CN104953132B - A kind of liquid flow pattern alcohol hydrogen peroxide fuel battery and its manufacture method - Google Patents
A kind of liquid flow pattern alcohol hydrogen peroxide fuel battery and its manufacture method Download PDFInfo
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- CN104953132B CN104953132B CN201510323198.1A CN201510323198A CN104953132B CN 104953132 B CN104953132 B CN 104953132B CN 201510323198 A CN201510323198 A CN 201510323198A CN 104953132 B CN104953132 B CN 104953132B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses the alcohol hydrogen peroxide fuel battery and its manufacture method of a kind of liquid flow model, including using PdNiCu/MWCNT catalyst as anode, using Ag/MWCNT catalyst as negative electrode, separated with cellulose acetate sheets piece between anode and negative electrode, anolyte is the 1mol L containing methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol or sec-butyl alcohol‑1NaOH solution, catholyte are the 1mol L containing hydrogen peroxide‑1NaOH solution.Anolyte and catholyte adopt the type of flow, and wherein anolyte liquid level is higher than catholyte liquid level, and anolyte flowing velocity is faster than catholyte flowing velocity, so ensures that the hydrogen peroxide in catholyte is not migrated to anolyte.The present invention can carry out stable discharging by various alcohol used in alkaline solution, and avoid and use ion exchange membrane, and battery structure is simple, and battery cost is also greatly reduced.
Description
Technical field
The invention belongs to new energy technology and field of fuel cell technology, and in particular to a kind of alcohol of liquid flow model-
Hydrogen peroxide fuel battery and its manufacture method.
Background technology
Alcohol fuel battery（AFC）Using simple alcohols such as methanol, ethanol, propanol or butanol as fuel, by cathode oxidation
The reduction of agent, so as to chemical energy is changed into battery.It has high-energy conversion efficiency, without hazardous emission and high-energy-density
The advantages of density, be the model electrochemical energy with very big using value.AFC is typically by anode, negative electrode, ionic membrane and electrolysis
Quality structure is into its Anodic is mainly the metallic catalyst such as platinum or palladium, and platinum is high due to price, and its resource scarcity, adds platinum
During catalytic alcohol is aoxidized, the intermediate product of formation can make platinum seriously be poisoned and lose activity, so as to significantly limit
Its extensive application.So people constantly explore other possible substitution material, wherein palladium is exactly current most suitable electro-catalysis
The material of alcohol oxidation.In alkaline solution, palladium is to alcohol（Including methanol, ethanol, propanol and butanol）Oxidation is urged with excellent electricity
Change activity.In order to further improve the catalysis activity of palladium, while reducing the load capacity of palladium, Jing is often by palladium and other metal nanos
Into complex, such as PtRu, PtNi, PtSn, PtIrRu and PtAu etc., these metal composite nanos granule Jing is often loaded particle shape
In carbon-based supports, including carbon dust, CNT（Many walls or single wall）Deng being so conducive to the stability of nano-particle.
The cathodic process of AFC is the reduction of oxidant, and the oxidant typically used is oxygen（Air）Or hydrogen peroxide.But
The speed of oxygen reduction is very slow, can hinder the operation of whole battery.Hydrogen peroxide can be reduced further into water, be a kind of excellent
Oxidant, and this reaction can be carried out on many metallic catalysts, and speed, is suitable for alcohol fuel battery
Cathodic process.
Anode and negative electrode are typically separated by AFC with ion diaphragm, not mutual so as to ensure anode reaction and cathode reaction
Affect, battery is normally run.But the use of ionic membrane not only substantially increases the cost of AFC, and makes the knot of battery
Structure is more complicated, increased the difficulty of battery maintenance.So there is important practical application using the fuel cell without ionic membrane
Value.
The content of the invention
It is an object of the invention to provide a kind of alcohol-hydrogen peroxide fuel battery of liquid flow model, the battery is not adopted
The ion exchange membrane used by common alcohol fuel battery, stable performance, simple structure, battery maintenance are convenient, and cost is reduced.This
The purpose of invention additionally provides a kind of preparation method of the alcohol-hydrogen peroxide fuel battery of liquid flow model.
