JP5594801B1 - Magnesium battery system - Google Patents

Abstract

In a magnesium battery system, power generation can be stopped and restarted at an arbitrary time during power generation. Magnesium hydroxide dissolved in the electrolyte is separated, and at the same time, the electrolyte is generated during power generation. Cooling so that the temperature of the battery does not rise too much, it is possible to operate continuously without replacing the electrolyte over a long period of time, and the electrolysis when connecting multiple power generation cells in series It is to provide a structure for preventing liquid junction caused by liquid.
SOLUTION: An electrolytic solution storage tank is provided so that a power generation operation can be freely stopped by transferring an electrolytic solution to and from a battery cell, and a product separation mechanism and an electrolytic solution cooling mechanism are provided in a plurality of battery cells. A time sharing mechanism was used to prevent liquid junctions.
[Selection] Figure 10

Description

The present invention is mainly composed of a battery using magnesium or a magnesium alloy as a cathode active material (hereinafter referred to as a magnesium battery). In particular, a mechanism for cooling heat generated by power generation, a mechanism for separating products and wastes generated by power generation, and power generation. In addition, the present invention relates to a magnesium battery system having a mechanism that can arbitrarily select stop and stop, and obtaining a high voltage by connecting a plurality of battery cells in series.

Magnesium batteries have high energy density, high safety, and light weight. The material magnesium is extremely abundant and inexpensive.

Magnesium batteries generate magnesium hydroxide by generating electricity, which can be converted to magnesium again by raising the temperature after separation from the electrolyte and is expected as a circulating battery material.

The reaction of the magnesium battery can be expressed by the following chemical formula.
2Mg + O ₂ + 2H ₂ O → 2Mg (OH) ₂ ↓ Chemical reaction formula 1
Alternatively, the reaction in the absence of oxygen around the electrode can be expressed by the following chemical formula.
Mg + 2H ₂ O → Mg (OH) ₂ ↓ + H _2. Chemical reaction formula 2
In practice, both reactions mix to generate electricity.

Magnesium has high activity, and when exposed to air, it reacts with oxygen to form a film on the surface, and when there is an electrolyte, self-discharge is large. When the electrolyte is made alkaline, self-discharge can be prevented, but a passive state is formed on the surface of magnesium, resulting in a poor reaction. Therefore, when magnesium is used as an alloy with calcium or the like, self-discharge is small, and magnesium hydroxide generated by power generation dissolves in the electrolytic solution, and a battery that can generate power stably without forming a passive layer on the surface can be configured.

In a metal-air battery, when power is generated, a route that circulates between the battery cell and the filtering means to remove the concentration of the metal hydroxide dissolved in the electrolyte and prevent the power generation performance from falling. A method of driving by connecting with the network has been proposed. (Patent Document 1)

Further, when using a metal-air battery, it is necessary to cool the battery in order to avoid a decrease in durability due to a temperature rise due to heat generation of the electrode. A method has been proposed in which an electrolytic solution is led to the outside of a battery cell, and the battery cell and the heat dissipation means are connected through a circulation path to generate power. (Patent Document 2)

A battery according to these technologies is an invention for a single cell. In order to obtain a high voltage, a plurality of battery cells are connected in series. However, when a product separation mechanism and an electrolyte cooling mechanism are commonly used in a plurality of battery cells, the electrolyte is electrically conducted. Therefore, there is a problem that a short circuit (hereinafter referred to as a liquid junction) occurs through the electrolytic solution.

Also, once the electrolyte is injected and power generation starts, it is assumed that power generation continues until the magnesium of the negative electrode is consumed, and there is a problem that it is not considered to temporarily stop power generation in the middle Yes. When a magnesium battery system is used as a power source for an electric vehicle, it is essential that the power generation mode and the parking stop mode can be repeatedly switched while the vehicle is operating.

In addition, batteries using these technologies have a problem that the treatment of hydrogen generated from battery cells during power generation is not taken into consideration.

JP 2010-170819 JP 2011-258889

SUMMARY OF THE INVENTION A first problem to be solved by the present invention is a magnesium battery system that can appropriately stop power generation from a state during power generation, stop operation, and restart power generation as needed. It is to provide a battery system.

The second problem is to filter the magnesium hydroxide dissolved in the electrolytic solution, cool the electrolytic solution so that it does not rise too much during power generation, and replace the electrolytic solution over a long period of time. And providing a magnesium battery system that can be operated continuously.

Moreover, the 3rd subject is providing the structure which prevents the liquid junction by the electrolyte solution generate | occur | produced when connecting several power generation cells in series.

The first invention is
A battery cell, a product separation mechanism, an electrolyte cooling mechanism, an electrolyte storage tank, one or more electrolyte pumps, a switching mechanism, and a plurality of pipes that connect them as constituent elements,
The battery cell is an activated carbon layer that serves as a positive electrode, a good conductor layer, and a porous body layer that takes in air in this order, is opposed to a magnesium layer that serves as a negative electrode, and is collectively housed in a housing.
The product separation mechanism separates products and waste such as magnesium hydroxide generated when the battery cell generates power from the electrolyte when the electrolyte circulates,
The electrolytic cooling mechanism, when the electrolytic solution heated by the heat generated when the battery cell generates electricity circulates, cools the temperature to an appropriate temperature,
The electrolyte storage tank can store an amount of electrolyte equal to or greater than the amount required when the battery cell generates power,
The battery cell, the first electrolytic solution pump, the product separation mechanism, the electrolytic solution cooling mechanism, and the switching mechanism are connected by the pipes, and the constituent elements of the annular first path through which the electrolytic solution circulates ,
On the electrolyte solution delivery side of the first electrolyte solution pump, a switching mechanism is used to form a branch path that can guide the electrolyte solution away from the annular route to the electrolyte solution storage tank. ,
When preparing for power generation, the electrolytic solution stored in the electrolytic solution storage tank was guided to the outside from the electrolytic solution storage tank, and all the components of the first path were filled with the electrolytic solution. As a state, a state in which a chemical reaction for power generation is possible,
At the time of power generation, a state in which a load is connected to both electrodes of the battery cell in a state filled with the electrolytic solution to generate power;
If necessary, the electrolytic solution is circulated through the first path by the first electrolytic solution pump, and product separation and cooling treatment is performed on the electrolytic solution by the product separation mechanism and the electrolytic solution cooling mechanism. The state of applying
When stopping power generation, the load is disconnected from both poles of the battery cell,
Further, the electrolytic solution filled in the battery cell is transferred to the electrolytic solution storage tank through a second path branched from the first path, and a chemical reaction for power generation is not caused in each battery cell. A possible state, the state stored in the transferred electrolyte storage tank, and
This is a magnesium battery system characterized in that its state can be switched in the order described and power generation operation can be started and stopped at any time.

The second invention is
A magnesium battery system according to the first invention,
The switching mechanism for forming the first and second paths is a switching valve,
The electrolyte storage tank has an inlet and an outlet for the electrolyte separately,
The inlet is connected to the switching valve;
The outlet is connected to a pipe connecting the switching valve of the first path and the electrolyte cooling mechanism via a second electrolyte pump,
When the electrolytic solution is stored, the first electrolytic solution pump is transferred to the electrolytic solution storage tank via the second path branched from the middle of the first path,
At the time of filling the electrolyte, the electrolyte is returned to the first path from the outlet of the electrolyte storage tank by the second electrolyte pump, and the first path below the battery cell is configured. A magnesium battery system characterized by being filled in an element.

