JPS6047373A - Redox battery - Google Patents

Abstract

PURPOSE:To obtain a battery which has a low internal resistance and in which no liquid leakage is caused by impregnating the area of each laminar carbon fiber body other than the central area of its one or both surfaces with a thermosetting resin and stacking thus obtained plates; the area of each plate impregnated with the resin works as a collector electrode and the other areas consisting of only carbon fiber work as reaction electrodes. CONSTITUTION:An electrode plate (A) is a thin rectangular laminar body made of carbon fiber. The central areas of the surfaces of the plate (A) consist of only carbon fiber and these areas work as reaction electrodes (C). The remaining area of the plate (A) consisting of its periphery and inner area, constitute a collector electrode (B) impregnated with a thermosetting resin. The reaction electrodes (C) can contain solution because they consist of fiber. They are conductive because they consist of carbon. An assembled cell is formed by interposing diaphragms (E1, E2,..., En-1) between n electrode plates (A1, A2,..., An) in such a manner as to stack them in their thickness direction. Each of the plates (A1) and (An) located in the ends of the assembled cell has only one reaction electrode (C) on its one surface. Anolyte and catholyte are introduced to the reaction electrodes (C).

Description

[Detailed description of the invention] (7') Technique Branch This section 1) relates to the structure of a redox battery.

A redox battery is a secondary battery in which an electrolytic tank is partitioned with a diaphragm, a positive electrode and a zero electrode are immersed in the electrolytic tank, and charging and discharging are repeatedly performed by an oxidation-reduction reaction of the positive electrode and negative electrode liquid. Both the positive and negative electrode fluids contain reactants that are in an ionic state after i[I of the redox reaction. Due to changes in ionic valence,
The charging and discharging reaction is made to take place.

Positive) local liquid 2 and negative electrode liquid are stored in two or one tank and are pumped to the electrolytic cell by a horn. Since it has good volumetric efficiency, it is promising as a secondary battery for power storage.

FIG. 6 is a diagram illustrating the concept of a redox battery for single force storage.

Electric power generated at the power generation station 1 is transformed by the substation equipment 2, converted to DC by the inverter 4, and then transferred to the redox battery 5.
to charge.

Conversely, the electromotive force of the redox battery 5 is converted into alternating current by the inverter 4, and drives the load 3 via the substation equipment 2.

The redox battery 5 is partitioned by positive electrode liquid tanks 6a, 6b, negative electrode liquid tanks 7a, 7b, a pump 8.9 for circulating the positive electrode liquid 14, negative electrode liquid 15, and a partition 13.

The positive and negative electrode liquids are a combination of ion having two types of ionic valences, and a solution that allows ions to exist in the form of an aqueous solution. The solutions used are hydrochloric acid, phosphoric acid, and birophosphoric acid solutions.

(a) Those using hydrochloric acid solution Fe (3/2), Cr (2/3) Fe (3/2), Ti (3/4) (b) Those using lysoic acid solution Mn (3/2), Cr (2/3) Mn (3
/2), Cu (1/2) Cr (6/3)
, Cr (2,/3) (C) Using birophosphoric acid solution Mn (3/2), Cr (2/8) Cr (6
/3), Cr (2/3), etc. are known. ) is the valence.

For example, in a hydrochloric acid solution, Fe3+/Fe is used as the catholyte.
% negative electrode liquid containing Cr2+/Cr3+ will be explained below. The battery reaction at the positive and negative electrodes can be written as discharge positive electrode Fe''10-4-e − Fe2+ charge and discharge negative electrode Cr2+'' Cr3+10 e-charge.

A positive electrode solution Fe3+/Fe"+41 is stored in a tank 6a16b, and during charging, the Fe2+ solution is sent to the positive electrode side 10a of the electrolytic cell 10 by a pump 8, where it is oxidized and becomes Fe3-
' and is stored in the other tank. At the time of discharge
Fe 31 is sent to the electrolytic cell 10 by liquid or pump.
It turns yellow, becomes Fe2+, and returns to its original tank.

For the negative electrode liquid, the redox reaction occurs in reverse.

(a) Conventional technology and its problems The positive and negative electrodes of a redox battery are a combination of a current collecting electrode and a reaction electrode that also serves as a current reservoir.

Figure 7 does not show one volume of a redox battery.

A positive electrode 20, a diaphragm 21, and a negative electrode 22 are combined in the thickness direction.

In both the positive electrode 20 and the negative electrode 22, the reaction electrode 23 attached to the diaphragm 21 is made of porous carbon. If pole.

The reaction electrode 23 must not contain an aqueous solution and must be porous so that the battery reaction occurs inside it. Also, it is not corroded by the solution at a ratio of 6:1. Therefore, porous carbon dioxide is used as the reaction electrode 2.

The current collecting electrode 24 is a graph eye 1 electrode plate.