For achieving the above object, embodiment of the present invention is：A kind of liquid flow pattern alcohol-hydrogen peroxide fuel battery, with many
Palladium ambrose alloy nano-particle (PdNiCu/MWCNT) of wall carbon nano tube load is pasted onto stainless (steel) wire surface as anode, Yi Duobi
Carbon nanotube loaded silver nano-grain (Ag/MWCNT) is pasted onto stainless (steel) wire surface as negative electrode, uses between anode and negative electrode
Cellulose acetate sheets piece separates, and anode chamber and cathode chamber are vertically disposed with anolyte import, anolyte outlet and catholyte and enter
Mouth and catholyte outlet, inject the anolyte liquid level of anode chamber higher than the catholyte liquid level for injecting cathode chamber.
1mol L of the anolyte for containing alcohol-1NaOH solution.The alcohol is methanol, ethanol, normal propyl alcohol, isopropanol, just
Butanol, isobutanol or sec-butyl alcohol.
The catholyte is the 1mol L containing hydrogen peroxide-1NaOH solution.
The present invention also provides a kind of manufacture method of liquid flow pattern alcohol-hydrogen peroxide fuel battery, comprises the following steps：
（1）Palladium chloride solution, nickel chloride solution and copper chloride solution are thoroughly mixed, ethylenediaminetetraacetic acid two is added
Sodium salt, is sufficiently stirred for 1 hour, adds multi-wall carbon nano-tube tube particle, stirs 1 hour, and then Deca sodium hydroxide solution is until mixed
The pH=7-8 of compound, in the case where being stirred continuously, is slowly added dropwise sodium borohydride solution, continues stirring mixture 2 hours after completion of dropping,
Mixture is filtered, gained solid washed with water to neutrality, room temperature in vacuo is dried, and obtains carbon multi-wall nano tube loaded palladium ambrose alloy and receives
Rice grain material (PdNiCu/MWCNT)；
（2）By stainless (steel) wire 10%（wt%）Sodium carbonate liquor in 500Process 30 minutes under C, with pure water rinsing extremely
It is standby after neutrality；
（3）Carbon multi-wall nano tube loaded palladium ambrose alloy nano-particle material (PdNiCu/MWCNT) is mixed with dehydrated alcohol
Close, add 5%（wt%）Nafion solution, gained mixture supersound process 1 hour, until forming the concentration of uniform ink shape
Liquid, the concentrated solution is coated on the above-mentioned rustless steel for processing, and is dried, obtains anode under room temperature, stand-by；
（4）By 20mmolL-1Silver nitrate solution is placed in hydrothermal reactor, adds disodium EDTA, in black out
Under the conditions of stir 10 minutes, add multi-wall carbon nano-tube tube particle, continuation to stir the mixture for 10 minutes under the conditions of black out, then
Molecular weight is added for the mol of 600g-1Polyethylene Glycol, hydrothermal reactor is heated to into 180oC, holding 10 is little at this temperature
When, after reaction terminates, hydrothermal reactor is taken out, is slowly cooled under room temperature filter reactant mixture, after being washed to 3 times,
It is dried 8 hours in vacuum desiccator at room temperature, it is multiple that the black particle for obtaining is carbon multi-wall nano tube loaded silver nanoparticle
Close granular materialss（Ag/MWCNT）；
（5）Carbon multi-wall nano tube loaded silver nanoparticle composite particulate material (Ag/MWCNT) is mixed with dehydrated alcohol, plus
Enter 5%（wt%）Nafion solution, gained mixture supersound process 1 hour, until form uniform ink shape concentrated solution, should
Concentrated solution is coated on the above-mentioned rustless steel for processing, and is dried, obtains negative electrode under room temperature, stand-by；
（6）The anode and negative electrode of above-mentioned preparation are respectively placed in into cellulose acetate sheets piece（Aperture 0.35m, thickness 290m）
Two sides, be assembled into alcohol-hydrogen peroxide fuel battery.