The third invention is
A magnesium battery system according to the first invention,
The switching mechanism for forming the first and second paths is a switching valve,
The electrolyte storage tank has a single inlet / outlet for the electrolyte at the bottom and is sealed at the top,
The inlet / outlet is connected to a switching valve disposed on the electrolyte delivery side of the first electrolyte pump,
When the electrolytic solution is stored, the electrolytic solution is pumped and accumulated in a space formed in the upper portion of the electrolytic solution storage tank through the second path branched from the first path by the switching valve. The electrolyte is pushed into the electrolyte storage tank against the pressure of the gas formed,
At the time of filling the electrolytic solution, the electrolytic solution is returned from the electrolytic solution storage tank through the second path to the first path by the pressure of the gas to form the first path. It is a magnesium battery system that is filled in all of the constituent elements.

The fourth invention is:
A magnesium battery system according to the first invention,
The switching mechanism for forming the second path is a switching valve,
The electrolyte storage tank is installed at a position higher than the battery cell, and has a single inlet / outlet for the electrolyte at the bottom,
When the electrolytic solution is stored, the electrolytic solution is pushed up against gravity by the electrolytic solution pump from the first route through the second route and stored in the electrolytic solution storage tank.
When filling the electrolytic solution, the electrolytic solution stored in the electrolytic solution storage tank is returned to the first route by gravity through the second route to constitute the first route. A magnesium battery system characterized in that all of the elements are filled.

The fifth invention is:
A magnesium battery system according to the first invention,
A plurality of the battery cells, electrically connected in series;
Each of the plurality of battery cells includes an electrolyte inlet valve and an outlet valve,
The inlet side of the inlet valve and the outlet side of the outlet valve are respectively connected in a multiple manner and consolidated into one, and are connected to the electrolyte pump, the product separation mechanism, the electrolyte cooling mechanism, and the piping, Configure the first path,
Of the plurality of battery cells, only the electrolyte of at least one of the battery cells can circulate through the first path, and the pipes constituting the first paths of all the remaining battery cells Alternatively, by having a space in which the electrolyte solution does not exist in the battery cell, the electrolyte solutions of the other battery cells are electrically connected to each other and the electrolyte solution in the first path excluding the battery cell. A magnesium battery system characterized by being separated.

FIG. 17 is a state transition diagram showing the operation of the magnesium battery system of the present invention. The operation of the magnesium battery has five modes called “operation stop mode”, “power generation possible mode”, “continuous power generation possible mode”, “power generation mode”, and “continuous power generation mode”. The “operation stop mode” is a mode in which the electrolyte plate is not immersed in the electrode plate in the battery cell and all functions including the operation of the electrolyte pump are stopped.

In the “operation stop mode”, when the battery cell is filled with the electrolyte, the “power generation possible mode” is entered. In the “power generation possible mode”, if a load is connected to both poles of the battery cell, the operation immediately proceeds to the “power generation mode” to generate power. Further, in the “power generation possible mode”, when the circulation of the electrolyte is started without connecting the load to both electrodes of the battery cell, the mode is shifted to the “continuous power generation possible mode”.

In the “continuous power generation possible mode”, the battery cell electrolyte circulates through the first path to perform product separation and electrolyte cooling treatment. It is possible to continue the power generation without changing the electrolytic solution by shifting to the “power generation mode”.
The operation of the magnesium battery system can be controlled by appropriately switching these modes.

Here, in the shutdown mode, the chemical reaction can be completely stopped to prevent the magnesium from being worn. In addition, by appropriately switching these modes, a magnesium battery system that does not generate liquid junction even when a plurality of battery cells are connected in series can be realized. Details will be described later. In the power generation possible mode, power generation is not performed normally because it is not connected to the load, but due to the presence of leakage current, a chemical reaction proceeds although it is minute, leading to consumption of magnesium over a long period of time. Sometimes.

In addition, in the power generation mode, the electrolytic solution is further circulated to switch to the continuous power generation mode, so that the product separation mechanism works and removes magnesium hydroxide and waste that dissolves in the electrolyte, so the electrolyte can be replaced for a long time. In addition, since the temperature of the electrolytic solution is appropriately maintained by the electrolytic solution cooling mechanism, a magnesium battery system that operates stably can be provided.

First overall configuration diagram of the magnesium battery system Flow diagram of electrolyte solution of first configuration Second overall configuration diagram of the magnesium battery system Flow diagram of electrolyte solution of second configuration Third overall configuration diagram of magnesium battery system Flow diagram of electrolyte solution of third configuration Cross section of battery cell Overall appearance of magnesium battery system Conceptual diagram of hybrid battery Overall configuration diagram with multiple battery cells connected in series Controller diagram Diagram of a controller that connects battery cells in series Electrolyte filling sequence chart Sequence chart during continuous power generation Electrolyte storage sequence chart Processing timing chart when battery cells are connected in series State transition diagram of magnesium battery

A first embodiment will be described with reference to the drawings. FIG. 1 is a first overall configuration diagram of the magnesium battery system, FIG. 2 is a flow diagram of the electrolyte solution of the first configuration, FIG. 7 is a cross-sectional configuration diagram of the battery cell, and FIG. It shows the controller to control.

As shown in FIG. 1, in this embodiment, the battery cell 11, the first electrolyte pump 41, the product separation mechanism 211, and the electrolyte cooling mechanism 212 are insulated from each other in the order described. An annular path through which the electrolytic solution 3 circulates is formed by connecting with a pipe 71 made of a material. This is called the first route. In addition, a switching valve 51 as a switching mechanism is installed in the middle of the pipe 71 connecting the product separation mechanism 211 and the electrolyte cooling mechanism 212, and one of the outlets is electrolyzed located at the bottom of the electrolyte storage tank 213. It is connected to the liquid inlet 215.

The electrolytic solution 3 is circulated counterclockwise in the figure by a first electrolytic solution pump 41 through an annular first path. In addition, a check valve (not shown) is provided at an appropriate position on the first circulation path so that the electrolytic solution 3 is not circulated clockwise.

The pipe 216 forming the electrolyte outlet of the electrolyte storage tank 213 is inserted into the inside from the top of the storage tank and the opening reaches near the bottom, and the portion of the pipe 216 outside the storage tank is the second Is connected to a pipe 71 connecting the switching valve 51 and the electrolyte cooling mechanism 212 via the electrolyte pump 42, and is joined to the annular first path. This route of the pipe 216 is referred to as a second route. Also on the second path, it is necessary to flow the electrolyte 3 in the order of the second electrolyte pump 42 from the bottom opening of the storage tank of the pipe 216, so that it is not shown so that it does not flow back by any chance. A check valve is installed.

The electrolytic solution storage tank 213 satisfies all the volumes of the battery cell 11, the product separation mechanism 211, the electrolytic solution cooling mechanism 212, the first electrolytic solution pump 41, and the pipes connecting them, and the battery cell 11 is generating power. It has a capacity capable of storing a sufficient amount of electrolyte solution to replenish the electrolyte solution 3 consumed.

As shown in a cross-sectional view in FIG. 7, the battery cell 11 is integrated inside the battery cell housing 13 with a magnesium alloy 122 as a negative electrode, activated carbon 113, a good conductor 112 such as copper, and a porous body 114 in the order described. These are used as positive electrodes, and are arranged facing each other with a certain gap.

As shown in FIG. 7, a large number of minute air holes 131 are opened on one surface (left surface in the drawing) of the battery cell housing 13. The porous body 114 of the positive electrode is installed so as to face the air hole 131 and cover the area with the opening. When the magnesium battery system 1 generates power, oxygen is required on the positive electrode side, but oxygen in the air is supplied into the battery cell 11 through the air holes 131 and the porous body 114.

The porous body 114 is made of a material that allows gas to pass but does not allow liquid to pass. The water repellency of the material is used to prevent liquid from passing through. For example, fluororesin porous membrane, or chloroprene, silicone resin, polytrimethylsilylpropyne, polypropylene, polymethylpentene, polyisoprene, polybutadiene, chloroprene, polystyrene, polyethylene, polycarbonate, silicon polycarbonate copolymer, polyphenylene sulfide, polyphenylene oxide, polyphenylene Foam sheets such as sulfide and polyester can be used.