What about redox batteries between the reaction electrode and the current collection electrode? t'? There should be no moisture, so use paragin, etc.

It is used by attaching or bonding. The reaction box 1 pole and the collector Ia pole must be electrically connected (.

Therefore, if the contact resistance is large, the internal resistance of the battery will increase when connected in series.

If you put Balagin in between, the resistance tends to increase. Also, there is a possibility of liquid leaking when the paragin is sandwiched.

This is a current collector electrode (graphite) for the positive and negative electrodes.
This is a drawback due to the fact that it is separated into a reaction electrode (porous carbon) and a reaction electrode (porous carbon).

Anti-rj1): ? In tfl 4i★, the redox reaction must occur as efficiently as possible in a small volume. For this reason, a porous electrode with a large effective surface area cannot be used. For this reason, porous carbon powder compacts, carbon fiber nonwoven fabrics, carbon fHII: woven fabrics, etc. are used.

[11] The electrode must not be corroded by the electrolyte and must have sufficient electrical conductivity with the reaction electrode. For this reason, carbon carbon or graphite sintered bodies have traditionally been used.

The electrodes are also required to be conductive and not corrode. For the reaction to open, the solution must penetrate, and the solution must not penetrate into the current collecting electrode. Further, the reaction electrode and current collecting electrode must be electrically connected.

(1) Structure of the redox battery of the present invention The redox battery of the present invention has an electrode structure in which a reaction electrode and a collection '11C'11L electrode are integrated.

(1) The integrated electrode is made of a carbon fiber laminate, and (2) one side of the carbon fiber laminate or both (j
1], leaving the center part, is impregnated with a thermosetting resin, and the impregnated part is used as a "Kameden JiQi".

(3) One σf1 which is not impregnated or the middle +b portion of both surfaces is used as the reaction' positive electrode.

Here, the thermosetting resin IN! should be impregnated into the electrode! teeth,
These include epoxy resin, unsaturated polyester resin, urethane resin, silicone resin, and phenolic resin.

Impregnating the current collecting electrode with a thermosetting resin prevents the solution from seeping into the current collecting electrode.

Since the portion where the thermosetting resin is not present remains a carbon fiber laminate, the positive and negative electrode fluids can penetrate and flow therethrough.In other words, the reaction electrodes act together.

Current collector: Is the L pole endowed with conductivity by carbon fibers? If it is necessary to further lower the resistance, add slag or IL fine particles.

For example, J5 carbon powder, graphite powder, silver powder, etc. are kneaded into a thermosetting resin, and this composite resin is impregnated into a carbon fiber laminate.

This will be explained using drawings.

Figure 1 shows the surface of the electrode used in the redox battery of the invention.
- If (iJi there is a drawing.

It can be used for both positive and negative electrodes.

Electrode plate A! "It is a thin rectangular carbon fiber laminate. Leave the center part on both sides, and heat harden the periphery and middle layer f]S'
Collecting electrode B is impregnated with 100% fat.

In the second case, the current collecting electrode B has an H-shaped cross section.

The central part of the surface, which is not impregnated with the thermosetting resin, remains the Kerr fiber as it is, and the kneaded part becomes the reaction electrode C. 1) Although the electrode C is made of fiber, it can contain a solution, and since it is made of carbon, it is conductive.

;:a What is shown in Figures 1 and 2 is an electrode in the middle that constitutes an aggregate cell, and the electric currents at both ends of the electrode are designed to produce an 8% reaction on one side.

The structure of the aggregate cell will be explained with reference to FIG.

Set cell G, n pieces? Li electrode plates A1, A2,...
..., An, with a diaphragm "'1 ' E2, """,
Sandwich En-1 to make it thicker.

They are superimposed on each other.

The electrode plate of A2, ..., An-1 for middle j has anti-one-core electrodes C on both sides, but the electrode plates of A1 and An at both ends
The illi plate only has a reaction electrode C on one side.

Reaction '1 Hypole C1C is separated by a diaphragm, +
W ++t,> allows only H ions or Cβ−·r ions to pass through. Collection't1゜Positive electrodes B and B must be insulated.

To the reaction electrodes C, C, and the part where the ion exchange membrane is present, j
I: Functions as an electrolytic cell into which the electrode liquid and negative electrode liquid are introduced.

AI and An correspond to either a positive electrode or a negative electrode.

The middle A2, the mountain, and An l serve as the positive and negative electrodes. This aggregate cell is a collection of (n-1) single cells.
Functions as a battery.

Embodiment The battery structure of the present invention is as explained in the previous section, but actually requires a flow path for circulating the positive and negative electrode fluids within the reaction electrode.

The solution flow path includes a convex shoulder 1 which connects the solution bow to the passage connected to the outside from each electrode by installing a passage 4'- to the side communicating with the outside. In this case, each electrode plate requires four or two short hoses and joints.

