CN105098199B - A kind of gas diffusion layers, preparation method and a kind of metal-air battery - Google Patents
A kind of gas diffusion layers, preparation method and a kind of metal-air battery Download PDFInfo
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- CN105098199B CN105098199B CN201510324569.8A CN201510324569A CN105098199B CN 105098199 B CN105098199 B CN 105098199B CN 201510324569 A CN201510324569 A CN 201510324569A CN 105098199 B CN105098199 B CN 105098199B
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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
- H01M4/8605—Porous electrodes
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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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
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
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Abstract
The present invention provides a kind of gas diffusion layers, it include: conductive porous supporter and hydrophobic layer, the hydrophobic layer is coated on the duct inner wall of the conductive porous supporting body surface and the conductive porous supporter, and the material of the conductive porous supporter is selected from conductivity ceramics.Conductive porous support body material of the present invention using conductivity ceramics as gas diffusion layers, electric conductivity with higher and higher bending strength can be used for preparing high performance metal-air battery with the gas diffusion layers that above-mentioned conductive porous support body material obtains.
Description
Technical field
The invention belongs to field of fuel cell technology, and in particular to a kind of gas diffusion layers and preparation method thereof and a kind of
Metal-air battery.
Background technique
Metal-air battery is generally made of metal anode, electrolyte and air cathode, and wherein the performance of cathode is battery
The core of performance, and the structure of air cathode is generally three-decker, is successively from inside to outside: it is urged with what electrolyte directly contacted
Agent layer provides the gas diffusion layers of reactant oxygen for catalyst layer, and third layer is current collector conductive layer；Wherein gas expands
Scattered layer is the key that cathode, takes into account the generation for preventing electrolyte from flooding reactant gas transport channel or even electrolyte leakage
The danger of battery out, while the function that gas is effectively diffused into catalyst layer is also taken into account, while it is strong to should also have certain machinery
Degree and conductivity come solve the problems, such as air cathode deformation and resistance it is bigger than normal, because entire oxygen reduction reaction occur gas-liquid-solid
Three phase boundary at, so if more efficient, reactant is transferred to interface will be the key that battery performance height.
Generally there are two types of structures for the current air cathode gas diffusion layers (GDL) for preparing metal-air battery.The first is
Carbon dust and hydrophobic bonding agent are configured to slurry, coated in forming gas diffusion layers on nickel screen or copper mesh；Be for second using
The supporter of carbon paper, charcoal felt or graphite felt as electronic conduction network uses polytetrafluoroethylene (PTFE) (PTFE) lotion impregnated carbon felt
Or graphite felt obtains gas diffusion layers.Since copper mesh in the first structure or nickel screen often " climbing liquid " can occur because being used for a long time
Corrosion phenomenon, therefore structure two is more favourable in recent years.
But above two structure has used carbon material as conductive support materials, and the electric conductivity of carbon material is poor, electricity
Conductance is generally less than 2S/cm, which results in using the cathode resistor of carbon material larger, seriously affects battery in high-power high current
Performance under discharge scenario；Furthermore gas diffusion layers limited strength of the carbon material as skeleton, in preparation large area air cathode
Often the case where will appear bending deformation.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of gas diffusion layers and preparation method thereof and
A kind of metal-air battery, gas diffusion layers intensity provided by the invention is high, and has good conductive property.
The present invention provides a kind of gas diffusion layers, comprising:
Conductive porous supporter and hydrophobic layer, the hydrophobic layer are coated on the conductive porous supporting body surface and described lead
The material of the duct inner wall of electric porous supporting body, the conductive porous supporter is selected from conductivity ceramics.
Preferably, the conductivity ceramics is selected from one of Ca-Ti ore type conductivity ceramics and metal based conductive ceramics or more
Kind.
Preferably, the Ca-Ti ore type conductivity ceramics is La1-xSrxCo1-yFeyO3、La1-zSrzMnO3Or Ba1-mSrmCo1- nFenO3, wherein the 0 < x≤0.6,0 n≤0.4 the < < of y≤0.6,0≤z≤0.6,0.2≤m≤0.8,0.
Preferably, the metal based conductive ceramics are Ni based conductive ceramics, Cu based conductive ceramics or Fe based conductive ceramics.
Preferably, the Ni based conductive ceramics are selected from Ni-ZrO2、Ni-Al2O3、Ni-CeO2, Ni- doped aluminium base pottery
Porcelain, Ni- doped zirconia base ceramics, Ni- doped cerium oxide base ceramics, Ni- silicon carbide, Ni- titanium oxide or Ni- titanium carbide；
The Cu based conductive ceramics are selected from Cu-ZrO2、Cu-Al2O3、Cu-CeO2, Cu- doped aluminium base ceramics, Cu- mix
Miscellaneous zirconia-based ceramics, Cu- doped cerium oxide base ceramics, Cu- silicon carbide, Cu- titanium oxide or Cu- titanium carbide；
The Fe based conductive ceramics are selected from Fe-ZrO2、Fe-Al2O3、Fe-CeO2, Fe- doped aluminium base ceramics, Fe- mix
Miscellaneous zirconia-based ceramics, Fe- doped cerium oxide base ceramics, Fe- silicon carbide, Fe- titanium oxide or Fe- titanium carbide.
Preferably, the mass ratio of the conductive porous supporter and hydrophobic layer is 20:1~1:20.
Preferably, the mass ratio of the conductive porous supporter and hydrophobic layer is 8:1~1:5.
Preferably, the material of the hydrophobic layer be selected from polytetrafluoroethylene (PTFE), Kynoar, fluorinated ethylene propylene copolymer,
Perfluoroalkoxy resin and ethylene-tetrafluoroethylene copolymer it is one or more.
Preferably, the material of the conductive porous supporter further includes carbon material, and the carbon material is selected from carbon felt or graphite
Felt.
Preferably, the mass ratio of the carbon material and the conductivity ceramics is 1:10~10:1.
Preferably, the material of the conductive porous supporter also includes non-conductive ceramic.
Preferably, the non-conductive ceramic is selected from aluminium oxide, zirconium oxide, cerium oxide, boron nitride, boron carbide, silicon nitride, carbon
One of SiClx or Nano diamond are a variety of.
Preferably, the mass ratio of the non-conductive ceramic and conductivity ceramics is 1:10~8:1.
Preferably, the average pore size of the conductive porous supporter is 0.05~100 μm.
Preferably, the average pore size of the conductive porous supporter is 0.1~50 μm.
The present invention also provides a kind of preparation methods of gas diffusion layers, comprising the following steps:
Hydrophobic material is coated on to the duct inner wall of conductive porous supporting body surface and conductive porous supporter, drying roasting
It burns, obtains gas diffusion layers, the material of the conductive porous supporter is selected from conductivity ceramics.
Preferably, the preparation method of the conductive porous supporter includes:
A1 Ca-Ti ore type conductivity ceramics biscuit) is obtained into conductive porous supporter through oversintering；
Or
A2), by reduction reaction, conductive porous supporter will be obtained after the sintering of molding composite powder, it is described compound
Material powder is the mixture of metal oxide powder and ceramic powders.
Preferably, the material of the conductive porous supporter further includes one of carbon material and non-conductive ceramic or two
Kind, the carbon material is selected from charcoal felt or graphite felt, and the non-conductive ceramic is selected from aluminium oxide, zirconium oxide or cerium oxide.
Preferably, the preparation method of the conductive porous supporter includes:
B1) molding composite material is sintered, obtains conductive porous supporter, the composite material is led for Ca-Ti ore type
The composite material of electroceramics and carbon material, the carbon material are selected from carbon felt or graphite felt；
Or
B2), by reduction reaction, conductive porous supporter, the composite material will be obtained after molding Composite Sintering
For the composite material of metal oxide powder, ceramic powders and carbon material, the carbon material is selected from carbon felt or graphite felt.
Preferably, the mass ratio of the carbon material and the conductivity ceramics is 1:10~10:1.
Preferably, the Ca-Ti ore type conductivity ceramics is La1-xSrxCo1-yFeyO3、La1-zSrzMnO3Or Ba1-mSrmCo1- nFenO3, wherein the 0 < x≤0.6,0 n≤0.4 the < < of y≤0.6,0≤z≤0.6,0.2≤m≤0.8,0.