In addition, the battery cell casing 13 has a surface in contact with the electrolytic solution 3 formed of an insulator. On the upper portion of the magnesium alloy 122, a negative electrode lead portion is provided. A positive electrode lead portion is installed on the top of the good conductor 112. The bipolar lead portions are insulated from the battery cell housing 13.

  As shown in FIG. 1, liquid level detectors 14 and 15 are installed outside the battery cell housing 13. The liquid level detector is of a known ultrasonic type, a capacitive type, or any other type. The liquid level detector 14 is installed at a position approximately the same as the height of the electrolyte inlet 135 above the battery cell 11. The liquid level detector 15 is installed at a position below the battery cell 11 and below the lower end of the electrodes. The liquid level detectors 14 and 15 generate an ON signal when the electrolytic solution 3 is present at a position opposite to the mounting position in the horizontal direction, and an OFF signal when there is no electrolytic solution 3.

The controller 8 shown in FIG. 11 receives an operation signal from the operation panel 81 and signals from the liquid level detectors 14 and 15. There are three operation signals: “electrolyte filling”, “electrolyte circulation”, and “electrolyte storage”. Based on these inputs, a power source for operating the first electrolyte pump 41 and the second electrolyte pump 42 and a switching signal of the switching valve 51 are output.

When the battery cell 11 is filled with the electrolyte 3 in the battery cell housing 13, the battery cell 11 is in a state where power generation is possible (power generation possible mode). The electrolytic solution 3 is salt water. If a load (not shown) is connected between the negative electrode lead and the positive electrode lead with the electrolyte 3 filled, power generation (power generation mode) starts by a chemical reaction as a battery.

Since hydrogen gas is generated during the power generation state, a gas discharge port 132 is provided in the upper part of the battery cell housing 13 so as to guide it to the outside. Further, when the electrolyte 3 is extracted from the battery cell 11 during the storage of the electrolyte described later, air enters the inside through the gas discharge port 132. When the battery cell 11 is filled with the electrolyte solution 3 when the electrolyte solution is filled, the internal air exits from the gas discharge port 132.

The operation of the magnesium battery system 1 shown in FIG. 1 will be described. FIG. 1A shows a state in which the present magnesium battery system is in a continuous power generation mode. That is, the power generation possible mode in which the battery cell 11 is filled with the electrolytic solution 3 is connected to a load (not shown) to enter the power generation mode, and the electrolytic solution is circulated to indicate the continuous power generation mode. These mode switching operations are controlled by the controller shown in FIG. Details will be described later.

In this FIG. 1 (a) continuous power generation mode, the switching valve shown in the “switching valve operation” diagram at the bottom of FIG. 1 is in the position “(w) electrolyte circulation”, and the electrolyte 3 is switched. Enter from the left side of the valve and go up. As indicated by arrows in the vicinity of the pipe 71 and the switching valve 51 in FIG. 1A, the pumped electrolyte 3 flows in the counterclockwise direction in FIG. Circulate on the path.

FIG. 2 shows the flow of the electrolytic solution 3 and is abbreviated and displayed so that the concept of each mode can be easily understood. The arrows in the figure indicate the flow direction of the electrolyte solution 3.

As shown in the continuous power generation mode in FIG. 2 (a), the first electrolyte pump 41 causes the electrolyte 3 to circulate counterclockwise through the annular first path. That is, the battery cell 11, the electrolyte pump 41, the product separation mechanism 211, and the electrolyte cooling mechanism 212 are arranged in this order. Here, the display of the switching valve 51 is omitted.

When the electrolytic solution 3 passes through the product separation mechanism 211, the power generation product such as magnesium hydroxide contained therein is separated. The electrolytic solution 3 exiting from the product separation mechanism 211 exits toward the upward piping by the switching valve 51, and then passes through the electrolytic solution cooling mechanism 212. When the electrolytic solution 3 passes through the electrolytic solution cooling mechanism 212, it is cooled to an appropriate temperature. An appropriate method such as water cooling or air cooling is used for cooling.

The electrolytic solution 3 exiting the electrolytic solution cooling mechanism 212 returns to the battery cell 11. When the electrolytic solution 3 circulates in the annular first path, it does not go out of the path, so that the amount of the electrolytic solution 3 in the path is constant. However, when power is generated, the water in the electrolyte 3 is consumed by the chemical reaction formulas 1 and / or 2. Therefore, in order to keep the amount of the electrolytic solution 3 in the battery cell constant, it is necessary to replenish the electrolytic solution.

Therefore, the position of the upper surface of the electrolytic solution 3 in the battery cell 11 is monitored by the liquid level detector 14, and when the electrolytic solution 3 is decreased and the liquid level is lowered, the liquid level detector 14 is turned off. The second electrolytic solution pump is operated for a short time to replenish the electrolytic solution 3 from the electrolytic solution storage tank 213, and control is performed so that the liquid level of the electrolytic solution 3 is always kept within a certain range. By doing so, power can be continuously supplied to a load (not shown) connected to the electrode.

Next, an operation in which the magnesium battery system shifts to the operation stop mode will be described. FIG. 2 (b) shows the operation of storing the electrolyte solution in which the electrolyte solution 3 is extracted from the battery cell 11 and transferred to the electrolyte solution storage tank 213.

When the magnesium battery system is in the continuous power generation mode, after disconnecting a load (not shown) from the battery cell 11 and stopping the power supply to the load, inputting “electrolyte storage” on the operation panel 81 shown in FIG. A switching signal is output from the controller 8 to the switching valve, and the switching valve 51 causes the switching valve 51 to switch from “(w) electrolyte circulation” to “switching the electrolyte solution” in the “switching valve operation” diagram shown at the bottom of FIG. By switching to the position indicated by “(x) Electrolyte storage”, the electrolyte 3 changes so as to enter from the left side of the switching valve and exit from the right side.

That is, the switching valve 51 connects the outlet of the electrolyte pump 41 and the electrolyte inlet 215 of the electrolyte storage tank 213, and the electrolyte flow is the operation of storing the electrolyte shown in FIG. The flow of the electrolytic solution 3 from the battery cell 11 stops the circulation on the annular first path and moves toward the electrolytic solution storage tank 213, and the electrolytic solution 3 is transferred to and stored in the electrolytic solution storage tank.

As long as the liquid level of the electrolytic solution 3 is above the lower end of the electrodes of the battery cell 11 and the liquid level detector 15 installed in the battery cell 11 is in the ON state, the operation of storing the electrolytic solution continues. . When the liquid level of the electrolytic solution 3 is lowered to the position where the liquid level detector 15 is attached below the lower end of the electrodes, the liquid level detector 15 is turned OFF and the operation of storing the electrolytic solution is completed. When the operation of storing the electrolyte solution is completed, the switching valve is switched from “(x) electrolyte solution storage” to “(z) stop” in the “switching valve operation” diagram on the lower side of FIG. The power supply to the electrolyte pump 41 is stopped.

FIG. 1B shows the operation stop mode. The state where the operation of storing the electrolytic solution is completed and the electrolytic solution 3 is almost stored in the electrolytic solution storage tank 213 except for the bottom portion of the battery cell 11 and the portion remaining in the pipe 71 is shown. At this time, as can be seen from the drawing, in the battery cell 11, since the electrolyte 3 is not in contact with each electrode, the battery cannot generate power and does not self-discharge, so that the complete operation stop mode is set.

Next, when “electrolyte filling” is input on the operation panel 81 in the operation stop mode, the second electrolyte pump 42 is activated by the power source output from the controller 8. At this time, the switching valve 51 remains in the (z) stop position.

That is, the flow of the electrolytic solution is the filling of the electrolytic solution in FIG. 2C, and the battery 3 is filled with the electrolytic solution 3 from the electrolytic solution storage tank 213. The electrolytic solution 3 stored in the electrolytic solution storage tank 213 is extracted by the second electrolytic solution pump 42 and filled into the battery cell 11 via the electrolytic solution cooling mechanism 212.

