituent material of the binder, is also decomposed by heat generated during operation of the bipolar battery 100 to generate hydrogen fluoride, as shown in the formula (5). Then, as shown in Formula (6), this hydrogen fluoride reacts with lithium ions occluded in graphite (Gr) constituting the negative electrode active material, so that hydrogen gas is similarly generated.

  Note that the above hydrogen generation mechanism is merely an estimation of the present inventors, and it goes without saying that the technical scope of the present invention is not limited by this mechanism.

  When hydrogen gas is generated from the bipolar battery 100, the hydrogen gas reacts with oxygen present around the bipolar battery 100 (for example, oxygen present inside the third exterior member 23), and relatively large heat energy is generated. Give rise to The generation of such thermal energy causes an increase in temperature of the bipolar battery 100, and as a result, a decrease in cycle characteristics and a decrease in charge / discharge characteristics occur. Therefore, in the electrical device 10 according to the present embodiment, by providing the third exterior member 23 with the hydrogen adsorption unit 60 having a function of adsorbing hydrogen, the occurrence of a temperature rise due to the generation of hydrogen gas is suppressed. Yes.

  The power generation element 110 constituting the bipolar battery 100 is sealed by the first exterior member 21 (see FIG. 3B), and the laminate 210 constituting the battery module 200 is sealed by the second exterior member 22. (See FIG. 2A), the exterior members 21 and 22 can prevent excessive hydrogen gas from flowing into the third closed space 53. However, the first exterior member 21 and the second exterior member 22 are passed through a slight gap that may occur during the operation of sealing the exterior members 21 and 22 and a slight gap that occurs in the mechanical connection portion. As a result, hydrogen gas may reach into the third closed space 53. According to the electric device 10, a small amount of hydrogen gas that has reached the third closed space 53 can be adsorbed by the hydrogen adsorption unit 60 provided in the third exterior member 23. The generation of thermal energy associated with the reaction can be effectively prevented.

  As shown in FIG. 4A, the hydrogen adsorbing unit 60 adsorbs hydrogen gas when hydrogen gas (indicated by the arrow a in the figure) is generated from the bipolar battery 100. The hydrogen gas is held as it is once adsorbed in the hydrogen adsorption unit 60. For this reason, it can suppress effectively that hydrogen gas reacts with the oxygen which exists in the 3rd closed space 53. FIG. In particular, since the hydrogen adsorbing portion 60 is disposed on the upper surface 36 side of the third exterior member 23, the hydrogen adsorbing is performed on the downstream side in the direction in which the mass of the hydrogen gas that is lighter than the surrounding air and high-temperature hydrogen gas moves by natural convection. Adsorption by the unit 60 can be performed. Therefore, hydrogen gas can be collected efficiently.

  Further, as described above, since the cross-sectional shape of the third exterior member 23 is a shape in which the central portion 31 in the width direction is recessed from both end portions 32, the third exterior member 23 reaches the upper surface 36 of the third exterior member 23. Hydrogen gas temporarily stays at both end portions 32. Thereby, the hydrogen gas can be efficiently adsorbed by the hydrogen adsorbing portions 60 arranged at the both end portions 32. Since the hydrogen adsorbing portion 60 disposed in the central portion 31 is disposed in the vicinity of each battery module 200 disposed so as to face each other, the hydrogen gas generated from each battery module 200 is efficiently adsorbed.

  The bipolar battery 100 can generate gas other than hydrogen gas depending on its use (charging / discharging, etc.). For example, in the hydrogen gas generation mechanism described above, carbon dioxide, ethylene gas, ethane fluoride and the like are generated together with the hydrogen gas. Although these gases do not contribute to the temperature rise of the bipolar battery 100 as much as hydrogen gas, if they are excessively released into the sealed third closed space 53, the performance of the bipolar battery 100 may be deteriorated. There is. In the electrical device 10, when the gas staying in the third closed space 53 increases to a predetermined amount, as shown in FIG. 4B, the exhaust valve 332 is opened, and the gas is outside the third closed space 53, that is, It discharges | emits to the surrounding environment of the assembled battery 300 (The discharge | emission of gas is shown by the arrow b in the figure). After the hydrogen gas is generated, the hydrogen gas is preferentially adsorbed by the hydrogen adsorbing portion 60, so that the amount of hydrogen gas discharged from the third exterior member 23 is very small. Therefore, by providing the assembled battery side gas discharge unit 330 together with the hydrogen adsorbing unit 60, it is possible to prevent the temperature increase caused by the reaction between hydrogen gas and oxygen outside the assembled battery 300, and in addition, the third exterior It is possible to prevent an increase in temperature caused by a gas other than hydrogen gas inside the member 23. In order to reduce the influence of various gases discharged from the third exterior member 23 on the surrounding environment, for example, a gas recovery mechanism or the like can be provided separately.

