JPH08227719A - Electrode for zinc-bromine battery and its manufacture - Google Patents

Abstract

PURPOSE: To provide an electrode for zinc-bromine battery in which a metal is adapted as the electrode material for a zinc-bromine battery to satisfy bromine resistance and electric characteristic, and the downsizing and higher efficiency of the battery itself can be attained, and a method for manufacturing it. CONSTITUTION: A metal base plate 33 is adapted as base material base for electrode, and a material having a carbon thin film adhered on the surface of the base plate 33 so as to impart bromine resistance by the sputtering means of a graphite electrode 36 using a high frequency power source 35 is used. As the manufacturing method, a base holder 32 and the graphite electrode 36 are arranged in a vacuum vessel 31, the bases 33 plate as the base material are juxtaposed on the base holder 32, and the incident power having a reflected power based on the slippage of load impedance is applied to the graphite electrode 36 from the high frequency power source 35 under the present of an inert gas, whereby the base plate 33 is coated with carbon particles in a thin film form by sputtering means from the graphite electrode 36.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode for a zinc-bromine battery as an electrolyte circulating type laminated secondary battery and a method for producing the same.

[0002]

2. Description of the Related Art A zinc-bromine battery is a secondary battery that uses bromine as a positive electrode active material and zinc as a negative electrode active material.
It is used to store electricity at night when electricity demand is low and to release it in the daytime.

Bromine generated on the positive electrode side at the time of charging reacts with the bromine complexing agent added to the electrolytic solution to form an oily precipitate which is returned to the positive electrode side storage tank, and at the time of discharging it is pumped to the unit cell. It is sent in and returned. The component of the electrolytic solution is ZnBr
₂ aqueous solution, a salt such as NH ₄ Cl for reducing resistance, Pb, Sn, quaternary ammonium salts for preventing dendrite on the negative electrode zinc side and promoting uniform electrodeposition, and a bromine complexing agent Is. A separator is inserted between the positive electrode and the negative electrode to prevent self-discharge caused by the bromine generated in the positive electrode diffusing into the negative electrode and reacting with zinc.

The chemical reaction of this zinc-bromine battery is

[0005]

[Chemical Formula 1] During charging: Positive electrode: 2Br ⁻ → Br ₂ + 2e ⁻ , Negative electrode: Zn ⁺⁺ + 2e ⁻ → Zn During discharging: Positive electrode: 2Br ⁻ ← Br ₂ + 2e ⁻ , Negative electrode: Zn
It is represented by ⁺⁺ + 2e ⁻ ← Zn.

In this zinc-bromine battery, the electrodes are mainly of a bipolar type, a battery main body in which a plurality of single cells (single cells) are electrically stacked in series, an electrolytic solution storage tank, and an electrolytic solution interposed therebetween. It is composed of a pump and a piping system for circulating the liquid.

FIG. 2 is an exploded perspective view showing an example of a battery main body constituting the zinc-bromine battery, in which an insulating frame 1b is arranged on the outer periphery of an electrode portion 1a of a rectangular flat bipolar intermediate electrode 1. Similarly, a rectangular flat plate-shaped separator plate 2
The frame 2a is formed on the outer periphery of the separator 3.
The separator plate 2 and, if necessary, the packing 4 and the spacer mesh 5 are stacked on the intermediate electrode 1 to form a single cell, and a plurality of the single cells are stacked to form a battery body.

A collector electrode 7 having a collector mesh 6 and a pair of tightening end plates 8 are provided at both ends of the stacked battery bodies.
A pressing laminated end plate 9 located inside thereof is arranged. Then, a bolt for tightening is passed between both tightening end plates 8 and 8 and tightened to form a battery body integrally laminated and fixed.

Inside each unit cell of the battery body constructed as described above, the frame 2a of each intermediate electrode 1 and separator plate 2 is provided.
Positive electrode manifold 10 formed in two corners above and below
Then, the electrolytic solution flows in and out from the negative electrode manifold 11 through the channels 12 and the microchannels 13 provided in the frame body 2a of the separator plate 2, respectively.

Usually, the tightening end plate 8 is made of fiber reinforced plastic resin (FRP), and the frame body 1 of the intermediate electrode 1 is used.
A vinyl chloride resin (PVC) is used for b, and a relatively hard polyethylene resin is used for the separator plate 2.

