JP2015053122A - Air battery system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve such a problem of a conventional air battery system that since air is supplied to an air battery while pressurizing, unionized gaseous oxygen enters the battery from the air electrode side to lower the discharge output.SOLUTION: An air cell system is constituted to include: a cell aggregation S where single cells 1 are arranged in multiple rows, and an air path Af for an air electrode 1A is formed between the single cells 1; a distribution case 2 for housing the cell aggregation S; a blower 33 arranged in a discharge section 2D of the distribution case 2 or on the downstream side thereof, and giving a negative pressure into the distribution case 2; and system control means 36 for controlling the blower. Discharge output is prevented from lowering by preventing the gaseous oxygen from entering the cell, and excellent discharge output is maintained even in a structure that is downsized by narrowing the air path Af.

Description

  The present invention relates to an air battery system including a cell assembly having a structure in which a plurality of single cells are arranged, and an air circulation system for the cell assembly.

  As this type of air battery system, there is one described in Patent Document 1. The air battery system described in Patent Literature 1 includes a metal air battery including a metal electrode, an air electrode, and an electrolytic solution section, and an air supply section having a supply passage that supplies air to the air electrode of the metal air battery. And an air battery system arrange | positions the air pump as an air supply source in the middle of a supply path, and pressurizes and supplies air with respect to a metal air battery.

JP 2012-204300 A

  However, since the conventional air battery system as described above is configured to supply air to the air battery under pressure, the oxygen pressure causes gaseous oxygen that is not ionized to flow into the battery from the air electrode side. The three-phase interface between the air electrode catalyst, the electrolyte and the ionized oxygen is reduced, resulting in a decrease in discharge output, and there is a problem in solving such a problem. Met.

  The present invention has been made paying attention to the above-described conventional problems, and provides an air battery system that can prevent gaseous oxygen from entering the battery and prevent a decrease in discharge output. It is aimed.

  An air battery system according to the present invention includes a cell assembly in which a plurality of single cells each having an air electrode, an electrolyte container, and a metal negative electrode are arranged, and an air flow path for the air electrode is formed between the single cells. A distribution case having an air introduction part and a discharge part with respect to the case main body. The air battery system includes a blower for applying a negative pressure to the inside of the distribution case, and a system control unit for controlling the blower. This is a means for solving the conventional problems.

  In the above configuration, the electrolyte container may be in a state in which the electrolyte is stored in advance, or may be in a state in which the electrolyte is not stored. In any case, the electrolyte is stored in the state during discharge. In addition, the air battery system is a liquid injection type air battery when the electrolyte container is not accommodated, and the electrolyte liquid used here is mixed into the electrolyte itself or the inside of the electrode structure. In addition, liquid (water) for melting the solute material for electrolyte is included.

  Since the air battery system according to the present invention employs the above-described configuration, it is possible to prevent the gaseous oxygen from entering the cell and to prevent the discharge output from decreasing by setting the air flow path to a negative pressure. In particular, it is possible to maintain a good discharge output even when the air flow path is narrowed to achieve a miniaturized structure.

It is a block diagram (A) explaining 1st Embodiment of the air battery system of this invention, sectional drawing (B) of a distribution case, and sectional drawing (C) based on the AA line in FIG. 1 (B). . It is sectional drawing (A) based on the BB line in FIG.1 (B), and sectional drawing (B) in the part of a cell integration body. It is a flowchart (A) (B) which shows the control process of the control means in FIG. FIG. 6 is a block diagram (A) illustrating a second embodiment of the air battery system of the present invention, a sectional view (B) of a distribution case, and a sectional view (C) based on the line AA in FIG. 4 (B). . Sectional view (A) based on line BB in FIG. 4 (B), a plan view (B) for explaining the movable plate of the tank opening means and the opening cap, an enlarged plan view (C) of the opening cap, a side view ( It is sectional drawing (E) of the distribution case which shows the state after D) and liquid injection. It is the flowchart (A) which shows the discharge mode of the control means in FIG. 4, and the flowchart (B) which shows stop mode.