  As described above, according to the electric device 10 according to the present embodiment, the hydrogen gas generated from the power generation element 110 included in the bipolar battery 100 is adsorbed by the hydrogen adsorbing unit 60 to accompany the reaction between hydrogen gas and oxygen. The occurrence of temperature rise can be suppressed. Therefore, it is possible to suitably prevent the deterioration of the cycle characteristics and the charge / discharge characteristics due to the generation of hydrogen gas.

  In addition, since the hydrogen adsorbing portion 60 is provided in the third exterior member 23 that seals the assembled battery 300 and forms the third closed space 53 around it, the hydrogen gas is preferably used in the third closed space 53. Can be adsorbed. As a result, it is possible to prevent the generated hydrogen gas from reacting with the oxygen present in the third closed space 53, so that the temperature rise of the bipolar battery 100 can be effectively prevented. It becomes.

  Further, since the hydrogen adsorbing portion 60 is provided on the upper surface 36 side of the third exterior member 23 in the third closed space 53, the generated hydrogen gas is adsorbed on the downstream side in the direction in which it moves by natural convection. Hydrogen gas can be collected efficiently.

Second Embodiment
Next, an electric device according to a second embodiment of the present invention will be described. In the description of the second embodiment, a configuration different from the configuration described in the first embodiment will be mainly described, and the description of the same configuration will be omitted.

  5A and 5B are partial cross-sectional views schematically showing the battery module 200 included in the electric device according to the second embodiment. 5A shows a cross section of the battery module 200 viewed from the side, and FIG. 5B shows a cross section of the battery module 200 viewed from the top.

  In the electrical device 10 according to the first embodiment, the hydrogen adsorbing portion 60 is provided in the third exterior member 23 that houses the assembled battery 300, but in the present embodiment, the stacked body 210 included in the battery module 200. The hydrogen adsorbing portion 60 is provided in the second exterior member 22 that accommodates. The first exterior member 21 that houses the power generation element 110 is provided with a predetermined gas discharge part 125.

  As described in the description of the first embodiment, various gases including hydrogen gas can be generated from the power generation element 110 when the bipolar battery 100 is used. If a large amount of the generated gas stays in the first closed space 51, the battery temperature may increase. Therefore, the first exterior member 21 is provided with a unit cell side gas discharge portion 125 that discharges the gas from the first closed space 51 when the gas in the first closed space 51 reaches a predetermined amount.

  Although schematically illustrated in FIG. 5B, the unit cell-side gas discharge unit 125 is configured such that when the pressure in the first closed space 51 reaches a predetermined pressure with the generation of gas, the first closed space 51 51 has a valve structure that forms an opening communicating with the inside and outside of 51. For example, when the pressure in the first closed space 51 is reduced by discharging the gas, the single cell side gas discharge unit 125 closes the opening and maintains the airtightness of the first closed space 51. It is also possible to configure.

  As shown in FIGS. 5A and 5B, the hydrogen adsorption unit 60 is provided at a position (opposite position) facing the cell-side gas discharge unit 125 in the second closed space 52 formed by the second exterior member 22. ing. When the hydrogen adsorption unit 60 is arranged in this way, the hydrogen gas discharged from each single cell side gas discharge unit 125 included in the battery module 200 is directly sprayed toward the hydrogen adsorption unit 60. The hydrogen gas immediately after being discharged from the cell-side gas discharge unit 125 is in a relatively high concentration and high temperature state, but can be quickly adsorbed by the hydrogen adsorption unit 60 after being discharged. It is possible to prevent the high-concentration and high-temperature hydrogen gas from diffusing into the closed space 52. In addition, although the hydrogen adsorption part 60 is comprised with the solid containing a hydrogen adsorption substance, as demonstrated in 1st Embodiment, the form is not specifically limited.

  According to the present embodiment, since the hydrogen gas generated from the power generation element 110 can be adsorbed by the hydrogen adsorbing portion 60 provided in the second exterior member 22, it is preferable to increase the temperature due to the generation of hydrogen gas. Can be prevented. Further, the unit cell-side gas discharge part 125 provided in the first exterior member 21 can prevent the pressure (temperature) in the first closed space 51 from excessively rising. Further, since the hydrogen adsorbing portion 60 is provided in the second closed space 52 at a position facing the unit cell side gas discharge portion 125, the hydrogen gas is efficiently adsorbed before diffusing into the second closed space 52. be able to.

