KR20190124941A - Non-precious metal electeode catalyst for high-temperature polymer electrolyte membrane fuel cell, preparation method thereof and high-temperature polymer electrolyte membrane fuel cell comprising the same - Google Patents

Abstract

The present invention relates to a nonprecious metal catalyst for a high temperature polymer electrolyte fuel cell, a manufacturing method thereof, and a high temperature polymer electrolyte fuel cell including the same. More specifically, the nonprecious metal catalyst manufacturing method comprises the following steps of: (a) performing a polymerization reaction to obtain a polymer by mixing aniline, a nonprecious metal precursor, silica particles, an oxidizing agent, and first acid solution; (b) washing the polymer with distilled water and drying the same so that the pH of polymer is 5 to 6; (c) thermally treating the dried polymer at 500 to 1,200°C under an inert gas atmosphere; (d) removing silica particles from the thermally treated polymer and obtaining a porous body; (e) washing the porous body with distilled water and drying the same so that the pH of the porous body is 5 to 6; (f) treating the dried porous body with acid in second acid solution; (g) washing the acid-treated porous body with distilled water and drying the same so that the pH of the acid-treated porous body is 5 to 6; and (h) thermally treating the dried porous body at 500 to 1,200°C under an ammonia atmosphere. The nonprecious metal catalyst manufacturing method is able to manufacture a porous Fe-N-C nonprecious catalyst, in which the size of pores is controlled, and the porous Fe-N-C nonprecious catalyst can be applied as an electrode catalyst for a high temperature polymer electrolyte fuel cell to be able to prevent a poisoning phenomenon by phosphate electrolyte.

Description

Non-precious metal electeode catalyst for high-temperature polymer electrolyte membrane fuel cell, preparation method about and high-temperature polymer electrolyte membrane fuel cell comprising the same}

The present invention relates to a non-noble metal catalyst for a high temperature polymer electrolyte fuel cell, a method of manufacturing the same, and a high temperature polymer electrolyte fuel cell including the same, and more particularly, to a porous Fe- having a pore size controlled through etching of silica particles. The present invention relates to a technique for preparing an NC non-noble metal catalyst and applying it as an electrode catalyst for a high temperature polymer electrolyte fuel cell, which can prevent poisoning caused by a phosphate electrolyte.

The high-temperature polymer electrolyte membrane fuel cell (HT-PEMFC) has a humidifier with an operating temperature of 100 to 200 ° C, compared to a low-temperature polymer electrolyte fuel cell with hydrogen ion conductivity under high humidity conditions. There is a systemic advantage as it is not needed. In addition, due to the high operating temperature, the electrochemical reaction is activated, and thus the activation overvoltage is reduced compared to the low temperature polymer electrolyte fuel cell, which may help improve performance. This high operating temperature also has the advantage of being recyclable even in drying and cooling. In addition, in the low-temperature polymer electrolyte fuel cell, since the catalyst is poisoned by CO to reduce the catalytic activity, a separate CO removal device is required, but in the case of the high-temperature polymer electrolyte fuel cell, the poisoning effect by CO is reduced due to the high operating temperature. Tolerance up to 3% in concentration.

High temperature mainly used in a polymer electrolyte fuel cell is a polymer membrane with H ₂ PO ₄ Polybenzimidazole (PBI) doped with a phosphoric film ^- and HPO ₄ ^- is a platinum catalyst is poisoned by a phosphate, such as is much less active. However, in the case of the non-platinum catalyst, the poisoning by the phosphate does not occur, so the performance may be maintained even in the electrolyte of the PBI membrane doped with phosphoric acid. In a paper measuring the activity of the oxygen reduction reaction in a phosphate electrolyte using a non-noble metal catalyst, there is an example showing the activity of the non-noble metal catalyst that exceeds the catalytic activity of the platinum catalyst in the phosphate electrolyte (Non Patent Literature 1). In addition, many examples of the synthesis of the non-noble metal catalyst and the activity for the oxygen reduction reaction in the half cell has been reported (Non-Patent Document 2).

