CN1938188A - Submarine boat - Google Patents

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Publication number
CN1938188A
CN1938188A CN 200580010258 CN200580010258A CN1938188A CN 1938188 A CN1938188 A CN 1938188A CN 200580010258 CN200580010258 CN 200580010258 CN 200580010258 A CN200580010258 A CN 200580010258A CN 1938188 A CN1938188 A CN 1938188A
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China
Prior art keywords
hydrogen
fuel
producing apparatus
underwater ship
hydrogen producing
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CN 200580010258
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CN100503361C (en
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奥山良一
山本好浩
元井昌司
芦田胜二
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GS Yuasa Corp
Yuasa Corp
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Yuasa Battery Corp
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    • Y02E60/523—
    • Y02E60/566—

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Abstract

A submersible vessel equipped with a hydrogen production system capable of supplying hydrogen easily to a fuel cell and capable of producing a gas containing hydrogen at low temperatures. A submersible vessel equipped with a fuel cell (30) which is supplied with hydrogen and an oxidizing agent and generates electric power, a hydrogen production system (10) for producing a gas containing hydrogen to be supplied to the fuel cell, and a propulsion unit driven with the electric power generated by the fuel cell, is characterized in that the hydrogen production system produces a gas containing hydrogen by decomposing fuel containing an organic matter and comprises a diaphragm (11), a fuel electrode (12) arranged on one side of the diaphragm, a means (16) for supplying the fuel electrode with a fuel containing an organic matter and water, an oxidizing electrode (14) arranged on the other side of the diaphragm, a means (17) for supplying the oxidizing electrode with an oxidizing agent, and a means for generating and collecting a gas containing hydrogen from the fuel electrode side.

Description

Underwater ship
Technical field
The underwater ships such as deep sea diving research vessel, Submarine, underwater craft that are used for supplying with the hydrogen producing apparatus of hydrogen have been the present invention relates to carry to fuel cell.
Background technology
At present, the good fuel cell of developing solemn silence, efficientibility is used as the propulsion source of underwater ships such as deep sea diving research vessel, Submarine, underwater craft.The fuel of fuel cell is generally hydrogen, is to use the huge problem that is faced in the exploitation of underwater ship of fuel cell but how to supply with hydrogen.
In the underwater ship in the past, the general storage high pressure hydrogen that adopts is with the mode (for example with reference to patent documentation 1～3) of such hydrogen fueling battery.In this mode, it is big that gas container must be that the quality of the container of pressure-resistance structure becomes, and the weight of underwater ship also increases the weight of, thus essential will cooresponding therewith buoyant material, thereby certainly exist because the such buoyant material of equipment and problem that underwater ship increases.In addition, in order to preserve hydrogen with the high pressure gas state, strictly also there is the problem of using difficulty in taking care property.
Patent documentation 1: the spy opens flat 10-100990 communique
Patent documentation 2: the spy opens flat 10-144327 communique
Patent documentation 3: the spy opens flat 10-181685 communique
In order to address the above problem, developed following apparatus for forming hydrogen: " diving machine apparatus for forming hydrogen; its hydrogen for employed fuel cell in the diving machine propulsion source of (comprising underwater ship) etc. is supplied with and in the generating means metal hydride (also comprising the coordination metal hydride) contacted to produce the apparatus for forming hydrogen of hydrogen with hydrogen generation accelerator; it is characterized in that; at least a in metal hydride or the hydrogen generation accelerator is liquid; this liquid container of configuration storage in machine, the outer hydraulic pressure of machine substantially for all pressure " (with reference to patent documentation 4).The metal hydride of in this apparatus for forming hydrogen, using, if although compare with high pressure hydrogen, usability is good, but, and use that to contain organic fuel different as the situation of hydrogen raw material, reactive big, before the reaction, need prevent with as the water or the pure contacted device of hydrogen generation accelerator, in addition, have the problem that is difficult to control reaction.
Patent documentation 4: the spy opens the 2002-187595 communique
In addition, known have on the diving machine carry the reformer of making hydrogen by reforming hydrocarbon fuel, supply with the hydrogen of making by reformer (for example with reference to patent documentation 4) to fuel cell.Act as a fuel, can consider methyl alcohol, dimethyl ether (DME), ethanol, natural fuels, propane or gasoline etc., wherein, the development progress of the reformer of the methyl alcohol that reforming temperature is minimum is the fastest.
Patent documentation 5: the spy opens flat 8-17456 communique
At present, reforming method as methyl alcohol has adopted steam reforming, partial oxidation to reform and also reform these three kinds (with reference to non-patent document 1) with also using of these two kinds of methods, even but adopt any reforming method, in order to make hydrogen-containing gas, must reform under the high temperature more than 200 ℃, removal, the partial oxidation of the CO that the problem of existence is the poisoning of reforming catalyst, contained in the gas (hydrogen-containing gas) after reforming reformed or and with the nitrogen in the entrained air in the gas after reforming in reforming etc.
Non-patent document 1: " solid polymer type fuel Electricity pond development と real usefulnessization ", the 141st Page～the 166th Page, on May 28th, 1999, (strain) skill Intraoperative feelings Reported Association Hui development are capable
In addition, also known have by electrochemical reaction produce the invention (with reference to patent documentation 6,8) of method of hydrogen and the invention (patent documentation 7～9) that utilizes the fuel cell of the hydrogen that produces by electrochemical method.
Patent documentation 6: specially permit communique No. 3328993
Patent documentation 7: specially permit communique No. 3360349
Patent documentation 8: US Patent the 6th, 299, No. 744 specification sheetss, the 6th, 368, No. 492 specification sheetss of US Patent, the 6th, 432, No. 284 specification sheetss of US Patent, the 6th, 533, No. 919 specification sheetss of US Patent, No. 2003/0226763 communique of U.S. Patent Publication
Patent documentation 9: the spy opens the 2001-297779 communique
In above-mentioned patent documentation 6, put down in writing following invention (claim 1): " hydrogen production method; it is characterized by; on cation-exchange membrane two faces in opposite directions, pair of electrodes is set; make the fuel that contains the first alcohol and water at least contact the electrode that contains catalyst that is arranged on another face; to derive electronics by described pair of electrodes is applied voltage from described electrode; on described electrode, carry out by described methyl alcohol and the hydrionic reaction of water generates, the electrode that on another face on a described cation-exchange membrane opposite in opposite directions, is provided with, the described hydrion that will produce by the supply electronics changes hydrogen molecule into ".In addition, also disclose: simultaneously supply with water or aqueous vapor with electrode with supplying with the methyl alcohol that acts as a fuel to fuel, connect external circuit, apply voltage, thus, carry out CH with electrode at fuel to derive electronics with electrode from fuel 3OH+2H 2O → CO 2+ 6e -+ 6H +Reaction makes consequent hydrion by cation-exchange membrane, passes through 6H in electrode side in opposite directions ++ 6e -→ 3H 2And selectivity generates hydrogen (paragraph [0033]～[0038]).And then, in patent documentation 7, put down in writing the invention (paragraph [0052]～[0056]) that utilizes the fuel cell of the hydrogen that produces by this method.
According to patent documentation 6 and 7 inventions of being put down in writing, can under low temperature, produce hydrogen (paragraph [0080] of the paragraph of patent documentation 6 [0042], patent documentation 7), but must apply voltage in order to produce hydrogen, in addition, the generation of hydrogen is in the in opposite directions electrode side of fuel with electrode (fuel electrodes), do not supply with oxidizer to electrode in opposite directions, thus with underwater ship of the present invention on the hydrogen producing apparatus that carries obviously different.
The invention of record is also same with above-mentioned patent documentation 6 and 7 inventions of being put down in writing in the above-mentioned patent documentation 8, its proton that is the anode 112 at the utmost point that acts as a fuel generates sees through barrier film 110, produce hydrogen at negative electrode 114 as counter electrode, but its with fuel very anode, be negative electrode and apply voltage with the counter electrode by direct supply 120, organic-fuels such as electrolysis methyl alcohol, and the generation of hydrogen is the counter electrode side in fuel electrodes, do not supply with oxidizer to counter electrode, thus with underwater ship of the present invention on the hydrogen producing apparatus that carries obviously different.
Put down in writing in the above-mentioned patent document 9 the hydrogen generation utmost point (claim 1) that produces hydrogen has been set in fuel cell system, also put down in writing and " supplied with the liquid fuel that contains alcohol and water to perforated electrode (fuel electrodes) 1; to gas-diffusion electrode (oxidizing agent pole) 2 air supplies of opposition side; when between the terminal of the terminal of perforated electrode 1 and gas-diffusion electrode 2, keeping load; from the positive pole of MEA2 with common fuel cell function is that gas-diffusion electrode 2 can apply positive potential with perforated electrode 1 by load, forms electrical connection like this.Consequently alcohol generates carbon dioxide and hydrion with the water reaction, and the hydrion of generation produces hydrogen through dielectric substrate 5 on the gas-diffusion electrode 6 of central authorities.On gas-diffusion electrode 6, reacting with the interface generating electrodes of another dielectric substrate 7, form hydrion once again and in dielectric substrate 7, move arrival gas-diffusion electrode 2.On gas-diffusion electrode 2, generate water with the reaction of airborne oxygen " (paragraph 0007); this shows; patent document 9 is to utilize the electric energy that is produced by fuel cell to produce the utmost point (gas-diffusion electrode 6) at hydrogen to produce hydrogen; again with its fueling battery; in addition; in the generation of hydrogen is counter electrode side this respect in fuel electrodes, identical with above-mentioned patent documentation 6～8.
In addition, also known employing clips proton-conductive films (ion-conducting material) and the reaction unit with barrier film of formation anode (electrode A) and negative electrode (electrode B), by applying or not applying voltage, perhaps derive electric energy, the invention of the method for simultaneous oxidation alcohol (methyl alcohol) (with reference to patent documentation 10 and 11), but all being about using the technology (resultant be carbonic diester, Formalin, methyl formate, dimethoxymethane etc.) of electrochemical cell with pure oxidation, is not by the technology of alcohol generation as the hydrogen of reduzate.
Patent documentation 10: the spy opens flat 6-73582 communique (claim 1～3, paragraph [0050])
Patent documentation 11: the spy opens flat 6-73583 communique ( claim 1,8, paragraph [0006], [0019])
Summary of the invention
Problem of the present invention is to solve the above problems, and provides to have carried can be easily to supply with hydrogen, can make the underwater ship of the hydrogen producing apparatus of hydrogen-containing gas at low temperatures to fuel cell.
In order to solve above-mentioned problem, following means have been adopted among the present invention.
(1) underwater ship, it has at least by supplying with the fuel cell that hydrogen and oxidizer generate electricity, manufacturing is used to supply with the hydrogen producing apparatus of hydrogen-containing gas of described fuel cell and the propelling unit that is driven by the electricity that described fuel cell produced, it is characterized in that, described hydrogen producing apparatus is to decompose the hydrogen producing apparatus that contains organic fuel and make hydrogen-containing gas, and described hydrogen producing apparatus has barrier film, be arranged on the fuel electrodes on the face of described barrier film, supply with the device of the fuel that contains organic matter and water to described fuel electrodes, be arranged on the oxidation utmost point on another face of described barrier film, supply with the device of oxidizer and the device that produces hydrogen-containing gas and take out by the fuel electrodes side to the described oxidation utmost point.
As (1) described underwater ship, it is characterized in that (2) described hydrogen producing apparatus is not made battery to the device of outside derivation electric energy and the open-circuit condition that is applied the device of electric energy by the outside to described hydrogen manufacturing battery for not having by the hydrogen that constitutes hydrogen producing apparatus.
As (1) described underwater ship, it is characterized in that (3) described hydrogen producing apparatus has with described fuel negative pole, very anodal and derive the device of electric energy to the outside with described oxidation very.
(4) as (1) described underwater ship, it is characterized in that, described hydrogen producing apparatus have with described fuel very negative electrode, with described oxidation anode and apply the device of electric energy from the outside very.
(5) as (1) described underwater ship, it is characterized in that, be used in combination the hydrogen producing apparatus of from following hydrogen producing apparatus, selecting more than 2 kinds or 2 kinds: do not have and make battery from described hydrogen and derive the device of electric energy and make the hydrogen producing apparatus of open-circuit condition of the device of battery supply of electrical energy from the outside to described hydrogen to the outside; Have with described fuel negative pole, very anodal very, derive the hydrogen producing apparatus of the device of electric energy to the outside with described oxidation; And have with described fuel very negative electrode, with described oxidation anode very, apply the hydrogen producing apparatus of the device of electric energy from the outside.
As (1) described underwater ship, it is characterized in that (6) in described hydrogen producing apparatus, the voltage between the described fuel electrodes and the described oxidation utmost point is 200～1000mV.
As (2) described underwater ship, it is characterized in that (7) in described hydrogen producing apparatus, the voltage between the described fuel electrodes and the described oxidation utmost point is 300～800mV.
As (3) described underwater ship, it is characterized in that (8) in described hydrogen producing apparatus, the voltage between the described fuel electrodes and the described oxidation utmost point is 200～600mV.
(9) as (3) or (8) described underwater ship, it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by regulating described derivation electric energy.
As (4) described underwater ship, it is characterized in that (10) in described hydrogen producing apparatus, the voltage between the described fuel electrodes and the described oxidation utmost point is 300～1000mV.
(11) as (4) or (10) described underwater ship, it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by regulating the described electric energy that applies.
(12) as any one the described underwater ship in (1)～(11), it is characterized in that, in described hydrogen producing apparatus, regulate the growing amount of described hydrogen-containing gas by regulating voltage between the described fuel electrodes and the described oxidation utmost point.
(13) as any one the described underwater ship in (1)～(12), it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by the delivery volume of regulating described oxidizer.
(14) as any one the described underwater ship in (1)～(13), it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by the concentration of regulating described oxidizer.
(15) as any one the described underwater ship in (1)～(14), it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by regulating the described delivery volume that contains the fuel of organic matter and water.
(16) as any one the described underwater ship in (1)～(15), it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by regulating the described concentration that contains the fuel of organic matter and water.
As any one the described underwater ship in (1)～(16), it is characterized in that (17) operating temperature of described hydrogen producing apparatus is smaller or equal to 100 ℃.
As (17) described underwater ship, it is characterized in that (18) described operating temperature is 30～90 ℃.
As any one the described underwater ship in (1)～(18), it is characterized in that (19) the described organic matter of supplying with the fuel electrodes of described hydrogen producing apparatus is one or both or the two or more organic matter of selecting from alcohol, aldehyde, carboxylic acid and ether.
(20) underwater ship described in (19) is characterized in that, described alcohol is methyl alcohol.
As any one the described underwater ship in (1)～(20), it is characterized in that (21) the described oxidizer of supplying with the oxidation utmost point of described hydrogen producing apparatus is oxygen-containing gas or oxygen.
(22) underwater ship described in (21) is characterized in that, the described oxidizer of supplying with the oxidation utmost point of described hydrogen producing apparatus is the gas (oxygen exhaust) from the unreacted oxygenate of described fuel cell or other described hydrogen producing apparatus discharges.
As any one the described underwater ship in (1)～(20), it is characterized in that (23) the described oxidizer of supplying with the oxidation utmost point of described hydrogen producing apparatus is the liquid that contains hydrogen peroxide.