  In 2nd Embodiment, although the one battery module 200 contained in the assembled battery 300 was demonstrated, you may apply the same structure about the several battery module 200 contained in the assembled battery 300, for example. Moreover, it is not necessary to provide the unit cell side gas exhaust part 125 in all the first exterior members 21 included in one battery module 200, and the unit cell side gas exhaust part 125 is selectively provided according to product specifications and the like. Is possible.

  Moreover, as the cell side gas discharge part 125, it is also possible to use what was comprised so that it might operate | move based on a temperature change similarly to the assembled battery side gas discharge part 330, for example.

<Third Embodiment>
Next, an electric device according to a third embodiment of the present invention will be described. In the description of the third embodiment, a configuration different from the configuration described in the second embodiment will be mainly described, and the description of the same configuration will be omitted.

  6A and 6B are partial cross-sectional views schematically showing the battery module 200 included in the electric device according to the third embodiment.

  In the electrical device according to the second embodiment, the hydrogen adsorbing portion 60 is provided in the second exterior member 22 that accommodates the stacked body 210 included in the battery module 200. However, in the present embodiment, the hydrogen adsorbing portion 60 is provided. The hydrogen adsorbing material forming the above is encapsulated in the first exterior member 21 in advance. Further, the hydrogen-adsorbing substance contained in the first exterior member 21 is released into the second closed space 52 as the pressure in the first closed space 51 increases (or the temperature rises due to the generated gas). Thus, the first exterior member 21 is configured.

  As shown in FIGS. 6A and 6B, the hydrogen adsorbing substance is, for example, arranged so that when the gas is discharged from the first closed space 51, it is injected into the second closed space 52 together with the gas. It can be provided in the gas discharge part 125 (the arrow b in the figure indicates the release of gas, and the arrow c in the figure indicates the release of the hydrogen adsorbing substance). In addition, for example, a part of the first exterior member 21 is provided with a mesh-like matrix structure to allow a hydrogen adsorbing substance to adhere thereto, and when the gas is discharged, the second closing is performed by the action of gas injection. It can be configured to inject into the space 52. Further, for example, the hydrogen adsorbing substance is released while being included in the constituent material (laminate) of the first exterior member 21 and breaking the laminate in accordance with the increase in pressure (or temperature) in the first closed space 51. It is also possible to configure so as to.

  As the hydrogen adsorbing substance, for example, a substance composed of liquid, powder, gas or the like can be used. By using a material composed of liquid, powder, gas, etc., it is possible to inject over a wider range when discharging from the first exterior member 21, thereby improving the adsorption efficiency of hydrogen gas Can be made.

  According to the present embodiment, the hydrogen adsorbing substance contained in the first exterior member 21 can be released into the second closed space 52 and diffused (sprayed) into the second closed space 52. Further, it is possible to further improve the adsorption efficiency of hydrogen gas by the hydrogen adsorbing substance.

<Fourth embodiment>
Next, an electric device according to a fourth embodiment of the present invention will be described. In the description of the fourth embodiment, a configuration different from the configuration described in the first embodiment will be mainly described, and the description of the same configuration will be omitted.

  FIG. 7 is a partial cross-sectional view schematically showing the assembled battery 300 included in the electric device according to the fourth embodiment.

  In the electrical device 10 according to the first embodiment, the hydrogen adsorbing portion 60 is provided in the central portion 31 and both end portions 32 located on the upper surface 36 side of the third exterior member 23. In the present embodiment, As shown in FIG. 7, the hydrogen adsorbing portion 60 is provided in the central portion 31 and the inclined portion 33 located between the central portion 31 and both end portions 32.

  If the hydrogen adsorption part 60 is provided near the central part 31 as in the present embodiment, the adsorption efficiency of hydrogen gas near the central part 31 is increased. Therefore, even when hydrogen gas is generated from any of the battery modules 200, the positional relationship between the position where the hydrogen gas is generated and the position where the hydrogen adsorbing portion 60 is provided is not significantly changed, and the third closed space 53 is not generated. It becomes possible to adsorb the hydrogen gas that has flowed into the interior without any unevenness. Further, in the inclined portion 33 of the third exterior member 23, hydrogen gas easily flows (convects) compared to other portions, and therefore the inclined portion 33 and the central portion 31 where the hydrogen gas flowing through the inclined portion 33 merges. Further, by providing the hydrogen adsorbing portion 60, the hydrogen gas adsorption efficiency can be further improved.

