JPS6037652A - Electrolyte circulation type concentric battery - Google Patents

Abstract

PURPOSE:To evenly distribute electrolyte to each electrolytic cell by forming the enlarged diameter part at the center of electrolyte supply piping or of exhaust piping while forming an electrolyte flowing-in port or a flowing-out port. CONSTITUTION:Positive pole liquid of the main pipe 29 for supplying positive pole liquid flows into the inside of the enlarged diameter part 31a from a flowing-in port 31b provided at the center of the enlarged diameter part 31a for being supplied to the piping parts 31c and 31c having the small pipe diameter near both ends from the enlarged diameter part 31a so as not to generate large fluid pressure even on the small piping parts 31c and 31c of the pipe while accordingly generating no large shunt loss inside the piping 31 thus being able to evenly supply the positive pole liquid supplied to the supply piping 31 to the respective positive pole liquid chambers 22,... of the respective electrolytic cells 21a-21n through each branch pipe. The same is with the piping for supplying the negative pole liquid. Further, the enlarged diameter part may be formed at the center of the piping for exhausting the positive pole liquid as well as of the piping for exhausting the negative pole liquid while providing the flowing-out port of electrolyte at the center of the enlarged diameter part.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the structure of an electrolyte flow type assembled battery, such as a redox flue type assembled battery, which is made possible to do so.

Electric power is easy to convert into various types of energy and easy to control.
Since there is no environmental pollution during consumption, the proportion of energy consumption is increasing every year.

A unique feature of electricity supply is that production and consumption occur simultaneously. Within this constraint, the environment for power technology is to reliably transmit high-quality power at a constant frequency and constant voltage while responding quickly to fluctuations in power consumption. In reality, nuclear power generation and new thermal power generation, whose output is difficult to change but are highly efficient, are operated at the highest efficiency rating, and hydropower is suitable for generating power in response to fluctuations in kinesthetic power consumption. Currently, the large increase in demand for electricity during the daytime is met through power generation and other means.

For this reason, pumped storage power generation is used to store surplus electricity at night from economically viable nuclear power generation and cutting-edge thermal power generation.
Location conditions for pumped storage power generation are becoming increasingly difficult.

In view of the above-mentioned circumstances, various types of secondary batteries are being researched as a method of storing electricity, which is a highly versatile energy without environmental pollution, and among these, redox batteries are attracting particular attention.

An outline of this principle will be explained using FIG. 1 and FIG. 2.

FIG. 1 shows a charging state of a power storage system using a redox battery, and FIG. 2 similarly shows a discharging state.

In these figures, l is the power plant, C is the substation equipment, 3 is the load, G is the inverter, S is the redox battery, and the tank 6αr'by7 (L+7b and pump K).

? and a flow-through type electrolytic cell 10.

The flow-through electrolytic cell IO is equipped with a positive electrode//, a negative electrode/co, and a diaphragm 13 that separates both electrodes, and the left and right chambers separated by the diaphragm/3 contain a cathode solution/l/-1 anode solution 15. The catholyte/11. For example, a hydrochloric acid solution containing PC ions is used for closing, and for example, a hydrochloric acid solution containing q ions is used for the negative electrode solution/S.

In the above configuration, the power generated at the power station/transformer equipment is transformed to an appropriate voltage and supplied to the load 3.

On the other hand, when surplus power is generated at night, the inverter 1 performs evening direct conversion and charges the redox battery 5. In this case, 6α from tank Ab as shown in Figure 1.
To, tank 7a, b, hebong, g, positive, negative electrode liquid/
lI, l! Charging is performed while gradually sending Fe ions in positive electrode solution/q, negative electrode solution/! When using Cτ ions for r, the reactions that occur in the flow-through electrolytic cell IO are shown in box (1) below.
This is the reaction on the charging side in equation (3).

In this way, power is stored in the catholyte/l11 anode/S.

Next, if the supplied power is less than the demanded power, as shown in FIG. positive and negative poles fttlI.