Preferably, the metal oxide is oxide, the oxide of Cu or the oxide of Fe of Ni；The ceramic powders
For aluminium oxide, zirconium oxide, cerium oxide, doped aluminium base ceramics, doped zirconia base ceramics, doped cerium oxide base ceramics, carbon
SiClx, titanium oxide or titanium carbide.
Preferably, step A1) described in the temperature of sintering be 900~1200 DEG C, time of sintering is 0.5~6 hour；Step
Rapid A2) described in the temperature of sintering be 900~1500 DEG C, time of sintering is 0.5~6 hour.
Preferably, step B1) described in sintering temperature be 300~1200 DEG C, sintering time be 0.5~10 hour；Step
B2 the temperature of sintering described in) is 900~1400 DEG C, and the time of sintering is 0.5~10 hour.
Preferably, the method for the coating is dipping, spraying or silk-screen printing.
Preferably, the temperature of the roasting is 280~370 DEG C, and the time of the roasting is 5~200 minutes.
The present invention also provides a kind of metal-air batteries, comprising: metal anode, electrolyte and air cathode, the sky
Gas cathode includes with the catalyst layer of the electrolyte contacts, is compound in the above-mentioned gas diffusion layer of the catalyst layer and answers
Together in the current collector layer of the gas diffusion layers.
Compared with prior art, the present invention provides a kind of gas diffusion layers, comprising: conductive porous supporter and hydrophobic
Layer, the hydrophobic layer is coated on the duct inner wall of the conductive porous supporting body surface and the conductive porous supporter, described
The material of conductive porous supporter is selected from conductivity ceramics.Conductive porous support of the present invention using conductivity ceramics as gas diffusion layers
Body material, electric conductivity with higher and higher bending strength, the gas obtained with above-mentioned conductive porous support body material
Diffusion layer can be used for preparing high performance metal-air battery.
The result shows that the conductivity of the porous supporting body in gas diffusion layers provided by the invention is 7~1350S/cm, hole
Gap rate is 24%~44%, and bending strength is 75~280MPa.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph for the conductive porous supporter that embodiment 1 is prepared；
Fig. 2 is magnesium-air cell performance map that embodiment 1 is prepared；
Fig. 3 is the scanning electron microscope (SEM) photograph for the conductive porous supporter of metal-ceramic that embodiment 2 is prepared；
Fig. 4 is magnesium-air cell performance map that embodiment 2 is prepared.
Specific embodiment
Metal-air battery is a kind of fuel cell, comprising: metal anode, electrolyte and air cathode, the air yin
Pole includes that the gas diffusion layers and current collector layer of oxygen are provided with the catalyst layer of the electrolyte contacts, for catalyst layer.
The present invention provides a kind of gas diffusion layers, comprising:
Conductive porous supporter and hydrophobic layer, the hydrophobic layer are coated on the conductive porous supporting body surface and described lead
The material of the duct inner wall of electric porous supporting body, the conductive porous supporter is selected from conductivity ceramics.
In the present invention, the gas diffusion layers include conductive porous supporter, the material of the conductive porous supporter
Selected from conductivity ceramics, it is preferred that the conductivity ceramics is selected from one of Ca-Ti ore type conductivity ceramics and metal based conductive ceramics
Or it is a variety of.
Wherein, the Ca-Ti ore type conductivity ceramics is preferably La1-xSrxCo1-yFeyO3、La1-zSrzMnO3Or Ba1- mSrmCo1-nFenO3, the La1-xSrxCo1-yFeyO3In 0 x≤0.6 <, preferably 0.1≤x≤0.5；0 y≤0.6 <, it is excellent
It is selected as 0.1≤x≤0.5；La1-zSrzMnO3In 0≤z≤0.6, preferably 0.1≤z≤0.5；Ba1-mSrmCo1-nFenO3In
0.2≤m≤0.8, preferably 0.3≤m≤0.7；0 n≤0.4 <, preferably 0≤n≤0.4.The conductivity ceramics is more preferably
La0.75Sr0.25MnO3、La0.5Sr0.5CoO3、Ba0.7Sr0.3Co0.8Fe0.2O3Or La0.6Sr0.4Co0.8Fe0.2O3。
Conductive porous support body material provided by the invention can also be metal based conductive ceramics, the Metal Substrate conduction pottery
Porcelain is Ni based conductive ceramics, Cu based conductive ceramics or Fe based conductive ceramics.The Ni based conductive ceramics are preferably Ni-ZrO2、Ni-
Al2O3、Ni-CeO2, Ni- doped aluminium base ceramics, Ni- doped zirconia base ceramics, Ni- doped cerium oxide base ceramics, Ni-
Silicon carbide, Ni- titanium oxide or Ni- titanium carbide；The Cu based conductive ceramics are preferably Cu-ZrO2、Cu-Al2O3、Cu-CeO2、Cu-
Doped aluminium base ceramics, Cu- doped zirconia base ceramics, Cu- doped cerium oxide base ceramics, Cu- silicon carbide, Cu- titanium oxide
Or Cu- titanium carbide；The Fe based conductive ceramics are preferably Fe-ZrO2、Fe-Al2O3、Fe-CeO2, Fe- doped aluminium base pottery
Porcelain, Fe- doped zirconia base ceramics, Fe- doped cerium oxide base ceramics, Fe- silicon carbide, Fe- titanium oxide or Fe- titanium carbide.Institute
Stating doped aluminium base ceramics is doped ceramics material in aluminium oxide, and the ceramic material is preferably silica；The doping oxygen
Changing zirconia-based ceramic is doped ceramics material in zirconium oxide, and the ceramic material is preferably ytterbium oxide, yttrium oxide or calcium oxide；It is described
Doped cerium oxide base ceramics are doped ceramics material in cerium oxide, and the ceramic material is preferably gadolinium oxide or zirconium oxide.It is described
Ceramic on metal is more preferably Ni-ZrO2、Ni-Al2O3、Ni-CeO2、Ni-CZ、Ni-YSZ、Ni-GDC、Cu-ZrO2、Cu-
Al2O3、Cu-CeO2, Cu-YSZ, Cu-GDC, wherein the YSZ be Y2O3Adulterate ZrO2, the GDC is Gd2O3Adulterate CeO2, institute
State Y2O3Adulterate ZrO2In, Y2O3Doping be 0mol%~8mol%, preferably 2mol%~6mol%；The Gd2O3It mixes
Miscellaneous CeO2In, Gd2O3Doping be 5mol%~50mol%, preferably 20mol%~30mol%, the CZ be cerium oxide
Doped zirconia, the doping of the zirconium oxide are 1~50mol%, preferably 4~45mol%.
In the present invention, the material of the conductive porous supporter can also include carbon material, and the carbon material is selected from carbon
Felt or graphite felt.Wherein, the mass ratio of the carbon material and the conductivity ceramics is 1:10~10:1.Preferred embodiment 1:3~3:
1。。
The material of the conductive porous supporter also includes non-conductive ceramic, type of the present invention to the non-conductive ceramic
Not specifically limited, well known to a person skilled in the art the non-conductive ceramic material that can play the role of support frame,
In the present invention, the non-conductive ceramic is preferably aluminium oxide, zirconium oxide, cerium oxide, boron nitride, boron carbide, silicon nitride, silicon carbide
Or one of Nano diamond or a variety of.More preferably aluminium oxide, zirconium oxide, boron nitride, boron carbide or Nano diamond.Institute
The mass ratio for stating non-conductive ceramic and the conductivity ceramics is 1:10~8:1, preferably 1:5~5:1.
Gas diffusion layers provided by the invention further include being coated on the conductive porous supporting body surface and the conduction is more
The material of the hydrophobic layer of the duct inner wall of hole supporter, the hydrophobic layer is selected from polytetrafluoroethylene (PTFE), Kynoar, perfluoroethylene
Propylene copolymer, perfluoroalkoxy resin and ethylene-tetrafluoroethylene copolymer it is one or more.
In the present invention, the mass ratio of the conductive porous supporter and hydrophobic layer be 20:1~1:20, preferably 8:1~
1:5。
Conductive porous support body material of the present invention has porous structure, wherein the conductive porous support body material
Average pore size be 0.05 μm~100 μm, preferably 0.1 μm~50 μm, more preferably less than 0.3 μm~10 μm, more preferably less than 0.5
μm~5 μm, further preferred 1 μm~3 μm.