The above zinc-bromine battery has been confirmed to have a battery efficiency of about 80% and a total energy efficiency of about 70% in a 50 KW class battery.

FIG. 3 is a schematic diagram for explaining the operating principle of the above zinc-bromine battery, in which 14 is a positive electrode side storage tank in which the positive electrode electrolyte solution 15 and bromine are contained. Complex compound 16 is stored. Reference numeral 17 denotes a negative electrode side storage tank in which the negative electrode electrolytic solution 18 is stored. The positive electrode electrolyte solution 15 is supplied to the positive electrode side pump 19
In accordance with the driving of the above, the single cell flows from the positive electrode manifold 10 of the battery main body through the four-way valve 20 as shown by the arrow in the figure and flows back to the positive electrode side storage tank 14, while the negative electrode electrolyte solution 18 As the side pump 21 is driven, the side pump 21 flows through the unit cell separated from the negative electrode manifold 11 of the battery body to the separator 3 and returns to the negative electrode side storage tank 17.

The current collecting electrode 7 is formed by sequentially stacking a carbon plastic electrode and a brass current collecting mesh on an insulating frame, and integrating them by heat pressing under a predetermined temperature and pressure condition. Being manufactured. A material obtained by laminating activated carbon cloth with a carbon plastic electrode is used as the positive electrode side intermediate electrode, and a carbon plastic electrode having a smooth surface is used as the negative electrode side intermediate electrode.

[0014]

In the case of such a zinc-bromine battery, a material having a thickness of about 1 mm is used as the intermediate electrode 1 in order to downsize the battery itself.
Since the heat pressing means is also used when the intermediate electrode 1 is manufactured, the intermediate electrode 1 has innumerable minute holes. Therefore, while the battery is used for a long period of time, the positive electrode and the negative electrode electrolytic solution may infiltrate into the pores and cause the swelling phenomenon of the intermediate electrode 1, which causes deformation or cracking of the electrode itself. Is more likely to occur, leading to a decrease in the life of the battery. In particular, zinc-bromine batteries are mainly used for electric power, and therefore, once installed, they are required to be used for many years.

Therefore, if a metal plate that does not swell with an electrolytic solution can be used as the material of the intermediate electrode, the above problems can be solved, but bromine contained in the electrolytic solution for a zinc-bromine battery can be eliminated. At present, no metal having extremely strong corrosiveness and bromine resistance enough to be practically adopted as the intermediate electrode 1 has been found.

In particular, when a metal plate is used as the intermediate electrode 1, the electric resistance is much smaller than that of the conventional material in which a carbon plastic electrode is bonded to activated carbon cloth, the current density is increased, and the battery performance is improved. In addition to improvement, it is expected that miniaturization and high efficiency of the battery itself are expected.

The present invention has been made in view of the above points, and employs a metal as a material for electrodes, has high bromine resistance, and improves battery performance by reducing electric resistance and increasing current density. It is an object of the present invention to provide an electrode for a zinc-bromine battery and a method for manufacturing the same, which enables miniaturization and high efficiency of the battery itself.

[0018]

In order to achieve the above object, the present invention forms a single cell by stacking a separator plate on a flat intermediate electrode and stacking a plurality of the single cells to form a battery body. At the same time, a current collecting electrode having a current collecting mesh and a pair of tightening end plates are arranged at both ends of the battery body, and a bolt between the tightening end plates is tightened by bolts to ensure liquid-tightness between the laminated members. In a zinc-bromine battery which is sealed below, first, as claim 1, a metal is adopted as a base material substrate of the intermediate electrode, and a graphite sputtering means using a high frequency power source is provided on the surface of the metal substrate. Provided is an electrode for a zinc-bromine battery, which uses a material having a carbon thin film for imparting bromine resistance.

According to a second aspect of the present invention, a substrate holder is arranged in a vacuum container, a graphite electrode is arranged at a position facing the substrate holder, and a metal substrate as a base material is juxtaposed on the substrate holder to form an inert gas. In the presence of a high frequency power source, an incident electric power having a reflected electric power based on a deviation of a load impedance is applied to the graphite electrode to coat the metal substrate with a thin film of carbon particles by a sputtering means from the zinc electrode.
Provided is a method for manufacturing an electrode for a bromine battery.

The incident power from the high frequency power source during the sputtering is 200 to 600 W, the ratio of the reflected power to the incident power is 0 to 15%, and the substrate temperature during film formation is 500 to 650 ° C. Further, as the inert gas, a mixed gas of argon gas and nitrogen gas is used,
The ratio of the reflected power to the incident power from the high frequency power source is 0 to 10%.