/S is gradually fed, a discharge is performed by the reaction on the discharge side in equations (1) to (3), orthogonal conversion is performed by inverter q, and power is supplied to load 3 via substation equipment λ. be done.

The above explanation is a common explanation for power storage systems using redox batteries, but in reality, the redox flow type batteries described above are made by connecting multiple cells in series to form an aggregate battery, and this aggregate battery is then combined into multiple batteries. By connecting in series and/or in parallel, the required voltage and the required capacity can be obtained.

By the way, the problems with flow-through type electrolyzers for such assembled batteries are: (1) The characteristics of each cell are the same. For this purpose, the amount of electrolyte supplied to each cell must be equal.

(2) Use a DC voltage control design. To do this, it is necessary to connect the main pipe to the ground side of the battery pack. If the main piping is not grounded, it will be difficult to prevent corrosion and direct current insulation of tanks, pumps, etc.

(3) Reduce the power of the pump that flows the electrolyte.

(4) Suppress chantrosity. etc.

However, no conventional redox flow type assembled battery structure has been found that satisfies all of the requirements (1) to (4).

Therefore, the inventors of the present application first proposed the piping method for redox flow batteries as described below.
No. 5654).

To explain this according to FIG. 3, 20 and 20B are a pair of assembled batteries composed of n pieces of circulating electrolytic cells lα~ko/n, and each flow type electrolytic cell ko/a~-/n is Each of them has a positive electrode liquid chamber (here), a negative electrode liquid chamber (3), a diaphragm (2) which partitions the compartments, and a positive electrode (2) left in the positive electrode liquid chamber (2), and a negative electrode (2) in the negative electrode liquid chamber (3).

Hiko's collective battery: In this example, lOA and 20B are the corresponding flow-through electrolytic cells, 21a, ~"n121 (L~
2/, are arranged facing each other, and the assembled batteries JoA and 2
One end of the battery assembly composed of 0B is grounded as a negative terminal, and the other end is a positive terminal.

On the other hand, 9 and 30 are negative electrode terminals, the main cathode liquid supply pipe and the main cathode liquid discharge pipe provided on the 27 side, and 3/ and 32 are the respective flow-through type electrolytic cells lα~, 2/? L, 2/a-2In positive electrode liquid supply piping, l? J, Jda are each of the above flow-type electrolytic cells, 2
/a~Y/n, , 21α~Co/n positive electrode liquid discharge piping.

The positive electrode supply pipes J/ and 3 are connected at high voltage sides p, , pf, and the ground side of the positive electrode supply pipe 3/ is connected to the main positive electrode supply pipe 29. Further, the cathode liquid discharge pipes j3 and 31I are connected at the high voltage sides Pt and P's, respectively, and the ground side of the cathode liquid discharge pipe 31I is connected to the main cathode discharge pipe 30.

3 again! ;,, 3A is the positive electrode liquid supply pipe, the negative electrode liquid main pipe and the negative electrode liquid discharge main pipe provided on the negative electrode terminal 27 side, similar to the positive electrode liquid discharge main pipe 30; 37°3g is the above-mentioned flow type electrolytic Tank 2/α ~ Co/n, U/(Z-co/71 negative electrode liquid supply piping, 39.QO is each flow type electrolytic cell 21α above
~21n, 21α~21fL negative electrode liquid discharge piping.

Similarly, on the negative electrode liquid side, the negative electrode liquid supply pipe 39°41o is connected on the high pressure side, and the negative electrode liquid supply pipe 3de is connected to the negative electrode liquid supply main pipe 33. Also, negative electrode liquid discharge pipe J9,
lIO is connected on the high voltage side, and the ground side of the negative electrode liquid discharge pipe qo is connected to the negative electrode liquid discharge main pipe 36.