The present invention provides additionally provide a kind of preparation method of gas diffusion layers, comprising the following steps:
Hydrophobic material is coated on to porous supporting body material surface and duct inner wall according to a certain percentage, drying roasting obtains
To gas diffusion layers, the porous supporting body material is the one or more of ceramic on metal, conductivity ceramics and other ceramics, also
But the compound support of ceramics and charcoal felt or graphite felt.
In the present invention, the electronic conduction porous supporting body material is prepared as follows:
A1 Ca-Ti ore type conductivity ceramics biscuit) is obtained into conductive porous supporter through oversintering；
Or
A2), by reduction reaction, conductive porous supporter will be obtained after the sintering of molding composite powder, it is described compound
Material powder is the mixture of metal oxide powder and ceramic powders.
In the present invention, when the conductive porous support body material is Ca-Ti ore type conductivity ceramics, as follows
It is prepared:
By Ca-Ti ore type conductivity ceramics biscuit by drying sintering, conductive porous supporter is obtained.
Wherein, the Ca-Ti ore type conductivity ceramics is preferably La1-xSrxCo1-yFeyO3、La1-zSrzMnO3Or Ba1- mSrmCo1-nFenO3, the La1-xSrxCo1-yFeyO3In 0 x≤0.6 <, preferably 0.1≤x≤0.5；0 y≤0.6 <, it is excellent
It is selected as 0.1≤x≤0.5；La1-zSrzMnO3In 0≤z≤0.6, preferably 0.1≤z≤0.5；Ba1-mSrmCo1-nFenO3In
0.2≤m≤0.8, preferably 0.3≤m≤0.7；0 n≤0.4 <, preferably 0≤n≤0.4.
The Ca-Ti ore type conductivity ceramics is more preferably La0.75Sr0.25MnO3、La0.5Sr0.5CoO3、
Ba0.7Sr0.3Co0.8Fe0.2O3Or La0.6Sr0.4Co0.8Fe0.2O3。
The present invention first forms the Ca-Ti ore type conductivity ceramics raw material powder, that is, the Ca-Ti ore type conduction is made pottery
Porcelain raw material powder is prepared into conductive porous supporter shape.The present invention to the molding mode there is no specifically limited, preferably
, the conductivity ceramics raw material powder is pressed into the shape of conductive support by the molding mode of curtain coating, tabletting or static pressure.
The curtain coating method particularly includes: configuration solid content is that 30wt%~80wt% is cast ceramic material powder slurry,
Certain target thickness biscuit 0.25~2.5mm of band is made through casting machine, Ca-Ti ore type conductivity ceramics biscuit is obtained, through burning
The support body material of 0.2~2mm of certain thickness is obtained after knot.
In the pressed disc method, the pressure is 2~50Mpa, and preferably 5~40MPa, the dwell time is 0.5~20 minute,
Preferably 1~15 minute.
In the isostatic pressing method, the temperature is 20~90 DEG C, preferably 30~80 DEG C；Pressure 1Mpa~40Mpa, preferably
For 5~35Mpa；Dwell time 1~40 minute, preferably 5~35 minutes.
Molding Ca-Ti ore type conductivity ceramics biscuit is sintered, conductive porous support body material is obtained.The temperature of the sintering
Degree is 900~1200 DEG C, preferably 1000~1100 DEG C；The time of sintering is 0.5~6 hour, preferably 1~5 hour.
When the porous supporting body material is metal based conductive ceramics, it is prepared as follows:
It will be restored after the sintering of molding composite powder, obtain conductive porous support body material, the conductive porous branch
Support material is metal based conductive ceramics, and the composite powder is the mixed of metal oxide powder and oxide ceramic powder
Close object；
In the present invention, using composite powder as raw material, the composite powder is metal oxide powder and pottery
The mixture of porcelain powder.Wherein, the mass ratio of the metal oxide powder and ceramic powders is (0.1~0.6): 1, preferably
(0.35~0.55): 1.The metal oxide powder is oxide, the oxide of Cu or the oxide of Fe of Ni, preferably
NiO or CuO；The ceramic powders are aluminium oxide, zirconium oxide, cerium oxide, doped aluminium base ceramics, doped zirconia base pottery
Porcelain, doped cerium oxide base ceramics, silicon carbide, titanium oxide or titanium carbide.The doped aluminium base ceramics are to adulterate in aluminium oxide
Ceramic material, the ceramic material are preferably silica；The doped zirconia base ceramics are doped ceramics material in zirconium oxide,
The ceramic material is preferably ytterbium oxide, yttrium oxide or calcium oxide；The doped cerium oxide base ceramics are that pottery is adulterated in cerium oxide
Ceramic material, the ceramic material are preferably gadolinium oxide or zirconium oxide.The composite powder is preferably NiO-ZrO2、NiO-
Al2O3、NiO-CeO2、NiO-CZ、NiO-YSZ、NiO-GDC、CuO-ZrO2、CuO-Al2O3、CuO-CeO2、CuO-YSZ、CuO-
GDC, wherein the YSZ is Y2O3Adulterate ZrO2, the GDC is Gd2O3Adulterate CeO2, the Y2O3Adulterate ZrO2In, Y2O3Mix
Miscellaneous amount is 0mol%~8mol%, preferably 2mol%~6mol%；The Gd2O3Adulterate CeO2In, Gd2O3Doping be
5mol%~50mol%, preferably 20mol%~30mol%, the CZ are cerium oxide-doped zirconium oxide, the zirconium oxide
Doping is 1mol%~50mol%, preferably 4mol%~45mol%.
The present invention first forms the composite powder, that is, the composite powder is prepared into conductive supporting
External shape.There is no specifically limited to the molding mode by the present invention, it is preferred that passes through the molding of curtain coating, tabletting or static pressure
The composite powder is pressed into the shape of conductive support by mode.Wherein, the molding side of the curtain coating, tabletting or static pressure
Formula is identical as the molding mode of above-mentioned Ca-Ti ore type conductivity ceramics biscuit, and details are not described herein.
After the sintering of molding composite powder, reduction reaction is carried out, conductive porous support body material is obtained.The burning
The temperature of knot is 900~1500 DEG C, preferably 1000~1400 DEG C；The time of sintering is 0.5~6 hour, and preferably 1~5 is small
When.Sintered molding composite powder is subjected to reduction reaction, specifically: by the sintered molding composite wood
Feed powder end is placed in reducibility gas, is restored 0.5~24 hour under conditions of 350 DEG C~1000 DEG C.In the present invention, described
Reducibility gas is preferably the mixed gas of hydrogen or hydrogen and inert gas.
The material of conductive porous supporter provided by the invention can also include carbon material, the carbon material be selected from charcoal felt or
Graphite felt.The i.e. described conductive porous support body material is the composite material of conductivity ceramics and carbon material.The carbon material with it is described
The mass ratio of conductivity ceramics is 0:1~2:1, preferably 0.5:1~1.5:1.
When the material of the conductive porous supporter includes carbon material, the preparation method packet of the conductive porous supporter
Contain:
B1) molding composite material is sintered, obtains conductive porous supporter, the composite material is led for Ca-Ti ore type
The composite material of electroceramics and carbon material, the carbon material are selected from carbon felt or graphite felt；
Or
B2), by reduction reaction, conductive porous supporter, the composite material will be obtained after molding Composite Sintering
For the composite material of metal oxide powder, ceramic powders and carbon material, the carbon material is selected from carbon felt or graphite felt.
When the material of the conductive porous supporter is the composite material of Ca-Ti ore type conductivity ceramics and carbon material, according to
It is prepared by following method:
Molding composite material is sintered, conductive porous supporter is obtained, the composite material is that Ca-Ti ore type is conductive
The composite material of ceramics and carbon material, the carbon material are selected from carbon felt or graphite felt.
The present invention is first by the composite molding, that is, first prepares Ca-Ti ore type conductivity ceramics biscuit, the present invention is to institute
To state the molding mode of Ca-Ti ore type conductivity ceramics biscuit there is no specifically limited, it is preferred that by curtain coating, tabletting or static pressure at
Type mode is by the conductivity ceramics raw material powder compression moulding.
Wherein, the molding side of the molding mode of the curtain coating, tabletting or static pressure and above-mentioned Ca-Ti ore type conductivity ceramics biscuit
Formula is identical, and details are not described herein.
After obtaining Ca-Ti ore type conductivity ceramics biscuit, carbon material is carried out by way of pressing or pasting with conductivity ceramics
It is compound, composite material is prepared.There is no specifically limited, those skilled in the art for mode of the present invention to the pressing or stickup
The well known pressing of member or bonding method.