[0021]

According to the electrode for a zinc-bromine battery according to claim 1, the metal itself is exposed to the electrolytic solution for a zinc-bromine battery by coating the surface of a metal substrate such as stainless steel with carbon in a thin film form. Even if the substrate on which the carbon film is formed is immersed in an aqueous zinc-bromine solution for a long time, the surface resistance after immersion does not change, and the deterioration phenomenon of the carbon film does not occur. An intermediate electrode effectively utilizing the bromine resistance of carbon can be obtained.

By adopting the method for manufacturing a zinc-bromine battery electrode according to claim 2, the high frequency power applied to the graphite electrode has reflected power due to deviation from the load impedance, and the substrate is formed by sputtering. The carbon film formed above is prevented from having a columnar structure, and the manufacturing conditions are established such that the obtained carbon film has high density and good bromine resistance.

When the ratio of the reflected power to the incident power from the high frequency power source is 10%, the increase in the surface electric resistance is the smallest, and the bromine resistance of the carbon film is increased as compared with the case where the ratio of the reflected power is 0%. The range of reflected power required for
15%. Further, when the substrate temperature during film formation is 400 ° C. or lower, the bondability with the substrate is deteriorated and bromine resistance and electric resistance characteristics are deteriorated. When the temperature is 700 ° C. or higher, the carbon film does not become a glassy carbon film. Since the bromine resistance is deteriorated, the film forming temperature is set to 500 ° C to 650 ° C to obtain a good carbon thin film.

Further, when a mixed gas of argon gas and nitrogen gas is used as the inert gas (sputtering gas), a carbon thin film having a high hardness with almost no increase in surface resistance after film formation can be obtained.

[0025]

EXAMPLES Hereinafter, a zinc-bromine battery electrode and a method for producing the same according to the present invention will be described based on specific examples. In the present embodiment, a metal such as various stainless steels or nickel is adopted as a base material substrate of the intermediate electrode 1, and a material in which carbon for imparting bromine resistance to the surface of the metal substrate is coated in a thin film by a sputtering means. It is characterized by using.

More specifically, by coating the surface of the metal substrate such as stainless steel or nickel with carbon in a thin film form, the metal itself is not exposed to the electrolytic solution, and the deposited carbon film is formed. Provided is an intermediate electrode that effectively utilizes the bromine resistance of the. Various examples of the electrode and the method for manufacturing the same according to the present invention will be described below.

[Embodiment 1] Stainless steel (SUS304) was adopted as a base metal, and this was made into a predetermined size (1
The substrate was cut into pieces of 0 mm × 20 mm × 1.0 mmt), and both surfaces of the substrate were puff-polished using alumina particles of 1.0 μm. Next, both surfaces of the substrate were coated with thin film carbon using a high frequency sputtering device.

FIG. 1 is a schematic view of a high frequency magnetron sputtering apparatus used in this embodiment. In the figure, 31 is a vacuum container, 32 is a substrate holder arranged in the vacuum container 31, and the substrate holder 32 is shown. And the ground portion E are connected in a direct current manner. 33 is a substrate using the stainless steel,
Reference numeral 36 denotes a graphite electrode as a load arranged at a position facing the substrate holder 32, and the high frequency power source 35 is connected to the graphite electrode 36. 34 is a vacuum pump.

A plurality of substrates 33, 33 made of stainless steel (SUS304) are juxtaposed on the substrate holder 32, the vacuum pump 34 is sufficiently operated, and a high frequency power source (13.56 MHz) is supplied in the presence of an inert gas. ) 35 to activate the stainless steel 33, 33 from the graphite electrode 36.
The plasma 37 of carbon particles was radiated.

Normally, when the above-mentioned sputtering apparatus is used, the carbon film formed on the substrate 33 tends to have a columnar (columnar) structure in a microscopic view. Therefore, when a thermal cycle is applied to the substrate 33, the carbon film has a columnar structure. Although there is a problem that cracks are likely to occur from the boundary portion, by adopting the film forming conditions according to the present embodiment, the formed carbon film does not have a columnar structure, and the bromine resistance is good. One of the features of this embodiment is that the sputtering conditions are established.