<Fifth Embodiment>
Next, an electrical device according to a fifth embodiment of the invention will be described. In the description of the fifth embodiment, a configuration different from the configuration described in the first embodiment will be mainly described, and the description of the same configuration will be omitted.

  FIG. 8A is a partial cross-sectional view schematically showing the assembled battery 300 included in the electric device according to the fifth embodiment, and FIG. 8B is an enlarged view of the broken line portion 8B shown in FIG. 8A.

  As shown in FIGS. 8A and 8B, in the electrical device according to the present embodiment, the hydrogen adsorbing unit 60 is provided in the periphery of the assembled battery side gas discharge unit 330 provided in the third exterior member 23. Specifically, in the exhaust pipe 331 of the assembled battery side gas discharge unit 330, around the gas inlet 331a disposed inside the third exterior member 23, and outside the third exterior member 23 in the exhaust pipe 331. A hydrogen adsorbing unit 60 is provided around the disposed gas discharge port 331b.

  As described above, when the pressure in the third closed space 53 increases to a predetermined pressure due to various gases generated from the power generation element 110, the assembled battery side gas discharge unit 330 opens the exhaust valve 332 and sends the gas to the outside. Let it drain. The gas includes hydrogen gas. For this reason, by disposing the hydrogen adsorbing portion 60 around the exhaust pipe 331, it becomes possible to adsorb hydrogen gas as the gas is discharged. If the exhaust valve 332 is configured to open when the pressure in the third closed space 53 becomes larger than the ambient atmospheric pressure (for example, atmospheric pressure), the exhaust valve 332 is opened. Thus, a gas flow toward the exhaust pipe 331 is generated. Therefore, by adopting such a configuration, it becomes possible to more efficiently adsorb hydrogen gas by the hydrogen adsorption unit 60 provided in the peripheral part of the assembled battery side gas discharge unit 330.

  As shown in FIG. 8B, the hydrogen gas is adsorbed in the vicinity of the gas inlet 331 a of the exhaust pipe 331 when being discharged from the third exterior member 23. Further, when there is hydrogen gas that has passed through the exhaust pipe 331 without being adsorbed by the hydrogen adsorption unit 60 provided at the gas inlet 331a, the hydrogen gas is adsorbed at the hydrogen adsorption unit 60 provided at the gas discharge port 331b. Is done. Therefore, it is possible to suitably prevent the hydrogen gas from being discharged to the outside (ambient environment) of the third exterior member 23.

  In addition, as long as the hydrogen adsorption unit 60 is arranged in the peripheral part of the assembled battery side gas discharge unit 330, hydrogen gas can be adsorbed as the gas is discharged. It is also possible to provide only on one side of the discharge port 331b or to provide inside the exhaust pipe 331.

  According to the present embodiment, since the hydrogen adsorption unit 60 is provided in the peripheral part of the assembled battery side gas discharge unit 330, hydrogen gas can be adsorbed together with the discharge of gas from the assembled battery side gas discharge unit 330. Therefore, it is possible to provide an electric device that has a gas discharge function by the assembled battery side gas discharge unit 330 and that can efficiently adsorb hydrogen gas.

<Sixth Embodiment>
Next, an electric device according to a sixth embodiment of the present invention will be described. In the description of the sixth embodiment, a configuration different from the configuration described in the first embodiment will be mainly described, and the description of the same configuration will be omitted.

  FIG. 9 is a partial cross-sectional view schematically showing the assembled battery 300 included in the electric device according to the sixth embodiment.

  As shown in FIG. 9, in the electrical device according to the present embodiment, the third exterior member 23 is provided with a supply unit 400 that supplies a hydrogen adsorbing material that forms the hydrogen adsorbing unit 60.

  As the supply unit 400, for example, a unit provided with a valve configured to detect heat in the third closed space 53 and supply a hydrogen adsorbing substance based on the detection result can be used. . For example, those equipped with an expansion valve that expands and opens by the action of heat, those equipped with a valve composed of a bimetal that opens to open when heat is sensed, control based on the measurement results of a thermocouple or pressure detector It is possible to use one equipped with an electromagnetic valve that is controlled by a part or the like to open and close.

  As the hydrogen adsorbing material to be supplied, for example, a material composed of liquid, powder, gas or the like can be used. By using a liquid, powder, gas, or the like, it is possible to inject over a wide range, so that the adsorption efficiency of hydrogen gas can be improved. The supply amount of the hydrogen adsorbing substance is not particularly limited, and can be appropriately adjusted based on the volume of the third exterior member 23 and the like.