As any one the described underwater ship in (1)～(23), it is characterized in that (24) barrier film of described hydrogen producing apparatus is the proton conductive solid electrolyte film.
As (24) described underwater ship, it is characterized in that (25) described proton conductive solid electrolyte film is that perfluorocarbon sulfonic acid is a solid electrolyte film.
As any one the described underwater ship in (1)～(25), it is characterized in that (26) catalyst of the fuel electrodes of described hydrogen producing apparatus is the catalyst that has supported the Pt-Ru alloy on carbon dust.
As any one the described underwater ship in (1)～(26), it is characterized in that (27) catalyst of the oxidation utmost point of described hydrogen producing apparatus is the catalyst that has supported Pt on carbon dust.
(28) as any one the described underwater ship in (1)～(27), it is characterized in that, the described circulating device that contains the fuel of organic matter and water is set on described hydrogen producing apparatus.
(29) as any one the described underwater ship in (1)～(28), it is characterized in that, on described hydrogen producing apparatus, be provided for absorbing the carbon-dioxide carbon dioxide absorption portion in the described hydrogen-containing gas that is included in generation.
(30) as any one the described underwater ship in (1)～(29), it is characterized in that, do not cool off by the described hydrogen-containing gas of described hydrogen producing apparatus generation and supply with described fuel cell.
(31) as any one the described underwater ship in (1)～(30), it is characterized in that, be provided for blocking the thermal insulating material of the heat that described hydrogen producing apparatus sends.
At this, the hydrogen producing apparatus that carries in the underwater ship of above-mentioned (2)～(4) has device from oxidizer to the hydrogen that constitutes hydrogen producing apparatus that make battery fueling and, and this device can use pump, air blower etc.In addition, the situation in above-mentioned (3) has the discharge control device that is used for making from hydrogen battery derivation electric energy; Situation in above-mentioned (4) has the electrolyzer that is used for applying to hydrogen manufacturing battery electric energy.Situation in above-mentioned (2), it is not have to be used for making the open-circuit condition that battery is derived the discharge control device of electric energy and is used for applying to hydrogen manufacturing battery the electrolyzer of electric energy from hydrogen.And the hydrogen producing apparatus that carries in the underwater ship of above-mentioned (1) comprises the hydrogen producing apparatus that carries in the underwater ship of above-mentioned (2)～(4).And then these hydrogen producing apparatus have following function: the electric energy (situations of above-mentioned (4)) that the growing amount of making the voltage of battery and/or hydrogen-containing gas by monitoring hydrogen is controlled the delivery volume of fuel and oxidizer or the electric energy of concentration and derivation (situations of above-mentioned (3)) or applied.Here, the basic structure that the hydrogen that constitutes hydrogen producing apparatus is made battery has on a face of barrier film fuel electrodes is set, be used for structure, and on another face of above-mentioned barrier film, the oxidation utmost point be set, be used for supplying with the structure of oxidizer to the above-mentioned oxidation utmost point to above-mentioned fuel electrodes fueling.
Underwater ship of the present invention, because having carried can be at ℃ such hydrogen producing apparatus of comparing fuel reforming under the significantly reduced temperature with reforming temperature in the past from room temperature～100, therefore, not only can shorten the needed time that starts, can also reduce the energy that is used to improve the reformer temperature, also can make to start and use the battery miniaturization.Also can not need to be used for to block the thermal insulating material of the heat that reformer produces in addition, can be not the hydrogen-containing gas that hydrogen producing apparatus produced not cooled off fueling battery easily.
In addition, owing to do not contain CO in the hydrogen-containing gas that hydrogen producing apparatus produced, so do not need to remove the device of CO.
In addition, the employed hydrogen producing apparatus of underwater ship of the present invention does not need to make the battery supply of electrical energy from the outside to hydrogen and can produce hydrogen, even in the situation with the device of deriving electric energy, having the situation that applies the device of electric energy from the outside, can produce hydrogen yet.
In the situation with the device of deriving electric energy, because this electric energy can be used for auxiliary enginies such as driving pump, air blower etc., or the driving that can be used as underwater ship utilizes with the part of power supply, and is therefore, remarkable from the angle effect of effective use of energy sources.
Have the situation that applies the device of electric energy from the outside, supplying with a spot of electric energy, can realize producing the effect of hydrogen that reaches or exceed the electric energy of input by making battery to hydrogen from the outside.
And then, for any situation, make the voltage of battery and/or the growing amount of hydrogen-containing gas by monitoring hydrogen, can carry out technology controlling and process, owing to can realize the densification of hydrogen producing apparatus, therefore can realize reducing the effect of underwater ship manufacturing cost.
Description of drawings
Fig. 1 (a) is the figure of an example of system flow of the fuel cell system of expression underwater ship of the present invention.
Fig. 1 (b) is the skeleton diagram of an example of the structure of box (package) fuel cell power generating system that carries on the underwater ship of the present invention of expression.
Fig. 1 (c) is the skeleton diagram of the relation of the hydrogen producing apparatus that carries on the underwater ship of the present invention of expression and fuel cell.
Fig. 2 is the skeleton diagram that the hydrogen among the embodiment 1 is made battery (not from outside supply of electrical energy).
Fig. 3 is the figure (hydrogen Production Example 1-1) of the relation of the following charge air of expression different temperatures (30～70 ℃) and hydrogen formation speed and open circuit voltage.
Fig. 4 is the figure (hydrogen Production Example 1-1) of the relation of following open circuit voltage of expression different temperatures (30～70 ℃) and hydrogen formation speed.
Fig. 5 is the figure (hydrogen Production Example 1-2) of the relation (70 ℃ of temperature) of charge air and hydrogen formation speed and open circuit voltage under the different fuel flow of expression.
Fig. 6 is the figure (hydrogen Production Example 1-2) of the relation (70 ℃ of temperature) of open circuit voltage and hydrogen formation speed under the different fuel flow of expression.
Fig. 7 is the figure (hydrogen Production Example 1-3) of the relation (70 ℃ of temperature) of charge air and hydrogen formation speed and open circuit voltage under the different fuel concentration of expression.
Fig. 8 is the figure (hydrogen Production Example 1-3) of the relation (70 ℃ of temperature) of open circuit voltage and hydrogen formation speed under the different fuel concentration of expression.
The figure (hydrogen Production Example 1-4) of the relation of charge air and hydrogen formation speed and open circuit voltage when Fig. 9 is the dielectric film of expression different-thickness.
The figure (hydrogen Production Example 1-4) of the relation of open circuit voltage and hydrogen formation speed when Figure 10 is the dielectric film of expression different-thickness.
Figure 11 is the figure (hydrogen Production Example 1-5) of the relation of the following charge air of expression different temperatures (30～90 ℃) and hydrogen formation speed and open circuit voltage.
Figure 12 is the relation (oxidizer: figure air) (hydrogen Production Example 1-5) of following open circuit voltage of expression different temperatures (30～90 ℃) and hydrogen formation speed.
Figure 13 is the figure (hydrogen Production Example 1-6) of the relation (50 ℃ of temperature) of charge air and hydrogen formation speed and open circuit voltage under the expression different fuel flow.
Figure 14 is the figure (hydrogen Production Example 1-6) of the relation (50 ℃ of temperature) of open circuit voltage and hydrogen formation speed under the expression different fuel flow.
Figure 15 is the figure (hydrogen Production Example 1-7) of the relation (50 ℃ of temperature) of charge air and hydrogen formation speed and open circuit voltage under the expression different fuel concentration.
Figure 16 is the figure (hydrogen Production Example 1-7) of the relation (50 ℃ of temperature) of open circuit voltage and hydrogen formation speed under the expression different fuel concentration.
Figure 17 is the figure (hydrogen Production Example 1-8) of the relation (50 ℃ of temperature) of oxidizing gas flow and hydrogen formation speed and open circuit voltage under the expression different oxygen concentrations.
Figure 18 is the figure (hydrogen Production Example 1-8) of the relation (50 ℃ of temperature) of open circuit voltage and hydrogen formation speed under the expression different oxygen concentrations.
Figure 19 is expression different temperatures (30～90 ℃) H down 2O 2The figure of the relation of flow and hydrogen formation speed and open circuit voltage (hydrogen Production Example 1-10).
Figure 20 is the relation (oxidizer: H of following open circuit voltage of expression different temperatures (30～90 ℃) and hydrogen formation speed 2O 2) figure (hydrogen Production Example 1-10).
Figure 21 is the skeleton diagram that the hydrogen among the embodiment 2 is made battery (having the device of deriving electric energy).
Figure 22 is the relation (discharge: figure 50 ℃ of temperature) (hydrogen Production Example 2-1) of the different charge airs of the expression density of current of deriving down and the voltage that turns round.
Figure 23 is the relation (discharge: figure 50 ℃ of temperature) (hydrogen Production Example 2-1) of the different charge airs of expression following running voltage and hydrogen formation speed.
Figure 24 is the relation (discharge: figure 30 ℃ of temperature) (hydrogen Production Example 2-2) of the different charge airs of the expression density of current of deriving down and the voltage that turns round.
Figure 25 is the relation (discharge: figure 30 ℃ of temperature) (hydrogen Production Example 2-2) of the different charge airs of expression following running voltage and hydrogen formation speed.
Figure 26 is the relation (discharge: figure 70 ℃ of temperature) (hydrogen Production Example 2-3) of the different charge airs of the expression density of current of deriving down and the voltage that turns round.
Figure 27 is the relation (discharge: figure 70 ℃ of temperature) (hydrogen Production Example 2-3) of the different charge airs of expression following running voltage and hydrogen formation speed.
Figure 28 is the relation (discharge: figure 90 ℃ of temperature) (hydrogen Production Example 2-4) of the different charge airs of the expression density of current of deriving down and the voltage that turns round.
Figure 29 is the relation (discharge: figure 90 ℃ of temperature) (hydrogen Production Example 2-4) of the different charge airs of expression following running voltage and hydrogen formation speed.
Figure 30 is that the density of current of deriving under the expression different temperatures (discharges: figure charge air 50ml/ branch) with the relation of running voltage.
Figure 31 is that the relation of running voltage and hydrogen formation speed under the expression different temperatures (is discharged: figure charge air 50ml/ branch).
Figure 32 is that the density of current of deriving under the expression different temperatures (discharges: figure charge air 100ml/ branch) with the relation of running voltage.
Figure 33 is that the relation of running voltage and hydrogen formation speed under the expression different temperatures (is discharged: figure charge air 100ml/ branch).
Figure 34 is the relation (discharge: figure 50 ℃ of temperature) (hydrogen Production Example 2-5) of expression different fuel the flow density of current of deriving down and the voltage that turns round.
Figure 35 is the relation (discharge: figure 50 ℃ of temperature) (hydrogen Production Example 2-5) of expression different fuel flow following running voltage and hydrogen formation speed.
Figure 36 is that the density of current of deriving under the expression different fuel concentration (discharges: figure 50 ℃ of temperature) (hydrogen Production Example 2-6) with the relation of running voltage.
Figure 37 is that running voltage (discharges: figure 50 ℃ of temperature) (hydrogen Production Example 2-6) with the relation of hydrogen formation speed under the expression different fuel concentration.
Figure 38 is that the density of current of deriving under the expression different oxygen concentrations (discharges: figure 50 ℃ of temperature) (hydrogen Production Example 2-7) with the relation of running voltage.
Figure 39 is that the relation of running voltage and hydrogen formation speed under the expression different oxygen concentrations (is discharged: figure 50 ℃ of temperature) (hydrogen Production Example 2-7).
Figure 40 is that the density of current of deriving under the expression different temperatures (discharges: oxidizer H with the relation of running voltage 2O 2) figure (hydrogen Production Example 2-8).
Figure 41 is that the relation of running voltage and hydrogen formation speed under the expression different temperatures (is discharged: oxidizer H 2O 2) figure (hydrogen Production Example 2-8).
Figure 42 is the skeleton diagram that the hydrogen among the embodiment 3 is made battery (having the device that applies electric energy from the outside).
Figure 43 is that the density of current that expression applies under the different charge airs (charges: figure 50 ℃ of temperature) (hydrogen Production Example 3-1) with the relation of hydrogen formation speed.
Figure 44 is the relation (charging: figure 50 ℃ of temperature) (hydrogen Production Example 3-1) of the different charge airs of expression following running voltage and hydrogen formation speed.
Figure 45 is that the density of current that applies under the different charge airs of expression (charges: figure 50 ℃ of temperature) (hydrogen Production Example 3-1) with the relation of running voltage.
Figure 46 is the relation (charging: figure 50 ℃ of temperature) (hydrogen Production Example 3-1) of the different charge airs of expression following running voltage and energy efficiency.
Figure 47 is that the density of current that expression applies under the different charge airs (charges: figure 30 ℃ of temperature) (hydrogen Production Example 3-2) with the relation of hydrogen formation speed.
Figure 48 is the relation (charging: figure 30 ℃ of temperature) (hydrogen Production Example 3-2) of the different charge airs of expression following running voltage and hydrogen formation speed.
Figure 49 is the relation (charging: figure 30 ℃ of temperature) (hydrogen Production Example 3-2) of the different charge airs of expression following running voltage and energy efficiency.
Figure 50 is that the density of current that expression applies under the different charge airs (charges: figure 70 ℃ of temperature) (hydrogen Production Example 3-3) with the relation of hydrogen formation speed.
Figure 51 is the relation (charging: figure 70 ℃ of temperature) (hydrogen Production Example 3-3) of the different charge airs of expression following running voltage and hydrogen formation speed.
Figure 52 is the relation (charging: figure 70 ℃ of temperature) (hydrogen Production Example 3-3) of the different charge airs of expression following running voltage and energy efficiency.
Figure 53 is that the density of current that expression applies under the different charge airs (charges: figure 90 ℃ of temperature) (hydrogen Production Example 3-4) with the relation of hydrogen formation speed.
Figure 54 is the relation (charging: figure 90 ℃ of temperature) (hydrogen Production Example 3-4) of the different charge airs of expression following running voltage and hydrogen formation speed.
Figure 55 is the relation (charging: figure 90 ℃ of temperature) (hydrogen Production Example 3-4) of the different charge airs of expression following running voltage and energy efficiency.
Figure 56 is that the density of current that expression applies under the different temperatures (charges: figure charge air 50ml/ branch) with the relation of hydrogen formation speed.
Figure 57 is that the relation of running voltage and hydrogen formation speed under the expression different temperatures (is charged: figure charge air 50ml/ branch).
Figure 58 is that the relation of running voltage and energy efficiency under the expression different temperatures (is charged: figure charge air 50ml/ branch).
Figure 59 is that the density of current that applies under the expression different fuel flow (charges: figure 50 ℃ of temperature) (hydrogen Production Example 3-5) with the relation of hydrogen formation speed.
Figure 60 is the relation (charging: figure 50 ℃ of temperature) (hydrogen Production Example 3-5) of expression different fuel flow following running voltage and hydrogen formation speed.
Figure 61 is the relation (charging: figure 50 ℃ of temperature) (hydrogen Production Example 3-5) of expression different fuel flow following running voltage and energy efficiency.
Figure 62 is that the density of current that applies under the expression different fuel concentration (charges: figure 50 ℃ of temperature) (hydrogen Production Example 3-6) with the relation of hydrogen formation speed.
Figure 63 is that running voltage (charges: figure 50 ℃ of temperature) (hydrogen Production Example 3-6) with the relation of hydrogen formation speed under the expression different fuel concentration.