In the composite material, the mass ratio of carbon material and Ca-Ti ore type conductivity ceramics is 1:10~10:1, preferably 1:3
~3:1.
In the present invention, the Ca-Ti ore type conductivity ceramics is preferably La1-xSrxCo1-yFeyO3、La1-zSrzMnO3Or Ba1- mSrmCo1-nFenO3, the La1-xSrxCo1-yFeyO3In 0 x≤0.6 <, preferably 0.1≤x≤0.5；0 y≤0.6 <, it is excellent
It is selected as 0.1≤x≤0.5；La1-zSrzMnO3In 0≤z≤0.6, preferably 0.1≤z≤0.5；Ba1-mSrmCo1-nFenO3In
0.2≤m≤0.8, preferably 0.3≤m≤0.7；0 n≤0.4 <, preferably 0≤n≤0.4.
The Ca-Ti ore type conductivity ceramics is more preferably La0.75Sr0.25MnO3、La0.5Sr0.5CoO3、
Ba0.7Sr0.3Co0.8Fe0.2O3Or La0.6Sr0.4Co0.8Fe0.2O3。
By molding Composite Sintering, conductive porous support body material is obtained.The temperature of the sintering is 300~1200
DEG C, preferably 500~1100 DEG C；The time of sintering is 0.5~6 hour, preferably 1~5 hour.
When the material of the conductive porous supporter is the composite material of metal based conductive ceramics and carbon material, according to such as
It is prepared by lower method:
, by reduction reaction, conductive porous supporter will be obtained, the composite material is after molding Composite Sintering
The composite material of metal oxide powder, ceramic powders and carbon material, the carbon material are selected from carbon felt or graphite felt.
In the present invention, using composite material as raw material, the composite material is metal oxide powder, ceramic powders and carbon
The composite material of material.Wherein, the mass ratio of the metal oxide powder, the quality summation of ceramic powders and carbon material is 1:
10~10:1, preferably 1:3~3:1.
The metal oxide powder is oxide, the oxide of Cu or the oxide of Fe of Ni, preferably NiO or CuO；
The ceramic powders are aluminium oxide, zirconium oxide, cerium oxide, doped aluminium base ceramics, doped zirconia base ceramics, doping oxidation
Cerium based ceramic, silicon carbide, titanium oxide or titanium carbide.The doped aluminium base ceramics are doped ceramics material in aluminium oxide, institute
Stating ceramic material is preferably silica；The doped zirconia base ceramics are doped ceramics material in zirconium oxide, the ceramics material
Material is preferably ytterbium oxide, yttrium oxide or calcium oxide；The doped cerium oxide base ceramics are doped ceramics material in cerium oxide, described
Ceramic material is preferably gadolinium oxide or zirconium oxide.The composite powder is preferably NiO-ZrO2、NiO-Al2O3、NiO-
CeO2、NiO-CZ、NiO-YSZ、NiO-GDC、CuO-ZrO2、CuO-Al2O3、CuO-CeO2, CuO-YSZ, CuO-GDC, wherein institute
Stating YSZ is Y2O3Adulterate ZrO2, the GDC is Gd2O3Adulterate CeO2, the Y2O3Adulterate ZrO2In, Y2O3Doping be
0mol%~8mol%, preferably 2mol%~6mol%；The Gd2O3Adulterate CeO2In, Gd2O3Doping be 5mol%~
50mol%, preferably 20mol%~30mol%, the CZ are cerium oxide-doped zirconium oxide, and the doping of the zirconium oxide is
1mol%~50mol%, preferably 4mol%~45mol%.
The present invention is first by the composite molding, that is, first by the mixture of metal oxide powder and ceramic powders
Molding, there is no specifically limited to the molding mode by the present invention, it is preferred that passes through the molding side of curtain coating, tabletting or static pressure
Formula is by the conductivity ceramics raw material powder compression moulding.
Wherein, the molding side of the molding mode of the curtain coating, tabletting or static pressure and above-mentioned Ca-Ti ore type conductivity ceramics biscuit
Formula is identical, and details are not described herein.
After obtaining molding material, carbon material is subjected to compound, system by way of pressing or pasting with molding material
It is standby to obtain composite material.The present invention to the mode of the pressing or stickup there is no specifically limited, it is well known to those skilled in the art
Pressing or bonding method.
After the sintering of molding composite powder, reduction reaction is carried out, conductive porous support body material is obtained.The burning
The temperature of knot is 900~1500 DEG C, preferably 1000~1400 DEG C；The time of sintering is 0.5~6 hour, and preferably 1~5 is small
When.Sintered molding composite material is subjected to reduction reaction, specifically: the sintered molding composite material is set
In reducibility gas, restored 0.5~24 hour under conditions of 350 DEG C~1000 DEG C.In the present invention, the reproducibility gas
Body is preferably the mixed gas of hydrogen or hydrogen and inert gas.
Hydrophobic material is coated on conductive porous support body material surface and duct inner wall by the present invention, and drying roasting obtains
Gas diffusion layers.Wherein, the conductive porous support body material is Ca-Ti ore type conductivity ceramics or metal based conductive ceramics, may be used also
To include non-conductive ceramic material and/or carbon material.
The hydrophobic material is selected from polytetrafluoroethylene (PTFE), Kynoar, fluorinated ethylene propylene copolymer, perfluoro alkoxy tree
Rouge and ethylene-tetrafluoroethylene copolymer it is one or more.The mass concentration of the hydrophobic material is 10wt%~60wt%, excellent
It is selected as 15wt%~55wt%.
In the present invention, the mass ratio of the conductive porous supporter and hydrophobic material is 20:1~1:20, preferably 8:1
~1:5.
The method of coating of the present invention preferably impregnate, spraying or silk-screen printing, the present invention to it is described dipping, spraying or
The method of silk-screen printing is there is no specifically limited, and well known to a person skilled in the art dipping, spraying or silk-screen printings.
The conductive porous support body material for being coated with hydrophobic material is subjected to drying roasting, obtains gas diffusion layers.Specifically
, after the porous supporting body material for being coated with hydrophobic material lotion is dried 0.5~4 hour at 20~60 DEG C, then 50~
After being dried 0.5~4 hour at 120 DEG C, through roasting 5~200 minutes acquisition porous gas diffusion layers at 280~370 DEG C.
After roasting, gas diffusion layers are obtained, which can be used for preparing high performance metal-air battery.
The present invention also provides a kind of metal-air batteries, comprising: metal anode, electrolyte and air cathode, the sky
Gas cathode includes with the catalyst layer of the electrolyte contacts, is compound in the above-mentioned gas diffusion layer of the catalyst layer and answers
Together in the current collector layer of the gas diffusion layers.Wherein, the metal-air battery is preferably magnesium-air cell or aluminium-air electricity
Pond.
The present invention using ceramic on metal or conductivity ceramics as the conductive porous support body material of gas diffusion layers, have compared with
High electron conduction, controlled porosity simultaneously have higher bending strength, are expanded with the gas that above-mentioned porous supporting body material obtains
Scattered layer can be used for preparing high performance metal-air battery.
The result shows that the conductivity of the conductive support in gas diffusion layers provided by the invention is 7~1350S/cm, hole
Gap rate is 24%~44%, and bending strength is 75~280MPa.
For a further understanding of the present invention, below with reference to embodiment to gas diffusion layers provided by the invention and its preparation side
Method and a kind of metal-air battery are illustrated, and protection scope of the present invention is not limited by the following examples.
The porous La of embodiment 10.75Sr0.25MnO3Conductivity ceramics porous supporting body prepares the metal-air electricity of gas diffusion layers
Pond
With 200 grams of La0.75Sr0.25MnO3Powder obtains for the pressure maintaining of 20MPa pressure 5 minutes at room temperature as raw material, by powder
It must be pressed into certain thickness biscuit sample, sample is roasted 4 hours at 1100 DEG C and obtained with a thickness of the conductive porous support of 1mm
Body.
The conductive porous supporter being prepared is subjected to electronic scanner microscope detection, the result is shown in Figure 1.It is real by Fig. 1
Apply the scanning electron microscope (SEM) photograph for the conductive porous supporter that example 1 is prepared.As shown in Figure 1, conductive support is prepared in embodiment 1
For porous structure.