  The position where the supply unit 400 is installed is not particularly limited. However, as shown in FIG. 9, the hydrogen adsorbing substance can be distributed to each part of the third closed space 53 as shown by the arrow c by being arranged on the upper surface 36 side of the third exterior member 23. Therefore, for example, it is preferable to dispose on the upper surface 36 side of the third exterior member 23. Further, the number of supply means 400 is not particularly limited, and a plurality of supply means 400 may be installed for one assembled battery 300.

  According to this embodiment, the hydrogen adsorbing material is appropriately supplied based on the temperature change in the third closed space 53 by the supply means 400 provided in the third exterior member 23 to adsorb hydrogen gas. it can. In order to supply a hydrogen adsorbing material composed of liquid, powder, gas, etc., hydrogen gas can be adsorbed using a chemical reaction (adsorption reaction), and a hydrogen adsorbing unit 60 composed of a solid or the like. Hydrogen gas can be adsorbed more quickly than in the case of using this.

  As mentioned above, although the electric device according to the present invention has been described through a plurality of embodiments, the present invention is not limited to the configuration described in each embodiment, and may be appropriately changed based on the description of the scope of claims. Is possible.

  For example, in the electrical device according to each embodiment, a configuration in which a hydrogen adsorption unit is provided in one of the first closed space, the second closed space, and the third closed space is shown. The unit can be provided in a plurality of closed spaces arbitrarily selected from these closed spaces. In addition, the hydrogen adsorbing portions shown in each embodiment can be appropriately combined and provided in one electric device.

  In the description of the embodiments, the electric device including the assembled battery has been described. However, the electric device according to the present invention is at least a battery including a power generation element and an exterior body that forms a closed space around the power generation element. Can be. Therefore, an electric device can be constituted by a battery including the power generation element and the first exterior member, and an electric device can also be constituted by a battery module including the second exterior member.

  In addition, the configuration of each part of the electric device (battery, battery module, assembled battery) can be changed as long as it is configured to include an exterior body that forms a closed space and a hydrogen adsorption unit that can adsorb hydrogen. The arrangement, shape, material, external dimensions, etc. of each member are not limited to those described, and other additional members can be used or omitted as appropriate. .

10 electrical devices,
20 exterior body,
21 1st exterior member,
22 2nd exterior member,
23 third exterior member,
36 top surface,
50 closed space,
51 first closed space,
52 second closed space,
53 Third closed space,
60 Hydrogen adsorption part,
100 Bipolar battery (battery),
110 power generation elements,
112 positive electrode,
113 negative electrode,
114 electrolyte layer,
125 unit cell side gas discharge part,
200 battery module,
210 laminate,
300 battery packs,
330 Gas discharge part on the assembled battery side,
400 supply means.

Claims (6)

An exterior body forming a sealed closed space;
A battery including a positive electrode, a negative electrode, and a power generation element configured by stacking a plurality of electrolyte layers interposed between the positive electrode and the negative electrode and disposed in the closed space;
And an hydrogen adsorbing part that adsorbs hydrogen gas generated from the power generation element. A battery module including a laminate in which a plurality of the batteries are stacked;
An assembled battery configured by electrically connecting a plurality of the battery modules;
The exterior body is
A first exterior member that seals the power generation element to form a first closed space around the power generation element;
A second exterior member that seals the laminate and forms a second closed space around it;
A third exterior member that seals the assembled battery to form a third closed space around it,
The electric device according to claim 1, wherein the hydrogen adsorption unit is provided so as to adsorb the hydrogen gas staying in at least one of the first to third closed spaces.   The electric device according to claim 2, wherein the hydrogen adsorption unit is provided at least on the upper surface side of the third exterior member in the third closed space. The first exterior member has a unit cell side gas discharge portion that discharges the gas from the first closed space with an increase in gas staying in the first closed space,
4. The electrical device according to claim 2, wherein the hydrogen adsorption unit is provided at least at a position facing the unit cell-side gas discharge unit in the second closed space. 5.   5. The hydrogen adsorbing portion includes a hydrogen adsorbing substance that is contained in the first exterior member and is released into the second closed space with an increase in gas that stays in the first closed space. The electrical device according to any one of the above. The third exterior member has an assembled battery side gas discharge portion that discharges the gas from the third closed space with an increase in the gas staying in the third closed space,
The electric device according to claim 2, wherein the hydrogen adsorption unit is provided at least in a peripheral part of the assembled battery side gas discharge unit.