Figure 64 is that running voltage (charges: figure 50 ℃ of temperature) (hydrogen Production Example 3-6) with the relation of energy efficiency under the expression different fuel concentration.
Figure 65 is that the density of current that expression applies under the different oxygen concentrations (charges: figure 50 ℃ of temperature) (hydrogen Production Example 3-7) with the relation of hydrogen formation speed.
Figure 66 is that the relation of running voltage and hydrogen formation speed under the expression different oxygen concentrations (is charged: figure 50 ℃ of temperature) (hydrogen Production Example 3-7).
Figure 67 is that the relation of running voltage and energy efficiency under the expression different oxygen concentrations (is charged: figure 50 ℃ of temperature) (hydrogen Production Example 3-7).
Figure 68 is that the density of current that expression applies under the different temperatures (charges: oxidizer H with the relation of hydrogen formation speed 2O 2) figure (hydrogen Production Example 3-8).
Figure 69 is that the relation of running voltage and hydrogen formation speed under the expression different temperatures (is charged: oxidizer H 2O 2) figure (hydrogen Production Example 3-8).
Figure 70 is that the relation of running voltage and energy efficiency under the expression different temperatures (is charged: oxidizer H 2O 2) figure (hydrogen Production Example 3-8).
Figure 71 is the relation (open circuit: figure 50 ℃ of temperature) (embodiment 8) of expression charge air and hydrogen formation speed.
Figure 72 is the relation (open circuit: figure 50 ℃ of temperature) (embodiment 8) of expression open circuit voltage and hydrogen formation speed.
Nomenclature
10: hydrogen is made battery, and 11: barrier film, 12: fuel electrodes,
13: be used for supplying with the stream of the fuel (methanol-water) that contains organic matter and water to fuel electrodes 12,
14: the oxidation utmost point (air pole), 15: be used for supplying with the stream of oxidizer (air) to the oxidation utmost point (air pole) 14,
16: petrolift, 17: air blowing fan, 18: fuel flow control valve,
19: air flow rate adjustment valve, 20: Fuel Tank, 21: the fuel adjusting groove,
22: voltage regulator, 23: gas-liquid separator (separating the hydrogen-containing gas and the unreacted methanol aqueous system), 24: the hydrogen jar, 25: the conduit that is used for the unreacted methanol aqueous system is returned fuel adjusting groove 21,26: the hydrogen flow control valve, 27: gas-liquid separator (from the oxygen exhaust, separating the water and the unreacted methanol aqueous system that generates), 28: the co 2 removal device, 29: the conduit that is used for the unreacted methanol aqueous system is returned fuel adjusting groove 21,30: fuel cell, 31: solid polyelectrolyte membrane, 32: the hydrogen utmost point, 33: the stream of hydrogen being supplied with the hydrogen utmost point 32,34: air pole, 35: with the stream of the air air supply utmost point 34,36: the direct current (DC) that fuel cell 30 is sent is converted to the power inverter of regulation electric power, 37: power generation assembly is carried out the whole control setup of controlling, 38: packing chest.
The specific embodiment
Following illustration is used to implement the specific embodiment of the present invention.
Particularly, the hydrogen producing apparatus of the lift-launch on the underwater ship of the present invention is new basically, only embodiment of the following stated, and the present invention is not limited thereto.
The basic structure of underwater ship of the present invention is, it possesses by supplying with fuel cell that hydrogen and oxidizer generate electricity, making the hydrogen producing apparatus of the hydrogen-containing gas that is used to supply with described fuel cell and the propelling unit that is driven by the electricity that described fuel cell produced.
One example of the system flow of the fuel cell system of Fig. 1 (a) expression underwater ship of the present invention.
Underwater ship of the present invention, shown in Fig. 1 (b), be the box fuel cell power generating system preferably: control setup of controlling by the hydrogen of supplying with fuel cell (30) that hydrogen and oxidizer generate electricity, making the hydrogen-containing gas that is used for fueling battery (30) is made battery (10), direct current (DC) that fuel cell (30) is produced is converted to regulation electric power transfer device (36), to power generation assembly integral body (37) and petrolift (16), air blowing fan auxiliary enginies such as (17) with following component mounting.
For underwater ship of the present invention make battery (10) and move at low temperatures owing to constitute the hydrogen of hydrogen producing apparatus, therefore different with apparatus for reforming of fuel in the past, control setup (37) can be configured in hydrogen manufacturing battery (10) near.In addition, can not need to be used to protect control setup (37) to avoid the thermal insulating material that hydrogen is made the heat that battery (10) produced.
In the figure, on underwater ship, carried Fuel Tank (20) and fuel adjusting groove (21), can not carry these and, also can on underwater ship, only carry fuel adjusting groove (21) by outside fueling (methanol aqueous solution).
In addition, make also direct fueling battery (10) of hydrogen-containing gas that battery (10) produced by hydrogen, but the hydrogen jar (24) of storing hydrogen-containing gas preferably is set, by hydrogen jar (24) fueling battery (30).
And, the gas-liquid separator (23) that separates the hydrogen-containing gas and the unreacted methanol aqueous system preferably is set, make the unreacted methanol aqueous system be circulated to hydrogen and make battery (10).In addition, the water of separation generation from the oxygen exhaust and the gas-liquid separator (27) of the unreacted methanol aqueous system also can be set.
In addition, do not show among the figure, but in addition emergency battery can also be set.
The hydrogen producing apparatus that carries in the underwater ship of the present invention shown in Fig. 1 (c), has hydrogen manufacturing battery (10) and the auxiliary engine of the hydrogen producing apparatus that is used to turn round.
The structure that hydrogen is made battery (10) is as follows: on a face of barrier film (11) fuel electrodes (12) is set, has the stream 13 that is used for supplying with the fuel (methanol aqueous solution) that contains organic matter and water to fuel electrodes (12), and the oxidation utmost point (14) is set on another face of barrier film (11), has the stream (15) that is used for supplying with oxidizer (air) to the oxidation utmost point (14).
As the auxiliary engine of the hydrogen producing apparatus that is used to turn round, be provided with petrolift (16) from methanol aqueous solution to fuel electrodes (12) that supply with.The stream of fuel electrodes (13) is connected by conduit with flow control valve (18) by petrolift (16).
Fuel (100% methyl alcohol) is stored in the Fuel Tank (20), is shifted into fuel adjusting groove (21) by Fuel Tank then, mixes with water in fuel adjusting groove (21), for example is adjusted to about 3% methanol aqueous solution and supplies to fuel electrodes (12).
In addition, same, air blowing fan (17) is set as auxiliary engine, can be directly to oxidation utmost point air supply, but in the figure, supply with the oxygen of autoxidator storage facilities by air blowing fan (17) to fuel cell (30), utilize the unreacted oxygen (oxygen exhaust) of discharging from fuel cell (30).
Wherein, will flow to hydrogen by the oxygen exhaust that the oxygen utmost point (34) of fuel cell (30) is discharged and make battery (10), thereby not need hydrogen to make the air blowing fan of battery (10) usefulness.The stream (15) that hydrogen is made the oxidation utmost point of battery (10) is connected with flow control valve (19), fuel cell (30) by air blowing fan (17).
And; because this oxygen exhaust has the essentially identical temperature of operating temperature (about 80 ℃) with fuel cell (30); therefore, when protection control setup (37) is avoided fuel cell (30) heat, can utilize the heat of oxygen exhaust to be used as heating the thermal source that hydrogen is made battery (10).
In addition, when being used in combination 2 above hydrogen producing apparatus, the oxygen (air) as the oxidation utmost point (14) from battery (10) a to hydrogen that make is supplied with can utilize by another hydrogen and make the oxygen exhaust (air exhaust) that battery (10) is discharged.
For hydrogen producing apparatus with said structure, make it running to petrolift (16) and air blowing fan (17) supply of electrical energy, and when opening flow control valve (18), methanol aqueous solution is supplied to fuel electrodes (12) from fuel adjusting groove (21) by stream (13) by petrolift (16); In addition, when opening flow control valve (19), by air blowing fan (17) in the future the oxygen of autoxidator storage facilities supply to the oxidation utmost point (14) via fuel cell (30) by stream (15).
Thus, in fuel electrodes and the oxidation utmost point (air pole) generation reaction as described later, produce hydrogen-containing gas by fuel electrodes (12) side.
In addition, make delivery volume or the electric energy of concentration and derivation or the electric energy that applies that the voltage regulator (22) of the voltage of battery (10) (open circuit voltage or running voltage) is controlled fuel and oxygen (air) by being provided for monitoring hydrogen, can regulate the growing amount of hydrogen-containing gas.
The hydrogen-containing gas that produces is separated into the hydrogen-containing gas and the unreacted methanol aqueous system by gas-liquid separator (23), and hydrogen-containing gas is stored in the hydrogen jar (24).
The part or all of isolated unreacted methanol aqueous system returns fuel adjusting groove (21) by conduit (25) and circulates.According to circumstances also can outside system, supply with water.
In the oxygen exhaust by the hydrogen producing apparatus discharge, contain the water of generation and because of " infiltration " phenomenon unreacted methanol aqueous system from the methanol aqueous solution that fuel electrodes sees through, therefore, gas-liquid separator (27) is passed through in this oxygen exhaust, the water that generates is separated with the unreacted methanol aqueous system,, be discharged in the atmosphere behind the co 2 removal by co 2 removal device (28).
The water of the generation after the some or all of separation and the unreacted methanol aqueous system turn back in the fuel adjusting groove (21) by conduit (29) and to circulate.
The hydrogen utmost point (32) to fuel cell (30) is supplied with the hydrogen that is stored in hydrogen jar (24) by flow control valve (26), pass through the oxygen of flow control valve (19) supply to the oxygen utmost point (34) from air blowing fan (17), reaction in the hydrogen utmost point one side and the oxygen utmost point one side difference production (1) and formula (2), the reaction of single-piece fuel cell generating polynomial (3), form water (aqueous vapor), produce electricity (direct current (DC)).
H 2→2H ++2e -……(1)
2H ++2e -+(1/2)O 2→H 2O……(2)
H 2+(1/2)O 2→H 2O……(3)
The battery (30) that acts as a fuel if fuel is hydrogen, can use any kind of, preferably the polymer electrolyte fuel cell that can turn round at the low temperature below 100 ℃ (PEFC).For polymer electrolyte fuel cell, can adopt a plurality of fuel cell packs that are laminated of known monocell.The mono-monocell have the solid polyelectrolyte membrane (31) that is called as Nafion (trade mark of E.I.Du Pont Company), this film of sandwich as the hydrogen utmost point (32) of diffusion electrode and the oxygen utmost point (34) and from both sides with 2 barrier films of two electrode clampings etc.Form concavo-convexly on the two sides of barrier film, between the hydrogen utmost point and the oxygen utmost point of clamping, form gas flow path (33), (35) in the monocell.Wherein, and the hydrogen utmost point between gas flow path (33) in the monocell that forms be used to the hydrogen that circulates and supply with, in addition, and the oxygen utmost point between gas flow path (35) in the monocell that forms be used to the oxygen that circulates.
As mentioned above, in the oxygen utmost point (34) one sides of fuel cell, generate aqueous vapor (H by formula (2) 2O), contain a large amount of aqueous vapors in the oxygen exhaust of therefore from fuel cell, discharging.Be not transported to hydrogen in the oxygen exhaust of being discharged by the oxygen utmost point (34) of fuel cell (30) and make under the situation of battery (10), the aqueous vapor that is contained in the oxygen exhaust is recovered as water preferably by condenser condenses.
Fuel cell (30) generating can be followed heating.Under the situation of above-mentioned polymer electrolyte fuel cell (PEFC), polyelectrolyte membrane is in saturation state, shows proton-conducting, therefore along with the heating of fuel cell, the polyelectrolyte membrane drying, the internal resistance of fuel cell increases if water ratio descends, and generating capacity descends.Therefore, in order to prevent the drying of polyelectrolyte membrane, essential cooled fuel cell keeps suitable operating temperature (about 80 ℃).On the other hand, hydrogen producing apparatus, shown in the embodiment, the formation efficiency of the high more then hydrogen of temperature is high more as described later, therefore, the device heating of doing hydrogen producing apparatus of the heating of this fuel cell being carried out interchange of heat is set preferably.
In addition, because hydrogen producing apparatus is at low-temperature working, therefore do not need the temperature booster that is provided for heating up, but can be provided with as required yet as Fig. 1 (b) with (c).
In the past, in order to keep polyelectrolyte at moisture state, reformed gas and/or reaction air are carried out humidification fueling battery main body afterwards, but the hydrogen producing apparatus that carries on the underwater ship of the present invention, by the fuel electrodes fuel electrodes one side output hydrogen-containing gas of having supplied with the fuel (methanol aqueous solution) that contains organic matter and water, owing to hydrogen has been carried out humidification, thereby can not need humidifier.And, make the hydrogen-containing gas that battery (10) produces by hydrogen, owing to the reformed gas that does not resemble reformer manufacturing in the past, be high-temperature gas, therefore need not cool off can fueling battery (30).
In addition, as the fuel of fueling battery, the situation that can consider only to supply with the situation of the hydrogen that is produced by hydrogen manufacturing battery (10) and supply with hydrogeneous methanol aqueous solution.Contain the situation of the methanol aqueous solution of hydrogen for supply, do not need gas-liquid separator (23).
By the direct current (DC) that fuel cell (30) is sent, be input to power inverter (36), by DC/DC current converter (converter) boost or change alternating current into by DC/AC inverter (inverter) after export.In addition, by auxiliary engine with current converter the direct current (DC) after stable, can be used as the driving power of petrolift (16), air blowing fan auxiliary enginies such as (17) etc., alternating current can be used as the driving power of underwater ship.
For this a series of generator operation, by control setup (37) to hydrogen make voltage regulator (22), fuel cell (30), power inverter (36), the petrolift (16) of battery (10), the operation of air blowing fan auxiliary enginies such as (17) is controlled.
As the propelling unit of underwater ship, can adopt motor and known equipment that the propelling of installing constitutes with screw propeller on the S. A. of this motor.By the direct current (DC) that fuel cell produced, change alternating current into by above-mentioned DC/AC inverter after, as underwater ship propulsion source supply motor, drive this motor, the propelling screw propeller of rotation drive installation on the S. A. of this motor.
In addition, visit sonar, search lamp, observation instrument etc. before the electricity that fuel cell sent is also supplied with.
In addition, for the electricity that fuel cell produced is carried out electric power storage, the electric energy storage facilities is set preferably.By using control setup, according to the load of motor and the charge capacity of electric energy storage facilities, with electric supply motor and the electric energy storage facilities that fuel cell produced.Specifically, for example, during acceleration etc. under the situation, when the load of motor is big, will be from the electric supply motor of fuel battery and electric energy storage facilities.Perhaps under the deceleration situation, when operation waits, the electric supply of electrical energy storage facilities of bringing back to life that will obtain by motor.As the electric energy storage facilities, can use for example secondary battery, double layer capacitor etc.
The hydrogen of the hydrogen producing apparatus that underwater ship of the present invention carried is made battery (10) and is formed following basic structure: the fuel electrodes (12) that is provided with on the face of barrier film (11), barrier film (11) and the oxidation utmost point (14) that is provided with on another face.For example, as such structure, the MEA (electrolyte/assembly of electrode) that can adopt picture in direct methanol fuel cell, to be adopted.