By above-mentioned conductive porous supporter through four electrode test conductivity be 10S/cm, measure hole through Archimedes's drainage
Gap rate is 33%, is 80MPa through three-point bending resistance test bending strength.
The porous, electrically conductive supporter is impregnated in the PTFE emulsion of 60wt% again, is dried, is roasted 1 hour at 350 DEG C
The porous gas diffusion layer that PTFE content is 20 grams is obtained, average pore size is 20 μm.
Then in above-mentioned porous gas diffusion layer surface screen-printed 6mg/cm2Cathod catalyst obtain air cathode,
The cathod catalyst includes 40wt%MnO2With 60wt% conductive carbon black, using 10wt%NaCl aqueous solution as electrolyte, magnesium
Magnesium-air cell is made as cathode in alloy, measures the performance of the magnesium-air cell, as a result as shown in Fig. 2, Fig. 2 is to implement
Magnesium-air cell performance map that example 1 is prepared.As shown in Figure 2, the magnesium-air cell maximum power density may be up to
85mW/cm2。
Again with above-mentioned porous gas diffusion layer surface screen-printed 6mg/cm2Cathod catalyst obtain air cathode, institute
Stating cathod catalyst includes 40wt%MnO2It is different using different electrolyte aqueous solutions as electrolyte with 60wt% conductive carbon black
Metal-air battery is made as cathode in alloy, measures the performance of different batteries, concrete outcome is shown in Table 1.
The performance of the different classes of metal-air battery of table 1
| Battery type | Electrolyte | Anode material | Maximum power density |
| Magnesium-air cell | 10% sodium-chloride water solution | Magnesium alloy | 85mW/cm2 |
| Aluminium-air cell | 6mol/L potassium hydroxide | Aluminium alloy | 175mW/cm2 |
| Zinc-air battery | 4mol/L sodium hydroxide | Kirsite | 98mW/cm2 |
The porous Ni-3YSZ metal-ceramic porous supporting body of embodiment 2 prepares the metal-air battery of gas diffusion layers
Powder is configured to casting slurry, and be cast as raw material for 10 grams of NiO and 3YSZ powder of 1:1 using mass ratio
At certain thickness biscuit sample, sample is roasted to the composite ceramics support obtained for 4 hours with a thickness of 0.4mm at 1300 DEG C
Body, 500 DEG C of reduction obtain porous Ni-3YSZ metal-ceramic conductive supporting in 10 hours under pure hydrogen atmosphere by the supporter
Body.
The metal-ceramic conductive support being prepared is subjected to electronic scanner microscope detection, as a result sees Fig. 3.By Fig. 3
For the scanning electron microscope (SEM) photograph for the metal-ceramic conductive support that embodiment 2 is prepared.From the figure 3, it may be seen that its show it is uniform more
Permeability.
By the metal-ceramic conductive support through four electrode test conductivity be 1200S/cm, drained through Archimedes
It is 27% that method, which measures porosity, is 200MPa through three-point bending resistance test bending strength.
The metal-ceramic conductive support is impregnated in the PTFE emulsion of 60wt% again, is dried, roasts 1 at 330 DEG C
Hour obtains the gas diffusion layers that PTFE content is 200 grams, and average pore size is 1 μm.
Then in the surface screen-printed 3mg/cm of the gas diffusion layers2Cathod catalyst obtain air cathode, institute
Stating cathod catalyst includes 40wt%MnO2With 60wt% conductive carbon black, using 10wt%NaCl aqueous solution as electrolyte, magnesium is closed
Magnesium-air cell is made as cathode in gold, measures the performance of the magnesium-air cell, as a result as shown in figure 4, Fig. 4 is embodiment
2 magnesium-air cell the performance maps being prepared.As shown in Figure 4, the magnesium-air cell maximum power density may be up to 86mW/
cm2。
Again with the surface screen-printed 3mg/cm of above-mentioned porous gas diffusion layer2Cathod catalyst obtain air cathode,
The cathod catalyst includes 40wt%MnO2With 60wt% conductive carbon black, using different electrolyte aqueous solutions as electrolyte, no
Metal-air battery is made as cathode with alloy, measures the performance of different batteries, concrete outcome is shown in Table 2.
The performance of the different classes of metal-air battery of table 2
| Battery type | Electrolyte | Anode material | Maximum power density |
| Magnesium-air cell | 10% sodium-chloride water solution | Magnesium alloy | 86mW/cm2 |
| Aluminium-air cell | 4mol/L sodium hydroxide | Aluminium alloy | 154mW/cm2 |
| Zinc-air battery | 6mol/L potassium hydroxide | Kirsite | 106mW/cm2 |
The porous La of embodiment 30.5Sr0.5CoO3Conductivity ceramics porous supporting body prepares the metal-air battery of gas diffusion layers
With 80 grams of La0.6Sr0.4CoO3Powder is as raw material, by powder in the warm isostatic pressing machine that temperature is 80 DEG C
Acquisition in the pressure maintaining of 10MPa pressure 5 minutes is pressed into certain thickness biscuit sample, sample is roasted 2 hours at 1050 DEG C and is obtained
With a thickness of the conductive porous supporter of 0.3mm.
By the conductive support through four electrode test conductivity be 15S/cm, measure porosity through Archimedes's drainage
It is 44%, is 75MPa through three-point bending resistance test bending strength.
The conductive porous supporter is impregnated in 30wt%PVDF lotion again, is dried, roasts 1 hour and obtains at 320 DEG C
The porous gas diffusion layer that PVDF content is 10 grams is obtained, average pore size is 100 μm.
Then silk-screen printing 5mg/cm is carried out on the porous gas diffusion layer surface again2Cathod catalyst obtain air
Cathode, the cathod catalyst include 40wt%MnO2With 60wt% conductive carbon black, using different electrolyte aqueous solutions as electrolysis
Liquid, different-alloy are made metal-air battery as cathode, measure the performance of different batteries, concrete outcome is shown in Table 3.
The performance of the different classes of metal-air battery of table 3
| Battery type | Electrolyte | Anode material | Maximum power density |
| Magnesium-air cell | 5% sodium-chloride water solution | Magnesium alloy | 65mW/cm2 |
| Aluminium-air cell | 4mol/L potassium hydroxide | Aluminium alloy | 135mW/cm2 |
| Zinc-air battery | 6mol/L sodium hydroxide | Kirsite | 98mW/cm2 |
The porous Ba of embodiment 40.7Sr0.3Co0.8Fe0.2O3Conductivity ceramics supporter prepares the metal-air electricity of gas diffusion layers
Pond
With 10 grams of Ba0.7Sr0.3Co0.8Fe0.2O3Powder in room temperature tablet press machine pressure is 30MPa as raw material by powder
Acquisition in pressure maintaining 2 minutes is pressed into certain thickness biscuit sample, sample is roasted at 1200 DEG C 1 hour obtain with a thickness of
The conductive porous supporter of 0.8mm.
By the conductive porous supporter through four electrode test conductivity be 20S/cm, measure hole through Archimedes's drainage
Gap rate is 24%, is 100MPa through three-point bending resistance test bending strength.
The conductive porous supporter is impregnated in 50wt%ECTE lotion again, is dried, roasts 8 hours and obtains at 340 DEG C
The porous gas diffusion layer that ECTE content is 50 grams is obtained, average pore size is 0.05 μm.
Then again in the gas diffusion layers surface screen-printed 2mg/cm2Cathod catalyst obtain air cathode, institute
Stating cathod catalyst includes 40wt%MnO2It is different using different electrolyte aqueous solutions as electrolyte with 60wt% conductive carbon black
Metal-air battery is made as cathode in alloy, measures the performance of different batteries, concrete outcome is shown in Table 4.
The performance of the different classes of metal-air battery of table 4
| Battery type | Electrolyte | Anode material | Maximum power density |
| Magnesium-air cell | 10% sodium-chloride water solution | Magnesium alloy | 95mW/cm2 |
| Aluminium-air cell | 4mol/L potassium hydroxide | Aluminium alloy | 131mW/cm2 |
| Zinc-air battery | 4mol/L sodium hydroxide | Kirsite | 88mW/cm2 |
The porous La of embodiment 50.6Sr0.4Co0.8Fe0.2O3Conductivity ceramics supporter prepares the metal-air electricity of gas diffusion layers
Pond
With 50 grams of La0.6Sr0.4Co0.8Fe0.2O3Powder is as raw material, the warm isostatic pressing machine for being 50 DEG C in temperature by powder
Acquisition the in middle pressure maintaining of 30MPa pressure 15 minutes is pressed into certain thickness biscuit sample, and sample is roasted 2 hours at 1150 DEG C and is obtained
It obtains with a thickness of the conductive porous supporter of 0.9mm.