One night of melting? It is also possible to drill lft paths in the thickness direction of the electrode plate. Figure 4 shows how to drill and install such a solution flow path. FIG. 1 is a perspective perspective view of the ij 1LIJi board.

Electricity (・ji 41 or A's current collector 'fL In the same material of pole B, there are 1 do f liquid passage holes 30, 31, 32, 33 in the j7 direction.
is perforated. Four holes are drilled at the same location G for all electrode plates. The diameter is the joint name of the through holes 30, . . . , 33, or a passage for the solution.

Two of the holes 4-1 are through holes for the positive electrode liquid, and the remaining two are through holes for the negative electrode liquid. and 2 positive, negative 1
It may be possible to use the through holes for the one-fold liquid, but in this case, a pair of diagonal holes are selected as the through holes for the same pole.

Since the solution must be conducted through the hole to the reaction electrode, a portion of the reaction electrode extends with a corresponding passage 6-5.

Does Figure 5 look like this? This is a cross-sectional view showing the flow of a solution when 1L electrode plates are stacked to form a collective cell, and for one electrode plate, it is a cross-sectional view taken along the line V-V in FIG. 4.

The positive electrode liquid (or negative electrode liquid) is energized by a pump, enters the reaction electrode C through the solution through hole 30, undergoes oxidation J'ζ (original reaction), and then is discharged through the solution through hole 32. state.

By overlapping carbon fiber woven fabrics with a thickness of 0.4 mm, IL
Make it into a pole plate. Epoxy resin and hardener I QQ il (
7111 Nj'ils and 60 parts by weight of conductive carbon powder
By kneading, a conductive t/1° thermosetting resin was prepared.

One electrode 41v was made from seven pieces of carbon fiber (0,4 questions), and three pieces were entirely impregnated with the resin.

Layer the 7 electrodes and heat them at 150°C with a pressure bath.3. Ofi”) was obtained.

This is an electrode plate having only two reaction electrodes, such as A and An shown in FIG.
It is also possible to make one with reaction electrodes on both sides, but the number and order of stacking is slightly different.

A T-cell battery was fabricated by integrating two electrode plates with a diaphragm sandwiched between them.
', the 1u release experiment was repeated. There are no leaks and there is enough water.
A 4-pole reaction was performed.

[Brief explanation of drawings]

FIG. 1 is a plan view of an electrode plate used in the present invention. FIG. 2 is a sectional view taken along the line n-l in FIG. 1. FIG. 3 is a sectional view showing the structure of an aggregate cell. FIG. 4 is a perspective S view of an electrode plate with a solution flow path formed therein. FIG. 5 is a cross-sectional view showing the flow of solution in the collective cell. (This corresponds to the cross-sections taken along the line V-V of the electrode plates in FIG. 4 that are overlapped.) FIG. 6 is a conceptual diagram of a redox battery for power storage. Figure 7 shows one unit of a conventional redox battery (single unit)
FIG. A ・・・・・・・・・ Electrode Plate B ・・・・・・・・・ Collection'tortoise electrode C ・・・・・・Reaction TIE electrode E ・・・・・・・・・Diaphragm 1... Power plant 2... Substation equipment 3... Load 4... Inverter - Ta 5
...... 1x batteries 5a, 5b...
...... Positive electrode liquid tank 7a, 7b... Negative electrode liquid tank 8.9 ...... Pump 10...
... Electrolytic cell 11 ...... Positive electrode plate 12 ...
・・・・・・ Negative electrode plate 13 ・・・・・・・・・ Spacing ) 1 da (14... ・・・ Positive electrode liquid 15 ・・・・・・・・・ Negative electrode liquid 20 ・・・・・・
...... Positive electrode 21 ...... Diaphragm 22 ...... Negative electrode 23 ...... Porous carbon electrode 24
・・・・・・・・・ Graphite wide electrode plate 3 to 32...
... Solution through hole Inventor Satoshi Shigematsu Visited Japan Yutaka Hino: 'I Applicant Sumitomo Electric Industries, Ltd. Figure 4 V 319- Figure 7

Claims (2)

[Claims] (1) Charging and discharging is performed by separating the positive and negative electrode liquids with a diaphragm and causing an oxidation-reduction reaction at each electrode.'1. f
In a uredox battery, an anti-16 current 1iφC and a current collector electrode B are integrated, and the integrated electrode plate A becomes a laminated layer of carbon fibers, and the force is - one side of the laminated body of carbon fibers.
Alternatively, leave the center portions of both ICs 11 and impregnate them with a thermosetting resin, and use the IJ-impregnated portions as current collecting electrodes B.
The central part of one side or both sides of 1゛ is used as a reaction electrode C,
A 1-node cell characterized in that electrode plates A are stacked to form a collective cell. (2) The S. de Sox battery according to claim (1), wherein the thermosetting resin is a conductive thermosetting resin kneaded with carbon powder, Granato powder, silver powder, etc.