In this way, when two battery packs, ZOA, and IOB are combined and piped, each flow-type electrolytic cell 21α to col lrL, ko/a to coi in each battery pack 20A, -0B is connected.
The lengths of the supply and discharge side piping for the positive and negative electrode liquids of n can be made equal, and the lengths of each main piping to ta, 3θ, and 36.8 can be made equal.
,3λ,3.3,Jke,8.3&,39,110
Since the connection can be made on the ground side, the characteristics of each cell can be made equal and a DC withstand voltage design can be achieved.

However, in the above piping method, (3) the pump power for flowing the electrolytic solution must be reduced. and (4) suppressing chantrosity. remains unresolved.

On the other hand, in order to solve problems (3) + (4), there is research by Ito et al. (Research on chemical energy, 1988 Research Results Report).

Among these, in a stack flow system as shown in Fig. 4, H=24, W=18.6=0.1, L
The relationship between the minimum diameter of the manifold required to flow an average flow rate Q per tank is shown when a stack is constructed by laminating 7 LN pipes with a diameter of 0.7.

The following correlation equation is shown under a=0.7 (constant).

N = 20,3 Q-0,fi [)L12 αa?
! (HAI) &H6, , (5) This equation is dimensional and Q (ml/x=tx, cell )f) Ccm
]a[1/crn], or the cell shape W, but it shows that it depends very much on the electrode area HXW.

On the other hand, the flow rate Q (→) in each tank of the stack is large at both ends of the stack and small at the center. The smaller D2 becomes, the larger it becomes.If D is increased, the flow rate of the six tanks will be made uniform, and the pump power will also become smaller.However, the shunt loss through the manifold will increase in proportion to D2.The shunt loss will become larger. Sometimes, it has been proposed that if only the diameters of both ends (N/1o) of the manifold are designed to be small, shunt loss can be suppressed without increasing the pump power.

However, if only the diameters at both ends of the pipe are reduced as described above, the flow rate will increase in the pipes that are the inlet of the electrolyte supply pipe and the outlet of the discharge pipe. @ Due to the external fluid pressure, the flow velocity of the electrolyte in the piping becomes uneven.

Therefore, there are disadvantages such as the electrolytic solution is not uniformly distributed to each electrolytic cell or a shunt loss occurs.

Therefore, in view of the above-mentioned circumstances, the inventors of the present application have solved the problem of inconveniences such as the electrolytic solution not being uniformly distributed to each electrolytic cell or the occurrence of shunt loss. As a result of intensive research to determine the solution, we found that in a redox flow type assembled battery, an enlarged diameter section was formed in the center of the electrolyte supply pipe, and an inflow port for the electrolyte was formed in the enlarged diameter section. We have discovered that such inconveniences can be solved.

That is, if an enlarged diameter section is formed in the center of the electrolyte supply piping as proposed by Ito et al. and the electrolyte is introduced from the end of the supply piping, a considerably large diameter portion will be generated at the end of the piping. Fluid pressure is generated, but if the inlet for the electrolyte is provided at the center of the enlarged diameter part and the electrolyte flows into the pipe from this as in this invention, the electrolyte will be subjected to a large fluid pressure. 〃It can be made to flow into the piping. Moreover, since the flow rate in the pipe decreases near the end of the pipe, there is no problem even if the pipe is made thinner. Therefore, the electrolytic solution can be uniformly distributed to each electrolytic cell without causing a shunt loss.

This invention is applied to an enlarged diameter portion 3/a in the center of the positive electrode liquid supply pipe 3/ in the redox flow type assembled battery shown in FIG.
To explain an embodiment in which an electrolyte inlet 3/l) is provided in the center of the enlarged diameter part 3/, the inflow 0.3/l) is provided.
i) is connected to the positive electrode liquid supply main pipe 29.