Method for making for MEA is unqualified, can utilize the such method same in two sides that is bonded on barrier film by hot pressing fuel electrodes and air pole to make.
Barrier film can use the proton conductive solid electrolyte film that is used as polyelectrolyte membrane in fuel cell.As the proton conductive solid electrolyte film, Nafion film that preferably uses E.I.Du Pont Company etc. has sulfonic perfluorocarbon sulfonic acid mesentery.
The electrode that the fuel electrodes and the oxidation utmost point (air pole) preferably have electric conductivity, have catalytic activity, for example, can make by painting catalyst slurry and drying on gas diffusion layers, described catalyst pulp contains the material that adhesivess such as the catalyst that supported noble metal on the carrier of being made by carbon dust etc., PTFE resin and Nafion solution etc. are used to give ionic conductivity.
As gas diffusion layers preferably by the carbon paper that has carried out hydrophobic treatment formations such as (carbon paper).
The electrode catalyst that acts as a fuel can use any material, but preferably uses the catalyst that has supported the Pt-Ru alloy on carbon dust.
Can use any material as the air pole catalyst, but preferably use the catalyst that on carbon dust, has supported Pt.
In the hydrogen producing apparatus of above-mentioned formation, supply with organic fuel such as containing methanol aqueous solution to fuel electrodes, and when oxidizers such as the oxidation utmost point (air pole) air supply, oxygen, hydrogen peroxide, under given conditions, can produce hydrogen-containing gas in fuel electrodes.
Carry in the underwater ship of the present invention the hydrogen production method of hydrogen producing apparatus different fully with the hydrogen production method in the past the hydrogen producing apparatus, in addition, also be difficult to illustrate its mechanism at present.The below present supposition of explanation can't be negated the possibility that produces the brand new reaction.
In the hydrogen producing apparatus that carries in the underwater ship of the present invention, as described later, under 30～90 ℃ low temperature, and by the fuel electrodes side generation hydrogen-containing gas of supplying with the first alcohol and water.In situation from the battery supply of electrical energy to hydrogen that do not make, can produce the gas of the hydrogen concentration about 70～80% from the outside; Making the situation that battery applies electric energy from the outside to hydrogen, can produce gas more than or equal to 80% hydrogen concentration.And the generation of knowing this gas depends on the open circuit voltage or the running voltage at the two poles of the earth.Infer following hydrogen mechanism of production from such result.Below, for mechanism is described simply, under open-circuit condition, describe.
For example, identical when using methyl alcohol to act as a fuel in the hydrogen producing apparatus with the situation of direct methanol fuel cell, can think at first to generate proton by catalyst in fuel electrodes.
CH 3OH+H 2O→CO 2+6H ++6e -……(1)
In the situation of using Pt-Ru as catalyst, reaction for above-mentioned (1), can think that methyl alcohol is adsorbed on the Pt surface, electrochemical oxidation reactions as described below takes place successively, carry out (" the battery brief guide third edition " February 20 calendar year 2001 by generating the absorption chemical seed that firmly is adsorbed on the surface, ball kind (strain) distribution, the 406th page).
CH 3OH+Pt→Pt-(CH 3OH)ads
→Pt-(CH 2OH)ads+H ++e -
Pt-(CH 2OH)ads→Pt-(CHOH)ads+H ++e -
Pt-(CHOH)ads→Pt-(COH)ads+H ++e -
Pt-(COH)ads→Pt-(CO)ads+H ++e -
Above-mentioned Pt-(CO) ads is if further oxidation, then the absorption OH that need be generated by water.
Ru+H 2O→Ru-(H 2O)ads
→Ru-(OH)ads+H ++e -
Ru-(OH)ads+Pt-(CO)ads→Ru+Pt+CO 2+H ++e -
In the situation of direct methanol fuel cell, by the H that fuel electrodes generates that is reflected at of (1) formula +(proton) moves in the proton conductive solid electrolyte film, thereby at the oxidation utmost point and the gas that contains aerobic or the oxygen that supply to the oxidation utmost point following reaction takes place.
3/2O 2+6H ++6e -→3H 2O……(2)
The hydrogen producing apparatus that carries on the underwater ship of the present invention under the situation of open circuit, the e that generates by the reaction of (1) formula -Do not supply to the oxidation utmost point, thereby in order to produce the reaction of (2) formula, need other take place at the oxidation utmost point and react and supply with e by external circuit -
On the other hand, in direct methanol fuel cell, as the situation of using proton conductive solid electrolyte films such as Nafion, known CH 3" infiltration " phenomenon that OH sees through to oxidation utmost point side from fuel electrodes.The electrolytic oxidation reaction of following infiltration methyl alcohol can take place most probably in oxidation.
CH 3OH+H 2O→CO 2+6H ++6e -……(3)
If the reaction of (3) formula takes place, by the e of this reaction generation -Be supplied to, can produce the reaction of (2) formula.
Subsequently, the H that reaction generated by (3) formula +Move in the proton conductive solid electrolyte film, the reaction below fuel electrodes takes place produces hydrogen.
6H ++6e -→3H 2……(4)
At this, by the H that fuel electrodes generates that is reflected at of (1) formula +And e -To moving and the H that the oxidation utmost point is generated that is reflected at by (3) formula of the oxidation utmost point +And e -Be considered to cancel each other on apparent to fuel electrodes mobile.
Can be estimated as in this case, at the oxidation utmost point because the H that reaction generated by (3) formula +And e -Produce the reaction of (2) formula, the H that reaction generated in fuel electrodes because by (1) formula +And e -The reaction of (4) formula of generation.
Suppose the reaction of on fuel electrodes, carrying out (1) formula and (4) formula, when in oxidation extremely, carrying out the reaction of (2) formula and (3) formula, can think that on the whole following (5) formula sets up.
2CH 3OH+2H 2O+3/2O 2→2CO 2+3H 2O+3H 2……(5)
The theoretical duty of this reaction is 59% (thermal output of the thermal output of 3mol hydrogen/2mol methyl alcohol).
But, for above-mentioned reaction, (1) the standard potential E0=0.046V of the reaction of formula, (4) the standard potential E0=0.0V of the reaction of formula is when making up the two, because the situation of (1) formula corresponds to positive pole under reference standard conditions, (4) situation of formula corresponds to negative pole, thereby (1) reaction of formula is carried out to the left side, and the reaction of (4) formula is also carried out to the left side, does not therefore produce hydrogen.
At this, for the reaction that makes (1) formula is also carried out to the right to the reaction of the right, (4) formula, it is essential making the corresponding negative pole of (1) formula, the corresponding positive pole of (4) formula, when the integral body of supposing fuel electrodes is equipotential, need makes the methanol oxidation current potential change or make hydrogen produce current potential and change to hot side to low potential side.
But, be not eqipotential situation in fuel electrodes, in fuel electrodes from methyl alcohol and water generates H +The reaction and the H of (1) formula +With e -Reaction in conjunction with (4) formula that forms hydrogen may be carried out simultaneously.
As described in the embodiment of back, the high situation of operating temperature is supplied to from exterior reaction heat from being easy to generate the angle of hydrogen, carries out to the right as the reaction meeting of (1) and (3) formula of the endothermic reaction.
For methyl alcohol, except the reaction of (1) and (3) formula, because phenomenon of osmosis, the methyl alcohol that sees through from fuel electrodes can produce by the following side reaction of oxygen institute oxidation on the surface of air pole catalyst.
2CH 3OH+3/2O 2→CO 2+2H 2O……(6)
Because the reaction of (6) formula of being somebody's turn to do is exothermal reaction, can be understood as, the heat of the reaction of (1) and (3) formula is supplied to by this heat release.
The situation of the hydrogen producing apparatus that is carried in the underwater ship of the invention that the application's claim 2 is related (hereinafter referred to as " open-circuit condition "), by embodiment described later as can be known, if the delivery volume of oxygen (air) tails off, open circuit voltage reaches 300～800mV, then can produce hydrogen, this is estimated to be, and the methyl alcohol that sees through the air pole side is suppressed the H of (3) formula by the oxidized situation of (6) formula +Reaction of formation becomes dominance, thereby produces hydrogen by the reaction of (4) formula.
The situation of the hydrogen producing apparatus that is carried in the underwater ship of the invention that the application's claim 3 is related (hereinafter referred to as " discharging condition "), can think with open-circuit condition under the similar mechanism of hydrogen mechanism of production produce hydrogen.But, different with the situation of open-circuit condition since with a considerable amount of H of discharge current +Moving to the oxidation Ghandler motion from fuel electrodes, therefore the cell integrated electroneutrality condition of essential maintenance can think that the reaction of (1) formula is better than (4) formula on fuel electrodes, and the reaction of extremely going up (2) formula in oxidation is better than (3) formula.
From embodiment described later as can be known, discharge current becomes big (to oxidation huge amount supply e -), when sparking voltage is lower than 200mV, not producing hydrogen, this is estimated to be, and does not produce hydrogen owing to reach the necessary voltage of electrolysis of methanol aqueous solution.
In addition, at a large amount of oxygen (air) of supplying with, perhaps sparking voltage is higher than the situation of 600mV, does not also produce hydrogen, and this is estimated to be, because it is oxidized by (6) formula to see through the methyl alcohol of air pole side, thereby does not carry out the H of (3) formula +Reaction of formation.
On the other hand, in the few situation of delivery volume of oxygen (air), if discharge current reduces, sparking voltage (running voltage) is 200～600mV, then produces hydrogen, and this is estimated to be, the methyl alcohol that sees through the air pole side is suppressed the H of (3) formula by the oxidized situation of (6) formula +Reaction of formation becomes dominance, thereby produces hydrogen by the reaction of (4) formula.
The situation of the hydrogen producing apparatus that carries in the underwater ship of the invention that the application's claim 4 is related (hereinafter referred to as " charge condition "), also can think with open-circuit condition under the similar mechanism of hydrogen mechanism of production produce hydrogen.But, different with the situation of open-circuit condition since with a considerable amount of H of Faradaic current +Move to fuel electrodes from the oxidation utmost point, therefore the cell integrated electroneutrality condition of essential maintenance can think that the reaction of (4) formula is better than (1) formula on fuel electrodes, and the reaction of extremely going up (3) formula in oxidation is better than (2) formula.
That is, the situation of charge condition of the present invention since with fuel electrodes as negative electrode, apply electric energy as anode from the outside with the oxidation utmost point and (provide e to fuel electrodes from the outside -), electrolysis can take place basically, by embodiment described later as can be known,, then can produce many hydrogen if increase the electric energy (applying voltage) that applies, this can think, the e that supplies with to fuel electrodes from the outside -Change is many, has promoted the electrolytic oxidation reaction of methyl alcohol of (3) formulas and the reaction 6H of (4) formula ++ 6e -→ 3H 2
But, as hereinafter described, few and when applying voltage (running voltage) and being the low like this scope of 400～600mV, energy efficiency increases in the delivery volume of oxygen (air).This is estimated to be, and in this scope, as mentioned above for not from the open-circuit condition of outside supply of electrical energy or the situation of discharging condition, the methyl alcohol that sees through the air pole side also is suppressed the H of (3) formula by the oxidized situation of (6) formula +Reaction of formation becomes dominance, thereby passes through the H of (4) formula +Reaction of formation produces hydrogen; In the situation of charge condition, except apply the part of electric energy from the outside, produce hydrogen equally with the situation of above-mentioned open-circuit condition or discharging condition.
At this, have any meaning at the current potential of battery and describe.In general the ion that the voltage of battery that clips dielectric film and constitute gas electrode at the two poles of the earth conducts electricity in owing to electrolyte produces in the difference of the chemical potential at the two poles of the earth.
That is, do not consider when the polarization at the two poles of the earth that owing to use proton (hydrion) conductive solid electrolyte film as electrolyte, the voltage of observation represents that battery is the poor of so-called hydrogen dividing potential drop in the chemical potential of the hydrogen at the two poles of the earth.
In the present invention, as described in the embodiment of back, the voltage between the fuel electrodes and the oxidation utmost point produces hydrogen by the fuel electrodes side when certain limit; Therefore, when the difference of the chemical potential of the hydrogen at the two poles of the earth is certain limit, can infer the reaction of carrying out above-mentioned (1)～(6) formula, produce hydrogen.
The hydrogen producing apparatus that is carried in the underwater ship of the present invention, do not make the battery supply of electrical energy, derive the situation of electric energy and the situation that applies electric energy from the outside from the outside from the outside to hydrogen for making, all can regulate the growing amount of hydrogen-containing gas by the voltage between the fuel metering utmost point and the oxidation utmost point (air pole) (open circuit voltage or running voltage).
By embodiment described later as can be known, in the situation of open-circuit condition, open circuit voltage is that 300～800mV produces hydrogen; In the situation of discharging condition, sparking voltage (running voltage) is that 200～600mV produces hydrogen; In the situation of charge condition, applying voltage (running voltage) is that 300～1000mV (energy efficiency height under 400～600mV) produces hydrogen, therefore, by regulating open circuit voltage or running voltage, can regulate the growing amount of hydrogen-containing gas in this scope.
Shown in the embodiment described as follows, the growing amount (hydrogen formation speed) of open circuit voltage or running voltage and/or hydrogen-containing gas, delivery volume, the concentration (oxygen concentration in the oxygen-containing gas) of regulating oxidizer that can be by regulating oxidizer (oxygen-containing gas or oxygen, contain the liquid of hydrogen peroxide), regulate the supply that contains organic fuel, the concentration that adjusting contains organic fuel is regulated.
In addition, except above-mentioned, situation at discharging condition, by the electric energy (electric current that adjusting to outside derive, the power supply that also have use can control constant voltage be so-called potentiostat regulate voltage to outside derivation) of adjusting to the outside derivation, situation at charge condition, by the electric energy (electric current that adjusting applies, the power supply that also has use can control constant voltage are that so-called potentiostat is regulated the voltage that applies) that adjusting applies, can regulate the growing amount of running voltage and/or hydrogen-containing gas.
The hydrogen producing apparatus that is carried in the underwater ship of the present invention, owing to can contain organic fuel smaller or equal to 100 ℃ of decomposition, the operating temperature that therefore can make hydrogen producing apparatus is smaller or equal to 100 ℃.Operating temperature is preferably 30～90 ℃.By at 30～90 ℃ range regulation operating temperature, embodiment described as follows is described, can regulate the growing amount of open circuit voltage or running voltage and/or hydrogen-containing gas.
In addition, in the past must more than 100 ℃ the running the reformation technology, water becomes aqueous vapor, contain organic fuel gasization, under such condition, even produce hydrogen, also need to adopt in addition the device of separation of hydrogen, thereby the present invention is favourable in this.
But, if contain organic fuel, then have above-mentioned shortcoming, but the present invention is surpassing the hydrogen producing apparatus that the underwater ship of the present invention that also can turn round under the situation of 100 ℃ of temperature to a certain degree carries in temperature decomposition more than or equal to 100 ℃.
Consider from the principle of inferring, as containing organic fuel can be to see through proton conductive barrier film, oxidized and generate the liquid or the gaseous fuel of proton with electrochemical means, preferably contain alcohol such as methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, aldehyde such as formaldehyde, the liquid fuel of ethers such as carboxylic acids such as formic acid, diethyl ether.Because containing organic fuel supplies with water, preferably contains the solution of alcohol and water, especially preferably contains methanol in water.Here, be the solution that contains the first alcohol and water at least as the methanol in water that contains of an example of above-mentioned fuel, in the field that produces hydrogen-containing gas, its concentration can be selected arbitrarily.