<First Embodiment>
The air battery system shown in FIG. 1A includes an air battery unit C and an air flow passage 31 having the inside of the air battery unit C as a part of the flow path. The air flow passage 31 is provided with an air filter 32 disposed on the upstream side (right side in the drawing) of the air battery unit C and a blower 33 disposed on the downstream side of the air battery unit C. The air flow passage 31 is provided with an upstream valve 34 that opens and closes between the air filter 31 and the air battery unit C, and a downstream valve 35 that opens and closes between the air battery unit C and the blower 33. .

  Further, the air battery system includes system control means 36 for controlling the blower 33. In this embodiment, the system control means 36 also has a function of controlling the opening and closing operations of the upstream and downstream valves 34 and 35. I have.

  As shown in FIGS. 1 and 2, the air battery unit C includes a cell integrated body S having a structure in which a plurality of single cells 1 are arranged, and a distribution case 2 that accommodates the cell integrated body S. The air battery unit C includes a sealing film 3 that shuts off the air flow to the cell assembly S accommodated in the distribution case 2 in a state where the single cell 1 has previously accommodated the electrolyte, and the sealing film 3. The sealing release means 9 which cancels | releases interruption | blocking by is provided. Here, for convenience of explanation, the arrow P shown in FIGS. 1 and 2 is the air flow direction, and the same applies to the embodiments described later.

  As shown in FIG. 2B, the unit cell 1 is formed by forming an electrolyte accommodating portion 1C between a flat air electrode 1A and a flat metal negative electrode 1B. A cell assembly S is constituted by the single cell 1 and the cell frame F that holds them. In the cell assembly S, the single cells 1 are arranged at a predetermined interval in a direction orthogonal to the air flow direction P, and an air flow path Af for the air electrode 1A is formed between the adjacent single cells 1. In each air flow path Af, a current collector (not shown) that electrically connects adjacent single cells 1 is arranged. Such a cell assembly S may be referred to as an assembled battery or a cartridge.

  The frame F closes the upper and lower ends of each single cell 1, the front and rear end portions in the air flow direction P, and the upper ends of adjacent single cells 1 in a liquid-tight (water-tight) manner. Further, the frame F is provided with a liquid inlet H to the electrolyte 1C of each unit cell 1 in the center of the upper end portion. The liquid injection port H is watertightly closed by the cap 4 after the electrolyte is filled. Further, the frame F has a hydrogen discharge hole 1D for discharging the hydrogen gas generated inside the single cell 1 to the outside on at least one of the upstream side and the downstream side in the air flow direction P at its upper end. Yes.

  The air electrode 1A constituting the single cell 1 is not shown in detail, but is composed of, for example, a positive electrode member made of a porous material and a liquid tight ventilation member arranged in the outermost layer. The positive electrode member includes, for example, a catalyst component and a conductive catalyst carrier that supports the catalyst component.

  A well-known thing can be used as a catalyst component for positive electrodes. The catalyst carrier functions as a carrier for supporting the above-described catalyst component and an electron conduction path involved in the exchange of electrons between the catalyst component and other members, and a known carbon can be used. it can.

  The liquid-tight ventilation member is a member having liquid-tightness with respect to the electrolyte and air-permeable with respect to oxygen. This liquid-tight ventilation member uses a water-repellent film such as polyolefin or fluororesin so that the electrolyte can be prevented from leaking to the outside, and on the other hand, a large number of microscopic members can supply oxygen to the positive electrode member. It has a hole.

  The metal negative electrode 1B constituting the single cell 1 includes a negative electrode active material made of a metal simple substance or alloy whose standard electrode potential is lower than that of hydrogen, and conventionally known materials applied to air batteries can be applied. .

  When the electrolyte is an electrolytic solution, for example, an aqueous solution of potassium chloride, sodium chloride, potassium hydroxide or the like can be applied, but the electrolyte is not limited thereto, and is a conventionally known electrolytic solution applied to an air battery. A liquid can be used.

  The distribution case 2 includes a case main body 2A having an upper opening that accommodates the cell aggregate S and the seal release means 9, and a lid 2B that hermetically closes the upper portion of the case main body 2A. The lid 2B has an air introduction part 2C on the upstream side in the air flow direction P and an air discharge part 2D on the downstream side. Thereby, the distribution case 2 has the air introduction part 2C and the discharge part 2D with respect to the case main body 2A that accommodates the cell aggregate A.