The positive electrode liquid in the main positive electrode supply pipe is supplied to the enlarged diameter section 3/α.
It flows into the enlarged diameter part 3/α from the inlet 31b provided in the center of the diameter part 3/α, and is supplied from the enlarged diameter part 3/α to the piping parts with small pipe diameters near both ends, 3/c, 3/c. Therefore, even in the small piping portions 3/c and 3/c of the pipe, large fluid pressure is not generated, and therefore a large shunt loss is not generated in the positive electrode liquid supply piping 3/, and the main supply piping is The positive electrode solution supplied to 3/ is passed through each branch pipe to each electrolytic cell 2.
1α to 2In catholyte chambers 2.2. ... can be uniformly supplied.

In the above embodiment, the positive electrode liquid supply pipe 3/ was explained, but other positive electrode liquid supply pipes 32, negative electrode liquid supply pipes, 3
By similarly configuring the electrodes 1 and 3g, the electrolytic solution can be uniformly supplied to each electrode solution chamber without causing a large shunt loss.

Also, positive electrode liquid discharge pipe 33.3'l, negative electrode liquid discharge pipe 39
．． An enlarged diameter portion may be formed at the center of the tube 410, and an outlet for the electrolytic solution may be provided at the center of the enlarged diameter portion.

In addition, when the battery pack becomes larger 1~, the positive electrode liquid supply piping 3/.

3.2 and when the length of the negative electrode liquid supply pipe 37.3g becomes long, provide a plurality of enlarged diameter parts at regular intervals along the length direction, and fill each of the enlarged diameter parts with electrolyte. An inlet may be provided.

Further, a positive electrode liquid discharge pipe 33. ．． 3'l and negative electrode liquid discharge piping 39, 11.0 as well, by forming an enlarged diameter part in the same manner as the above-mentioned electrode liquid supply pipe, the same effect as when providing an enlarged diameter part in the above supply pipe can be obtained. Hope can lead to hope.

According to research by the inventors of the present application, in the electrolyte flow type assembled battery as described above, when an enlarged diameter portion having an inlet and an outlet for the electrolyte is formed in the supply pipe and the discharge pipe for the electrolyte, respectively. ,'rIf the end of the supply port of the PLM liquid service line piping is located in the center of the electrolyte discharge piping,
Shunt loss can be suppressed and electrolyte can be uniformly supplied to the electrolytic cell.

That is, with the above configuration, even if the flow rate of the electrolyte becomes uneven in the supply pipe, for example, this uneven flow can be corrected by the discharge pipe installed asymmetrically. Ru.

Therefore, the shunt loss is suppressed, and at the same time, a uniform liquid solution can be supplied to each cell.

To explain this more specifically with the illustrated embodiment, FIG. 7 shows that in a redox flow type assembled battery, positive electrode liquid supply pipes J/ , . . , and the cathode liquid supply piping 3/, .
An enlarged diameter portion 3/α, . . . is formed at the center of the enlarged diameter portion 3/σ2. An electrolyte inlet 31b is located in the center of the
... is formed, while the above-mentioned flow-through type electrolytic cell 2/a -,
On the other side of /7L, there is a positive electrode liquid discharge pipe 33 along the length direction.
．． ... is provided, and an enlarged diameter portion 33α is formed in the center of the positive electrode liquid discharge pipe 33, and the enlarged diameter portion, 33c
In the center of L,..., 'gi dissolution outlet 33b,...
form.

From the above cathode liquid supply pipe 3/, a plurality of cathode liquid supply branch pipes 31, 1. Establish...
The branch pipes 3/d, . . . are flow-through type electrolytic cells, 2/α to λ/1
A plurality of positive electrode liquid discharge branch pipes 33d, . . . are connected to the negative side of the positive electrode chamber 33, and are provided along the length direction from the positive electrode liquid discharge pipe 33, and the branch pipes 33d, . ... in the positive electrode chamber 2. ... is connected to the other side, and at least one end supply port 3/e of the cathode liquid supply branch pipes aid, ... is connected to the central supply 1 of the cathode liquid discharge branch pipe 33d, ... ': It is arranged so as to correspond to J33e.