Step（1）In, the multi-walled carbon nano-tubes, palladium chloride solution, nickel chloride solution, copper chloride solution, ethylenediamine tetraacetic
The proportioning of acetic acid disodium salt is 200～400 mg:75～150 mL:9～20mL:5～15 mL: 350
～550 mg, the concentration of palladium chloride solution, nickel chloride solution and copper chloride solution are 10 mmol L-1.The sodium hydroxide
The concentration of solution is 20 mmol L-1, the concentration of sodium borohydride solution is 30%（wt%）, the addition of sodium borohydride solution is
45 ~ 150 mL；
Step（3）With（5）In, PdNiCu/MWCNT the and Ag/MWCNT nano-particle is respectively 100 mg, dehydrated alcohol
20 mL, 5%（wt%）1 mL of Nafion solution；
Step（4）In, the silver nitrate solution volume is 100-300 mL, and disodium EDTA quality is 750-
2250 mg, multi-walled carbon nano-tubes quality are 540-1600mg, and the volume of Polyethylene Glycol is 8-25 mL；
PdNiCu/MWCNT granules are pasted onto stainless (steel) wire surface as anode for the present invention, and Ag/MWCNT granules are pasted
On stainless (steel) wire surface as negative electrode, the anode for so obtaining and negative electrode are put in into the two sides group of cellulose acetate sheets piece respectively
Into an aggregation, battery is divided into anode and negative electrode by the aggregation, by the outflow speed for controlling anode chamber and negative electrode indoor liquid
Degree, prevents catholyte from migrating to anode chamber, it is ensured that battery normally runs.This new alcohol-hydrogen peroxide fuel battery can be with
Common alcohol is fuel, is smoothly discharged, and stable performance, simple structure are easy to maintenance, are a kind of alcohol with important application prospect
Fuel cell.
Figure of description
Fig. 1 is alcohol-hydrogen peroxide fuel battery structural representation
In figure, 1- anodes, 2- cellulose acetate sheets pieces, 3- negative electrodes, 4- anode chambers, 5- cathode chambers, 6, anolyte import,
7- anolyte outlets, 8- catholyte imports, the outlet of 9- catholytes.
Specific embodiment
Embodiment 1：
（1）By 10 mmol L-175 mL of palladium chloride solution, 10 mmol L-19 mL of nickel chloride solution and 10 mmol L-1
Copper chloride solution 5mL is sufficiently stirred for, mixes, and is subsequently added 350 mg disodium EDTAs, and mixture is continued abundant
Stirring 1 hour, afterwards, adds 200 mg multi-wall carbon nano-tube tube particles, stirs the mixture for 1 hour, and then Deca concentration is
20 mmol L-1Sodium hydroxide solution until mixture pH=7-8.In the case where being stirred continuously, concentration is slowly added dropwise for 30%
（wt%）45 mL of sodium borohydride solution, stirring mixture is further continued for after completion of dropping 2 hours, mixture is filtered, gained is solid
Body is washed with water to neutrality, and room temperature in vacuo is dried, and obtains carbon multi-wall nano tube loaded palladium-nickel-copper nano composite material
（PdNiCu/MWCNT）.
（2）By stainless (steel) wire 10%（wt%）Sodium carbonate liquor in, in 500Process 30 minutes under C, rushed with pure water afterwards
It is washed till standby after neutrality.
（3）100 mg PdNiCu/MWCNT nano-particle are mixed with 20 mL dehydrated alcohol, 5% is added（wt%）'s
1 mL of Nafion solution, gained mixture supersound process 1 hour, until uniform ink shape concentrated solution is formed, by the concentrated solution
It is coated on the above-mentioned rustless steel for processing, is dried under room temperature, obtains anode, it is stand-by；
（4）By 20 mmol L-1100 mL of silver nitrate solution is placed in hydrothermal reactor, adds disodiumedetate
Salt 750mg, stirs under the conditions of black out 10 minutes, afterwards, adds multi-wall carbon nano-tube tube particle 540mg, continue in black out condition
Under stir the mixture for 10 minutes.Finally, molecular weight is added to be 600g mol-18 mL of Polyethylene Glycol, by hydrothermal reactor plus
Heat is to 180oC, is kept for 10 hours at this temperature.After reaction terminates, hydrothermal reactor is taken out, is slowly cooled under room temperature
Reactant mixture is filtered, after being washed to 3 times, is dried 8 hours in vacuum desiccator at room temperature, the black particle for obtaining is i.e.
For carbon multi-wall nano tube loaded argentum nano composite material (Ag/MWCNT).