Therefore, the present inventors can manufacture a porous Fe-NC non-noble metal catalyst having a pore size controlled through etching of silica particles, and this can prevent poisoning caused by phosphate electrolyte, for a high temperature polymer electrolyte fuel cell. The present invention has been completed by focusing on the applicability of the electrode catalyst.

Patent Document 1. US Patent Publication No. 2011-0319257

[Non-Patent Document 1] Li, Qing, et al. ACS Catalysis 4.9 (2014): 3193-3200. [Non-Patent Document 2] Chung, Hoon T., et al. Science 357.6350 (2017): 479-484. [Non-Patent Document 3] Guo, Donghui, et al. Science 351.6271 (2016): 361-365.

The present invention has been made in view of the above problems, and an object of the present invention is to prepare a porous Fe-NC non-noble metal catalyst having a pore size controlled through etching of silica particles, the poisoning phenomenon by the phosphate electrolyte To prevent the, it is intended to be applied as an electrode catalyst for a high temperature polymer electrolyte fuel cell.

One aspect of the present invention for achieving the above object is (a) a polymerization process by mixing aniline, silica particles, non-noble metal precursor, oxidizing agent and the first acid solution; (b) washing with distilled water so as to have a pH of 5 to 6 and drying the polymer; (c) heat treating the dried polymer at 500 to 1200 ° C. under an inert gas atmosphere; (d) removing the silica particles from the heat treated polymer to obtain a porous body; (e) washing with distilled water such that the pH of the porous body is 5 to 6 and then drying; (f) acid treating the dried porous body in a second acid solution; (g) washing with distilled water and drying the pH of the acid-treated porous body to 5 to 6; And (h) heat treating the dried porous body at 500 to 1200 ° C. under an ammonia atmosphere.

Another aspect of the present invention relates to a non-noble metal electrode catalyst prepared by the production method according to the present invention.

Another aspect of the present invention relates to a high temperature type polymer electrolyte fuel cell comprising a non-noble metal electrode catalyst according to the present invention.

Another aspect of the present invention is an electric device comprising a non-noble metal electrode catalyst according to the present invention, the electric device is characterized in that the electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle and a power storage device selected from the It relates to an electrical device.

According to the present invention, a porous Fe-NC non-noble metal catalyst having a pore size controlled through etching of silica particles is prepared, and this can prevent poisoning caused by a phosphate electrolyte, and an electrode catalyst for a high temperature polymer electrolyte fuel cell It can be applied as

1 is a schematic diagram listing the process for producing a Fe-NC non-noble metal electrode catalyst according to an embodiment of the present invention.
Figure 2 is a scanning electron microscope (SEM) image of the Fe-NC non-noble metal electrode catalyst prepared from Examples 1 to 6 of the present invention [a: Example 1, b: Example 2, c: Example 3, d : Example 5, e: Example 4, f: Example 6].
Figure 3 is a Fe-NC non-noble metal electrode catalyst prepared from Examples 1 to 6 of the two electrolytes, 5 MH ₃ PO ₄ and 0.1 M HClO ₄ under oxygen using a Rotating Disk Electrode (RDE) electrode It is a graph showing the result of measuring oxygen reduction reactivity.
4 is hydrogen peroxide produced through a two-electron reaction in an oxygen reduction reaction measured under oxygen using a Rotating Ring Disk Electrode (RRDE) electrode of a Fe-NC non-noble metal electrode catalyst prepared in Examples 1 to 6 of the present invention. This graph shows selectivity.
5 is a flow rate of hydrogen and oxygen 200, 600 ml at an operating temperature of 150 degrees using a MEA (Membrane Electrode Assembly) made by spraying the Fe-NC non-noble metal electrode catalyst prepared in Examples 1 to 4 of the present invention / min This is a graph of (a) current density-voltage and (b) current density-output density measured in the state.
6 is an oxygen transfer resistance measured under helium and nitrogen in a high-temperature polymer electrolyte fuel cell of a Fe-NC non-noble metal electrode catalyst prepared from Examples 1 to 4 of the present invention and (c) It is a graph measuring the hydrogen transfer resistance measured under hydrogen and nitrogen in the high-temperature polymer electrolyte fuel cell of the Fe-NC non-noble metal electrode catalyst prepared from Examples 1 to 3.
FIG. 7 is a graph showing (a to f) porosity distribution of Fe-NC non-noble metal electrode catalysts prepared from 1 to 6 of the present invention, and (h) a table summarizing BET surface area, total pore volume, and average pore size [ a: Example 1, b: Example 2, c: Example 3, d: Example 4, e: Example 5, f: Example 6].