  The blower 33 is for applying a negative pressure to the inside of the distribution case 2 and is arranged so as to blow in the outlet direction at the discharge portion 2D of the distribution case 2 or downstream thereof.

  Further, in the distribution case 2, the cell aggregate S is arranged with its bottom part in contact with the bottom part of the case body 2A, and the introduction part 2C and the discharge part 2D are provided upstream and downstream in the air flow direction P. An upstream space 2E and a downstream space 2F that respectively communicate with each other are formed. Thereby, each air flow path Af between the adjacent single cells 1 communicates in one direction (air flow direction P) from the upstream space 2E to the downstream space 2F.

  Further, in the distribution case 2, a temperature sensor TS is provided in the air flow path Af at the center of the cell assembly S as shown in FIG. The temperature sensor TS can be provided in at least one of the inside of the cell assembly S as shown in the drawing, the air introduction part 2C, and the air discharge part 2D, and the measured value is the system control means. 36.

  As the sealing film 3, a single-layer or multi-layer film having a high carbon dioxide, oxygen and water barrier performance and hydrogen gas permeability can be used. Specifically, a known film made of a material selected from the group consisting of polyethylene, polypropylene, and polysulfone can be used, and the material is not particularly limited.

  Further, the sealing film 3 of this embodiment is attached to the upstream and downstream end surfaces of the cell assembly S in a state of sealing the air flow path Af so as to be peeled off. Air circulation to the cell aggregate S accommodated in the distribution case 2 is blocked. At this time, the sealing film 3 closes the outside of the hydrogen discharge hole 1D formed in the frame F of the cell assembly S. However, since the sealing film 3 has hydrogen gas permeability, the hydrogen gas can be discharged.

  In this embodiment, the seal release means 9 is disposed between the lid 2B and the cell aggregate S in the distribution case 2, and is attached to the upstream and downstream end faces of the cell aggregate S. Each of the sealing films 3 and 3 has the same configuration.

  The sealing release means 9 includes a pair of connecting ropes 5 and 5 connected to a lower end part which is a peeling start end part of the sealing film 3, a winding shaft 6 which fixes the ends of both connecting ropes 5 and 5, A drive source 7 that rotationally drives the winding shaft 6 is provided. Further, the sealing release means 9 includes a winding shaft 6 and a cover member 8 that houses the sealing film 3 wound on the winding shaft 6.

  The material of the connecting rope 5 is not particularly limited, but it is freely deformable and has sufficient strength to peel off the sealing film 3. As shown in FIG. The film 3 is connected to both sides of the lower end of the film 3. As shown in FIG. 2A, both ends of the winding shaft 6 are rotatably held by the distribution case 2. The drive source 7 is, for example, a motor, and is disposed outside the distribution case 2 to rotate the winding shaft 6.

  As shown in FIG. 1B, the cover member 8 is a U-shaped member having a winding shaft 6 as a center. As shown in FIG. And a slit 8A through which the sealing film 2 passes. In the cover member 8, the flange surface having the slits 8 </ b> A forms part of the inner surfaces of the upstream space 2 </ b> E and the downstream space 2 </ b> F in the distribution case 2.

  The air battery system having the above-described configuration is mounted on a vehicle as an auxiliary power source for an automobile, for example. When the air battery unit C is not used (stored), the air flow to the cell assembly S is blocked by the sealing film 3, and therefore the air battery unit C maintains a state in which no discharge occurs. At this time, hydrogen gas may be generated in the electrolyte 1 </ b> C of each single cell 1. The hydrogen gas is discharged from the hydrogen discharge hole 1D, and further passes through the sealing film 3 and discharged to the outside. Therefore, the air battery unit C does not have a concern that hydrogen gas accumulates inside the cell assembly S.

  Next, when the air battery system is used, for example, by operating switches arranged around the driver's seat, the drive source 7 of the seal release means 9, the blower 33, the upstream and downstream valves 34, 35 is activated. These operation sequences can be executed by programming the system control means 36, and are not particularly limited. For example, the downstream valve 35 is opened and the drive source 7 of the seal release means 9 is operated. Thereafter, the blower 33 is operated and the upstream valve 34 is opened.