Can using gases or the oxidizer of liquid as oxidizer.Preferably contain the gas of aerobic or oxygen as gaseous oxidant.The oxygen concentration that contains the gas of aerobic is preferably more than and equals 10%.The liquid that preferably contains hydrogen peroxide is as liquid oxidizer.
In the present invention, owing to put into fuel disposable being consumed in this device of hydrogen producing apparatus, the ratio that resolves into hydrogen is low, and therefore the recycle unit of fuel preferably is set, and improves the conversion ratio to hydrogen.
The hydrogen producing apparatus that underwater ship of the present invention carried has the device that goes out hydrogen-containing gas from the fuel electrodes side-draw, and it is the device that is used for reclaiming hydrogen, preferably also reclaims carbon dioxide.Owing to be under smaller or equal to 100 ℃ of such low temperature, to turn round, therefore the carbon-dioxide carbon dioxide absorption portion that is included in the hydrogen-containing gas that absorbs can be set by easy means.
Below, expression embodiments of the invention (hydrogen Production Example), but can also be to the ratio of catalyst, PTFE, Nafion etc., the thickness of catalyst layer, gas diffusion layers, dielectric film etc. suit to change, and is not limited to these embodiment.
Embodiment 1
Below employed hydrogen producing apparatus (open-circuit condition) is made the example of the situation of hydrogen in the underwater ship of expression according to the related invention of the application's claim 2.
Hydrogen Production Example 1-1
Embodiment 1 (make battery and form and the identical structure of representational direct methanol fuel cell by the hydrogen among the Production Example 1-1～1-10).
The skeleton diagram of this hydrogen manufacturing battery as shown in Figure 2.
Promptly, the proton conductive dielectric film (Nafion115) that uses E.I.Du Pont Company's system is as electrolyte, carbon paper (East レ is made) in the polytetrafluoroethyldispersion dispersion of 5% concentration behind the dipping, burn till and carry out hydrophobic treatment at 360 ℃, coating air pole catalyst pulp on one face, thereby on air pole, form the gas diffusion layers that has the air pole catalyst, described air pole catalyst pulp is by mixing air electrode catalyst (support the carbon of platinum, Tanaka's noble metal is made), PTFE micropowder and 5% Nafion solution (ア Le De リ Star チ manufacturing) and make.At this, the weight ratio of air pole catalyst, PTEF, Nafion is 65%: 15%: 20%.To be converted into platinum be 1mg/cm to the catalytic amount of the air pole of Zhi Zuoing like this 2
And then, making uses the same method carries out hydrophobic treatment to carbon paper, on one face, be coated with the fuel electrode catalyst slurry then, thereby form the gas diffusion layers that has fuel electrode catalyst, described fuel electrode catalyst slurry is made by the Nafion solution of composite fuel electrode catalyst (support the carbon of Pt-Ru, Tanaka's noble metal make), PTFE micropowder and 5%.At this, the weight ratio of fuel electrode catalyst, PTEF, Nafion is 55%: 15%: 30%.To be converted into Pt-Ru be 1mg/cm to the catalytic amount of the fuel electrodes of Zhi Zuoing like this 2
With above-mentioned dielectric film, have the air pole catalyst gas diffusion layers, have the gas diffusion layers of fuel electrode catalyst at 40 ℃, 100kg/cm 2Down by the incompatible making of thermo-compressed MEA.So the active electrode area of the MEA that makes is 60.8cm 2The thickness of the gas diffusion layers of the air pole after the making and the catalyst layer of fuel electrodes, air pole and fuel electrodes is respectively about 30 μ m and 170 μ m, and basic identical separately.
Be provided for the stream of ventilating air and circulation fuel respectively, and then in order to prevent gas leakage, the air pole dividing plate and the above-mentioned MEA of fuel electrodes dividing plate clamping of the graphite system by soaking into phenol resin, thus constitute monocell.In addition, in order to prevent fuel and leakage of air, the encapsulation of silaatic system is set at peripheral part of MEA.
The hydrogen of making is like this made battery to be arranged in the electric furnace of hot air circulation type, under 30～70 ℃ of battery temperatures (operating temperature), at the traffic flow air of air pole side with 0～400ml/ branch, the methanol aqueous solution (fuel) of the traffic flow 0.5M～2M that divides with 2～15ml/ in the fuel electrodes side, the gas flow, the gas composition that produce to the voltage difference (open circuit voltage) of the fuel electrodes of this moment and air pole, in the fuel electrodes side are studied.
At first, the constant flow that makes the methanol aqueous solution (fuel) that flows to battery changes charge air at the 8ml/ branch at each temperature at 30 ℃, 50 ℃, 70 ℃, measures the growing amount of the gas that is produced by the fuel electrodes side.Make the mid-method of changing of water measure gas generating amount.In addition, use the hydrogen concentration in the gc analysis generation gas, obtain the hydrogen formation speed.
Its result as shown in Figure 3.
Thus, at each temperature,, can confirm to produce hydrogen by the fuel electrodes side of battery by reducing charge air.In addition we know, temperature is high more, and the hydrogen formation speed is big more.And then, studied the relation between the open circuit voltage of charge air and battery, find to be accompanied by the minimizing of charge air, there is the tendency that descends in the open circuit voltage of battery.
Result with Fig. 3 among Fig. 4 puts in order as the relation of open circuit voltage and hydrogen formation speed.
Hence one can see that, and hydrogen formation speed (hydrogen growing amount) demonstrates the tendency that exists with ... open circuit voltage, is to produce hydrogen under 400～600mV at open circuit voltage.In addition, under any temperature, all near 450mV, observe the peak value of hydrogen formation speed.
Then, under the condition that 70 ℃ of temperature, fuel flow 8ml/ branch, charge air 120ml/ divide, produce gas, utilize the hydrogen concentration in the gas chromatography determination gas.
Its result can confirm, contains have an appointment 70% hydrogen, about 15% carbon dioxide in the generation gas.In addition, do not detect CO.
Hydrogen Production Example 1-2
Use the hydrogen manufacturing battery same with hydrogen Production Example 1-1, then, change charge air respectively under the condition of be 2,8 at methanol aqueous solution (fuel) flow of 70 ℃ of battery temperatures, concentration 1M, 15ml/ dividing, the relation of the open circuit voltage of fuel flow, charge air and the hydrogen formation speed of expression this moment, battery among Fig. 5.
Hence one can see that, fuel flow hour, and the hydrogen formation speed is big.
Result with Fig. 5 among Fig. 6 puts in order as the relation of open circuit voltage and hydrogen formation speed.
Hence one can see that, and the hydrogen formation speed under condition separately exists with ... open circuit voltage.In addition, under any fuel flow, 1-1 is same with the hydrogen Production Example, all observes the peak value of hydrogen formation speed near 450mV.
And then, in this Production Example, similarly utilize gas chromatographic method to obtain condition (70 ℃ of operating temperatures, fuel concentration 1M, fuel flow 2ml/ branch, charge air 100ml/ branch) when obtaining the open circuit voltage 442mV that maximum hydrogen formation speed 14.48ml/ divides with hydrogen Production Example 1-1 and produce hydrogen concentration in the gas down, the result is about 70%.
Hydrogen Production Example 1-3
Use the hydrogen manufacturing battery same with hydrogen Production Example 1-1, then, be 0.5,1 at constant flow rate, fuel concentration that 70 ℃ of battery temperatures, methanol aqueous solution (fuel) divide for 8ml/, change charge air respectively under the condition of 2M, the relation of the open circuit voltage of fuel flow, charge air and the hydrogen formation speed of expression this moment, battery among Fig. 7.
Hence one can see that, and when fuel concentration hanged down, the hydrogen formation speed was big.
Result with Fig. 7 among Fig. 8 puts in order as the relation of open circuit voltage and hydrogen formation speed.
Hence one can see that, and the hydrogen formation speed under condition separately exists with ... open circuit voltage, produces hydrogen under 300～600mV.In addition, under any fuel concentration, 1-1 is same with the hydrogen Production Example, all observes the peak value of hydrogen formation speed near 450mV.
Hydrogen Production Example 1-4
Then, studied of the influence of the thickness of dielectric film to gas generating amount.
In hydrogen Production Example 1-1～1-3, the Nafion115 (thickness is 130 μ m) that adopts E.I.Du Pont Company's system is as dielectric film, Nafion112 (thickness is 50 μ m) with same E.I.Du Pont Company's system constitutes same hydrogen manufacturing battery, under the condition that 70 ℃ of temperature, fuel concentration 1M, fuel flow 8ml/ are divided, change charge air respectively, studied the relation of open circuit voltage of fuel flow, charge air and hydrogen formation speed, the battery of this moment.
Nafion115 and Nafion112 are same material, have studied the influence of the thickness of dielectric film purely at this.Result of study as shown in Figure 9.
Result with Fig. 9 among Figure 10 puts in order as the relation of open circuit voltage and hydrogen formation speed.
Hence one can see that, and for any dielectric film, the hydrogen formation speed is all equal substantially.As seen from the figure, the hydrogen formation speed under condition separately exists with ... open circuit voltage, still observes the peak value of hydrogen formation speed near 450mV.
Hydrogen Production Example 1-5
Use the hydrogen manufacturing battery same with hydrogen Production Example 1-1, hydrogen is made in the electric furnace that battery is arranged on the hot air circulation type, at battery temperature is under 30 ℃, 50 ℃, 70 ℃, 90 ℃, is that 0～250ml/ divides the air that flows in the air pole side with flow, in the fuel electrodes side is divide the to flow methanol aqueous solution (fuel) of 1M of 5ml/ with the flow, the open circuit voltage of the battery of research this moment, the hydrogen formation speed that produces in the fuel electrodes side.
Figure 11 has represented the relation between charge air and the hydrogen formation speed.
Identical with the situation of hydrogen Production Example 1-1, at each temperature,, can confirm to produce hydrogen by the fuel electrodes side of battery by reducing charge air.In addition we know, temperature is high more, and the hydrogen formation speed is big more.And then, studied the relation of the open circuit voltage of charge air and battery, can confirm to be accompanied by the minimizing of charge air, the open circuit voltage of battery has the tendency of decline.
Result with Figure 11 among Figure 12 puts in order as the relation of open circuit voltage and hydrogen formation speed.
Hence one can see that, and the hydrogen formation speed exists with ... open circuit voltage, produces hydrogen under 300～700mV.In addition, under 30～70 ℃, near 470～480mV, observe the peak value of hydrogen formation speed; Under 90 ℃, near 440mV, observe the peak value of hydrogen formation speed.
Hydrogen Production Example 1-6
Use the hydrogen manufacturing battery same with hydrogen Production Example 1-1, at battery temperature is to change charge air respectively under the condition that 50 ℃, fuel flow are 1.5,2.5,5.0,7.5,10.0ml/ divides, the relation of fuel flow, charge air and the hydrogen formation speed of expression this moment among Figure 13.
Hence one can see that, different with 70 ℃ the result of above-mentioned hydrogen Production Example 1-2, fuel flow for a long time, the hydrogen formation speed has the tendency of increase.
Result with Figure 13 among Figure 14 puts in order as the relation of open circuit voltage and hydrogen formation speed.
Hence one can see that, and the hydrogen formation speed under condition separately exists with ... open circuit voltage, produces hydrogen under 300～700mV.In addition, near 450～500mV, observe the peak value of hydrogen formation speed.
Calculating is methanol consumption amount and the hydrogen formation speed in the fuel when changing fuel flow, uses following formula to calculate the energy efficiency of open-circuit condition (this energy efficiency is different with the energy efficiency of the charge condition that is calculated by calculating formula described later).Its result is that the energy efficiency of open-circuit condition is 17% at fuel flow for the 5.0ml/ timesharing, is 22% in the 2.5ml/ timesharing.
The energy efficiency of open-circuit condition (%)
=(enthalpy change of the methyl alcohol of the standard enthalpy change/consumption of the hydrogen of generation) * 100
Hydrogen Production Example 1-7
Use the hydrogen manufacturing battery same with hydrogen Production Example 1-1, be at battery temperature that constant flow rate, fuel concentration that 50 ℃, methanol aqueous solution (fuel) divide for 5ml/ are 0.5,1,2, change charge air respectively under the condition of 3M, the charge air of expression this moment and the relation of hydrogen formation speed among Figure 15.
Along with fuel concentration reduces, charge air diminishes, and observes the peak value of hydrogen formation speed.
Result with Figure 15 among Figure 16 puts in order as the relation of open circuit voltage and hydrogen formation speed.
Hence one can see that, and the hydrogen formation speed under condition separately exists with ... open circuit voltage, produces hydrogen under 300～700mV.In addition, under any fuel concentration, all near 470mV, observe the peak value of hydrogen formation speed.
Hydrogen Production Example 1-8
Use the hydrogen manufacturing battery (but air pole form the oxidation utmost point of flow oxidizing gas) same with hydrogen Production Example 1-1, at battery temperature is that 50 ℃, fuel concentration are that 1M, fuel flow are that 5ml/ branch, oxygen concentration are to change the oxidizing gas flow respectively under 10,21,40,100% the condition, the oxidizing gas flow of expression this moment and the relation between the hydrogen formation speed among Figure 17.At this, the gas of oxygen concentration 21% uses air, and the gas of oxygen concentration 10% uses the gas that mixes nitrogen and modulate in air, and the gas of oxygen concentration 40% uses mixture of oxygen (oxygen concentration 100%) in air and the gas of modulation.
Along with oxygen concentration improves, the oxidizing gas flow descends, and observes the peak value of hydrogen formation speed.
Result with Figure 17 among Figure 18 puts in order as the relation of open circuit voltage and hydrogen formation speed.
Hence one can see that, and the hydrogen formation speed under condition separately exists with ... open circuit voltage, produces hydrogen under 400～800mV.In addition, near 490～530mV, observe the peak value of hydrogen formation speed.
Hydrogen Production Example 1-9
Use the hydrogen manufacturing battery same with hydrogen Production Example 1-1, at battery temperature is under 50 ℃, in the air pole side is that 60ml/ divides the air that flows with the flow, in the fuel electrodes side is the methanol aqueous solution (fuel) that 2.6ml/ divides the 1M that flows with the flow, thereby generation gas, sampling 200cc uses the CO concentration in the gas chromatography determination gas.Consequently, from sample, do not detect CO (smaller or equal to 1ppm).Here, the battery open circuit voltage under this condition is 477mV, and the hydrogen formation speed is about the 10ml/ branch.
Hydrogen Production Example 1-10
Use the hydrogen manufacturing battery (but air pole form oxidation utmost point of working fluid hydrogen peroxide) same with hydrogen Production Example 1-1, hydrogen is made in the electric furnace that battery is arranged on the hot air circulation type, at battery temperature is under 30 ℃, 50 ℃, 70 ℃, 90 ℃, is the H that 1～8ml/ divides the 1M that flows in oxidation utmost point side with flow 2O 2(hydrogen peroxide) is divide the to flow methanol aqueous solution (fuel) of 1M of 5ml/ with the flow in the fuel electrodes side, the hydrogen formation speed of having studied the open circuit voltage of the battery of this moment, having produced in the fuel electrodes side.
Represented H among Figure 19 2O 2Relation between flow and the hydrogen formation speed.