In the above configuration, in this embodiment, a pipe 29a5 is connected from the main cathode liquid supply pipe 29 to the cathode liquid supply pipe 3/.
Branch pipes 29b are connected from the pipes 2.9a to the positive electrode liquid inlets 31b, respectively.

... are provided, and the positive electrode liquid is supplied from the branch pipes 29b, ... to the enlarged diameter a3/a r... formed in the positive electrode liquid supply pipe 3/.

On the other hand, from the main cathode liquid discharge pipe g3θ, a pipe 30α is provided substantially parallel to the cathode liquid discharge pipe 33, and from the pipe 33σ, each of the pipes 33σ is connected to a positive electrode liquid outlet 33b, .

Branch pipes 3θb, . ? J
The cathode liquid discharged from J... is returned to the cathode liquid discharge main pipe 30 through the branch pipes 33b,..., piping, 3.30.

In the above structure, the positive electrode liquid supplied through the inlet 31b, . . . is supplied into the 2 positive electrode chambers, . Here,·
The positive electrode liquid discharged from the positive electrode liquid discharge pipe 33 passes through the outlet ports 33b formed in the enlarged diameter portion 33α, .
..., but in this case, the positive electrode liquid supply pipe 3/ and the discharge amount ga3 are the enlarged diameter section 3/α, ... and the enlarged diameter section 33α.
,... are established in the above relationship, so
For example, even if the flow rate of the electrolyte becomes non-uniform within the positive electrode solution supply pipe 3/, the above-described non-uniformity in the flow rate of the electrolyte is canceled out and corrected by the positive electrode solution discharge pipe 33.

Furthermore, with the above structure, the main flow of the cathode liquid connecting the cathode liquid supply pipe 3/, the cathode chamber unit, ... and the cathode liquid discharge pipe 33 is as shown by the arrow, The positive electrode liquid supplied to the enlarged diameter section 3/a passes through the shortest distance between the enlarged diameter section 3/α and the discharge pipe located at the above position, the enlarged diameter section 3 of 33.
Take the path that flows into 3α. This route is the same for all of the 1L disassembly tanks 2/a to 2In, and there is no difference in route, so there is no excess or deficiency in the supply of electrolyte.

On the other hand, if the enlarged diameter portions 31α, . . . and 33α, . , a flow path for the catholyte is formed at the end of the electrolytic cell, 2/cL-co/n, which is longer than the others, resulting in excess or deficiency in the supply of the catholyte.

The above description has been about the positive electrode liquid supply pipe 31 and discharge pipe 33, but the other positive electrode liquid supply pipe 32 and its discharge pipe 3da, and the negative electrode liquid supply pipe 37°3g and its discharge pipe 39, 3g can also be configured in exactly the same way.

On the other hand, as shown in FIG. 8, the cells of the above-mentioned assembled battery are placed inside a graphite plate 11. /cL and frame material such as PVC on the outside.
Bipolar plate Il/ with l/b, carbon cloth 4 (
, 2α, a positive electrode plate l/, 2 provided with a particle 1.2b such as PVC on the outside, a diaphragm plate 3 provided with an ion exchange membrane l/, 2cL inside, a carbon cloth tlIα provided inside, Frame material such as PVC on the outside 11. It is common practice to construct a battery by stacking negative electrode plates provided with a negative electrode plate, and by integrating 20 to 50 cells of these single cells to form an assembled battery.

In the above configuration, the positive electrode liquid supply pipe 3/, the negative electrode liquid supply pipe 3, the positive electrode liquid discharge pipe 33, and the negative electrode liquid discharge pipe 3
Reference numeral 9 indicates holes 31z provided in the bipolar plate, the positive electrode plate dowel, the diaphragm plate 3, and the negative electrode plate 41 at corresponding positions, respectively.
..., hole 372..., hole 33S..., hole 39'.

... is formed by overlapping each other, and Z is
In the nine assembled batteries as described above, the hole 3/'
, 37', ,? ,? Since the diameters of ', , 79' are standardized, as mentioned above, the pipes 3/, 3, 33.3
It is extremely difficult to form an enlarged diameter portion at the center of the diameter.