  In the air battery unit C, the winding shaft 6 is rotationally driven by the drive source 7, and the seal attached to the end surface of the cell assembly S as the connecting cable 5 is wound around the winding shaft 6. The film 3 is peeled off from the lower end, and finally, the sealing film 3 is entirely wound on the winding shaft 6. In this way, the air battery unit C releases the block of air flow by the sealing film 3.

  The air battery unit C applies a negative pressure to the inside of the distribution case 2 by the blower 33, and thereby introduces air into the distribution case 2 from the introduction part 2 </ b> C through the air filter 32. The introduced air is evenly distributed from the upstream space 2E to each air flow path Af, supplied to the air electrode 1B of each single cell 1, and cools each single cell 1. Thereafter, the air is discharged from the downstream space 2F to the outside through the discharge portion 2D and the blower 33.

  The air battery system includes the cell assembly S, the distribution case 2, the blower 33, and the system control means 36, and applies air pressure by applying a negative pressure to the inside of the distribution case 2 by the blower 33 at startup. Since the introduced air is supplied to the air electrode 1A of each single cell 1, it is possible to prevent gaseous oxygen that has not been ionized from entering the cell. Thereby, in the single cell 1, the three-phase interface of an air electrode catalyst, electrolyte solution, and ionized oxygen is maintained favorably, and the fall of discharge output can be prevented.

  Further, since the air cell system makes the inside of the air flow path Af have a negative pressure, the air remaining in the air electrode 1A can be forcibly discharged to improve the wettability of the electrolyte (liquid) of the positive electrode catalyst layer. Even when the air flow path Af is narrowed to reduce the size, it is possible to prevent gaseous oxygen from entering the cell and maintain a good discharge output. In addition, since the single cell 1 is not pressurized, there is no concern that the electrolyte (liquid) in the cell leaks from the gaps between the constituent members.

  Further, in the air battery system, the cooling efficiency of the cell assembly S is improved. For example, when a blower is arranged on the introduction side of the cell assembly and the air is compressed, the air temperature at the blower outlet rises according to the blower loss. On the other hand, in the air battery system, since the air supplied to the cell assembly S does not rise in temperature by applying a negative pressure to the air flow path Af, the cell assembly S is efficiently cooled even with a small air flow rate. be able to.

  Furthermore, the air battery system is in a state in which the electrolyte accommodating portion 1C of the single cell 1 accommodates the electrolyte (liquid), and has a simple configuration by adopting the sealing film 3 and its sealing release means 9. The activation can be easily realized, and when used for an auxiliary power source for automobiles, the activation can be promptly activated even during traveling.

  Here, in the air battery system, as a more preferred embodiment, the system control unit 36 determines the target discharge current value from the required output for the cell assembly S, and calculates the heat generation amount of the cell assembly S from the target discharge current value. The number of revolutions of the blower 33 is controlled based on the estimated heat generation amount, the preset value of the cooling performance of the cell integrated body, and the measured value of the temperature sensor TS (temperature of the cell integrated body S / battery temperature Tc). It may be a means. A specific example is shown in FIG.

FIG. 3A is a flowchart for explaining the discharge mode.
That is, at the time of discharge, in step S1, a target discharge current value Ac is determined based on a required output for the cell assembly S, and in step S2, a heat generation amount Qc of the cell assembly S is estimated from the target discharge current value Ac. In step S3, the battery temperature Tc is detected by the temperature sensor TS.

  Next, in step S4, it is determined whether or not the battery temperature Tc is the target battery temperature TcO. If the battery temperature Tc is the target battery temperature TcO (Yes), the process returns to step S3, and the battery temperature Tc is If it is not the target battery temperature TcO (No), the process proceeds to step S5 to detect the cooling performance detection value T1. As the cooling performance detection value T1, an actual value such as an air temperature at the inlet 2C of the distribution case 2 or the inlet of the air flow path Af or a temperature change rate of the cell integrated body S can be used. That is, the measured value of the temperature sensor TS can be used.

  In step S6, the rotational speed R2 of the blower 33 is calculated based on the cooling performance detection value T1, the estimated heat generation amount Qc, and the measured value (battery temperature Tc) of the temperature sensor TS so as to obtain the target air flow rate. To do. Subsequently, the rotational speed of the blower 33 is adjusted in step S7, and the discharge voltage Vc is detected in step S8. Thereafter, in step S9, it is determined whether or not the discharge voltage Vc is equal to or lower than the stop threshold voltage Vth2. If the discharge voltage Vc exceeds the stop threshold voltage Vth2 (No), the process returns to step S1 and the discharge voltage When Vc is equal to or lower than the stop threshold voltage Vth2 (Yes), the mode shifts to the stop mode shown in FIG.