（5）100mgAg/MWCNT nano-particle is mixed with 20mL dehydrated alcohol, 5 are added（wt%）Nafion solution
The concentrated solution, until forming uniform ink shape concentrated solution, is coated in above-mentioned place by 1mL, gained mixture supersound process 1 hour
On the rustless steel managed, it is dried under room temperature, obtains negative electrode, it is stand-by；
（6）The anode and negative electrode of above-mentioned preparation are respectively placed in into cellulose acetate sheets piece（Aperture 0.35m, thickness 290m）
Two sides, be assembled into alcohol-hydrogen peroxide fuel battery by accompanying drawing 1.As shown in figure 1, alcohol-the hydrogen peroxide fuel battery with
Carbon multi-wall nano tube loaded palladium ambrose alloy nano-particle (PdNiCu/MWCNT) be pasted onto stainless (steel) wire surface as anode 1 and with
Carbon multi-wall nano tube loaded silver nano-grain (Ag/MWCNT) is pasted onto stainless (steel) wire surface as negative electrode 3, anode 1 and negative electrode
Separated with cellulose acetate sheets piece 2 between 3, anode chamber 4 and cathode chamber 5 are vertically disposed with anolyte import 6, anolyte outlet
7 and catholyte import 8 and catholyte outlet 9, anolyte import 6 higher than catholyte import 8, injection anode chamber 4 anolyte liquid
Catholyte liquid level of the face higher than injection cathode chamber 5.
（7）Fuel cell shown in Fig. 1 is carried out into discharge test.As a result show, be 1molL in anolyte-1
NaOH+0.5 mol L-1Methanol, catholyte are 1 mol L-1NaOH+0.1mol L-1Hydrogen peroxide, battery open circuit
0.48 V of voltage, 25 mW cm of maximum power density-2, corresponding electric current density is 80 mA cm-2。
Embodiment 2：
（1）By 10 mmol L-1110 mL of palladium chloride solution, 10 mmol L-1Nickel chloride solution 15mL and 10 mmol L-110 mL of copper chloride solution is sufficiently stirred for, mixes, and is subsequently added 450 mg disodium EDTAs, mixture is continued to fill
Point stirring 1 hour, afterwards, adds 300 mg multi-wall carbon nano-tube tube particles, stirs the mixture for 1 hour, and then Deca concentration is
20 mmol L-1Sodium hydroxide solution until mixture pH=7-8.In the case where being stirred continuously, concentration is slowly added dropwise for 30%
（wt%）95 mL of sodium borohydride solution, stirring mixture is further continued for after completion of dropping 2 hours, mixture is filtered, gained is solid
Body is washed with water to neutrality, and room temperature in vacuo is dried, and obtains carbon multi-wall nano tube loaded palladium-nickel-copper nano composite material
PdNiCu/MWCNT。
（2）Stainless (steel) wire is 10%（wt%）Sodium carbonate liquor in, in 500Process 30 minutes under C, use pure water rinsing afterwards
It is standby to neutrality.
（3）100 mg PdNiCu/MWCNT nano-particle are mixed with 20 mL dehydrated alcohol, 5% is added（wt%）'s
1 mL of Nafion solution, gained mixture supersound process 1 hour, until uniform ink shape concentrated solution is formed, by the concentrated solution
It is coated on the above-mentioned rustless steel for processing, is dried under room temperature, obtains anode, it is stand-by；
（4）By 20 mmol L1150 mL of silver nitrate solution is placed in hydrothermal reactor, adds disodiumedetate
Salt 1500mg, stirs under the conditions of black out 10 minutes, afterwards, adds multi-wall carbon nano-tube tube particle 1100mg, continue in black out bar
10 minutes are stirred the mixture under part.Finally, molecular weight is added to be 600g mol-115 mL of Polyethylene Glycol, by hydrothermal reactor
It is heated to 180oC, is kept for 10 hours at this temperature.After reaction terminates, hydrothermal reactor is taken out, room temperature is slowly cooled to
It is lower that reactant mixture is filtered, after being washed to 3 times, it is dried 8 hours in vacuum desiccator at room temperature, the black particle for obtaining
As carbon multi-wall nano tube loaded argentum nano composite material Ag/MWCNT.
（5）100mgAg/MWCNT nano-particle is mixed with 20mL dehydrated alcohol, 5% is added（wt%）Nafion solution 1
The concentrated solution, until forming uniform ink shape concentrated solution, is coated in above-mentioned place by mL, gained mixture supersound process 1 hour
On the rustless steel managed, it is dried under room temperature, obtains negative electrode, it is stand-by；
（6）The anode and negative electrode of above-mentioned preparation are respectively placed in into cellulose acetate sheets piece（Aperture 0.35m, thickness 290m）
Two sides, be assembled into alcohol-hydrogen peroxide fuel battery by accompanying drawing 1.