The operation of filling the electrolytic solution is performed when the upper surface of the electrolytic solution 3 inside the battery cell 11 rises above the level of the liquid level detector 14 installed in the battery cell housing 13. Is detected, and the controller 8 recognizes this, stops the power supply to the second electrolyte pump 42, ends, and enters the power generation possible mode. If the load is connected, the power generation mode is set even if the electrolyte 3 is not circulating.

Next, when “electrolyte circulation” is input on the operation panel 81 shown in FIG. 11, the power to the electrolyte pump 41 is output, and the switching valve 51 is “(z) stopped” by the switching signal output from the controller 8. From this position, the position is switched to the position “(w) Electrolyte circulation”, and the electrolyte 3 starts to circulate through the first path, and becomes an electrolyte circulation operation. As described above, if a load is connected in the power generation enable mode, power generation is started.However, until the operation of the electrolyte circulation starts to ensure the separation and cooling of the electrolyte solution, the load connection is started. You may wait and start power generation. The cycle of the operating state has been described above.

In addition, although it demonstrated from Fig.1 (a) continuous electric power generation mode, it is always set as the electric power generation mode, and continuous electric power generation is performed only when the concentration of the product in the electrolytic solution or the temperature of the electrolytic solution becomes higher than the reference value. The electrolyte may be circulated as a mode.

In this embodiment, the electrolytic solution storage tank 213 is installed in a pipe connecting the product separation mechanism 211 and the electrolytic solution cooling mechanism 212, but not limited thereto, if the electrolytic solution delivery side of the electrolytic solution pump 41, You may install in any position between the electrolyte solution pump 41 and the product separation mechanism 211, or between the electrolyte solution cooling mechanism 212 and the battery cell 11.

In this embodiment, the electrolyte pump, the product separation mechanism, and the electrolyte cooling mechanism are connected to the first path in this order. However, the electrolyte pump, the electrolyte cooling mechanism, and the product separation mechanism are also connected in this order. good.

FIG. 8A is an external view of the entire magnesium battery system 1. Elements other than the battery cell 11 are collected in a separate housing as the electrolyte treatment module 21. FIG. 8B shows a state where a plurality of magnesium battery systems 1 can be installed in close parallel by combining the battery cell 11 and the electrolyte treatment module 21. The plurality of magnesium battery systems 1 can be operated by being connected in series or in parallel.

Hydrogen gas is generated from the battery cells 11 during power generation. FIG. 9 shows a hybrid battery in which the magnesium battery system 1 and the hydrogen fuel cell 9 are combined. The gas discharge port of the battery cell 11 of the magnesium battery system 1 is hermetically connected to the gas inlet 911 of the hydrogen fuel cell 9 and is sent to the hydrogen fuel cell 9 with the pressure of the generated hydrogen gas. The outlets of the plurality of magnesium battery systems 1 may be connected to one hydrogen fuel cell 9 in an airtight manner.

Further, in this case, an air circulation port 133 having an air valve 134 through which air enters and exits is installed in the battery cell housing 13 of the battery cell 11 so that air can be circulated when storing or filling the electrolyte solution 3. The air valve 134 is kept open. On the other hand, the air valve 134 is closed so that hydrogen generated by the magnesium battery system 1 does not escape during power generation.

A second embodiment will be described with reference to FIGS. FIG. 3 is a second overall configuration diagram of the magnesium battery system, and FIG. 4 is a flowchart of the electrolyte solution of the second configuration.

As shown in FIG. 3, in this embodiment, the battery cell 11 and the electrolyte pump 41 (in this embodiment, only one pump is required in the present embodiment, which is simply referred to as the electrolyte pump 41), and the product separation in the power generation state. The mechanism 211 and the electrolyte cooling mechanism 212 are the same as in the first embodiment in that an annular first path that circulates by connecting with each other in the order described is formed.

A switching valve 51 as a switching mechanism is installed in the middle of the pipe 71 connecting the product separation mechanism 211 and the electrolytic solution cooling mechanism 212, and the only electrolytic solution that has one outlet at the bottom of the electrolytic solution storage tank 213. It is connected to the entrance / exit 217.

The electrolytic solution storage tank 213 has no other entrance / exit for the electrolytic solution 3, and is different from the first embodiment in that when the electrolytic solution 3 enters from the bottom, a sealed space is formed at the top thereof. The space is previously filled with air or inert gas at an appropriate pressure.

Further, this embodiment is the same as the first embodiment except that the controller 8 of the first embodiment shown in FIG. 11 does not output to the second electrolyte pump 42.

The flow of the electrolytic solution will be described in detail with reference to FIG. The continuous power generation mode shown in FIG. 4A is the same as that in FIG. 2A of the first embodiment. That is, when “electrolyte circulation” is input on the operation panel 81 in the power generation possible mode or the power generation mode, the controller 8 outputs power to the electrolyte pump 41 to start operation, and switches to the switching valve 51. By the output of the signal, the switching valve 51 is switched from “(z) stop” to “(w) electrolyte circulation” as shown in the “operation of the switching valve” at the bottom of FIG. Electrolyte 3 that has entered from the left side of the liquid comes out to the right side. As a result, the continuous power generation mode shown in FIG. 4A is entered, the outlet of the product separation mechanism 211 is connected to the inlet of the electrolyte cooling mechanism 212, and the electrolyte 3 circulates through the first path.

Next, in the continuous power generation mode, when the load is disconnected, the mode shifts to the continuous power generation possible mode. When “electrolyte storage” is input on the operation panel 81, the mode shifts to the power generation possible mode and the controller 8 switches to the switching valve 51. On the other hand, a switching signal is output, and the switching valve 51 changes from “(w) electrolyte circulation” to “(x) electrolyte storage” as shown in the “switching valve operation” diagram at the bottom of FIG. The electrolyte solution 3 entering from the left side of the switching valve 51 comes out upward.

That is, as shown in the flow chart of FIG. 4 (b) electrolyte storage, the outlet of the electrolyte pump 41 and the electrolyte inlet / outlet 217 of the electrolyte storage tank 213 are connected. Thereby, the flow of the electrolytic solution 3 is separated from the first circulation path, and the electrolytic solution 3 pumped by the electrolytic solution pump 41 is transferred to the electrolytic solution storage tank 213 via the electrolytic solution inlet / outlet 217, Stored.

At this time, since the electrolyte storage tank 213 is sealed without any inlet / outlet other than the electrolyte inlet / outlet 217, the electrolyte 3 is pressed into the electrolyte storage tank 213 by the electrolyte pump 41 and stored. The more gas is, the more the gas in the upper space is compressed.

The operation of storing the electrolytic solution is continued as long as the liquid level of the electrolytic solution 3 is above the lower end of the electrodes in the battery cell 11 and the liquid level detector 15 installed in the battery cell housing 13 is in an ON state. To do. When the liquid level detector 15 detects that the liquid level of the electrolytic solution 3 is below the lower end of the electrodes and is turned OFF, the controller 8 recognizes it and switches from the controller 8 to the switching valve 51. When the signal is output, the switching valve 51 is moved from “(x) electrolyte storage” to “(z) stop”, the power supply to the electrolyte pump 41 is cut off, the pump is stopped, and the electrolyte storage is stopped. The operation ends.

At this time, in the battery cell 11, since the positive and negative electrodes do not come into contact with the electrolyte solution 3, the power generation is stopped and the self-discharge is not performed. The operation stop mode in FIG. 3 (b) shows the state of the electrolyte 3 when the operation of storing the electrolyte is completed and the operation stop mode is entered.