  At the time of stop, when the discharge is stopped in step S10, the blower 33 is set to the stop mode rotation speed R3 in step S11, and the battery temperature Tc is detected by the temperature sensor TS in step S12. In step S13, it is determined whether or not the battery temperature Tc is equal to or lower than the stop threshold temperature Tth. If the battery temperature Tc exceeds the stop threshold temperature Tth (No), the process returns to step S11 to return to the battery temperature. When Tc is equal to or lower than the stop threshold temperature Tth (Yes), the process proceeds to step S14 and the blower 33 is stopped.

  In this type of air battery, control for determining an air flow rate required for a reaction based on a target discharge current value is common. On the other hand, in the air battery system of this embodiment, based on the calorific value Qc estimated from the target discharge current value Ac, the cooling performance detection value T1, and the measurement value (battery temperature Tc) of the temperature sensor TS, The air flow rate is determined by controlling the rotation speed.

  In the air battery system including the system control means 36 described above, since the air flow path Af in the distribution case 2 is set to a negative pressure, the output fluctuation sensitivity with respect to the internal pressure of the air flow path Af can be ignored. Even when the air flow rate fluctuates in order to stabilize the temperature of the cell integrated body S when the outside air temperature or the required power fluctuates, the deviation from the target output is small and output control is easy.

Second Embodiment
4 and 5 are views showing a second embodiment of the air battery system according to the present invention. Note that the same components as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof is omitted.
In the air battery unit C of this embodiment, the cell assembly S has the liquid injection port H to the electrolyte storage part 1C of each single cell 1 in the open state at the top, and the electrolyte storage part 1C of each single cell 1 includes In this state, the electrolyte is not accommodated. That is, the single cell 1 of this embodiment is a liquid injection type air battery.

  In addition, the air battery unit C is disposed above the cell assembly S and has a liquid storage tank T in which the electrolyte liquid 12 is stored, and a lower part of the liquid storage tank T is opened so that the electrolyte liquid 12 is injected into the liquid inlet H. And a manifold 13 for connecting the liquid storage tank T and the cell assembly S is provided. Further, the air battery unit C has a structure in which the liquid storage tank accommodates the deformable internal tank 15 in the housing 14, and the 14 housing has a tank pressure adjusting port for holding the interior at atmospheric pressure. 16.

  The cell assembly S of this embodiment has a slope at the top, and in the example shown in the drawing, the slope is such that the upstream side in the air flow direction P is the lower side and the downstream side is the higher side. The cell assembly S has a liquid inlet H to each electrolyte container 1C on the lower side of the slope and a liquid return port R to each electrolyte container 1C on the upper side of the slope. Yes. The electrolyte liquid 12 includes the electrolytic solution itself or a liquid (water) for melting the solid electrolyte mixed in the single cell 1.

  The casing 14 constituting the liquid storage tank T has a slightly flat rectangular parallelepiped shape, and has an opening 14C opposed to the upper side of the liquid injection port H group of the frame F on the bottom surface. The movable plate 17 constituting the tank opening means is assembled. The opening 14 </ b> C has a horizontal portion that extends in the width direction of the bottom surface of the housing 14 (a direction orthogonal to the air flow direction P) and a vertical portion that is continuous with both side surfaces of the housing 14.

  On the other hand, the movable plate 17 is a plate member having a width dimension corresponding to the width of the opening 14C and a longitudinal dimension longer than the width of the bottom surface of the housing 14, and has a slit 17A at the center. The movable plate 17 is restricted from moving upward at the vertical portions on both sides of the opening 14C, and passes through the bottom of the housing 14 as shown in FIG.

  The internal tank 15 is, for example, a resin bag. In this case, the resin to be used is not particularly limited as long as it can be freely deformed. However, when the electrolyte liquid (electrolyte) 12 is an alkaline aqueous solution, at least a portion in contact with the electrolyte liquid 12 is used. It is necessary to use an alkali resistant resin. The inner tank 15 should not be made of a material that can break when deformed and cause liquid leakage.