（7）Fuel cell shown in Fig. 1 is carried out into discharge test.As a result show, be 1 mol L in anolyte-1NaOH+
0.5 mol L-1Methanol, catholyte are 1 mol L-1NaOH+0.1 mol L-1Hydrogen peroxide, 0.51 V of battery open circuit voltage,
30 mW cm of maximum power density-2, corresponding electric current density is 100 mA cm-2。
Embodiment 3：
（1）By 10 mmol L-1150 mL of palladium chloride solution, 10 mmol L-1Nickel chloride solution 20mL and 10 mmol L-115 mL of copper chloride solution is sufficiently stirred for, mixes, and is subsequently added 550 mg disodium EDTAs, mixture is continued to fill
Point stirring 1 hour, afterwards, adds 400 mg multi-wall carbon nano-tube tube particles, stirs the mixture for 1 hour, and then Deca concentration is
20 mmol L-1Sodium hydroxide solution until mixture pH=7-8.In the case where being stirred continuously, concentration is slowly added dropwise for 30%
（wt%）150 mL of sodium borohydride solution, stirring mixture is further continued for after completion of dropping 2 hours, mixture is filtered, gained is solid
Body is washed with water to neutrality, and room temperature in vacuo is dried, and obtains carbon multi-wall nano tube loaded palladium-nickel-copper nano composite material
PdNiCu/MWCNT。
（2）Stainless (steel) wire is 10%（wt%）Sodium carbonate liquor in, in 500Process 30 minutes under C, use pure water rinsing afterwards
It is standby to neutrality.
（3）100 mg PdNiCu/MWCNT nano-particle are mixed with 20 mL dehydrated alcohol, 5% is added（wt%）'s
1 mL of Nafion solution, gained mixture supersound process 1 hour, until uniform ink shape concentrated solution is formed, by the concentrated solution
It is coated on the above-mentioned rustless steel for processing, is dried under room temperature, obtains anode, it is stand-by；
（4）By 20 mmol L1300 mL of silver nitrate solution is placed in hydrothermal reactor, adds disodiumedetate
2250 mg of salt, stirs under the conditions of black out 10 minutes, afterwards, adds 1600 mg of multi-wall carbon nano-tube tube particle, continue in black out
Under the conditions of stir the mixture for 10 minutes.Finally, molecular weight is added to be 600g mol-125 mL of Polyethylene Glycol, by hydro-thermal reaction
Device is heated to 180oC, is kept for 10 hours at this temperature.After reaction terminates, hydrothermal reactor is taken out, room is slowly cooled to
Reactant mixture is filtered under temperature, after being washed to 3 times, be dried 8 hours in vacuum desiccator at room temperature, the black for obtaining
Grain is carbon multi-wall nano tube loaded argentum nano composite material Ag/MWCNT.
（5）100 mg Ag/MWCNT nano-particle are mixed with 20 mL dehydrated alcohol, 5% is added（wt%）Nafion it is molten
1 mL of liquid, gained mixture supersound process 1 hour, until forming uniform ink shape concentrated solution, the concentrated solution are coated in
State on the rustless steel for processing, be dried under room temperature, obtain negative electrode, it is stand-by；
（6）The anode and negative electrode of above-mentioned preparation are respectively placed in into cellulose acetate sheets piece（Aperture 0.35m, thickness 290m）
Two sides, be assembled into alcohol-hydrogen peroxide fuel battery by accompanying drawing 1.
（7）The fuel cell is carried out into discharge test.As a result show, be 1 mol L in anolyte-1NaOH+0.5 mol
L-1Methanol, catholyte are 1 mol L-1NaOH+0.1 mol L-1Hydrogen peroxide, 0.47 V of battery open circuit voltage, peak power
22 mW cm of density-2, corresponding electric current density is 85 mA cm-2。
Embodiment 4：
Step in the present embodiment（1）、（2）、（3）、（4）、（5）With（6）Respectively with embodiment 2 in step（1）、
（2）、（3）、（4）、（5）With（6）It is identical.