The high frequency power applied to the graphite electrode 36 is taken out from the high frequency power source 35 through a coaxial cable having a characteristic impedance of 50Ω and a load impedance of 50.
In the case of Ω, the high frequency power can be extracted from the high frequency power supply 35 to the load most efficiently. Generally, if the load impedance deviates from 50Ω, reflected power is generated and the output loss of high frequency power increases, so usually a matching box is used to convert the load impedance to 50Ω and efficiently extract power from the high frequency power supply. The film is formed in. However, in this example, when the load impedance was intentionally shifted from 50Ω to form the film while generating the reflected power, the columnar structure of the obtained carbon thin film disappeared,
It was found that a carbon film having high density and good bromine resistance can be obtained.

The sputtering conditions according to this embodiment are as follows. (1) Target: φ100 graphite electrode (2) Distance between electrodes: 20 mm (3) Incident high frequency power: 200 W (4) Sputtering gas: Argon gas (gas flow rate 5
ccm) (5) Degree of vacuum during film formation: 0.15 Torr The substrate temperature is 400 ° C, 500 ° C, 600 ° C, 700
The film formation time was adjusted to ℃ and the film thickness was 2.0 μm each.
As a result, sputtering was performed on both surfaces of the SUS substrate under the above conditions. Next, the outer periphery of the SUS substrate 33 was sealed with an epoxy resin having high bromine resistance, and the above-mentioned substrate 33 on which carbon films were formed on both sides was prepared using a bromine prepared for bromine resistance accelerated life test of the carbon film. Immerse in a high concentration zinc-bromine aqueous solution for 500 hours to reduce the surface electrical resistance of the carbon film to 4
It was measured by the deep needle method. The composition of this zinc-bromine aqueous solution is Z
_{nBr 2: 0.7 (mol / l} ), Br 2: 1.5 (mol
/ L), NH ₄ Cl: a 2.0 (mol / l).

Table 1 shows a list of film forming conditions, surface resistance (Ω · cm) after film formation, and increase in surface resistance after immersion in an aqueous zinc-bromine solution.

[0034]

[Table 1]

According to Table 1, the increase in the surface electric resistance is smallest when the ratio of the reflected power to the incident power is 10% at all the measured temperatures, and when the reflected power is increased to 20%, the reflected power becomes 0%. The electrical resistance increased more than in the case. The reason for this is considered to be that if the ratio of the reflected power is increased too much, the kinetic energy of the carbon particles perpendicular to the substrate, which is necessary for improving the bonding strength between the carbon film and the substrate, decreases.

The range of the reflected power required to improve the bromine resistance of the carbon film is 0 to 15% as compared with the case where the ratio of the reflected power is 0%.

Regarding the substrate temperature at the time of film formation, if the temperature is 400 ° C. or lower, the bromine resistance is poor due to the decrease in the bondability with the substrate, and the electric resistance value of the formed carbon film is the carbon currently used. The temperature must be 500 ° C or higher because it will be higher than that of polyethylene-containing polyethylene resin. It was also found that when the temperature was 700 ° C. or higher, the formed carbon film had a graphite structure instead of the glassy carbon film, and the bromine resistance deteriorated. Therefore, it is desirable that the film forming temperature be 500 ° C to 650 ° C.

[Embodiment 2] In Embodiment 1, it was found that the film forming temperature is preferably 500 ° C. to 650 ° C. Therefore, the film forming temperature is 600 ° C. and the incident power is 100 W, 200.
The film forming experiment was performed with W, 400 W, and 600 W. Table 2
Table 1 shows the film forming conditions, the surface resistance (Ω · cm) after film formation, and the increase in surface resistance after immersion in a zinc-bromine solution.

[0039]

[Table 2]

According to Table 2, when the incident power was 100 W, the adhesion between the film and the substrate was poor, so that all sample films were peeled from the substrate. When the incident power was increased to 200 W and 400 W, the increase in surface resistance decreased. It is considered that this is because the adhesion strength between the substrate and the glassy carbon film became stronger as the incident power was increased from 200 W to 400 W. Further, it was confirmed from the analysis result of the Raman spectrum that the carbon film formed at the incident power of 600 W had a graphite structure. Example 1 regarding the reflected power
Similarly, the electric resistance value after immersion in a zinc-bromine solution showed the smallest increase when the reflected power was 10%, and the reflected power was 2%.
When it increased to 0%, the electric resistance value after immersion increased.