  The internal tank 15 of this embodiment stores the electrolyte liquid 12 and is partially lifted by the movable plate 17 assembled to the opening 14C of the housing 14 as shown in FIG. 4B. Is accommodated in the housing 14. In addition, it is very effective that the internal tank 15 is configured to be easily contracted and deformed, for example, formed into a bellows shape or provided with an appropriate crease, and the volume is reduced as much as possible when contracted and deformed. . Note that the contraction deformation of the internal tank 15 is a deformation so as to reduce its volume, and does not require a stretchable material.

  In this embodiment, the tank opening means is mainly means for opening the lower portion of the internal tank 15 of the liquid storage tank T, and is constituted by the movable plate 17, the pair of electromagnetic actuators 18 and 18, and the plurality of opening caps 19. It is configured. As shown in FIGS. 4C and 5A, the electromagnetic actuators 18 and 18 are fixed to the left and right sides of the casing 14 with respect to the air flow direction P, and the output shafts facing downward are movable plates. The movable plate 17 is held at the ascending limit by being connected to the end portion 17.

  As shown in FIGS. 5B to 5D, the opening cap 19 is a rectangular tube-like member, and has a saw blade-shaped cutting blade 19 </ b> A at the upper end. A plurality of opening caps 19 (five in the illustrated example) are arranged in series on the upper surface of the frame F of the cell assembly S within a range corresponding to the slits 17 </ b> A of the movable plate 17. Here, the slit 17A is within the range of the liquid injection port H group of the frame F due to the positional relationship between the opening 14C of the housing 14 and the movable plate 17 described above. Further, in the opening cap 19, the cutting edge 19 </ b> A is positioned on the lower side of the upper surface of the movable plate 17. At this time, since the internal tank 15 is partially lifted by the movable plate 17 as described above, it is separated from the cutting edge 19A of the opening mouthpiece 19. FIG. 4C shows only a part of the opening caps 19 in an enlarged manner.

  In the above air battery system, the tank opening means includes a movable plate 17 that partially lifts and holds the bottom of the internal tank 15, an electromagnetic actuator 18 that lowers the movable plate 17, and a movable plate disposed in the manifold 13. 17 is provided with an opening cap 19 that cuts and opens the bottom portion of the internal tank 15 that has been lowered together.

  The manifold 13 is a deformable annular body that liquid-tightly connects the liquid storage tank T and the cell assembly S, and is formed of the same material as the internal tank 15 in order to ensure resistance to the electrolyte liquid 12. be able to.

  More specifically, the manifold 13 has an upper end portion that surrounds the opening portion of the liquid storage tank T by the tank opening means, that is, a portion that surrounds the facing portion of the inner tank 15 facing the opening cap 19. It is liquid-tightly adhered to. The upper end of the manifold 13 is also bonded to the upper surface of the movable plate 17. At this time, the manifold 13 is bonded to the upper surface of the movable plate 17 together with the bottom of the internal tank 15. An intermediate portion of the manifold 13 passes through the inside of the slit 17 </ b> A of the movable plate 17.

  Furthermore, the manifold 13 is liquid-tightly bonded to the portion surrounding the liquid injection port H group and the liquid return port R group of the cell assembly S at the lower end. In this embodiment, the manifold 13 has a frame portion 13A on the entire periphery of the lower end portion, and the frame portion 13A is bonded and fixed to the entire periphery of the upper end portion of the cell assembly S. In this way, the manifold 13 forms a closed space for liquid injection between the opening portion of the liquid storage tank T by the tank opening means and each liquid injection port H of the cell assembly S. The opening portion of the liquid storage tank T by the tank opening means is formed at the position of the opening portion 14 </ b> C of the housing 14.

  The distribution case 2 of this embodiment stores the liquid storage tank T and the cell aggregate S in the case main body 2A so as to overlap each other, and the air introduction part 2C and the discharge part with the cell aggregate S therebetween. 2D. And the blower 33 for providing a negative pressure inside the distribution case 2 is arrange | positioned in the discharge part 2D or its downstream.

  The tank pressure adjusting port 16 is composed of a pipe, and is fixed in a state of penetrating the upper part of the distribution case 2 and the upper part of the casing 14 of the liquid storage tank T, and communicates the outside with the inside of the casing 14. It is in a state.