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

One aspect of the present invention comprises the steps of (a) polymerization by mixing aniline, silica particles, non-noble metal precursor, oxidizing agent and the first acid solution; (b) washing with distilled water so as to have a pH of 5 to 6 and drying the polymer; (c) heat treating the dried polymer at 500 to 1200 ° C. under an inert gas atmosphere; (d) removing the silica particles from the heat treated polymer to obtain a porous body; (e) washing with distilled water such that the pH of the porous body is 5 to 6 and then drying; (f) acid treating the dried porous body in a second acid solution; (g) washing with distilled water and drying the pH of the acid-treated porous body to 5 to 6; And (h) heat treating the dried porous body at 500 to 1200 ° C. under an ammonia atmosphere.

A conventional high-temperature type polymer membrane commonly used in polymer electrolyte fuel cells is H ₂ PO ₄ as Polybenzimidazole (PBI) a phosphoric acid-doped ^membrane is a problem that activity is significantly reduced were present are platinum catalyst is poisoned by a phosphate, such as ^- and HPO ₄ .

In order to solve the above problems, in the present invention, a porous non-noble metal catalyst having a pore size controlled through etching of silica particles is prepared, and this can prevent poisoning caused by a phosphate electrolyte. It was applied as an electrocatalyst. In particular, the performance of the catalyst according to the size of the silica particles in the unit cell was confirmed to determine the size of the silica particles showing the best oxygen reduction reaction results.

According to one embodiment, the size of the silica particles may be 8 to 16 nm, preferably 10 to 14 nm, more preferably 11 to 13 nm, the particle size of the non-noble metal electrocatalyst is 1 to 500 μm , Preferably 30 to 300 μm, more preferably 50 to 100 μm, and the BET surface area of the non-noble metal electrocatalyst is 500 to 1500 m ² / g, preferably 600 to 1000 m ² / g, more Preferably from 700 to 800 m ² / g.

In particular, the silica particles are out of the size of 8 to 16 nm, the silica size is out of the 8 to 16 nm and at the same time the particle size of the non-noble metal electrocatalyst is out of 1 to 500 μm, or the silica size is When the particle size of the non-noble metal electrocatalyst deviates from 8 to 16 nm and the particle size of the non-noble metal electrocatalyst is outside the range of 1 to 500 μm and the BET surface area of the non-noble metal electrocatalyst is outside the range of 500 to 1500 m ² / g, the catalyst is agglomerated at 150 ° C. or more. As a result, it was confirmed that the polarization resistance was increased and the catalytic activity was significantly decreased. On the other hand, when all the above conditions fall within the numerical range, it was confirmed that no aggregation phenomenon of the catalyst occurred.

According to another embodiment, the non-noble metal precursor may be at least one selected from iron, copper, nickel, zinc, manganese, titanium and vanadium, but is not limited thereto. Preferably an iron precursor can be used.

The iron precursor is FeCl ₃ · 6H ₂ O (ferric chloride), C ₃₂ H ₁₆ N ₈ Fe, FeCl ₂ , FeSO ₄ ㆍ 6H ₂ O, Fe (SO ₄ ) ₂ ㆍ 6H ₂ O, Fe (COO) ₂ ㆍ 2H ₂ O, FeC ₂ O ₄ ㆍ 2H ₂ O, FeC ₆ H ₈ O ₇ ㆍ nH ₂ O, (NH ₄ ) ₂ Fe (SO ₄ ) ₂ ㆍ 6H ₂ O, Fe ₃ (PO ₄ ) _It may be one or more selected from ₂ O and salts thereof, but is not limited thereto. Preferably FeCl ₃ .6H ₂ O can be used.