Identical with the situation of hydrogen Production Example 1-1, reducing H at each temperature 2O 2Flow can be confirmed to produce hydrogen by the fuel electrodes side of battery.In addition we know, temperature is high more, and the hydrogen formation speed is big more.And then, studied H 2O 2The relation of the open circuit voltage of flow and battery can be confirmed along with H 2O 2The minimizing of flow, the open circuit voltage of battery has the tendency of decline.
Result with Figure 19 among Figure 20 puts in order as the relation of open circuit voltage and hydrogen formation speed.
Hence one can see that, and the hydrogen formation speed demonstrates the tendency that exists with ... open circuit voltage, produces hydrogen under open circuit voltage 300～600mV.In addition, under 30～50 ℃, near 500mV, observe the peak value of hydrogen formation speed; Under 70～90 ℃, near 450mV, observe the peak value of hydrogen formation speed.
Here focus on, from the outside hydrogen is not made battery and apply all electric currents or voltage in the foregoing description 1, only measure open circuit voltage with internal resistance more than or equal to the potentiometer of 1G Ω, the while is fueling and oxidizer only.
In other words, make battery, except fueling and oxidizer,, just the part of fuel can be converted to hydrogen not from outside energize for the hydrogen of embodiment 1.
And it is the reformation under 30～90 ℃ of so surprising low temperatures, can think the brand new hydrogen producing apparatus that in the past do not have, and it is remarkable therefore this hydrogen producing apparatus to be equipped on the underwater ship its effect.
Embodiment 2
Below the hydrogen producing apparatus (discharging condition) that is carried in the underwater ship of expression according to the related invention of the application's claim 3 is made the example of the situation of hydrogen.
Hydrogen Production Example 2-1
Figure 21 represents that (hydrogen that has the electric energy let-off gear(stand) among the Production Example 2-1～2-8) is made the skeleton diagram of battery to embodiment 2.
Except with fuel negative pole, very anodal and be provided with the equipment of deriving electric energy with air very, to make battery structure identical with the hydrogen of hydrogen Production Example 1-1.
This hydrogen is made battery to be arranged in the electric furnace of hot air circulation type, at battery temperature (operating temperature) is under 50 ℃, is that 10～100ml/ divides the air that flows in the air pole side with flow, in the fuel electrodes side is the methanol aqueous solution (fuel) that 5ml/ divides the 1M that flows with the flow, change the electric current circulate between air pole and fuel electrodes this moment, gas flow, the gas composition that produces to the running voltage of fuel electrodes and air pole, in the fuel electrodes side simultaneously studied.In addition, utilize gas chromatographic method that the hydrogen concentration that produces in the gas is analyzed, obtain the hydrogen formation speed.
In this test, the relation between the density of current of derivation and running voltage as shown in figure 22.
Along with charge air diminishes, running voltage reduces, and observes the limiting current density that can discharge and descends.
Result with Figure 22 among Figure 23 puts in order as the relation of running voltage and hydrogen formation speed.
Hence one can see that, and hydrogen formation speed (hydrogen growing amount) demonstrates the tendency that exists with ... running voltage, is to produce gas under 300～600mV at running voltage.In addition we know, charge air is easy to produce hydrogen most in 50～60ml/ timesharing.And then charge air is difficult to produce hydrogen during more than this flow, when being the 100ml/ timesharing, produces hydrogen hardly.
Then,, temperature 50 ℃ big, fuel flow 5ml/ branch, charge air 60ml/ branch, density of current 8.4mA/cm at the hydrogen formation speed 2Condition under produce gas, utilize the hydrogen concentration in the gas chromatography determination gas.
Its result shows, produces to contain 74% the hydrogen of having an appointment in the gas, and the hydrogen formation speed is the 5.1ml/ branch.In addition, do not detect CO.
Hydrogen Production Example 2-2
Use the hydrogen manufacturing battery same with hydrogen Production Example 2-1, at battery temperature is under 30 ℃, is that 30～100ml/ divides the air that flows in the air pole side with flow, in the fuel electrodes side is the methanol aqueous solution (fuel) that 5ml/ divides the 1M that flows with the flow, change the electric current circulate between air pole and fuel electrodes this moment, the formation speed of the hydrogen that produces to the running voltage of fuel electrodes and air pole, in the fuel electrodes side is studied simultaneously.
In this test, the relation between the density of current of derivation and running voltage as shown in figure 24.
Along with charge air diminishes, running voltage reduces, and observes the limiting current density that can discharge and descends.
Result with Figure 24 among Figure 25 puts in order as the relation of running voltage and hydrogen formation speed.
Hence one can see that, and the hydrogen formation speed demonstrates the tendency that exists with ... running voltage, is to produce hydrogen under 200～540mV at running voltage.In addition we know, be that 30～70ml/ timesharing produces hydrogen at charge air.When being the 100ml/ timesharing, produce hydrogen hardly.
Hydrogen Production Example 2-3
Use the hydrogen manufacturing battery same with hydrogen Production Example 2-1, at battery temperature is under 70 ℃, is that 50～200ml/ divides the air that flows in the air pole side with flow, in the fuel electrodes side is the methanol aqueous solution (fuel) that 5ml/ divides the 1M that flows with the flow, change the electric current circulate between air pole and fuel electrodes this moment, the formation speed of the hydrogen that produces to the running voltage of fuel electrodes and air pole, in the fuel electrodes side is studied simultaneously.
In this test, the relation between the density of current of derivation and running voltage as shown in figure 26.
Along with charge air diminishes, running voltage reduces, and observes the limiting current density that can discharge and descends.
Result with Figure 26 among Figure 27 puts in order as the relation of running voltage and hydrogen formation speed.
Hence one can see that, and the hydrogen formation speed demonstrates the tendency that exists with ... running voltage, is to produce hydrogen under 200～500mV at running voltage.In addition we know, be that 50～100ml/ timesharing is easy to produce hydrogen at charge air.When charge air increases to picture 150,200ml/ timesharing, produce hydrogen hardly.
Hydrogen Production Example 2-4
Use the hydrogen manufacturing battery same with hydrogen Production Example 2-1, at battery temperature is under 90 ℃, is that 50～250ml/ divides the air that flows in the air pole side with flow, in the fuel electrodes side is the methanol aqueous solution (fuel) that 5ml/ divides the 1M that flows with the flow, change the electric current circulate between air pole and fuel electrodes this moment, the formation speed of the hydrogen that produces to the running voltage of fuel electrodes and air pole, in the fuel electrodes side is studied simultaneously.
In this test, the relation between the density of current of derivation and running voltage as shown in figure 28.
Along with charge air diminishes, running voltage reduces, and observes the limiting current density that can discharge and descends.
Result with Figure 28 among Figure 29 puts in order as the relation of running voltage and hydrogen formation speed.
Hence one can see that, and the hydrogen formation speed demonstrates the tendency that exists with ... running voltage, is to produce hydrogen under 200～500mV at running voltage.In addition we know, be that 50～100ml/ timesharing is easy to generate hydrogen at charge air.When being the 250ml/ timesharing, produce hydrogen hardly.
Then, the density of current that the charge air at each temperature of hydrogen Production Example 2-1～2-4 is derived for the 50ml/ timesharing is shown among Figure 30 with the relation of running voltage, and the relation of running voltage and hydrogen formation speed is shown among Figure 31.
Hence one can see that, and the hydrogen formation speed demonstrates the tendency that exists with ... temperature, when temperature is high, will produce hydrogen under low running voltage, and the hydrogen growing amount increases.
And then the density of current that the charge air at each temperature of hydrogen Production Example 2-1～2-4 is derived for the 100ml/ timesharing is shown among Figure 32 with the relation of running voltage, and the relation of running voltage and hydrogen formation speed is shown among Figure 33.
Hence one can see that, and the hydrogen formation speed demonstrates the tendency that exists with ... temperature, when temperature is high, will produce hydrogen under low running voltage, and the hydrogen growing amount increases.In addition, charge air increases to picture 100ml/ timesharing, under 30 ℃ of temperature, 50 ℃ of such low temperature, produces hydrogen hardly.
Hydrogen Production Example 2-5
Use the hydrogen manufacturing battery same with hydrogen Production Example 2-1, at battery temperature is under 50 ℃, in the air pole side is that 50ml/ divides the air that flows with the flow, change in the fuel electrodes side that fuel flow is 1.5,2.5,5.0,7.5, the 10.0ml/ branch, change the electric current circulate between air pole and fuel electrodes this moment, the formation speed of the hydrogen that produces to the running voltage of fuel electrodes and air pole, in the fuel electrodes side is studied simultaneously.
In this test, the relation between the density of current of derivation and running voltage as shown in figure 34.
Change even can observe fuel flow, the limiting current density that can discharge does not have big variation yet.
Result with Figure 34 among Figure 35 puts in order as the relation of running voltage and hydrogen formation speed.
Hence one can see that, and the hydrogen formation speed under condition separately exists with ... running voltage, produces hydrogen under 300～500mV.In addition, it is big to observe the hydrogen formation speed near 450～500mV.
Can know that the hydrogen formation speed not too exists with ... fuel flow.
Hydrogen Production Example 2-6
Use the hydrogen manufacturing battery same with hydrogen Production Example 2-1, at battery temperature is under 50 ℃, in the air pole side is that 50ml/ divides the air that flows with the flow, at fuel electrodes side fuel is the constant flow rate that 5ml/ divides, change fuel concentration and be 0.5,1,2,3M, change the electric current circulate between air pole and fuel electrodes this moment, the formation speed of the hydrogen that produces to the running voltage of fuel electrodes and air pole, in the fuel electrodes side is studied simultaneously.
In this test, the relation between the density of current of derivation and running voltage as shown in figure 36.
Along with the increase of fuel concentration, running voltage reduces, and observes the limiting current density that can discharge and descends.
Result with Figure 36 among Figure 37 puts in order as the relation of running voltage and hydrogen formation speed.
Hence one can see that, and the hydrogen formation speed under condition separately exists with ... running voltage, produces hydrogen under 300～600mV.
When fuel concentration is 1M, be easy to produce hydrogen most.
Hydrogen Production Example 2-7
Use the hydrogen manufacturing battery (but air pole form the oxidation utmost point of flow oxidizing gas) same with hydrogen Production Example 2-1, at battery temperature is under 50 ℃, at the fuel of fuel electrodes side with the fuel concentration of the mobile 1M of constant flow rate of 5ml/ branch, at the traffic flow oxidizing gas of oxidation utmost point side with the 14.0ml/ branch, changing oxygen concentration is 10,21,40,100%, change the electric current circulate between the oxidation utmost point and fuel electrodes this moment, the formation speed of the hydrogen that produces to the running voltage of the fuel electrodes and the oxidation utmost point, in the fuel electrodes side is studied simultaneously.Here, the gas of oxygen concentration 21% uses air, and the gas of oxygen concentration 10% is modulated by mix nitrogen in air, and the gas of oxygen concentration 40% is modulated by mix oxygen (oxygen concentration 100%) in air.
In this test, the relation between the density of current of derivation and running voltage as shown in figure 38.
When oxygen concentration hanged down, running voltage reduced, and observed the limiting current density that can discharge and descended.
Result with Figure 38 among Figure 39 puts in order as the relation of running voltage and hydrogen formation speed.
Hence one can see that, and the hydrogen formation speed under condition separately exists with ... running voltage, produces hydrogen under 300～600mV.
When oxygen concentration is high, observe the tendency that the hydrogen formation speed increases.
Hydrogen Production Example 2-8
Use the hydrogen manufacturing battery (but air pole form oxidation utmost point of working fluid hydrogen peroxide) same with hydrogen Production Example 2-1, hydrogen is made in the electric furnace that battery is arranged on the hot air circulation type, battery temperature is 30 ℃, 50 ℃, 70 ℃, 90 ℃, at the methanol aqueous solution (fuel) of fuel electrodes side, at the H of oxidation utmost point side with the traffic flow 1M of 2.6～5.5ml/ branch with the traffic flow 1M of 5ml/ branch 2O 2(hydrogen peroxide) changes the electric current circulate this moment between the oxidation utmost point and fuel electrodes, the formation speed of the hydrogen that produces to the running voltage of the fuel electrodes and the oxidation utmost point, in the fuel electrodes side is studied simultaneously.At this, with the flow regulating of hydrogen peroxide to being roughly 500mV at open circuit voltage at each temperature.
In this test, the relation between the density of current of derivation and running voltage as shown in figure 40.
If temperature is 70～90 ℃, the relation of the increase of running decline of voltage and density of current is basic identical, and when drop in temperature to 30 ℃, running voltage sharply reduces, and observes the limiting current density that can discharge and descends.
Result with Figure 40 among Figure 41 puts in order as the relation of running voltage and hydrogen formation speed.
Hence one can see that, and the hydrogen formation speed demonstrates the tendency that exists with ... running voltage, produces hydrogen under 300～500mV.In addition, when temperature is 90 ℃, be easy to produce hydrogen most, when temperature is hanged down, do not improve running voltage then can not produce hydrogen if observe.
Here emphasis is to make battery to outside derived current from hydrogen in the foregoing description 2.In other words, make battery,, can change the part of fuel into hydrogen when electric energy is derived in the outside for the hydrogen of embodiment 2.And it is the reformation under 30～90 ℃ of so surprising low temperatures, can think the brand new hydrogen producing apparatus that in the past do not have, and it is remarkable therefore this hydrogen producing apparatus to be equipped on the underwater ship effect.
Embodiment 3
The example of below representing the situation of employed hydrogen producing apparatus (charge condition) manufacturing hydrogen in the underwater ship according to the related invention of the application's claim 4.
Hydrogen Production Example 3-1
Figure 42 represents that (hydrogen that has the equipment that applies electric energy from the outside among the Production Example 3-1～3-8) is made the summary of battery to embodiment 3.
Except with fuel very negative electrode, with above-mentioned oxidation very anode and be provided with apply the equipment of electric energy from the outside, to make battery structure identical with the hydrogen of hydrogen Production Example 1-1.
This hydrogen is made battery to be arranged in the hot air circulation type electric furnace, at battery temperature (operating temperature) is under 50 ℃, is that 10～80ml/ divides the air that flows in the air pole side with flow, in the fuel electrodes side is the methanol aqueous solution (fuel) that 5ml/ divides the 1M that flows with the flow, use direct supply and change the electric current that circulates this moment between air pole and fuel electrodes from the outside, gas flow, the gas composition that produces to the running voltage of fuel electrodes and air pole, in the fuel electrodes side simultaneously studied.Here, the chemical power of the hydrogen that generates is set at the energy efficiency of charge condition with respect to the ratio of the electric energy of input.In addition, utilize gas chromatographic method that the hydrogen concentration that produces in the gas is analyzed, obtain the hydrogen formation speed.
The energy efficiency of charge condition (hereinafter referred to as " energy efficiency ") is calculated by following calculating formula.
Calculating formula:
Energy efficiency (%)=(H 2The electric energy of heat of combustion/apply) * 100
The H that generates in 1 minute 2Heat of combustion (KJ)=(H 2Formation speed ml/ branch/24.47/1000) * 286KJ/mol[HHV]
The electric energy that applies in 1 minute (KJ)=[voltage mV/1000 * electric current A * 60sec] Wsec/1000
At this, for the purpose of prudent, to put down in writing, but the objective of the invention is to obtain the hydrogen of chemical power more than or equal to the electric energy of input, this is not to ignore the determined energy conservation criteria of thermodynamics.As a whole, because partial organic substances fuel is oxidized,, then be smaller or equal to 100% if comprise the chemical power that is consumed by the organic matter fuel oxidation in the electric energy of input.In the present invention, in order clearly to make the different of hydrogen with water electrolysis in the past, energy efficiency is expressed as energy efficiency with the chemical power of the hydrogen that generates with respect to the ratio of the electric energy of input.