  When the air battery system having the above-described configuration is activated, the blower 33 is operated in response to an input of an activation command, and then the tank opening means is operated, and then the upstream valve 34 is opened to introduce air. It is desirable to adopt a method. Hereinafter, based on the flowchart of FIG. 6, an activation method will be described together with the operation of the air battery unit C. This activation method can be executed by the system control means 36.

  That is, when an activation instruction is detected in step S21, the downstream valve 35 is opened in step S22, and the blower 33 is operated at the activation mode rotational speed R1. Next, in step S23, the tank opening means of the liquid storage tank T is operated. The operation of the tank opening means is as follows.

  In the air battery unit C, when both electromagnetic actuators 18 are operated, the output shafts of both electromagnetic actuators 18 move downward and the movable plate 17 descends. Then, the bottom of the internal tank 15 is lowered together with the movable plate 17, the opening base 19 protrudes from the slit 17 </ b> A relative to the downward movement of the movable plate 17, and the bottom of the internal tank 15 is cut by the cutting blade 19 </ b> A of the opening base 19. Open. At this time, since the opening cap 19 has a rectangular tube shape, it does not hinder the flow of the electrolyte liquid 12 at all.

  As a result, in the air battery unit C, the electrolyte liquid 12 in the internal tank 15 flows down in the manifold 13, so that the liquid injection from the liquid injection ports H of the frame F to the electrolyte storage portions 1 </ b> C of the single cells 1 is performed. Be started. At this time, the manifold 13 functions to distribute the electrolyte liquid 12 flowing out from one place at the bottom of the liquid storage tank T to the electrolyte accommodating portion 1C of each unit cell 1, and prevents leakage and scattering of the electrolyte liquid 12. It has a function.

  When the tank opening means is operated as described above to start supplying the electrolyte liquid 12 to the electrolyte accommodating portion 1C of each single cell 1, the time after the start of the operation of the blower 33 is greater than or equal to the predetermined elapsed time t1 in step S24. If the time after the start of operation is less than the predetermined elapsed time t1 (No), the process returns to step S22, and the time after the start of operation is equal to or longer than the predetermined elapsed time t1 In (No), the process proceeds to step S25, and the upstream valve 34 is opened.

  At this time, in the open cell battery system, the blower 33 and the tank opening means are operated before the upstream valve 34 is opened, so that the inside of the distribution case 2 is decompressed. Thereby, in the air battery unit C, the air remaining in the air electrode 1A is forcibly discharged, and at the same time, the electrolyte liquid 12 is quickly injected.

  Thereafter, the air battery unit C opens the upstream side valve 34 to introduce air from the introduction part 2C into the air flow path Af of the distribution case 2 and supply air to the air electrode 1A of each single cell 1. The discharge is continued and the cell assembly S is also cooled by the introduced air. Further, as shown in FIG. 5E, the air battery unit C is deformed so that the internal tank 15 of the liquid storage tank T is crushed together with the injection of the electrolyte liquid 12, and the tank pressure is adjusted in accordance with the deformation. Outside air is introduced into the housing 14 through the mouth 16.

  Further, the air battery system detects the open end voltage OCV of the cell integrated body in step S26, and determines in step S27 whether or not the open end voltage OCV is equal to or higher than a preset voltage V1. Here, when the open-circuit voltage OCV is less than the preset voltage V1 (No), the process proceeds to step S28, the preliminary discharge is performed for a predetermined time, and then the process returns to step S26. Further, when the open end voltage OCV is equal to or higher than the preset voltage V1 (Yes), the operation proceeds to the discharge mode as it is. By performing preliminary discharge in this way, wetting of the electrode surface of the air electrode 1A and the electrolyte liquid 12 can be promoted.

  In the air battery system and the starting method thereof, in particular, in the configuration including the cell assembly S composed of the injection type single cell 1, by applying a negative pressure to the inside of the distribution case 2, gaseous oxygen Can be prevented from entering the inside of the cell to prevent the discharge output from being lowered. In particular, even when the air flow path Af is narrowed to achieve a miniaturized structure, a good discharge output can be maintained. it can.