The following film forming conditions were established by the first and second embodiments described above. That is, as a sputtering condition, the ratio of reflected power to incident power is 0 to 15%, the substrate temperature during film formation is 500 to 650 ° C., and the incident power is 200.
~ 600W.

[Embodiment 3] In the case of Embodiments 1 and 2, pure argon gas (gas flow rate 5 ccm) is used as the inert gas (sputtering gas) under the sputtering condition (4).
However, in the present Example 3, a mixed gas obtained by adding an argon gas (gas flow rate: 4.5 ccm) and a nitrogen gas (gas flow rate: 0.5 ccm) as the sputtering gas was used. Other sputtering conditions are the same as those in Examples 1 and 2 above.
Same as.

Table 3 shows film forming temperatures of 400 ° C., 500 ° C. and 6 ° C.
When the temperature is set to 00 ° C and 700 ° C, and only argon gas (gas flow rate 5 ccm) is used as the sputtering gas,
Incident power of 200 W using a mixed gas of argon gas (gas flow rate 4.5 ccm) and nitrogen gas (gas flow rate 0.5 ccm)
The results of measuring the surface resistance (Ω · cm) and the hardness of the carbon thin film after film formation are shown below.

[0044]

[Table 3]

The hardness of the carbon thin film in Table 3 is shown as a relative hardness based on the case where the film forming temperature is 400 ° C., the incident power is 200 W, and the sputtering gas is 100% argon gas (gas flow rate 5 ccm). There is. The hardness of the carbon thin film is Shimadzu dynamic ultra micro hardness tester (D
It was measured using UH-201).

According to Table 3, when a mixed gas of argon gas (gas flow rate 4.5 ccm) and nitrogen gas (gas flow rate 0.5 ccm) is used as the sputtering gas, the surface resistance after film formation does not increase so much. Moreover, a carbon thin film having a high hardness was obtained. Analysis of this carbon thin film confirmed that the thin film contained nitrogen atoms.

[Embodiment 4] Similar to Embodiment 3 above, argon gas (gas flow rate: 4.5 cc) was used as a sputtering gas.
Using a mixed gas of m) and nitrogen gas (gas flow rate 0.5 ccm), the substrate temperature was kept constant at 600 ° C., and the incident power was changed to carry out a film forming experiment. The other sputtering conditions were the same as in Examples 1 and 2.

Table 4 shows incident power of 100 W, 200 W, 4
00W and 600W, surface resistance (Ω · cm) and carbon thin film after film formation when using only argon gas (gas flow rate 5 ccm) as sputtering gas and when using mixed gas of argon gas and nitrogen gas The result of having measured hardness is shown. The hardness of the carbon thin film in Table 4 is 40 at the film forming temperature.
The relative hardness is shown with reference to the case where argon gas 100% (gas flow rate 5 ccm) is used as a sputtering gas at 0 ° C. and incident power 200 W.

[0049]

[Table 4]

According to Table 4, when a mixed gas of argon gas (gas flow rate of 4.5 ccm) and nitrogen gas (gas flow rate of 0.5 ccm) is used as the sputtering gas, the film formation after film formation is not affected at any film formation temperature. A carbon thin film was obtained in which the surface resistance did not change significantly and the hardness was increased.

[Embodiment 5] As in Embodiment 4 above, argon gas (gas flow rate: 4.5 cc) was used as a sputtering gas.
Using a mixed gas of m) and nitrogen gas (gas flow rate 0.5 ccm), the substrate temperature was kept constant at 600 ° C., and the film formation experiment was conducted with the ratio of reflected power to incident power being 0% and 10%. The other sputtering conditions were the same as in Examples 1 and 2.

Table 5 shows incident power of 100 W, 200 W, 4
The results of measuring the surface resistance (Ω · cm) and the hardness of the carbon thin film after the film formation under the above sputtering conditions are shown as 00 W and 600 W. The hardness of the carbon thin film is 400 at the film forming temperature.
The relative hardness is shown with reference to the case where argon gas 100% (gas flow rate 5 ccm) is used as a sputtering gas at a temperature of 200 ° C. and an incident power of 200 W.

[0053]

[Table 5]

According to Table 5, when a mixed gas of argon gas (gas flow rate: 4.5 ccm) and nitrogen gas (gas flow rate: 0.5 ccm) is used as the sputtering gas, the film formation rate after film formation is high at any film formation temperature. A carbon thin film was obtained in which the surface resistance did not change significantly and the hardness was increased. Further, by setting the ratio of the reflected power to the incident power to 10%, the carbon thin film hardness was further enhanced and the mechanical strength was increased.