In addition, the amount of the non-noble metal precursor may be 1 to 100 mol% compared to the oxidizing agent.

In particular, the silica nanoparticles have a size of 8 to 16 nm, the particle size of the non-noble metal electrocatalyst is 1 to 500 μm, and the BET surface area of the non-noble metal electrocatalyst is 500 to 1500 m ² / g, When the non-noble metal precursor is an iron precursor, the hydrogen transfer resistance and the oxygen transfer resistance were less than 2.7 Ohm cm ^2, and it was confirmed that the remarkably excellent activity in the oxygen reduction reaction (ORR). On the other hand, the size of the silica nanoparticles, the particle size of the non-noble metal electrocatalyst and the BET surface area of the non-noble metal electrocatalyst are out of the range, or the size of the silica nanoparticles, the particle size of the non-noble metal electrocatalyst and the ratio The BET surface area of the noble metal electrode catalyst was out of the above range, and the use of other kinds of non-noble metal precursors resulted in a hydrogen transfer resistance and an oxygen transfer resistance of 3.5 Ohm m ² or more, which significantly reduced the activity in the oxygen reduction reaction (ORR). Confirmed.

According to another embodiment, the inert gas may be argon, nitrogen, neon, helium or a mixture of two or more thereof, preferably argon may be used.

According to another embodiment, the step (d) may be carried out by hydrothermally reacting the heat treated polymer in a sodium hydroxide solution at 80 to 200 ℃, preferably 90 to 150 ℃, more preferably 95 to 110 ℃ have.

According to another embodiment, the oxidizing agent is at least one selected from ammonium persulfate, iron chloride, copper chloride and potassium persulfate, wherein the first acid solution and the second acid solution are the same as or different from each other, and each independently It may be one or more selected from formic acid, sulfuric acid, hypochlorous acid, nitric acid, hydrochloric acid and phosphoric acid, but is not limited thereto. Preferably, the oxidizing agent may use ammonium persulfate, the first acid solution is formic acid, and the second acid solution is sulfuric acid.

In particular, although not explicitly described in the following Examples or Comparative Examples, in the method for producing a non-noble metal electrode catalyst according to the present invention, the size of the silica particles, the particle size of the non-noble metal electrode catalyst, the BET of the non-noble metal electrode catalyst Surface area, non-noble metal precursors, oxidants, and types of first and second acid solutions, temperature of steps (a), (b), (e) and (g), types of inert gases, and methods of performing step (d) By applying the non-noble metal electrode catalyst prepared by differently to the cathode of the high-temperature polymer electrolyte fuel cell, the coagulation and loss of the non-noble metal electrode catalyst applied to the cathode after operating at a high temperature of 200 ℃ for 800 hours was confirmed. .

As a result, unlike the other conditions and other numerical ranges, when all of the following conditions were satisfied, even after operating at high temperature for 800 hours, no agglomeration and loss of the catalyst applied to the air electrode were observed, thereby confirming the excellent thermal stability. .

(1) the silica particle size is 8 to 16 nm, (2) the particle size of the non-noble metal electrocatalyst is 1 to 500 μm, (3) the BET surface area of the non-noble metal electrocatalyst is 500 to 1500 m ² / g, (4 ) Non-noble metal precursor is ferric chloride, (5) the polymerization of step (a) is carried out at 1 to 20 ℃, (6) the drying of steps (b), (e) and (g) is from 30 to 100 ℃ (7) the inert gas is argon, and (8) step (d) is carried out by hydrothermally reacting the heat-treated polymer at 80 to 200 ° C. in sodium hydroxide solution, (9) oxidizing agent is ammonium persulfate, (10) agent 1 acid solution is formic acid, and (11) second acid solution is sulfuric acid.