By the conductive porous supporter through four electrode test conductivity be 9S/cm, measure hole through Archimedes's drainage
Gap rate is 38%, is 87MPa through three-point bending resistance test bending strength.
The conductive porous supporter is impregnated in 55wt%PTFE lotion again, is dried, is roasted 1 hour at 355 DEG C
The porous gas diffusion layer that PTFE content is 50 grams is obtained, average pore size is 0.1 μm.
Then again in the porous gas diffusion layer surface screen-printed 4mg/cm2Cathod catalyst obtain air yin
Pole, the cathod catalyst include 40wt%MnO2With 60wt% conductive carbon black, using different electrolyte aqueous solutions as electrolyte,
Metal-air battery is made as cathode in different-alloy, measures the performance of different batteries, concrete outcome is shown in Table 5.
The performance of the different classes of metal-air battery of table 5
| Battery type | Electrolyte | Anode material | Maximum power density |
| Magnesium-air cell | 10% sodium-chloride water solution | Magnesium alloy | 98mW/cm2 |
| Aluminium-air cell | 3mol/L potassium hydroxide | Aluminium alloy | 136mW/cm2 |
| Zinc-air battery | 5mol/L sodium hydroxide | Kirsite | 106mW/cm2 |
The porous Ni-Al of embodiment 62O3Metal-ceramic supporter prepares the metal-air battery of gas diffusion layers
It is the NiO and Al of 1:2 with mass ratio2O350 grams of powder are used as raw material, powder are configured to casting slurry, and be cast
At certain thickness biscuit sample, sample is roasted to the composite ceramics support obtained for 2 hours with a thickness of 1.8mm at 1450 DEG C
Body, 500 DEG C of reduction obtain porous Ni-Al in 10 hours under 10% hydrogen-argon-mixed atmosphere by the supporter2O3Metal-pottery
Porcelain conductive support.
By the metal-ceramic conductive support through four electrode test conductivity be 900S/cm, through Archimedes's drainage
Measuring porosity is 25%, is 280MPa through three-point bending resistance test bending strength.
Metal-ceramic conductive support is impregnated in 55wt%PTFE lotion again, is dried, it is small that 0.5 is roasted at 345 DEG C
When to obtain PTFE content be 50 grams of porous gas diffusion layer, average pore size is 5 μm.
Then again in the porous gas diffusion layer surface screen-printed 2mg/cm2Cathod catalyst obtain air yin
Pole, the cathod catalyst include 40wt%MnO2With 60wt% conductive carbon black, using different electrolyte aqueous solutions as electrolyte,
Metal-air battery is made as cathode in different-alloy, measures the performance of different batteries, concrete outcome is shown in Table 6.
The performance of the different classes of metal-air battery of table 6
| Battery type | Electrolyte | Anode material | Maximum power density |
| Magnesium-air cell | 10% sodium-chloride water solution | Magnesium alloy | 75mW/cm2 |
| Aluminium-air cell | 5mol/L potassium hydroxide | Aluminium alloy | 178mW/cm2 |
| Zinc-air battery | 3mol/L sodium hydroxide | Kirsite | 102mW/cm2 |
The metal-ceramic supporter of the porous Ni- doped cerium oxide of embodiment 7 prepares the metal-air battery of gas diffusion layers
It is 30 grams of the ceria oxide powder (CZ25) of the NiO of 2:3 and doping 25mol% zirconium oxide as raw material using mass ratio,
Powder is configured to casting slurry, and is cast into certain thickness biscuit sample, sample is roasted 4 hours at 1200 DEG C and is obtained
With a thickness of the composite ceramics supporter of 1.2mm, by the supporter, 340 DEG C of reductase 12 hours obtain porous Ni- under pure hydrogen atmosphere
CZ25 metal-ceramic conductive support.
By the metal-ceramic conductive support through four electrode test conductivity be 850S/cm, through Archimedes's drainage
Measuring porosity is 31%, is 150MPa through three-point bending resistance test bending strength.
The conductive support is impregnated in 15wt%PTFE lotion again, is dried, roasts 1 hour and obtains at 320 DEG C
The porous gas diffusion layer that PTFE content is 15 grams, average pore size are 4 μm.
Then again in the porous gas diffusion layer surface screen-printed 5mg/cm2Cathod catalyst obtain air yin
Pole, the cathod catalyst include 40wt%MnO2With 60wt% conductive carbon black, using different electrolyte aqueous solutions as electrolyte,
Metal-air battery is made as cathode in different-alloy, measures the performance of different batteries, concrete outcome is shown in Table 7.
The performance of the different classes of metal-air battery of table 7
| Battery type | Electrolyte | Anode material | Maximum power density |
| Magnesium-air cell | 10% sodium-chloride water solution | Magnesium alloy | 69mW/cm2 |
| Aluminium-air cell | 6mol/L potassium hydroxide | Aluminium alloy | 188mW/cm2 |
| Zinc-air battery | 5mol/L sodium hydroxide | Kirsite | 122mW/cm2 |
8 porous C u-5YSZ metal-ceramic supporter of embodiment prepares the metal-air battery of gas diffusion layers
Powder is configured to casting slurry, and be cast as raw material for 40 grams of CuO and 5YSZ powder of 3:4 using mass ratio
At certain thickness biscuit sample, sample is roasted to the composite ceramics support obtained for 3 hours with a thickness of 0.6mm at 1250 DEG C
Body, by the supporter under pure hydrogen atmosphere 380 DEG C of reduction, 7 hours acquisition porous C u-5YSZ metal-ceramic conductive supportings
Body.
By the conductive support through four electrode test conductivity be 1350S/cm, measure hole through Archimedes's drainage
Rate is 37%, is 140MPa through three-point bending resistance test bending strength.
The conductive support is impregnated in 45wt%PTFE lotion again, is dried, roasts 0.5 hour and obtains at 360 DEG C
The porous gas diffusion layer that PTFE content is 80 grams, average pore size are 2 μm.
Then again in the gas diffusion layers surface screen-printed 4mg/cm2Cathod catalyst obtain air cathode, institute
Stating cathod catalyst includes 40wt%MnO2It is different using different electrolyte aqueous solutions as electrolyte with 60wt% conductive carbon black
Metal-air battery is made as cathode in alloy, measures the performance of different batteries, concrete outcome is shown in Table 8.
The performance of the different classes of metal-air battery of table 8
| Battery type | Electrolyte | Anode material | Maximum power density |
| Magnesium-air cell | 10% sodium-chloride water solution | Magnesium alloy | 66mW/cm2 |
| Aluminium-air cell | 6mol/L potassium hydroxide | Aluminium alloy | 184mW/cm2 |
| Zinc-air battery | 4mol/L sodium hydroxide | Kirsite | 124mW/cm2 |
The porous La of embodiment 90.7Sr0.3MnO3The compound porous supporter preparation of conductivity ceramics/non-conductive ceramic of/zirconium oxide
The metal-air battery of gas diffusion layers
With 50 grams of La0.6Sr0.4MnO3Powder and Zirconium oxide powder are as raw material, by powder in temperature at a temperature of 90 °C etc.
It obtains within the pressure maintaining of 15MPa pressure 6 minutes in static pressure machine and is pressed into certain thickness biscuit sample, sample is roasted 2 at 1050 DEG C
Hour obtains with a thickness of the conductive porous supporter of 0.35mm.
By the conductive support through four electrode test conductivity be 10S/cm, measure porosity through Archimedes's drainage
It is 43%, is 78MPa through three-point bending resistance test bending strength.
The conductive porous supporter is impregnated in 32wt%PVDF lotion again, is dried, is roasted 0.5 hour at 340 DEG C
The porous gas diffusion layer that PVDF content is 5 grams is obtained, average pore size is 80 μm.
Then silk-screen printing 4mg/cm is carried out on the porous gas diffusion layer surface again2Cathod catalyst obtain air
Cathode, the cathod catalyst include 40wt%MnO2With 60wt% conductive carbon black, using different electrolyte aqueous solutions as electrolysis
Liquid, different-alloy are made metal-air battery as cathode, measure the performance of different batteries, concrete outcome is shown in Table 9.