（7）Fuel cell shown in Fig. 1 is carried out into discharge test.As a result show, be 1 mol L in anolyte-1NaOH+
0.5 mol L-1Ethanol, catholyte are 1 mol L-1NaOH+0.1 mol L-1Hydrogen peroxide, battery open circuit voltage 0.57V, most
36 mW cm of high power density-2, corresponding electric current density is 95 mA cm-2。
Embodiment 5：
Step in the present embodiment（1）、（2）、（3）、（4）、（5）With（6）Respectively with embodiment 2 in step（1）、
（2）、（3）、（4）、（5）With（6）It is identical.
（7）Fuel cell shown in Fig. 1 is carried out into discharge test.As a result show, be 1molL in anolyte-1
NaOH+0.5 mol L-1Normal propyl alcohol, catholyte are 1 mol L-1NaOH+0.1 mol L-1Hydrogen peroxide, battery are opened
0.56 V of road voltage, 32 mW cm of maximum power density-2, corresponding electric current density is 90 mA cm-2。
Embodiment 6：
Step in the present embodiment（1）、（2）、（3）、（4）、（5）With（6）Respectively with embodiment 2 in step（1）、
（2）、（3）、（4）、（5）With（6）It is identical.
（7）Fuel cell shown in Fig. 1 is carried out into discharge test.As a result show, be 1 mol L in anolyte-1NaOH+
0.5 mol L-1Isopropanol, catholyte are 1 mol L-1NaOH+0.1 mol L-1Hydrogen peroxide, battery open circuit voltage 0.55V,
30 mW cm of maximum power density-2, corresponding electric current density is 78 mA cm-2。
Embodiment 7：
Step in the present embodiment（1）、（2）、（3）、（4）、（5）With（6）Respectively with embodiment 2 in step（1）、
（2）、（3）、（4）、（5）With（6）It is identical.
（7）Fuel cell shown in Fig. 1 is carried out into discharge test.As a result show, be 1 mol L in anolyte-1NaOH+
0.5 mol L-1N-butyl alcohol, catholyte are 1 mol L-1NaOH+0.1 mol L-1Hydrogen peroxide, battery open circuit voltage 0.57V,
30 mW cm of maximum power density-2, corresponding electric current density is 85 mA cm-2。
Embodiment 8：
Step in the present embodiment（1）、（2）、（3）、（4）、（5）With（6）Respectively with embodiment 2 in step（1）、
（2）、（3）、（4）、（5）With（6）It is identical.
（7）Fuel cell shown in Fig. 1 is carried out into discharge test.As a result show, be 1 mol L in anolyte-1NaOH+
0.5 mol L-1Isobutanol, catholyte are 1 mol L-1NaOH+0.1 mol L-1Hydrogen peroxide, battery open circuit voltage 0.55V,
25 mW cm of maximum power density-2, corresponding electric current density is 75 mA cm-2。
Embodiment 9：
Step in the present embodiment（1）、（2）、（3）、（4）、（5）With（6）Respectively with embodiment 2 in step（1）、
（2）、（3）、（4）、（5）With（6）It is identical.
（7）Fuel cell shown in Fig. 1 is carried out into discharge test.As a result show, be 1 mol L in anolyte-1NaOH+
0.5 mol L-1Sec-butyl alcohol, catholyte are 1 mol L-1NaOH+0.1 mol L-1Hydrogen peroxide, battery open circuit voltage 0.54
V, 15 mW cm of maximum power density-2, corresponding electric current density is 50 mA cm-2。
Claims (8)
1. a kind of liquid flow pattern alcohol-hydrogen peroxide fuel battery, it is characterised in that with carbon multi-wall nano tube loaded palladium ambrose alloy nanometer
Granule is pasted onto stainless (steel) wire surface as anode, is pasted onto rustless steel netlist with carbon multi-wall nano tube loaded silver nano-grain
Face is separated with cellulose acetate sheets piece between anode and negative electrode as negative electrode, and anode chamber and cathode chamber are vertically disposed with anode
Liquid import, anolyte outlet and catholyte import and catholyte outlet, inject the anolyte liquid level of anode chamber higher than injection negative electrode
The catholyte liquid level of room.
2. liquid flow pattern alcohol-hydrogen peroxide fuel battery according to claim 1, it is characterised in that the anolyte be containing
The 1mol L of alcohol-1NaOH solution, the alcohol are methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol or sec-butyl alcohol.
3. liquid flow pattern alcohol-hydrogen peroxide fuel battery according to claim 1, it is characterised in that the catholyte be containing
The 1mol L of hydrogen peroxide-1NaOH solution.