However, when any one of the above conditions is not satisfied, it was confirmed that after operating at a high temperature for 800 hours, the agglomeration and loss of the catalyst applied to the air electrode were marked.

Another aspect of the present invention relates to a high temperature type polymer electrolyte fuel cell comprising a non-noble metal electrode catalyst according to the present invention.

Another aspect of the present invention is an electric device comprising a non-noble metal electrode catalyst according to the present invention, the electric device is characterized in that the electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle and a power storage device selected from the It relates to an electrical device.

Hereinafter, the production examples and embodiments according to the present invention will be described in detail with the accompanying drawings.

<Example>

Examples 1 to 6: Preparation of Fe-N-C non-noble metal electrode catalyst

FeCl _{3 ·} 6H ₂ O (ferric chloride) 32 g, aniline 2 ml, silica particles 16 g (particle size: 5 nm, 12 nm, 20 nm, 5 + 12 nm, 12 + 20 nm, 5 + 12 + 20 nm), ammonium persulfate (NH ₄ ) ₂ S ₂ O ₈ 3.14 g of the solution was reacted under a formic acid solution, which was then subjected to a polymerization process of 5 ° C. The resulting material was washed with distilled water to a pH value of about 5-6, and then dried in an oven at 60-70 ° C. for one day. The material thus produced was heat-treated for 2 hours at 800 ° C. under argon atmosphere, and then silica particles were removed through a hydrothermal reaction for 24 hours at 100 ° C. in a solution of 1 M NaOH. Thereafter, the resulting material was washed with distilled water to a pH value of about 5-6, and then dried in an oven at a temperature of 60-70 ° C. for one day. The resulting material was then acid treated in a 0.5 M H ₂ SO ₄ solution through agitation for one day, washed with distilled water to a pH value of 5-6, and then at a temperature of 60-70 ° C. for one day. It was dried to some extent. Thereafter, the produced material was heat-treated at a temperature of 900 ° C. for 2 hours in an ammonia atmosphere to prepare a Fe-NC non-noble metal electrode catalyst for a high temperature type polymer electrolyte fuel cell (see FIG. 1).

According to the silica particle size (5 nm, 12 nm, 20 nm, 5 + 12 nm, 12 + 20 nm, 5 + 12 + 20 nm) was set to Examples 1 to 6, respectively.

Experimental Example

Experimental Example 1: Evaluation of Reactivity to Oxygen Reduction (ORR)

First, the oxygen reduction reactivity is composed of a counter electrode using a Pt-wire, a reference electrode using a saturated calomel electrode (SCE), and a working electrode using a catalyst. Experiments were carried out in three electrode systems.

At this time, the working electrode was mixed with 50 mg of Nafion solution and 500 µl of isopropyl alcohol solution in ink solution, and then 30 minutes of sonication process followed by rotating ring- 15 μl of the solution was placed on the disk electrode of the rotating ring disk electrode.

Subsequently, the oxygen reduction reaction was carried out with 1 M HClO _{4 and} 5 M H ₃ PO ₄ saturated with oxygen. The experiment was carried out in an electrolyte, and the amount of hydrogen peroxide produced during the oxygen reaction was obtained through a rotating ring disk electrode to which a voltage of 1.0 V vs RHE was applied.

Experimental Example 2: Evaluation as a Cathode Catalyst in a Unit Cell

The catalyst produced according to the embodiment was sprayed onto 38 BC, a gas diffusion layer (GDL) manufactured by Sigracet, in a solution dispersed in water and isopropyl alcohol using a polytetrafluoroethylene (PTFE) ionomer with an ionomer / catalyst amount of 0.25. Was prepared. As an anode catalyst, 46.7% platinum catalyst was dispersed in water and isopropyl alcohol solution using PTFT ionomer in the same ionomer / catalyst amount, and sprayed on 38BC GDL to prepare an electrode. In the cell assembly of the unit cell, a cell was assembled by placing a polybenzimidazole (PBI) membrane doped with BASF's phosphoric acid between the sprayed positive electrode and negative electrode GDL.