In this case, if the diameter reducing members lIg, qs are inserted from both ends into the standardized piping having the same diameter, and an enlarged diameter portion is formed in the gap between the ends, the expansion can be achieved very easily and economically. A diameter portion can be formed.

゛Although specific examples have been described above regarding redox flow type batteries, this invention is basic and common to battery packs in which an electrolyte is allowed to flow.

For this reason, secondary batteries such as zinc-chlorine batteries, zinc-bromine batteries, hydrogen-chlorine batteries, and hydrogen-bromine batteries that require circulation of electrolyte like redox flow batteries, and fuels such as methanol or hydrazine are used. It is also possible to configure an electrolyte distributor assembly battery having a similar piping structure for a fuel dissolving type fuel cell and an electrolyte circulation type hydrogen fuel cell that supply the electrolyte by dissolving it in an electrolyte.

[Brief explanation of the drawing]

Figures 1 and 2 are diagrams explaining the operating principle of a redox battery, Figure 3 is a diagram showing the conventional piping method for a redox battery, and Figure 4 is a diagram illustrating the operating principle of a redox battery.
The figure is a flow system diagram of the stack, and Figure 5 shows H=24.
W-18, when a stack is constructed by stacking N cells with b = 0.1 and L = 0.7, the relationship diagram of the minimum diameter of the manifold required to flow an average flow rate Q per tank, Figure 6 is a diagram showing a piping method for a redox battery according to an embodiment of the first invention of the present application, Figure 7 is a diagram showing a piping method of a redox battery according to an embodiment of the second invention of the present application, and Figure 8 is a diagram showing a piping method for a redox battery according to an embodiment of the second invention of the present application. FIG. 9 is a perspective view showing an example of the configuration of a unit cell in a redox battery, and FIG. 9 is a perspective view showing an example of forming an enlarged diameter portion in the pipe in the above embodiment. In the figure, ko/α~:2/n is an electrolyte flow type electrolytic cell, and 3/. 32 is the positive electrode liquid supply pipe 1. ? ,? ,,? Da is the positive electrode liquid discharge pipe, 37.3g is the negative electrode liquid supply pipe 1.39. lIO is a negative electrode liquid discharge pipe, 3/α, 33a is an enlarged diameter part, 31b is a positive electrode liquid inlet, and 33b is a positive electrode liquid outlet. Figure 1 Figure 2 Introduction 1

Claims (4)

[Claims] (1) In an electrolyte flow-through type battery that obtains electricity by supplying electrolyte through electrolyte supply piping to a flow-through electrolytic cell in which multiple electrolytes are connected in series and discharging the electrolyte through electrolyte discharge piping, the electrolyte supply piping is Alternatively, an electrolyte flow type assembled battery characterized in that an enlarged diameter part is formed in the center of the discharge pipe, and an inlet or an outlet for the electrolyte is formed in the enlarged diameter part. (2) A method according to claim 1, wherein pipes having the same diameter are used as the electrolytic solution supply pipe or discharge pipe, and a diameter reducing member is inserted into the pipe to form an enlarged diameter part in the center thereof. collective battery. (3) In an electrolyte flow-through type battery that obtains electricity by feeding electrolyte through electrolyte supply piping to a flow-through electrolytic cell in which multiple electrolytes are connected in series and discharging it through electrolyte discharge piping, the electrolyte supply piping is An enlarged diameter portion is formed in each of the and discharge piping, and an inlet and an outlet for the electrolyte are formed in the enlarged diameter portion, respectively, and the end of the supply port of the supply piping is located in the center of the discharge piping. An electrolyte flow type assembled battery characterized by being configured to (4) Use the same diameter as the electrolyte supply piping and electrolyte discharge piping, insert a diameter reducing member into the piping, and insert the inner diameter reducing member to form an enlarged diameter part inside the piping. The assembled battery according to claim 5.