  In addition, the air battery system and the starting method thereof improve the wettability of the electrolyte (liquid) of the positive electrode catalyst layer by operating the blower 33 and the tank opening means before opening the upstream side valve 34, and Liquid time and start-up time can be shortened. Moreover, there is no concern that the electrolyte liquid 12 will flow backward to the liquid storage tank T side.

  Furthermore, since the air battery system described above is a liquid injection type single cell 1 and employs the liquid storage tank T and the tank opening means (17, 18, 19), it is easy to automate the liquid injection of the electrolyte liquid 12. Even under conditions where vibration, inclination, and acceleration are applied, liquid injection can be reliably performed without causing liquid leakage, and power generation can be started promptly. Therefore, when the air battery system is used as an auxiliary power source for automobiles, it can reliably inject liquid even while traveling, and can prevent liquid leakage with certainty. It is very effective for application to high power air batteries.

  Further, the air battery system described above employs the liquid storage tank T having a structure in which the deformable internal tank 15 is accommodated in the housing 14 and the tank pressure adjusting port 16 that maintains the interior of the housing 14 at atmospheric pressure. Thus, the inner tank 15 can be smoothly deformed so that the volume thereof decreases with the liquid injection, and the liquid injection operation becomes smoother.

  The configuration of the air battery system according to the present invention is not limited to the above-described embodiments, and details of the configuration such as the shape, number, and material of each part are appropriately selected within the scope not departing from the gist of the present invention. It is possible to change. Further, a system without a mechanism for circulating the electrolytic solution can be provided for replenishing water and adjusting the concentration of the electrolytic solution, which is an electrolyte.

Af Air flow path H Injection port S Cell aggregate T Liquid storage tank TS Temperature sensor 1 Single cell 1A Air electrode 1B Metal negative electrode 1C Electrolyte container 2 Distribution case 2A Case body 2C Introducing part 2D Discharge part 3 Sealing film 9 Sealing Stop releasing means 12 Liquid for electrolyte 16 Tank pressure adjusting port 17 Movable plate (tank opening means)
18 Actuator (Tank opening means)
19 Opening cap (tank opening means)
33 Blower 34 Upstream valve 36 System control means

Claims (8)

A cell assembly in which a plurality of single cells each having an air electrode, an electrolyte container, and a metal negative electrode are arranged and an air flow path for the air electrode is formed between the single cells;
A distribution case having an air introduction part and a discharge part with respect to a case main body for housing the cell assembly;
A blower which is disposed on the air discharge part or downstream thereof and for applying a negative pressure to the inside of the distribution case;
An air battery system comprising system control means for controlling a blower.   2. The air battery system according to claim 1, wherein a temperature sensor is provided in at least one of the inside of the cell assembly, the air introduction unit, and the air discharge unit.   The system control means determines the target discharge current value from the required output for the cell assembly, estimates the heat generation amount of the cell assembly from the target discharge current value, the estimated heat generation amount, the preset cooling performance of the cell assembly 3. The air battery system according to claim 2, wherein the air battery system is means for controlling the rotational speed of the blower based on the detected value and the measured value of the temperature sensor. The electrolyte storage part is in a state of storing the electrolyte in advance,
A sealing film that blocks the flow of air to the cell assembly accommodated in the distribution case;
The air battery system according to any one of claims 1 to 3, further comprising a sealing release unit that releases the blocking by the sealing film. The cell assembly has a liquid inlet to the electrolyte storage part of each single cell at the top, and the electrolyte storage part is in a state where the electrolyte is not stored,
A liquid storage tank disposed on the upper side of the cell assembly and storing the electrolyte liquid;
The tank lowering means for opening the lower part of a liquid storage tank and injecting the electrolyte liquid from an injection port to an electrolyte container is provided. Air battery system. The liquid storage tank has a structure that houses a deformable internal tank in the housing,
6. The air battery system according to claim 5, wherein the casing has a tank pressure adjusting port for maintaining the inside thereof at atmospheric pressure. The distribution case has an upstream valve that opens and closes the air inlet,
7. The air battery system according to claim 6, wherein the system control means has a function of controlling the opening / closing operation of the upstream side valve. In starting the air battery system according to claim 7,
A method for starting an air battery system, comprising: operating a blower in response to an input of a start command; then operating a tank opening means; then opening an upstream valve and introducing air.

Images