Next, a procedure for restarting power generation will be described. When “electrolyte filling” is input on the operation panel 81 in the operation stop mode, a switching signal is output from the controller 8 to the switching valve 51 and is shown in the “switching valve operation” diagram at the bottom of FIG. Thus, the switching valve 51 is switched from “(z) stop” to the position “(y) electrolyte filling”, and the electrolyte 3 entering from the upper side of the switching valve 51 comes out to the right.

That is, as shown in the flow chart of FIG. 4 (c) electrolyte filling, by switching the switching valve 51, the electrolyte inlet / outlet 217 of the electrolyte storage tank 213 and the inlet of the electrolyte cooling mechanism 212 are connected, and the electrolyte filling is performed. Become a mode. The electrolytic solution 3 is filled into the battery cell housing 13 from the inlet of the electrolytic solution of the battery cell 11 via the electrolytic solution cooling mechanism 212.

At this time, the electrolytic solution 3 stored in the electrolytic solution storage tank 213 is pushed out by the pressure by appropriately increasing the gas pressure in the space above the electrolytic solution storage tank 213 in advance. Then, it flows into the battery cell 11 via the electrolytic solution cooling mechanism 212. Even if the electrolyte 3 flows out of the electrolyte storage tank to some extent, the tank is maintained at a sufficient pressure so that the electrolyte continues to flow out of the electrolyte storage tank 213 and is supplied to the battery cells. Since the initial pressure of the gas in the tank is set, even if the battery cell 11 is at a high position, it can be filled with the electrolyte from the electrolyte inlet 135 at the top thereof, so a special transfer device such as a pump is used. unnecessary.

The electrolyte filling operation is performed when the upper surface of the electrolyte 3 inside the battery cell 11 rises beyond the position where the liquid level detector 14 installed in the battery cell housing 13 is installed. 14 is detected and changed from OFF to ON, the controller 8 recognizes this, sends a switching signal to the switching valve 51, and the switching valve 51 is shown in the “switching valve operation” diagram on the lower side of FIG. 3. By switching from “(y) electrolyte solution filling” to a position of “(z) stop”, the electrolyte solution filling mode ends.

Since other operations are the same as those in the first embodiment, the description thereof is omitted.

A third embodiment will be described with reference to the drawings. FIG. 5 is a third overall configuration diagram of the magnesium battery system, and FIG. 6 is a flowchart of the electrolyte solution of the third configuration.

As shown in FIG. 5, in this embodiment, the battery cell 11, the electrolyte pump 41 (only one pump is required in this embodiment, so simply called the electrolyte pump 41), the product separation mechanism 211, and The electrolyte solution cooling mechanism 212 is the same as that of the first embodiment in that an annular first path that circulates by connecting with piping in the order described is formed.

Further, a switching valve 51 as a switching mechanism is installed in the middle of the pipe 71 connecting the product separation mechanism 211 and the electrolytic solution cooling mechanism 212, and an electrolytic solution that has one outlet at the bottom of the electrolytic solution storage tank 213. The point connected to the entrance / exit 217 is the same as in the second embodiment.

In the present embodiment, the electrolyte storage tank 213 has an air circulation port 214 in the upper part and is circulating in the atmosphere. Therefore, even if the electrolyte 3 enters and exits from the lower electrolyte inlet / outlet 217, the electrolyte storage tank The pressure inside 213 does not change.

Further, as can be seen from the description of FIG. 5, the electrolyte solution inlet / outlet 217 at the bottom of the electrolyte solution storage tank 213 is installed at a position higher than the electrolyte solution inlet at the top of the battery cell 11. Therefore, since the battery cell 11 is disposed at a position lower than the electrolyte storage tank 213, the electrolyte cell 3 can be filled into the battery cell 11 by gravity through the electrolyte cooling mechanism 212. No special transfer device is required.

Therefore, in the present embodiment, the second electrolyte pump 42 existing in the first embodiment is not necessary, except that there is no output to the electrolyte pump 42 in the controller 8 of the first embodiment shown in FIG. That is, the same as in the first embodiment.

The flow of the electrolytic solution 3 will be described in detail with reference to FIG. The continuous power generation mode shown in FIG. 6A is the same as that in the first embodiment. That is, the power generation is possible mode (the electrolytic solution 3 is filled in the battery cell 11, the product separation mechanism 211, the electrolytic solution cooling mechanism 212, the piping 71 connecting them, and the like, and is in a state where electric power can be generated) or power generation. When “electrolyte circulation” is input on the operation panel 81 in the middle mode (the load is connected in the power generation enable mode), the power supply from the controller 8 to the electrolyte pump 41 is output and the operation is started. At the beginning, by the output of the switching signal to the switching valve 51, the switching valve 51 changes from “(z) stop” to “(w) electrolyte circulation” as shown in the “operation diagram” of the switching valve at the bottom of FIG. ”And the electrolyte 3 entering from the lower side of the switching valve comes out to the left.

As a result, the outlet of the product separation mechanism 211 is connected to the inlet of the electrolyte cooling mechanism 212, and the electrolyte solution passes through the first path of the battery cell 11 -electrolyte pump 41 -product separation mechanism 211 -electrolyte cooling mechanism 212. 3 circulates. In this state, power generation starts when a load is connected to the battery cell 11, or power generation is continued when a load is connected, and power is continuously supplied to the load as in the first and second embodiments. It is.

Next, when in the continuous power generation mode, when the load is disconnected and “electrolyte storage” is input on the operation panel 81, a switching signal is output from the controller 8 to the switching valve 51, and the lower part of FIG. The switching valve 51 is switched from the position “(w) electrolyte circulation” or “(z) stop” to the position “(x) electrolyte storage” as shown in FIG. The electrolyte 3 that has entered from the lower side of the valve comes to the right.

That is, by switching the switching valve 51 to “(x) electrolyte storage”, the outlet of the product separation mechanism 211 and the electrolyte storage tank 213 are changed as shown by the electrolyte storage in the flowchart of FIG. An electrolyte outlet / inlet 217 is connected. As a result, the flow of the electrolytic solution 3 is separated from the first circulating circular path, and the electrolytic solution 3 pumped by the electrolytic solution pump 41 passes through the product separation mechanism 211 and is further electrolyzed in the electrolytic solution storage tank 213. It is transferred to the electrolyte storage tank 213 via the liquid inlet / outlet 217 and stored.

The operation of storing the electrolytic solution continues as long as the liquid level of the electrolytic solution 3 is above the lower ends of the electrodes and the liquid level detector 15 installed in the battery cell 11 is in an ON state. When the liquid level of the electrolytic solution 3 is below the lower end of the electrodes and the liquid level detector 15 detects this and turns OFF, the controller 8 recognizes this, and a switching signal is output to the switching valve to switch. The valve 51 is in the “(z) stop” position, the power supply to the electrolyte pump 41 is cut off, and the electrolyte pump 41 stops its operation.

At this time, since the positive and negative electrodes do not come into contact with the electrolyte solution 3 in the battery cell 11, the power generation is stopped and no self-discharge occurs. The same as in Examples 1 and 2. The operation stop mode in FIG. 5B shows the state of the electrolyte 3 when the operation of storing the electrolyte is completed and the operation stop mode is entered.

Next, a procedure for restarting power generation will be described. When "electrolyte filling" is input on the operation panel 81 in the operation stop mode, a switching signal is output from the controller 8 to the switching valve 51, and the "switching valve operation" shown in the lower part of FIG. As shown, the switching valve 51 is switched from the “(z) stop” position to the “(y) electrolyte filling” position, and the electrolyte 3 entering from the right side of the switching valve comes to the left.

That is, in FIG. 6C, in the electrolyte filling mode, the switching valve 51 is switched to connect the electrolyte inlet / outlet 217 of the electrolyte storage tank 213 and the inlet of the electrolyte cooling mechanism 212. The electrolytic solution 3 in the electrolytic solution storage tank 213 is filled into the battery cell housing 13 from the electrolytic solution inlet 135 of the battery cell 11 via the electrolytic solution cooling mechanism 212 by the action of gravity. At this time, since the electrolyte solution 3 is transferred by gravity, a special transfer device for transferring the electrolyte solution 3 such as a pump is not necessary.