In this test, the relation between density of current that applies and the hydrogen formation speed as shown in figure 43.
At density of current smaller or equal to 40mA/cm 2Condition under, hydrogen produces efficient (producing the electric weight efficient of hydrogen) and has zone more than or equal to 100% (dot among Figure 43 hydrogen produce efficient be 100% line), if in this zone running, then can obtain the hydrogen more than or equal to the input electric energy.
Result with Figure 43 among Figure 44 puts in order as the relation of running voltage and hydrogen formation speed.
Hence one can see that, hydrogen formation speed (hydrogen growing amount) demonstrates the tendency that exists with ... running voltage, produces hydrogen during more than or equal to 400mV at running voltage, and the hydrogen formation speed is certain substantially more than or equal to 600mV the time, charge air hour, hydrogen formation speed big (being easy to produce hydrogen).
The relation of density of current that applies and running voltage as shown in figure 45.
The hydrogen generation efficient of confirming in Figure 43 is among Figure 45 less than the running voltage that equals 600mV more than or equal to 100% zone.
In addition, the relation of running voltage and energy efficiency as shown in figure 46.
Can know, though running voltage near 1000mV, energy efficiency is also more than or equal to 100%, the situation that the voltage that particularly turns round divides smaller or equal to 600mV, charge air 30～50ml/, energy efficiency height.
Then, at energy efficiency height (1050%), 50 ℃ of temperature, fuel flow 5ml/ branch, charge air 50ml/ branch, density of current 4.8mA/cm 2Condition under produce gas, utilize the hydrogen concentration in the gas chromatography determination gas.Its result shows, produces to contain 86% the hydrogen of having an appointment in the gas, and the hydrogen formation speed is the 7.8ml/ branch.In addition, do not detect CO.
Hydrogen Production Example 3-2
Use the hydrogen manufacturing battery same with hydrogen Production Example 3-1, at battery temperature is 30 ℃, is that 10～70ml/ divides the air that flows in the air pole side with flow, in the fuel electrodes side is the methanol aqueous solution (fuel) that 5ml/ divides the 1M that flows with the flow, use direct supply and change the electric current that circulates this moment between air pole and fuel electrodes from the outside, formation speed, the energy efficiency of the hydrogen that produces to the running voltage of fuel electrodes and air pole, in the fuel electrodes side are studied simultaneously.
In this test, the relation between density of current that applies and the hydrogen formation speed as shown in figure 47, the relation of running voltage and hydrogen formation speed is as shown in figure 48.
Hence one can see that, and hydrogen formation speed (growing amount of hydrogen) demonstrates the tendency that exists with ... running voltage, produces hydrogen during more than or equal to 400mV at running voltage, and charge air hour is easy to produce hydrogen.When charge air is the situation that 10ml/ divides, the hydrogen formation speed is certain substantially more than or equal to 600mV the time; When charge air is the situation that 30ml/ divides, more than or equal to 800mV the time, demonstrate the tendency of increase; When charge air than its higher situation, just not can not produce hydrogen if do not improve running voltage.
In addition, the relation of running voltage and energy efficiency as shown in figure 49.
Can know that even turn round voltage near 1000mV, energy efficiency is also more than or equal to 100%, the voltage that particularly turns round is the situation that 30ml/ divides smaller or equal to 600mV, charge air, the energy efficiency height.
Hydrogen Production Example 3-3
Except making battery temperature is 70 ℃, to test with the condition identical with hydrogen Production Example 3-2, formation speed, the energy efficiency of the hydrogen that produces to the running voltage of fuel electrodes and air pole, in the fuel electrodes side are studied.
In this test, the relation between density of current that applies and the hydrogen formation speed as shown in figure 50, the relation of running voltage and hydrogen formation speed is shown in Figure 51.
Hence one can see that, and the hydrogen formation speed demonstrates the tendency that exists with ... running voltage, produces hydrogen during more than or equal to 400mV at running voltage, and charge air hour is easy to produce hydrogen.When charge air is the situation that 10ml/ divides, the hydrogen formation speed is certain substantially more than or equal to 600mV the time; When charge air is the situation that 30ml/ divides, more than or equal to 800mV the time, demonstrate the tendency of increase; When charge air than its higher situation, just not can not produce hydrogen if do not improve running voltage.
In addition, the relation of running voltage and energy efficiency is shown in Figure 52.
Can know, though running voltage near 1000mV, energy efficiency is also more than or equal to 100%, the situation that the voltage that particularly turns round divides smaller or equal to 600mV, charge air 10～30ml/, energy efficiency height.
Hydrogen Production Example 3-4
Use the hydrogen manufacturing battery same with hydrogen Production Example 3-1, at battery temperature is under 90 ℃, is that 10～200ml/ divides the air that flows in the air pole side with flow, in the fuel electrodes side is the methanol aqueous solution (fuel) that 5ml/ divides the 1M that flows with the flow, use direct supply and change the electric current that circulates this moment between air pole and fuel electrodes from the outside, formation speed, the energy efficiency of the hydrogen that produces to the running voltage of fuel electrodes and air pole, in the fuel electrodes side are studied simultaneously.
In this test, the relation between density of current that applies and the hydrogen formation speed is shown in Figure 53, and the relation of running voltage and hydrogen formation speed is shown in Figure 54.
Hence one can see that, the hydrogen formation speed demonstrates the tendency that exists with ... running voltage, produce hydrogen during more than or equal to 300mV at running voltage, charge air hour is easy to produce hydrogen, and when charge air is the situation that 10ml/ divides, the hydrogen formation speed is certain substantially more than or equal to 500mV the time, when charge air is the situation that 50～100ml/ divides, more than or equal to 800mV the time, demonstrate the tendency of increase, when charge air is the situation that 200ml/ divides, equals 800mV and just can not produce hydrogen if be not more than.
In addition, the relation of running voltage and energy efficiency is shown in Figure 55.
Can know that even turn round voltage near 1000mV, energy efficiency is also more than or equal to 100%, the voltage that particularly turns round is the 50ml/ timesharing smaller or equal to 500mV, charge air, the energy efficiency height.
Then, the density of current that the charge air at each temperature of hydrogen Production Example 3-1～3-4 is applied for the 50ml/ timesharing and the relation of hydrogen formation speed are shown among Figure 56, and the relation of running voltage and hydrogen formation speed is shown among Figure 57.
Hence one can see that, and the hydrogen formation speed demonstrates the tendency that exists with ... temperature, when operating temperature is high, just produces hydrogen under low running voltage, and the hydrogen formation speed is also big.
In addition, the relation of running voltage and energy efficiency is shown in Figure 58.
Can know, though running voltage near 1000mV, energy efficiency is also more than or equal to 100%, the voltage that particularly turns round is during smaller or equal to 600mV, the energy efficiency height.
Hydrogen Production Example 3-5
Use the hydrogen manufacturing battery same with hydrogen Production Example 3-1, at battery temperature is under 50 ℃, in the air pole side is that 50ml/ divides the air that flows with the flow, the fuel flow that changes the fuel electrodes side is 1.5,2.5,5.0,7.5, the 10.0ml/ branch, under this condition, use direct supply and change the electric current that circulates this moment between air pole and fuel electrodes from the outside, formation speed, the energy efficiency of the hydrogen that produces to the running voltage of fuel electrodes and air pole, in the fuel electrodes side are studied simultaneously.
In this test, the relation between density of current that applies and the hydrogen formation speed is shown in Figure 59, and the relation of running voltage and hydrogen formation speed is shown in Figure 60.
Hence one can see that, the hydrogen formation speed demonstrates the tendency that exists with ... running voltage, produces hydrogen during more than or equal to 400mV at running voltage, and fuel flow is easy to produce hydrogen for a long time, for the situation of any fuel flow, all observe the tendency that more than or equal to 800mV time hydrogen formation speed has increase.
In addition, the relation of running voltage and energy efficiency is shown in Figure 61.
Can know, for the situation of any fuel flow, even running voltage near 1000mV, energy efficiency is also more than or equal to 100%, the voltage that particularly turns round is during smaller or equal to 600mV, the energy efficiency height.
Hydrogen Production Example 3-6
Use the hydrogen manufacturing battery same with hydrogen Production Example 3-1, at battery temperature is under 50 ℃, in the air pole side is that 50ml/ divides the air that flows with the flow, at fuel electrodes side fuel is the constant flow rate that 5ml/ divides, change fuel concentration and be 0.5,1,2,3M, under this condition, use direct supply from the outside and change the electric current that between air pole and fuel electrodes, circulates this moment, formation speed, the energy efficiency of the hydrogen that produces to the running voltage of fuel electrodes and air pole, in the fuel electrodes side are studied simultaneously.
In this test, the relation between density of current that applies and the hydrogen formation speed is shown in Figure 62, and the relation of running voltage and hydrogen formation speed is shown in Figure 63.
Hence one can see that, for any fuel concentration, more than or equal to 0.02A/cm 2The zone, density of current that applies and hydrogen formation speed are proportional substantially.
In addition, the hydrogen formation speed demonstrates the tendency that exists with ... running voltage, produces hydrogen during more than or equal to 400mV at running voltage, when fuel concentration is high, also is easy to produce hydrogen even running voltage is low.For fuel concentration is the situation of 2M, 3M, and the hydrogen formation speed sharply increases when 400～500mV; When fuel concentration is the situation of 1M, the hydrogen formation speed is certain substantially when 400～800mV, demonstrates the tendency of increase more than or equal to 800mV the time; Than its lower situation, just not can not produce hydrogen at fuel concentration if do not improve running voltage.
In addition, the relation of running voltage and energy efficiency is shown in Figure 64.
Can know, except fuel concentration is the situation of 0.5M, even running voltage near 1000mV, energy efficiency is also more than or equal to 100%, the voltage that particularly turns round is during smaller or equal to 600mV, when fuel concentration is 1,2, the situation of 3M, the energy efficiency height.In addition, fuel concentration is the situation of 0.5M, owing to do not produce hydrogen at low-voltage region, the performance of energy efficiency is different fully with the situation of other conditions.
Hydrogen Production Example 3-7
Use the hydrogen manufacturing battery (but air pole form the oxidation utmost point of flow oxidizing gas) same with hydrogen Production Example 3-1, at battery temperature is under 50 ℃, fuel at fuel electrodes side concentration 1M is the constant flow rate that 5ml/ divides, at oxidation utmost point side oxidizing gas is the flow that 14.0ml/ divides, changing oxygen concentration is 10,21,40,100%, under this condition, use direct supply and change the electric current that circulates this moment between the oxidation utmost point and fuel electrodes from the outside, simultaneously to the running voltage of the fuel electrodes and the oxidation utmost point, the formation speed of the hydrogen that produces in the fuel electrodes side, energy efficiency is studied.Here, the gas of oxygen concentration 21% uses air, and the gas of oxygen concentration 10% is modulated by mix nitrogen in air, and the gas of oxygen concentration 40% is modulated by mix oxygen (oxygen concentration 100%) in air.
In this test, the relation between density of current that applies and the hydrogen formation speed is shown in Figure 65, and the relation of running voltage and hydrogen formation speed is shown in Figure 66.
Hence one can see that, for any oxygen concentration, more than or equal to 0.03A/cm 2The zone, density of current that applies and hydrogen formation speed are proportional substantially.
In addition, the hydrogen formation speed demonstrates the tendency that exists with ... running voltage, produce hydrogen during more than or equal to 400mV at running voltage, when oxygen concentration is high, even hanging down, running voltage also is easy to produce hydrogen, the hydrogen formation speed is certain substantially when 400～800mV, demonstrates the tendency of increase more than or equal to 800mV the time.
In addition, the relation of running voltage and energy efficiency is shown in Figure 67.
Can know that even apply voltage near 1000mV, energy efficiency particularly applies voltage smaller or equal to 600mV, when oxygen concentration is high, the energy efficiency height also more than or equal to 100%.
Hydrogen Production Example 3-8
Use the hydrogen manufacturing battery (but air pole form oxidation utmost point of working fluid hydrogen peroxide) same with hydrogen Production Example 3-1, hydrogen is made in the electric furnace that battery is arranged on the hot air circulation type, battery temperature is 30 ℃, 50 ℃, 70 ℃, 90 ℃, in the fuel electrodes side is the methanol aqueous solution (fuel) that 5ml/ divides the concentration 1M that flows with the flow, is the H that 2.6～5.5ml/ divides the 1M that flows in oxidation utmost point side with flow 2O 2(hydrogen peroxide) uses direct supply from the outside and change the electric current that circulates between the oxidation utmost point and fuel electrodes this moment, and formation speed, the energy efficiency of the hydrogen that produces to the running voltage of the fuel electrodes and the oxidation utmost point, in the fuel electrodes side are studied simultaneously.
At this, the flow of adjusting hydrogen peroxide open circuit voltage extremely at each temperature is 500mV substantially.
In this test, the relation between density of current that applies and the hydrogen formation speed is shown in Figure 68, and the relation of running voltage and hydrogen formation speed is shown in Figure 69.
Hence one can see that, and the hydrogen formation speed demonstrates the tendency that exists with ... running voltage, produces hydrogen during more than or equal to 500mV at running voltage, demonstrates the tendency of increase more than or equal to 800mV the time, is easy to produce hydrogen when operating temperature is high.
In addition, the relation of running voltage and energy efficiency is shown in Figure 70.
Can know, though running voltage near 1000mV, energy efficiency is also more than or equal to 100%, the voltage that particularly turns round is smaller or equal to 800mV, when temperature is 90 ℃, the energy efficiency height.
Here emphasis is, the foregoing description 3 is to obtain from the hydrogen of outside more than the electric current that hydrogen manufacturing battery applies.In other words, make battery, can make hydrogen more than or equal to the energy of the electric energy that applies for the hydrogen of embodiment 3.And it is the reformation under 30～90 ℃ of so surprising low temperatures, can think the brand new hydrogen producing apparatus that in the past do not have, and therefore the hydrogen producing apparatus lift-launch by will be such can obtain remarkable result in underwater ship.
In following embodiment, show and use methyl alcohol fuel in addition, make the example of hydrogen by the hydrogen producing apparatus that carries in the underwater ship of the present invention.
Embodiment 4
Use ethanol to be fuel, employed hydrogen producing apparatus (open-circuit condition) is made hydrogen in the underwater ship by the related invention of the application's claim 2.
Use the hydrogen identical to make battery with hydrogen Production Example 1-1, battery temperature is 80 ℃, fuel electrode one side flows through the ethanol water that concentration is 1M with the flow that 5ml/ divides, air pole one side flows through air with the flow that 65ml/ divides, and measures the open circuit voltage of battery, the formation speed that the fuel electrodes side produces gas.Use the hydrogen concentration in the gc analysis generation gas, obtain the hydrogen formation speed.
The result is as shown in table 1.