[0055]

As described in detail above, according to the zinc-bromine battery electrode and the method for producing the same according to the present invention, the surface of the metal substrate is coated with carbon in a thin film so that the metal itself is zinc- Since it is not exposed to the electrolyte for bromine batteries, it does not change the shape of glassy carbon even if it is immersed in an aqueous zinc-bromine solution for a long time, and the surface resistance does not change. It is possible to obtain an electrode that effectively utilizes bromination. In addition, compared with the conventional electrode material with minute pores, there is no fear that the swelling phenomenon will occur due to the infiltration of the positive and negative electrode electrolytes even during long-term use, and the electrode itself will be deformed or cracked accordingly. It is possible to eliminate the cause of the occurrence of such problems, and it is effective in extending the life of the power battery.

By adopting the electrode manufacturing method of the present invention, the carbon film formed on the substrate by sputtering does not have a columnar structure due to the presence of reflected power due to the deviation of the high frequency power from the load impedance. The obtained carbon film is densified, and the manufacturing conditions in which the strength is also improved are established.

In particular, the electrode according to the present invention has a lower electric resistance than the conventional material in which a carbon plastic electrode is bonded to an activated carbon cloth, the current density is increased to improve the battery performance, and the mechanical strength is improved. Accordingly, the thickness of the electrode can be reduced correspondingly, and the electrode area can be increased, so that the battery itself can be downsized and the efficiency can be improved.

Furthermore, by using a mixed gas of argon gas and nitrogen gas as an inert gas (sputtering gas), a carbon thin film having a high hardness and a surface resistance after film formation hardly increased can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a method for producing an electrode for a zinc-bromine battery according to the present invention.

FIG. 2 is an exploded perspective view showing the configuration of a zinc-bromine battery body.

FIG. 3 is a schematic diagram showing the operating principle of a zinc-bromine battery.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Intermediate electrode 1b ... Frame body 2 ... Separator plate 2b ... Frame body 3 ... Separator 8 ... Clamping end plate 9 ... Laminated end plate 10 ... Positive electrode manifold 11 ... Negative electrode manifold 12 ... Channel 13 ... Micro channel 14 ... Positive side storage Tank 15 ... Positive electrode electrolytic solution 17 ... Negative electrode side storage tank 18 ... Negative electrode electrolytic solution 19 ... Positive electrode side pump 21 ... Negative electrode side pump 31 ... Vacuum container 32 ... Substrate holder 33 ... Substrate 34 ... Vacuum pump 35 ... High frequency power supply 36 ... Graphite electrode

Claims (5)

[Claims] 1. A single cell is formed by stacking a separator plate on a flat plate-shaped intermediate electrode, and a plurality of the single cells are laminated to form a battery main body, and a current collecting mesh is provided at both ends of the battery main body. Arranging a current collecting electrode and a pair of tightening end plates,
In a zinc-bromine battery, in which each laminated member is sealed liquid-tightly by bolting between both clamped end plates, a metal is adopted as the base material substrate of the intermediate electrode, and the surface of this metal substrate An electrode for a zinc-bromine battery, comprising a material on which a carbon thin film for imparting bromine resistance is attached by a graphite sputtering means using a high frequency power source. 2. A substrate holder is provided in a vacuum container, a graphite electrode is arranged at a position facing the substrate holder, and a metal substrate as a base material is juxtaposed on the substrate holder in the presence of an inert gas. By applying an incident power having a reflected power based on the shift of the load impedance from the high frequency power source to the graphite electrode, carbon particles are coated in a thin film form on the metal substrate by the sputtering means from the graphite electrode. A method for manufacturing an electrode for a zinc-bromine battery. 3. The incident power from the high frequency power source during the sputtering is 200 to 600 W, the ratio of the reflected power to the incident power is 0 to 15%, and the substrate temperature during film formation is 500 to 650 ° C. 2. The method for producing an electrode for a zinc-bromine battery according to 2. 4. The method for producing an electrode for a zinc-bromine battery according to claim 2, wherein a mixed gas of argon gas and nitrogen gas is used as the inert gas. 5. The ratio of the reflected power to the incident power from the high frequency power source is set to 0 to 10%.
A method for producing the described zinc-bromine battery electrode.