The operation of filling the electrolytic solution is performed when the upper surface of the electrolytic solution 3 inside the battery cell 11 rises above the level of the liquid level detector 14 installed in the battery cell housing 13. Is detected, and the controller 8 recognizes this, sends a switching signal to the switching valve 51, and switches to the “(z) stop” position in the figure showing “switching valve operation”. The process ends and shifts to the power generation possible mode.

Since other operations are the same as those in the first embodiment, the description thereof is omitted.

A fourth embodiment will be described with reference to the drawings. The present embodiment is a configuration for realizing a high voltage output by connecting a plurality of power generation cells in series. FIG. 10 is an overall configuration diagram of battery cells connected in series. As already described, in order to reduce the cost of the configuration of the magnesium battery system, a problem of liquid junction occurs when trying to share the product separation mechanism and the electrolyte cooling mechanism among a plurality of battery cells. This embodiment solves the problem of liquid junction.

In FIG. 10, a plurality of battery cells 11 (battery cells 11a to 11n) are connected in series by electrical wiring (not shown) and can be connected to or disconnected from a load (not shown). For convenience of illustration, the plurality of battery cells 11a to 11n are written so as to be arranged vertically, but in actuality, they are arranged horizontally with the bottom surface at the same height. Moreover, it is placed with the electrode terminal facing up.

In addition, alphabets a to n in the respective symbols appearing in the following description indicate that the components and parts of the symbols are related to the corresponding battery cells 11a to 11n. Here, n represents, for example, a case where there are 14 battery cells, and may be m (13), p (16), or the like depending on the actual number of cells.

Each battery cell 11 is provided with an inlet valve 61 and an outlet valve 62 for the electrolytic solution 3, and the outlet valve 62 is combined and combined into a single unit by a plurality of battery cells 11. The product separation mechanism 211 and the electrolyte solution cooling mechanism 212 are connected in this order. The output side of the electrolyte solution cooling mechanism 212 is connected in a multiple manner so as to be distributed to the inlet valves 61 of the plurality of battery cells 11, and the electrolyte solution 3 circulates. The first route is configured.

In the present embodiment, the electrolytic solution storage tank 213 is connected to the pipe 71 between the product separation mechanism 211 and the electrolytic solution cooling mechanism 212 as in the third embodiment, and is connected to the battery cell 11. The electrolytic solution is filled by gravity.

An inverted U-shaped pipe 73 is installed on the outlet side of each outlet valve 62. An air conduction pipe 72 extending above the height of the battery cell 11 is connected to the apex of the inverted U-shaped pipe 73 (the position of the bottom of the U-shape), and each air conduction pipe 72 is connected in a multiple manner and integrated into one. Thus, the air is released to the atmosphere via the air release valve 63 that is normally closed.

The inlet valves 61a to 61n and the outlet valves 62a to 62n are formed of an insulating material, and the passage of the electrolytic solution 3 of the battery cell 11 is blocked by the inlet valve 61 and the outlet valve 62. Can also be blocked. However, in the inlet valve 61 and the outlet valve 62, the inlet side and the outlet side of the valve are close to each other in distance, and there is a risk of energization due to current leakage through the gap of the valve mechanism. In the present invention, by providing a part where the electrolyte does not exist in the middle of the electrolyte passage, and providing a sufficient separation distance between the front and rear electrolytes, the electrolytes in the plurality of battery cells are completely electrically insulated. It is devised to take.

That is, at a certain moment, at least one of the plurality of battery cells is connected to the first path of the electrolytic solution, and the other battery cells are electrically connected from the first path by the portion without the electrolytic solution. As a result, the electrolytes of all battery cells are always electrically isolated from one another during power generation. Therefore, power generation operation can be performed in series connection without generating a liquid junction.

In FIG. 10, only the first battery cell 11a is connected to the first path through which the electrolytic solution circulates, and the other battery cells 11b to 11n are disconnected from the first path through which the electrolytic solution circulates. Indicates the state. That is, the inlet valve 61a and the outlet valve 62a of the first battery cell 11a are open, and the electrolytic solution 3 can be freely circulated. The other inlet cells 61b to 61n and outlet valves 62b to 62n of the battery cells 11b to 11n are all closed.

In the battery cells 11b to 11n other than the first battery cell 11a, the presence of the electrolyte solution between the valve opening on the battery cell side of the inlet valves 61b to 61n and the upper surface of the electrolyte solution 3 of the battery cells 11b to 11n. In addition, in the outlet valves 62b to 62n, a space in which the electrolyte 3 does not exist is provided above the inverted U-shaped tubes 73b to 73n respectively installed on the valve ports opposite to the battery cells 11. Thus, each electrolyte solution 3 of the plurality of battery cells 11 is configured to be electrically insulated from the first path and not to cause a liquid junction.

In this state, the electrolytic solution 3 of the first battery cell 11a can flow through the first path, but the first path is not connected to the other battery cells 11b to 11n as the electrolytic solution. Therefore, since the first battery cell 11a is in a state that constitutes the first path that circulates in the same manner as in the third embodiment, the electrolyte solution 3 of the battery cell 11a does not generate a liquid junction. Can circulate through the first annular path to separate the product in the electrolyte and to cool the electrolyte itself.

When the concentration of the product in the electrolytic solution 3 of the first battery cell 11a is sufficiently lowered, and the temperature of the electrolytic solution is sufficiently lowered, and the treatment is completed, the first battery cell 11a Is separated from the first path through which the electrolyte circulates, and then the second battery cell 11b is connected to the first path, and the product separation that has been performed on the electrolyte from the battery cell 11a so far By using the mechanism 211 and the electrolyte cooling mechanism 212 as they are, the electrolyte 3 from the second battery cell 11b can be processed.

Thus, the product separation mechanism 211 and the electrolyte solution cooling mechanism 212 can be used in a time-sharing manner with the plurality of battery cells 11a to 11n. FIG. 16 is a timing chart in which a plurality of battery cells 11a to 11n are connected in series and the electrolytic solution in each battery cell 11 is sequentially processed.

On the time axis of the plurality of battery cells 11a to 11n shown in the column of electrolytic solution circulation in FIG. 16, the portions rising in a pulse form indicate the time tx during which the electrolytic solution of the battery cell 11 is processed. Yes. Processing of the electrolyte solution of one battery cell is performed every time tw. The time required to process the electrolyte of one battery cell is tx (tx <tw). When the processing of the electrolyte solution of one battery cell is completed, the processing of the next battery cell starts. When the processing of the electrolytic solution of the final battery cell 11n is finished, the process returns to the first battery cell 11a, and the time T (T> 14tw, 14 of the battery cells 11a to 11n from the time when the first processing is started first. In the case of a single cell), the electrolytic solution treatment is repeated in the same manner from the first battery cell 11a.

Here, the processing capacity of the product separation mechanism 211 and the electrolyte cooling mechanism 212 is determined so that the time tx is shorter than the time tw and 14tw (in the case of the battery cells 11a to 11n) is shorter than T. Needless to say, is important. Thus, even if it is the structure by which the some battery cell was connected in series, electric power generation can be continued without stopping on the way by carrying out product separation and cooling of electrolyte solution one by one.

This will be described in detail with reference to the sequence charts of FIGS. 13 to 15 in order to obtain a space in which the electrolytic solution 3 does not exist in the middle of the electrolytic solution passage as described above. It is assumed that the electrolytic solution 3 is circulated like the first battery cell 11a shown in FIG.