The performance of the different classes of metal-air battery of table 9
| Battery type | Electrolyte | Anode material | Maximum power density |
| Magnesium-air cell | 10% sodium-chloride water solution | Magnesium alloy | 60mW/cm2 |
| Aluminium-air cell | 5mol/L potassium hydroxide | Aluminium alloy | 123mW/cm2 |
| Zinc-air battery | 5mol/L sodium hydroxide | Kirsite | 94mW/cm2 |
The porous La of embodiment 100.5Sr0.5CoO3The compound porous support system of conductivity ceramics/non-conductive ceramic of/aluminium oxide
The metal-air battery of standby gas diffusion layers
With 10 grams of La0.6Sr0.4CoO3Powder and alumina powder are as raw material, the temperature etc. for being 95 DEG C in temperature by powder
It obtains within the pressure maintaining of 13MPa pressure 10 minutes in static pressure machine and is pressed into certain thickness biscuit sample, sample is roasted 3 at 1000 DEG C
Hour obtains with a thickness of the conductive porous supporter of 0.3mm.
By the conductive support through four electrode test conductivity be 11S/cm, measure porosity through Archimedes's drainage
It is 39%, is 75MPa through three-point bending resistance test bending strength.
The conductive porous supporter is impregnated in 35wt%PVDF lotion again, is dried, roasts 1 hour and obtains at 330 DEG C
The porous gas diffusion layer that PVDF content is 100 grams is obtained, average pore size is 0.8 μm.
Then silk-screen printing 5mg/cm is carried out on the porous gas diffusion layer surface again2Cathod catalyst obtain air
Cathode, the cathod catalyst include 40wt%MnO2With 60wt% conductive carbon black, using different electrolyte aqueous solutions as electrolysis
Liquid, different-alloy are made metal-air battery as cathode, measure the performance of different batteries, concrete outcome is shown in Table 10.
The performance of the different classes of metal-air battery of table 10
| Battery type | Electrolyte | Anode material | Maximum power density |
| Magnesium-air cell | 10% sodium-chloride water solution | Magnesium alloy | 73mW/cm2 |
| Aluminium-air cell | 4mol/L potassium hydroxide | Aluminium alloy | 153mW/cm2 |
| Zinc-air battery | 3mol/L sodium hydroxide | Kirsite | 92mW/cm2 |
The porous La of embodiment 110.6Sr0.4MnO3The compound porous supporter of conductivity ceramics/carbon material of/charcoal felt prepares gas
The metal-air battery of diffusion layer
With 60 grams of La0.6Sr0.4MnO3Powder is as raw material, by powder in the warm isostatic pressing machine that temperature is 100 DEG C
Acquisition in the pressure maintaining of 20MPa pressure 5 minutes is pressed into certain thickness biscuit sample, sample is roasted 2 hours at 1050 DEG C and is obtained
With a thickness of the conductive porous supporter of 0.4mm.
By the conductive support through four electrode test conductivity be 17S/cm, measure porosity through Archimedes's drainage
It is 40%, is 90MPa through three-point bending resistance test bending strength.
The conductive porous supporter is impregnated in 30wt%PVDF lotion again, is dried, roasts 1 hour and obtains at 320 DEG C
The porous gas diffusion layer that PVDF content is 20 grams is obtained, average pore size is 60 μm.
Charcoal felt and above-mentioned porous supporting body are passed through 200 DEG C again, 2 minutes acquisition porous gas diffusion layers of 2MPa hot pressing, so
Silk-screen printing 5mg/cm is carried out on the porous gas diffusion layer surface again afterwards2Cathod catalyst obtain air cathode, it is described
Cathod catalyst includes 40wt%MnO2With 60wt% conductive carbon black, using different electrolyte aqueous solutions as electrolyte, difference is closed
Metal-air battery is made as cathode in gold, measures the performance of different batteries, concrete outcome is shown in Table 11.
The performance of the different classes of metal-air battery of table 11
| Battery type | Electrolyte | Anode material | Maximum power density |
| Magnesium-air cell | 8% sodium-chloride water solution | Magnesium alloy | 86mW/cm2 |
| Aluminium-air cell | 6mol/L potassium hydroxide | Aluminium alloy | 182mW/cm2 |
| Zinc-air battery | 6mol/L sodium hydroxide | Kirsite | 123mW/cm2 |
The porous Ba of embodiment 120.6Sr0.4Co0.6Fe0.4O3The compound porous support system of conductivity ceramics/carbon material of/charcoal felt
The metal-air battery of standby gas diffusion layers
With 10 grams of Ba0.6Sr0.4Co0.6Fe0.4O3Powder is as raw material, by powder in temperature isostatic pressing machine at a temperature of 90 °C
Acquisition the in middle pressure maintaining of 22MPa pressure 3 minutes is pressed into certain thickness biscuit sample, and sample is roasted 2 hours at 1050 DEG C and is obtained
It obtains with a thickness of the conductive porous supporter of 0.3mm.
By the conductive support through four electrode test conductivity be 15S/cm, measure porosity through Archimedes's drainage
It is 38%, is 88MPa through three-point bending resistance test bending strength.
The conductive porous supporter is impregnated in 35wt%PTFE lotion again, is dried, is roasted 0.5 hour at 325 DEG C
The porous gas diffusion layer that PTFE content is 30 grams is obtained, average pore size is 0.8 μm.
Charcoal felt and above-mentioned porous supporting body are passed through 200 DEG C again, 2 minutes acquisition porous gas diffusion layers of 1.5MPa hot pressing,
Then silk-screen printing 5mg/cm is carried out on the porous gas diffusion layer surface again2Cathod catalyst obtain air cathode, institute
Stating cathod catalyst includes 40wt%MnO2It is different using different electrolyte aqueous solutions as electrolyte with 60wt% conductive carbon black
Metal-air battery is made as cathode in alloy, measures the performance of different batteries, concrete outcome is shown in Table 12.
The performance of the different classes of metal-air battery of table 12
| Battery type | Electrolyte | Anode material | Maximum power density |
| Magnesium-air cell | 8% sodium-chloride water solution | Magnesium alloy | 91mW/cm2 |
| Aluminium-air cell | 5mol/L potassium hydroxide | Aluminium alloy | 184mW/cm2 |
| Zinc-air battery | 3mol/L sodium hydroxide | Kirsite | 115mW/cm2 |
The porous La of embodiment 130.6Sr0.4MnO3The compound porous supporter of conductivity ceramics/carbon material of/graphite felt prepares gas
The metal-air battery of body diffused layer
With 15 grams of La0.6Sr0.4MnO3Powder is as raw material, by powder in the warm isostatic pressing machine that temperature is 100 DEG C
Acquisition in the pressure maintaining of 20MPa pressure 5 minutes is pressed into certain thickness biscuit sample, sample is roasted 2 hours at 1050 DEG C and is obtained
With a thickness of the conductive porous supporter of 0.25mm.
By the conductive support through four electrode test conductivity be 17S/cm, measure porosity through Archimedes's drainage
It is 40%, is 90MPa through three-point bending resistance test bending strength.
The conductive porous supporter is impregnated in 30wt%PVDF lotion again, is dried, roasts 1 hour and obtains at 320 DEG C
The porous gas diffusion layer that PVDF content is 15 grams is obtained, average pore size is 15 μm.
Graphite felt and above-mentioned porous supporting body are passed through 200 DEG C again, 1 minute acquisition porous gas diffusion layer of 2MPa hot pressing,
Then silk-screen printing 4mg/cm is carried out on the porous gas diffusion layer surface again2Cathod catalyst obtain air cathode, institute
Stating cathod catalyst includes 40wt%MnO2It is different using different electrolyte aqueous solutions as electrolyte with 60wt% conductive carbon black
Metal-air battery is made as cathode in alloy, measures the performance of different batteries, concrete outcome is shown in Table 13.