Table 1
Air (ml/min) Open circuit voltage (mV) Gas formation speed (ml/min) H 2Concentration (%) H 2Formation speed (ml/min)
65 478 0.6 65.2 0.39
As shown in table 1, when open circuit voltage 478mV, confirm to have produced hydrogen, but the formation speed of hydrogen is little.
Embodiment 5
Making spent glycol is fuel, and the hydrogen producing apparatus (open-circuit condition) that is carried in the underwater ship by the related invention of the application's claim 2 is made hydrogen.
Use the hydrogen identical to make battery with hydrogen Production Example 1-1, battery temperature is 80 ℃, fuel electrode one side flows through the glycol water that concentration is 1M with the flow that 5ml/ divides, air pole one side flows through air with the flow that 105ml/ divides, and measures the open circuit voltage of battery, the formation speed that the fuel electrodes side produces gas.Use the hydrogen concentration in the gc analysis generation gas, obtain the hydrogen formation speed.
The result is as shown in table 2.
Table 2
Air (ml/min) Open circuit voltage (mV) Gas formation speed (ml/min) H 2Concentration (%) H 2Formation speed (ml/min)
105 474 2.4 88.4 2.12
As shown in table 2, when open circuit voltage 474mV, confirm to have produced hydrogen, the formation speed of hydrogen is big when using ethanol water as fuel, but little when comparing the use methanol aqueous solution.
Embodiment 6
Use isopropyl alcohol to be fuel, the hydrogen producing apparatus (open-circuit condition) that is carried in the underwater ship by the related invention of the application's claim 2 is made hydrogen.
Use the hydrogen identical to make battery with hydrogen Production Example 1-1, battery temperature is 80 ℃, fuel electrode one side flows through the isopropanol water solution that concentration is 1M with the flow that 5ml/ divides, air pole one side flows through air with the flow that 35ml/ divides, and measures the open circuit voltage of battery, the formation speed that the fuel electrodes side produces gas.Use the hydrogen concentration in the gc analysis generation gas, obtain the hydrogen formation speed.
The result is as shown in table 3.
Table 3
Air (ml/min) Open circuit voltage (mV) Gas formation speed (ml/min) H 2Concentration (%) H 2Formation speed (ml/min)
35 514 3.96 95.6 3.78
As shown in table 3, when open circuit voltage 514mV, confirm to have produced hydrogen, the formation speed of hydrogen is big when using ethanol water, glycol water as fuel, near the situation of methanol aqueous solution.Particularly, produce the very high concentrations of hydrogen in the gas.
Embodiment 7
Use diethyl ether to be fuel, the hydrogen producing apparatus (open-circuit condition) that is carried in the underwater ship by the related invention of the application's claim 2 is made hydrogen.
Use the hydrogen identical to make battery with hydrogen Production Example 1-1, battery temperature is 80 ℃, fuel electrodes one side flows through the diethyl ether aqueous system that concentration is 1M with the flow that 5ml/ divides, air pole one side flows through air with the flow that 20ml/ divides, and measures the open circuit voltage of battery, the formation speed that the fuel electrodes side produces gas.Use the hydrogen concentration in the gc analysis generation gas, obtain the hydrogen formation speed.
The result is as shown in table 4.
Table 4
Air (ml/min) Open circuit voltage (mV) Gas formation speed (ml/min) H 2Concentration (%) H 2Formation speed (ml/min)
20 565 3.0 7.6 0.23
As shown in table 4, when open circuit voltage 565mV, confirm to have produced hydrogen, to compare when using alcohol as fuel, the hydrogen concentration in the generation gas is low, and the formation speed of hydrogen is also low.
Embodiment 8
Use formaldehyde, formic acid to be fuel, the hydrogen producing apparatus (open-circuit condition) that is carried in the underwater ship by the related invention of the application's claim 2 is made hydrogen.
Use the hydrogen identical to make battery with hydrogen Production Example 1-1, battery temperature is 50 ℃, it is the aqueous formic acid of 1M that the flow that fuel electrodes one side is divided with 5ml/ flows through formalin, the concentration that concentration is 1M respectively, air pole one side flows through air with the flow that 0～100ml/ divides, and measures the open circuit voltage of battery, the formation speed that the fuel electrodes side produces gas.Use the hydrogen concentration in the gc analysis generation gas, obtain the hydrogen formation speed.
The result who measures is shown in Figure 71,72 when using methyl alcohol.
Shown in Figure 71, use formaldehyde, formic acid, methyl alcohol is same with using, and confirms to have produced hydrogen by reducing charge air in fuel electrodes one side of battery.In addition, the formation speed of hydrogen is maximum with methyl alcohol, is followed successively by formaldehyde, formic acid, and, under this order,, just do not produce hydrogen if do not reduce charge air.
By Figure 72 as can be known, use formaldehyde, formic acid, methyl alcohol is same with using, and the formation speed of hydrogen (hydrogen generating capacity) shows the tendency that exists with ... open circuit voltage, and open circuit voltage finds to produce hydrogen when 200～800mV.In addition, when using formic acid, produce hydrogen than methyl alcohol, formaldehyde under lower open circuit voltage, the peak value of hydrogen formation speed is about 500mV for methyl alcohol, formaldehyde, and is lower open circuit voltage (350mV) for formic acid.
The possibility of utilizing on the industry
As mentioned above, the hydrogen producing apparatus that carries in the underwater ship of the present invention can be made hydrogen-containing gas containing organic fuel less than or equal to 100 ℃ of decomposition, thereby can directly be equipped on the underwater ship, can easily supply with hydrogen to fuel cell, so the various underwater ships that the electricity that the present invention goes for being sent with fuel cell drives.

Claims (46)

1. underwater ship, it has at least by supplying with the fuel cell that hydrogen and oxidizer generate electricity, manufacturing is used to supply with the hydrogen producing apparatus of the hydrogen-containing gas of described fuel cell, the propelling unit that drives by the electricity that described fuel cell produced, it is characterized in that, described hydrogen producing apparatus is to decompose the hydrogen producing apparatus that contains organic fuel and make hydrogen-containing gas, and described hydrogen producing apparatus has barrier film, be arranged on the fuel electrodes on the face of described barrier film, supply with the device of the fuel that contains organic matter and water to described fuel electrodes, be arranged on the oxidation utmost point on another face of described barrier film, supply with the device of oxidizer and the device that produces hydrogen-containing gas and take out by the fuel electrodes side to the described oxidation utmost point.
2. underwater ship as claimed in claim 1 is characterized in that, described hydrogen producing apparatus is not made the open-circuit condition that battery is derived the device of electric energy and applied the device of electric energy from the outside to described hydrogen manufacturing battery to the outside for not having by the hydrogen that constitutes hydrogen producing apparatus.
3. underwater ship as claimed in claim 1 is characterized in that, described hydrogen producing apparatus has with described fuel negative pole, very anodal and derive the device of electric energy to the outside with described oxidation very.
4. underwater ship as claimed in claim 1 is characterized in that, described hydrogen producing apparatus have with described fuel very negative electrode, with described oxidation anode and apply the device of electric energy from the outside very.
5. underwater ship as claimed in claim 1, it is characterized in that, be used in combination the hydrogen producing apparatus of from following hydrogen producing apparatus, selecting more than 2 kinds or 2 kinds: do not have and make battery from described hydrogen and derive the device of electric energy and make the hydrogen producing apparatus of open-circuit condition of the device of battery supply of electrical energy from the outside to described hydrogen to the outside; Have with described fuel negative pole, very anodal and derive the hydrogen producing apparatus of the device of electric energy to the outside very with described oxidation; And have with described fuel very negative electrode, with described oxidation anode and apply the hydrogen producing apparatus of the device of electric energy from the outside very.
6. underwater ship as claimed in claim 1 is characterized in that, in described hydrogen producing apparatus, the voltage between the described fuel electrodes and the described oxidation utmost point is 200～1000mV.
7. as described underwater ship as described in the claim 2, it is characterized in that in described hydrogen producing apparatus, the voltage between the described fuel electrodes and the described oxidation utmost point is 300～800mV.
8. underwater ship as claimed in claim 3 is characterized in that, in described hydrogen producing apparatus, the voltage between the described fuel electrodes and the described oxidation utmost point is 200～600mV.
9. underwater ship as claimed in claim 3 is characterized in that, in described hydrogen producing apparatus, regulates the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by the electric energy of regulating described derivation.
10. underwater ship as claimed in claim 4 is characterized in that, in described hydrogen producing apparatus, the voltage between the described fuel electrodes and the described oxidation utmost point is 300～1000mV.
11. underwater ship as claimed in claim 4 is characterized in that, in described hydrogen producing apparatus, regulates the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by regulating the described electric energy that applies.
12. any one the described underwater ship as in the claim 1～11 is characterized in that, in described hydrogen producing apparatus, regulates the growing amount of described hydrogen-containing gas by regulating voltage between the described fuel electrodes and the described oxidation utmost point.
13. as any one the described underwater ship in the claim 1～11, it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by the delivery volume of regulating described oxidizer.
14. underwater ship as claimed in claim 12 is characterized in that, in described hydrogen producing apparatus, regulates the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by the delivery volume of regulating described oxidizer.
15. as any one the described underwater ship in the claim 1～11, it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by the concentration of regulating described oxidizer.
16. underwater ship as claimed in claim 12 is characterized in that, in described hydrogen producing apparatus, regulates the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by the concentration of regulating described oxidizer.
17. underwater ship as claimed in claim 13 is characterized in that, in described hydrogen producing apparatus, regulates the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by the concentration of regulating described oxidizer.
18. as any one the described underwater ship in the claim 1～11, it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by regulating the described delivery volume that contains the fuel of organic matter and water.
19. underwater ship as claimed in claim 12, it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by regulating the described delivery volume that contains the fuel of organic matter and water.
20. underwater ship as claimed in claim 13, it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by regulating the described delivery volume that contains the fuel of organic matter and water.
21. underwater ship as claimed in claim 15, it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by regulating the described delivery volume that contains the fuel of organic matter and water.
22. as any one the described underwater ship in the claim 1～11, it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by regulating the described concentration that contains the fuel of organic matter and water.
23. underwater ship as claimed in claim 12, it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by regulating the described concentration that contains the fuel of organic matter and water.
24. underwater ship as claimed in claim 13, it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by regulating the described concentration that contains the fuel of organic matter and water.
25. underwater ship as claimed in claim 15, it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by regulating the described concentration that contains the fuel of organic matter and water.
26. underwater ship as claimed in claim 18, it is characterized in that, in described hydrogen producing apparatus, regulate the voltage between the described fuel electrodes and the described oxidation utmost point and/or the growing amount of described hydrogen-containing gas by regulating the described concentration that contains the fuel of organic matter and water.
27. any one the described underwater ship as in the claim 1～11 is characterized in that the operating temperature of described hydrogen producing apparatus is smaller or equal to 100 ℃.
28. underwater ship as claimed in claim 27 is characterized in that, described operating temperature is 30～90 ℃.
29. underwater ship as claimed in claim 12 is characterized in that, the operating temperature of described hydrogen producing apparatus is smaller or equal to 100 ℃.
30. underwater ship as claimed in claim 13 is characterized in that, the operating temperature of described hydrogen producing apparatus is smaller or equal to 100 ℃.
31. underwater ship as claimed in claim 15 is characterized in that, the operating temperature of described hydrogen producing apparatus is smaller or equal to 100 ℃.
32. underwater ship as claimed in claim 18 is characterized in that, the operating temperature of described hydrogen producing apparatus is smaller or equal to 100 ℃.
33. underwater ship as claimed in claim 22 is characterized in that, the operating temperature of described hydrogen producing apparatus is smaller or equal to 100 ℃.
34. any one the described underwater ship as in the claim 1～11 is characterized in that, the described organic matter of supplying with the fuel electrodes of described hydrogen producing apparatus is one or both or the two or more organic matter of selecting from alcohol, aldehyde, carboxylic acid and ether.
35. underwater ship as claimed in claim 34 is characterized in that, described alcohol is methyl alcohol.
36. any one the described underwater ship as in the claim 1～11 is characterized in that the described oxidizer of supplying with the oxidation utmost point of described hydrogen producing apparatus is oxygen-containing gas or oxygen.
37. underwater ship as claimed in claim 36 is characterized in that, the described oxidizer of supplying with the oxidation utmost point of described hydrogen producing apparatus is the gas of the unreacted oxygenate of described fuel cell or other described hydrogen producing apparatus discharges.
38. any one the described underwater ship as in the claim 1～11 is characterized in that the described oxidizer of supplying with the oxidation utmost point of described hydrogen producing apparatus is the liquid that contains hydrogen peroxide.
39. any one the described underwater ship as in the claim 1～11 is characterized in that the barrier film of described hydrogen producing apparatus is the proton conductive solid electrolyte film.
40. underwater ship as claimed in claim 39 is characterized in that, described proton conductive solid electrolyte film is that perfluorocarbon sulfonic acid is a solid electrolyte film.
41. any one the described underwater ship as in the claim 1～11 is characterized in that, the catalyst of the described fuel electrodes of described hydrogen producing apparatus is the catalyst that has supported the Pt-Ru alloy on carbon dust.
42. any one the described underwater ship as in the claim 1～11 is characterized in that the catalyst of the oxidation utmost point of described hydrogen producing apparatus is the catalyst that has supported Pt on carbon dust.
43. any one the described underwater ship as in the claim 1～11 is characterized in that, the described circulating device that contains the fuel of organic matter and water is set on described hydrogen producing apparatus.
44. any one the described underwater ship as in the claim 1～11 is characterized in that, is provided for absorbing the carbon-dioxide carbon dioxide absorption portion that is included in the described hydrogen-containing gas on described hydrogen producing apparatus.
45. any one the described underwater ship as in the claim 1～11 is characterized in that, does not cool off by the described hydrogen-containing gas of described hydrogen producing apparatus generation and supplies with described fuel cell.
46. any one the described underwater ship as in the claim 1～11 is characterized in that, is provided for blocking the thermal insulating material of the heat that described hydrogen producing apparatus sends.
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CN102145743A (en) * 2011-03-07 2011-08-10 上海海事大学 Ship electric propulsion system with fuel cell and application method thereof
CN102760901A (en) * 2012-07-25 2012-10-31 太仓克莱普沙能源科技有限公司 Marine power supply system and marine power generation method
CN103328321A (en) * 2011-01-21 2013-09-25 西门子公司 Floating or submerging device with an electrolyser
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CN107800128A (en) * 2017-11-06 2018-03-13 中国舰船研究设计中心 A kind of ship integrated power system
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103328321A (en) * 2011-01-21 2013-09-25 西门子公司 Floating or submerging device with an electrolyser
CN102145743A (en) * 2011-03-07 2011-08-10 上海海事大学 Ship electric propulsion system with fuel cell and application method thereof
CN102760901A (en) * 2012-07-25 2012-10-31 太仓克莱普沙能源科技有限公司 Marine power supply system and marine power generation method
CN106059095A (en) * 2016-06-01 2016-10-26 中国科学院工程热物理研究所 Energy supply system based on seawater and application thereof
CN107800128A (en) * 2017-11-06 2018-03-13 中国舰船研究设计中心 A kind of ship integrated power system
CN112104062A (en) * 2020-08-10 2020-12-18 珠海格力电器股份有限公司 Control device and method of ship power supply system and ship power supply system
CN112104062B (en) * 2020-08-10 2021-11-23 珠海格力电器股份有限公司 Control device and method of ship power supply system and ship power supply system

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