FIG. 14 is a sequence chart during operation (power generation and electrolyte circulation mode). When the inlet valve 61a and the outlet valve 62a of the battery cell 11a are opened at the place where the sequence number S01 is added outside the frame, the electrolyte pump 41 is already activated, so that the electrolyte 3 circulates in the first path. To start. When the time tx for completing the processing required for the electrolytic solution 3 by the product separation mechanism and the electrolytic solution cooling mechanism elapses (S02, YES), the inlet valve 61a is closed and the switching valve is simultaneously set to “(x) electrolytic solution storage”. ”(S03).

When the liquid level of the electrolytic solution falls and the liquid level detector 14a is turned off (S04, YES), the outlet valve 62a is closed. At this time, a space where the electrolyte 3 does not exist is formed between the inlet valve 61a and the liquid surface, and as a result, insulation between the electrolyte 3 of the battery cell 11a and the inlet valve 61a is established.

Thereafter, the atmosphere release valve 63 is opened and closed for a short time (S06). When the air release valve 63 is closed, the switching valve 51 is simultaneously switched to the position “(w) electrolyte circulation” (S07). At this time, the electrolytic solution 3 inside the right portion in the figure of the inverted U-shaped tube 73 is extracted by the suction force of the electrolyte pump 41, and the left portion in the diagram of the inverted U-shaped tube 73 is electrolyzed. A space in which the electrolytic solution 3 does not exist is formed between the liquids 3. As a result, insulation of the electrolyte 3 of the battery cell 11a from the electrolyte 3 of the other battery cells 11b to 11n is established by the space generated in the inverted U-shaped tube.

When the processing of the electrolytic solution inside the battery cell 11a is finished and the processing of the battery cell 11a is started and the time tw has elapsed, the process proceeds to the next processing of the second battery cell 11b. After the processing of the electrolytic solution 3 of all the battery cells 11 is finished, the processing of the first battery cell 11a is started again after waiting for the time T to elapse after the processing of the first battery cell 11a is started. To do. By repeating this procedure, power generation can be continued.

Next, the procedure for stopping the power generation and storing the electrolyte 3 will be described with reference to the sequence chart of FIG. First, the load connected to the magnesium battery system is disconnected. The switching valve 51 is switched to the position “(x) electrolyte storage”, and at the same time, the inlet valves 61 that are open at that time are closed (all the inlet valves are closed), and all the outlet valves 62 are turned on. open. The electrolytic solution 3 stops circulating through the first path, and proceeds to the second path toward the electrolytic solution storage tank 213.

This procedure can be started in any battery cell during treatment of the electrolyte. In the timing chart shown in FIG. 16, the storing operation is started during the processing of the battery cell 11m immediately before the battery cell 11n.

Since the liquid level of the electrolyte solution 3 in all the battery cells 11 is gradually lowered, when the output of each of the liquid level detectors 15a to 15n is turned OFF after the level of the liquid level detector 15 is lowered, The outlet valves 62a to 62n of the battery cell 11 are each quickly closed individually. When all the liquid level detectors 15a to 15n are turned off, the electrolytic solution storage mode is ended. Therefore, the electrolytic solution pump is stopped, and the switching valve 51 is switched to the “(z) stop” position.

Next, a procedure for filling the battery cell 11 with the electrolyte 3 in preparation for power generation will be described with reference to the sequence chart of FIG. First, all the inlet valves 61a to 61n are opened, and at the same time, the switching valve 51 is switched from the “(z) stop” to the “(y) electrolyte filling” position. The electrolytic solution 3 stored in the electrolytic solution storage tank 213 passes through the electrolytic solution cooling mechanism 212 and flows into each battery cell 11 by gravity.

As can be seen from “electrolyte capacity in battery cell” in FIG. 16, the liquid level of the electrolyte solution 3 in each of the battery cells 11 a to 11 n gradually rises. When the level of the liquid level detector 14 rises and the outputs of the level detectors 14a to 14n are turned on, the inlet valves 61a to 61n of the battery cell 11 are individually closed. When all the liquid level detectors 14a to 14n are turned on, the switching valve is switched to the “(z) stop” position.

Next, a procedure for starting power generation when the battery cell 11 is filled with the electrolytic solution 3 will be described along the first half of the sequence chart of FIG. First, the electrolyte pump 41 is activated. Subsequently, the switching valve 51 is switched to the position “(w) electrolyte circulation”. Subsequently, a load is connected. Thereafter, the processing of the electrolytic solution 3 of each of the battery cells 11a to 11n is sequentially started in accordance with the steps after S01 already described.

The operation of the magnesium battery system connected in series described here can be automatically controlled by the controller shown in FIG. The difference in hardware from the controller when there is one battery cell shown in FIG. 11 is that there are a plurality of inputs from the liquid level detector and outputs to the inlet and outlet valves in accordance with the number of battery cells ( In this embodiment, the number is 14). The difference in software is that the logic for using the product separation mechanism and the electrolyte cooling mechanism in a time division manner in a plurality of battery cells as described above is added.

The other points are the same as in the third embodiment. In this way, a plurality of battery cells can share the same pump, product separation mechanism and electrolyte cooling mechanism in a time-sharing manner, and a simple configuration can be realized.

The fourth embodiment has been described as the same as the third embodiment in which the electrolyte storage tank is installed between the product separation mechanism and the electrolyte cooling mechanism, but even if the same as the first embodiment or the second embodiment, The inlets of the electrolyte inlet valves of the plurality of battery cells 11a to 11n are combined into one connected in a double connection, connected to the outlet of the electrolyte cooling mechanism 212, and the outlet of the inverted U-shaped pipe is connected in a multiple connection. If the control logic is integrated into one and connected to the electrolyte pump 41 to match the characteristics of the electrolyte storage tank to be used, it can be similarly applied.

Further, the inlet valve, the outlet valve, and the inverted U-shaped pipe can be integrated into a manifold type for miniaturization.

Moreover, it can replace with an air conduction pipe | tube using an appropriate air pressure source and an air valve instead of atmospheric pressure.

If two electrolytic solution storage tanks are installed, the first tank is used for storing unprocessed electrolytic solution, and the processed and low temperature electrolytic solution is stored in the second tank. The electrolytic solution contaminated with the product is extracted from each battery cell and stored in the first tank, and then the cycle is performed to fill the battery cell with the treated electrolytic solution from the second tank. Regardless of the power generation, the electrolyte in the first tank can be processed and stored in the second tank. According to this separation operation method, the entire cycle time T can be shortened. Alternatively, the throughput of the product separation mechanism and the electrolyte cooling mechanism can be reduced.

By storing and filling the electrolytic solution, it can be used as a magnesium battery system that can generate power or stop. Magnesium, which is an active material of a battery, can be used as a recyclable energy resource that can be reduced and reused.

DESCRIPTION OF SYMBOLS 1 Magnesium battery generation system 11 Battery cell 111 Positive electrode 112 Good conductor 113 Activated carbon 114 Porous body 121 Negative electrode 122 Magnesium alloy 13 Battery cell housing 131 Air hole 132 Gas discharge port 133 Air distribution port 134 Air valve 135 Electrolyte inlet 136 Electrolyte outlet 14 Liquid level detector 15 Liquid level detector 21 Electrolyte treatment module 211 Product separation mechanism 212 Electrolyte cooling mechanism 213 Electrolyte storage tank 214 Air flow port 215 Electrolyte inlet 216 Pipe 217 Electrolyte inlet / outlet 3 Electrolyte 41 First Electrolyte pump 42 Second electrolyte pump 51 Switching valve 61 Inlet valve 62 Outlet valve 63 Atmospheric release valve 64 Check valve 71 Pipe 72 Air conduction pipe 73 Reverse U-shaped pipe 8 Controller 81 Operation panel 9 Fuel cell 911 Gas flow entrance

Claims (5)