Figure 2 is a scanning electron microscope (SEM) image of the Fe-NC non-noble metal electrode catalyst prepared from Examples 1 to 6 of the present invention [a: Example 1, b: Example 2, c: Example 3, d : Example 5, e: Example 4, f: Example 6].

Referring to FIG. 2, it can be seen that the non-noble metal electrode catalyst of the embodiments is formed of spherical particles having a size of 50 to 100 μm.

Figure 3 is a Fe-NC non-noble metal electrode catalyst prepared from Examples 1 to 6 of the two electrolytes, 5 MH ₃ PO ₄ and 0.1 M HClO ₄ under oxygen using a Rotating Disk Electrode (RDE) electrode It is a graph showing the result of measuring oxygen reduction reactivity.

Referring to FIG. 3, 12 nm, 5 nm, 5 + 12 nm, 12 + 20 nm, 3mix, and 20 nm in order of 5 MH ₃ PO ₄ electrolyte showed high activity, and 12 nm, 5 nm, 5 + 12 nm, in 0.1 M HClO ₄ electrolyte. It showed high activity in the order of 3mix, 12 + 20nm, 20nm. In addition, the half-wave potentials of both electrolytes were 0.72 V and 0.73 V, respectively, and the 12 nm sample of Example 2 showed the highest value.

4 is hydrogen peroxide produced through a two-electron reaction in an oxygen reduction reaction measured under oxygen using a Rotating Ring Disk Electrode (RRDE) electrode of a Fe-NC non-noble metal electrode catalyst prepared in Examples 1 to 6 of the present invention. This graph shows selectivity.

4 is n = 4 * I _d / (I _d + (I _r / N)) and H ₂ O ₂ (%), respectively, using the difference between the ratio of the disk current value and the ring disk current value obtained according to FIG. The selectivity of hydrogen peroxide and the value of n, which is the electron transfer number calculated by the formula = 200 * (I _r / N) / (I _d + (I _r / N)), are shown. In the above formula, I _d and I _r represent the disc current value and the ring disc current value, respectively, on which argon, which is an inert gas, has been corrected, and N value is 0.37 as a collection efficiency value.

Looking at Figure 4, it can be seen that when using the catalyst prepared according to all the examples shows the hydrogen peroxide generation value of less than 5% at all potential values.

5 is a flow rate of hydrogen and oxygen 200, 600 ml at an operating temperature of 150 degrees using a MEA (Membrane Electrode Assembly) made by spraying the Fe-NC non-noble metal electrode catalyst prepared in Examples 1 to 4 of the present invention This is a graph of (a) current density-voltage and (b) current density-output density measured in / min.

Referring to FIG. 5, it was confirmed that when the size of silica was 12 nm (Example 2), the maximum energy density showed a value corresponding to 20 mW / cm ² .

6 is an oxygen transfer resistance measured under helium and nitrogen in a high-temperature polymer electrolyte fuel cell of a Fe-NC non-noble metal electrode catalyst prepared from Examples 1 to 4 of the present invention, and (c). It is a graph measuring the hydrogen transfer resistance measured under hydrogen and nitrogen in the high-temperature polymer electrolyte fuel cell of the Fe-NC non-noble metal electrode catalyst prepared from Examples 1 to 3.

Referring to FIG. 6, the 12 nm sample of Example 2 showed the lowest hydrogen transfer resistance value (2.61 Ohm cm ² ), which was lower than 3.54 and 4.38 Ohm cm ² values of 5 nm and 20 nm. In the case of the oxygen transfer resistance value was also the lowest value in the 12 nm sample of Example 2, it was confirmed that the mass transfer to oxygen and hydrogen at 12 nm was the best.

FIG. 7 is a graph showing (a to f) porosity distribution of Fe-NC non-noble metal electrode catalysts prepared from 1 to 6 of the present invention, and (h) a table summarizing BET surface area, total pore volume, and average pore size [ a: Example 1, b: Example 2, c: Example 3, d: Example 4, e: Example 5, f: Example 6].