4. a kind of manufacture method of liquid flow pattern alcohol-hydrogen peroxide fuel battery, it is characterised in that comprise the following steps：
（1）Palladium chloride solution, nickel chloride solution and copper chloride solution are thoroughly mixed, disodiumedetate is added
Salt, is sufficiently stirred for 1 hour, adds multi-wall carbon nano-tube tube particle, stirs 1 hour, and then Deca sodium hydroxide solution is until mixing
The pH=7-8 of thing, in the case where being stirred continuously, is slowly added dropwise sodium borohydride solution, continues stirring mixture 2 hours after completion of dropping, will
Mixture is filtered, gained solid washed with water to neutrality, and room temperature in vacuo is dried, and obtains carbon multi-wall nano tube loaded palladium ambrose alloy nanometer
Granular materialss；
（2）By stainless (steel) wire in the sodium carbonate liquor of 10wt% 500Process 30 minutes under C, with pure water rinsing to neutral standby
With；
（3）Carbon multi-wall nano tube loaded palladium ambrose alloy nano-particle material is mixed with dehydrated alcohol, concentration 5% is added
Nafion solution, gained mixture supersound process 1 hour, until forming uniform ink shape concentrated solution, the concentrated solution are coated
On the above-mentioned stainless (steel) wire for processing, it is dried under room temperature, obtains anode, it is stand-by；
（4）By 20mmol L-1Silver nitrate solution is placed in hydrothermal reactor, adds disodium EDTA, in black out bar
Stir 10 minutes under part, add multi-wall carbon nano-tube tube particle, continuation that 10 minutes are stirred the mixture under the conditions of black out, Ran Houjia
Enter molecular weight for 600g mol-1Polyethylene Glycol, hydrothermal reactor is heated to into 180oC, is kept for 10 hours at this temperature,
After reaction terminates, hydrothermal reactor is taken out, is slowly cooled under room temperature filter reactant mixture, after being washed to 3 times, in room
It is dried 8 hours in vacuum desiccator under temperature, the black particle for obtaining is compound of carbon multi-wall nano tube loaded silver nanoparticle
Grain material；
（5）Carbon multi-wall nano tube loaded silver nanoparticle composite particulate material is mixed with dehydrated alcohol, concentration 5% is added
Nafion solution, gained mixture supersound process 1 hour, until forming uniform ink shape concentrated solution, the concentrated solution are coated
On the above-mentioned rustless steel for processing, it is dried under room temperature, obtains negative electrode, it is stand-by；
（6）The anode and negative electrode of above-mentioned preparation are respectively placed in into the two sides of cellulose acetate sheets piece, alcohol-hydrogen peroxide is assembled into
Fuel cell.
5. the manufacture method of liquid flow pattern alcohol-hydrogen peroxide fuel battery according to claim 4, it is characterised in that step
（1）In, the multi-walled carbon nano-tubes, palladium chloride solution, nickel chloride solution, copper chloride solution, disodiumedetate
The proportioning of salt is 200 ~ 400 mg: 75 ~ 150 mL : 9 ~ 20mL : 5 ~ 15 mL :350 ~ 550 mg,
The concentration of palladium chloride solution, nickel chloride solution and copper chloride solution is 10 mmol L-1。
6. the manufacture method of liquid flow pattern alcohol-hydrogen peroxide fuel battery according to claim 4, it is characterised in that step
（1）In, the concentration of the sodium hydroxide solution is 20 mmol L-1, the concentration of sodium borohydride solution is 30%, sodium borohydride
The addition of solution is 45 ~ 150 mL.
7. the manufacture method of liquid flow pattern alcohol-hydrogen peroxide fuel battery according to claim 4, it is characterised in that step
（3）With（5）In, the carbon multi-wall nano tube loaded palladium ambrose alloy nano-particle material and carbon multi-wall nano tube loaded silver nanoparticle
Composite particulate material is respectively 100mg, dehydrated alcohol 20mL, 5% 1 mL of Nafion solution.
8. the manufacture method of liquid flow pattern alcohol-hydrogen peroxide fuel battery according to claim 4, it is characterised in that step
（4）In, the silver nitrate solution volume be 100-300mL, disodium EDTA quality be 750-2250mg, many wall carbon
Nanotube quality is 540-1600mg, and the volume of Polyethylene Glycol is 8-25mL.
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