A battery cell, a product separation mechanism, an electrolyte cooling mechanism, an electrolyte storage tank, one or more electrolyte pumps, a switching mechanism, and a plurality of pipes and electrolytes that connect them as constituent elements,
The battery cell is an activated carbon layer that serves as a positive electrode, a good conductor layer, and a porous body layer that takes in air in this order, is opposed to a magnesium layer that serves as a negative electrode, and is collectively housed in a housing.
The product separation mechanism separates products and waste such as magnesium hydroxide generated when the battery cell generates power from the electrolyte when the electrolyte circulates,
The electrolyte cooling mechanism, when the electrolyte heated up by heat generated when the battery cells generate electricity circulates, cools the temperature to an appropriate temperature,
The electrolytic solution storage tank can store the electrolytic solution in an amount equal to or more than a predetermined amount required when the battery cell generates power,
The battery cell, the first electrolyte pump, the product separation mechanism, the electrolyte cooling mechanism, and the switching mechanism are connected by the pipes, and the components of the annular first path through which the electrolyte circulates None,
On the electrolyte delivery side of the first electrolyte pump, the switching mechanism forms a branch path that can guide the electrolyte away from the annular first path to the electrolyte storage tank. 2 routes and none,
An operation stop mode in which almost all of the electrolyte in the system is transferred and stored in the electrolyte storage tank, and the battery cell does not have an amount of the electrolyte necessary for power generation and cannot perform power generation operation;
Although the electrolyte does not circulate in the first path, the battery cell has a predetermined amount of the electrolyte necessary for power generation, and as long as a load is connected to both electrodes of the battery cell, power generation is immediately performed. Power generation possible mode,
The electrolyte does not circulate in the first path, but a predetermined amount of the electrolyte necessary for power generation exists in the battery cell, and loads are connected to both electrodes of the battery cell to generate power and connect A generating mode in which electricity is supplied to the generated load;
The electrolyte circulates in the first path, whereby a predetermined amount of the electrolyte necessary for power generation circulates in the battery cell, and circulates by the product separation mechanism and the electrolyte cooling mechanism. Performing the product separation and the cooling treatment on the electrolyte, and by connecting a load to both electrodes of the battery cell, continuous power generation capable of immediately starting power generation,
The electrolyte circulates in the first path, whereby a predetermined amount of the electrolyte necessary for power generation circulates in the battery cell, and circulates by the product separation mechanism and the electrolyte cooling mechanism. 5 modes including continuous power generation mode in which the product is separated from the liquid and the cooling process is performed, loads are connected to both electrodes of the battery cell, power generation is started, and electricity is supplied to the connected loads. Have
In the shutdown mode, induce electrolytic solution stored in the electrolytic liquid storage tank so as to fill all of the components of the first path from the electrolytic liquid storage tank, the generation of the battery cell By charging with the required amount of the electrolyte solution, as long as a load is connected to both electrodes of the battery cell, the state transition can be made to the power generation possible mode in which a chemical reaction for power generation is possible,
On the other hand, in the power generation possible mode, the electrolytic solution filled in the battery cell that is a component of the first path is passed through the second path branched from the first path. By transferring and storing in a liquid storage tank and emptying the electrolyte in each battery cell, it is possible to transition to the operation stop mode in which a chemical reaction for power generation is impossible,
Furthermore, by connecting a load to both poles of the battery cell in the power generation possible mode, it is possible to start power generation and transition to the power generation mode for supplying power to the connected load,
Conversely, by disconnecting the load from both electrodes of the battery cell in the power generation mode, the power generation is stopped, and whenever the load is connected, the state can be changed to the power generation possible mode in which power generation can be started.
Furthermore, in the power generation mode, the product separation mechanism and the electrolyte cooling are performed with respect to the electrolyte by operating the first electrolyte pump to circulate the electrolyte through the first path. The state can be changed to the continuous power generation mode in which the product separation and the cooling treatment are performed by a mechanism,
Conversely, in the continuous power generation mode, the first electrolyte pump is stopped to stop the electrolyte from circulating through the first path, thereby separating the product from the electrolyte. It is possible to make a state transition to the power generation mode without performing the cooling process,
Furthermore, in the continuous power generation mode, by disconnecting the load from both poles of the battery cell, the power generation is stopped, and the state transition can be made to the continuous power generation capable mode where the power generation can be started at any time by connecting the load,
Conversely, in the continuous power generation possible mode, by connecting a load to both poles of the battery cell, the state can be changed to the continuous power generation mode,
Furthermore, in the continuous power generation possible mode, the first electrolytic solution pump is stopped, and the electrolytic solution is stopped from circulating through the first path, thereby separating the product from the electrolytic solution as well as the electrolytic solution. It is possible to make a state transition to the power generation possible mode without performing the cooling process,
Conversely, in the power generation possible mode, the product is separated and cooled by operating the first electrolyte pump and circulating the electrolyte through the first path. State transition to continuous power generation possible mode,
A magnesium battery system, wherein power generation is started / stopped and operation stopped by appropriately changing the state in each of the five modes. The magnesium battery system according to claim 1,
The switching mechanism for forming the first and second paths is a switching valve;
The electrolyte storage tank has an inlet and an outlet for the electrolyte separately,
The inlet is connected to the switching valve;
The outlet is connected to a pipe connecting the switching valve and the electrolyte cooling mechanism of the first path via a second electrolyte pump,
When the electrolyte is stored, it is transferred to the electrolyte storage tank by the first electrolyte pump via the second path branched from the middle of the first path,
At the time of filling the electrolyte, the electrolyte is returned to the first path from the outlet of the electrolyte storage tank by the second electrolyte pump, and the first path below the battery cell is returned to the first path. The magnesium battery system, wherein the component is filled. The magnesium battery system according to claim 1,
The switching mechanism for forming the first and second paths is a switching valve;
The electrolyte storage tank has a single inlet / outlet for the electrolyte at the bottom and is sealed at the top,
The inlet / outlet is connected to the switching valve arranged on the electrolyte delivery side of the first electrolyte pump,
When the electrolytic solution is stored, the electrolytic solution is pumped and accumulated in a space formed in the upper portion of the electrolytic solution storage tank through the second path branched from the first path by the switching valve. The electrolyte is pushed into the electrolyte storage tank against the pressure of the gas formed,
At the time of filling the electrolytic solution, the electrolytic solution is returned from the electrolytic solution storage tank through the second path to the first path by the pressure of the gas to form the first path. A magnesium battery system characterized in that all of the constituent elements are filled. The magnesium battery system according to claim 1,
The switching mechanism for forming the second path is a switching valve;
The electrolyte storage tank is installed at a position higher than the battery cell, and has a single inlet / outlet for the electrolyte at the bottom,
When the electrolytic solution is stored, the electrolytic solution is pushed up against gravity by the electrolytic solution pump from the first route through the second route and stored in the electrolytic solution storage tank.
At the time of filling the electrolytic solution, the electrolytic solution stored in the electrolytic solution storage tank is returned to the first route by gravity through the second route, and the configuration of the first route is set. A magnesium battery system characterized in that all of the elements are filled. The magnesium battery system according to claim 1,
A plurality of the battery cells, electrically connected in series;
Each of the plurality of battery cells includes an electrolyte inlet valve and an outlet valve,
The piping for connecting the plurality of battery cells, the electrolyte pump, the product separation mechanism, and the electrolyte cooling mechanism to configure the first path is from the outlet side of the electrolyte cooling mechanism, A plurality of battery cells are branched so that they can be distributed to the plurality of battery cells, and the branch destinations are connected to the inlet sides of the plurality of inlet valves, respectively.
Also, the outlet sides of the plurality of outlet valves of the plurality of battery cells are aggregated into one pipe.
Of the plurality of battery cells, only the electrolyte solution of at most one battery cell can circulate in the first path, and constitute each first path of all the remaining battery cells. By having a space in which the electrolyte solution does not exist in the pipe or the battery cell, the electrolyte solutions of the other battery cells are electrically separated from each other and the electrolyte solution in the first path. Magnesium battery system characterized in that