Referring to FIG. 7, the BET surface area of the non-noble metal catalyst was found to be 690 to 1065 m ² / g, and the pore size distribution showed almost similar pore sizes according to the silica particle size.

Therefore, according to the present invention, a porous Fe-NC non-noble metal catalyst can be prepared through etching of silica particles, and this can be applied as an electrode catalyst for a high temperature polymer electrolyte fuel cell, which can prevent poisoning by phosphate electrolyte.

The embodiments of the present invention described above should not be construed as limiting the technical spirit of the present invention. The protection scope of the present invention is limited only by the matters described in the claims, and those skilled in the art can change and change the technical idea of the present invention in various forms. Therefore, such improvements and modifications will fall within the protection scope of the present invention as long as it will be apparent to those skilled in the art.

Claims (10)

(a) polymerizing aniline, silica particles, a non-noble metal precursor, an oxidizing agent, and a first acid solution;
(b) washing with distilled water so as to have a pH of 5 to 6 and drying the polymer;
(c) heat treating the dried polymer at 500 to 1200 ° C. under an inert gas atmosphere;
(d) removing the silica particles from the heat treated polymer to obtain a porous body;
(e) washing with distilled water such that the pH of the porous body is 5 to 6 and then drying;
(f) acid treating the dried porous body in a second acid solution;
(g) washing with distilled water and drying the pH of the acid-treated porous body to 5 to 6; And
(h) heat-treating the dried porous body at 500 to 1200 ° C. under an ammonia atmosphere. The method of claim 1,
The size of the silica particles is 8 to 16 nm,
The particle size of the non-noble metal electrocatalyst is 1 to 500 μm,
BET surface area of the non-noble metal electrocatalyst is a method of producing a non-noble metal electrode catalyst, characterized in that 500 to 1500 m ² / g. The method of claim 2,
The non-noble metal precursor is a method for producing a non-noble metal electrode catalyst, characterized in that the iron precursor. The method of claim 1,
The inert gas is argon, nitrogen, neon, helium or a method for producing a non-noble metal electrode catalyst, characterized in that a mixture of two or more thereof. The method of claim 1,
The step (d) is a method for producing a non-noble metal electrode catalyst, characterized in that carried out by hydrothermal reaction of the heat-treated polymer in a sodium hydroxide solution at 80 to 200 ℃. The method of claim 1,
The oxidizing agent is at least one selected from ammonium persulfate, iron chloride, copper chloride and potassium persulfate,
The first acid solution and the second acid solution is the same or different from each other, each independently a method of producing a non-noble metal electrode catalyst, characterized in that at least one selected from formic acid, sulfuric acid, hypochlorous acid, nitric acid, hydrochloric acid and phosphoric acid. The method of claim 1,
The size of the silica particles is 8 to 16 nm,
The particle size of the non-noble metal electrocatalyst is 1 to 500 μm,
The BET surface area of the non-noble metal electrode catalyst is 500 to 1500 m ² / g,
The non-noble metal precursor is ferric chloride,
The polymerization of step (a) is carried out at 1 to 20 ℃,
Drying of the steps (b), (e) and (g) is carried out at 30 to 100 ℃,
The inert gas is argon,
The step (d) is carried out by hydrothermally reacting the heat treated polymer in a sodium hydroxide solution at 80 to 200 ℃,
The oxidant is ammonium persulfate,
The first acid solution is formic acid,
The second acid solution is a method for producing a non-noble metal electrode catalyst, characterized in that sulfuric acid. A non-noble metal electrode catalyst prepared by the manufacturing method according to any one of claims 1 to 7. A high temperature type polymer electrolyte fuel cell comprising the non-noble metal electrode catalyst according to claim 8. An electrical device comprising the non-noble metal electrocatalyst according to claim 8
The electric device is an electric device, characterized in that one kind selected from among electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles and power storage devices.

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