The performance of the different classes of metal-air battery of table 13
| Battery type | Electrolyte | Anode material | Maximum power density |
| Magnesium-air cell | 8% sodium-chloride water solution | Magnesium alloy | 81mW/cm2 |
| Aluminium-air cell | 6mol/L potassium hydroxide | Aluminium alloy | 179mW/cm2 |
| Zinc-air battery | 6mol/L sodium hydroxide | Kirsite | 116mW/cm2 |
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (23)
1. a kind of gas diffusion layers characterized by comprising
Conductive porous supporter and hydrophobic layer, the hydrophobic layer is coated on the conductive porous supporting body surface and the conduction is more
The duct inner wall of hole supporter,
The conductivity of the conductive porous supporter be 7~1350S/cm, porosity be 24%~44%, bending strength be 75~
280MPa；
The material of the conductive porous supporter is selected from one of Ca-Ti ore type conductivity ceramics and metal based conductive ceramics or more
Kind,
The Ca-Ti ore type conductivity ceramics is La1-xSrxCo1-yFeyO3、La1-zSrzMnO3Or Ba1-mSrmCo1-nFenO3, wherein institute
State 0 < x≤0.6,0 n≤0.4 the < < of y≤0.6,0≤z≤0.6,0.2≤m≤0.8,0,
The metal based conductive ceramics are Ni based conductive ceramics, Cu based conductive ceramics or Fe based conductive ceramics；
The Ni based conductive ceramics are selected from Ni-ZrO2、Ni-Al2O3、Ni-CeO2, Ni- doped aluminium base ceramics, Ni- adulterate oxygen
Change zirconia-based ceramic, Ni- doped cerium oxide base ceramics, Ni- silicon carbide, Ni- titanium oxide or Ni- titanium carbide；
The Cu based conductive ceramics are selected from Cu-ZrO2、Cu-Al2O3、Cu-CeO2, Cu- doped aluminium base ceramics, Cu- adulterate oxygen
Change zirconia-based ceramic, Cu- doped cerium oxide base ceramics, Cu- silicon carbide, Cu- titanium oxide or Cu- titanium carbide；
The Fe based conductive ceramics are selected from Fe-ZrO2、Fe-Al2O3、Fe-CeO2, Fe- doped aluminium base ceramics, Fe- adulterate oxygen
Change zirconia-based ceramic, Fe- doped cerium oxide base ceramics, Fe- silicon carbide, Fe- titanium oxide or Fe- titanium carbide.
2. gas diffusion layers according to claim 1, which is characterized in that the matter of the conductive porous supporter and hydrophobic layer
Amount is than being 20:1~1:20.
3. gas diffusion layers according to claim 1, which is characterized in that the matter of the conductive porous supporter and hydrophobic layer
Amount is than being 8:1~1:5.
4. gas diffusion layers according to claim 1, which is characterized in that the material of the hydrophobic layer is selected from polytetrafluoroethyl-ne
Alkene, Kynoar, fluorinated ethylene propylene copolymer, perfluoroalkoxy resin and ethylene-tetrafluoroethylene copolymer one kind or
It is a variety of.
5. gas diffusion layers according to claim 1, which is characterized in that the material of the conductive porous supporter further includes
Carbon material, the carbon material are selected from carbon felt or graphite felt.
6. gas diffusion layers according to claim 5, which is characterized in that the quality of the carbon material and the conductivity ceramics
Than for 1:10~10:1.
7. gas diffusion layers according to claim 1, which is characterized in that the material of the conductive porous supporter also includes
Non-conductive ceramic.
8. gas diffusion layers according to claim 7, which is characterized in that the non-conductive ceramic is selected from aluminium oxide, oxidation
One of zirconium, cerium oxide, boron nitride, boron carbide, silicon nitride, silicon carbide or Nano diamond are a variety of.
9. gas diffusion layers according to claim 7, which is characterized in that the quality of the non-conductive ceramic and conductivity ceramics
Than for 1:10~8:1.
10. gas diffusion layers according to claim 7, which is characterized in that the average pore size of the conductive porous supporter
It is 0.05~100 μm.
11. gas diffusion layers according to claim 7, which is characterized in that the average pore size of the conductive porous supporter
It is 0.1~50 μm.
12. a kind of preparation method of the gas diffusion layers as described in claim 1~11 any one, which is characterized in that including
Following steps:
Hydrophobic material is coated on to the duct inner wall of conductive porous supporting body surface and conductive porous supporter, drying roasting obtains
To gas diffusion layers, the material of the conductive porous supporter is in Ca-Ti ore type conductivity ceramics and metal based conductive ceramics
It is one or more.
13. preparation method according to claim 12, which is characterized in that the preparation method packet of the conductive porous supporter
Contain:
A1 Ca-Ti ore type conductivity ceramics biscuit) is obtained into conductive porous supporter through oversintering；
Or
A2), by reduction reaction, conductive porous supporter, the composite material will be obtained after the sintering of molding composite powder
Powder is the mixture of metal oxide powder and ceramic powders.
14. preparation method according to claim 12, which is characterized in that the material of the conductive porous supporter further includes
One or both of carbon material and non-conductive ceramic, the carbon material are selected from charcoal felt or graphite felt, the non-conductive ceramic choosing
Self-alumina, zirconium oxide or cerium oxide.
15. preparation method according to claim 14, which is characterized in that the preparation method packet of the conductive porous supporter
Contain:
B1) molding composite material is sintered, obtains conductive porous supporter, the composite material is Ca-Ti ore type conduction pottery
The composite material of porcelain and carbon material, the carbon material are selected from carbon felt or graphite felt；
Or
B2), by reduction reaction, conductive porous supporter will be obtained, the composite material is gold after molding Composite Sintering
Belong to the composite material of oxide powder, ceramic powders and carbon material, the carbon material is selected from carbon felt or graphite felt.
16. preparation method according to claim 14, which is characterized in that the quality of the carbon material and the conductivity ceramics
Than for 1:10~10:1.
17. preparation method described in 3 or 15 according to claim 1, which is characterized in that the Ca-Ti ore type conductivity ceramics is La1- xSrxCo1-yFeyO3、La1-zSrzMnO3Or Ba1-mSrmCo1-nFenO3, wherein the 0 < x≤0.6,0 < y≤0.6,0≤z≤
0.6,0.2≤m≤0.8,0 n≤0.4 <.
18. preparation method described in 3 or 15 according to claim 1, which is characterized in that the metal oxide is the oxidation of Ni
The oxide of object, the oxide of Cu or Fe；The ceramic powders are aluminium oxide, zirconium oxide, cerium oxide, doped aluminium base pottery
Porcelain, doped zirconia base ceramics, doped cerium oxide base ceramics, silicon carbide, titanium oxide or titanium carbide.
19. preparation method according to claim 13, which is characterized in that step A1) described in sintering temperature be 900~
1200 DEG C, the time of sintering is 0.5~6 hour；Step A2) described in sintering temperature be 900~1500 DEG C, the time of sintering
It is 0.5~6 hour.
20. preparation method according to claim 15, which is characterized in that step B1) described in sintering temperature be 300~
1200 DEG C, sintering time is 0.5~10 hour；Step B2) described in sintering temperature be 900~1400 DEG C, the time of sintering
It is 0.5~10 hour.
21. preparation method according to claim 12, which is characterized in that the method for the coating is dipping, spraying or silk
Wire mark brush.
22. preparation method according to claim 12, which is characterized in that the temperature of the roasting is 280~370 DEG C, institute
The time for stating roasting is 5~200 minutes.
23. a kind of metal-air battery characterized by comprising metal anode, electrolyte and air cathode, the air yin
Pole include with the catalyst layer of the electrolyte contacts, be compound in the catalyst layer claim 1~11 any one weigh
Benefit requires gas diffusion layers described or that claim 12~22 any one preparation method is prepared and is compound in institute
State the current collector layer of gas diffusion layers.
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| CN105119007B (en) * | 2015-08-05 | 2017-12-08 | 黄河科技学院 | A kind of preparation method of corrosion-resistant fuel battery gas diffusion layer |
| CN107482283A (en) * | 2017-04-25 | 2017-12-15 | 浙江地坤键新能源科技有限公司 | A kind of high-performance metal air cell and its application |
| CN107706436B (en) * | 2017-10-13 | 2019-04-09 | 吉林大学 | A kind of air cathode of imitative fish gill surface micro-nano structure |
| CN109962210A (en) * | 2017-12-25 | 2019-07-02 | 北京纳米能源与系统研究所 | Electrode preparation method, electrode and battery |
| CN108736019A (en) * | 2018-04-10 | 2018-11-02 | 云南铝业股份有限公司 | Metal fuel battery air electrode and preparation method thereof |
| EP3686966A1 (en) | 2019-01-23 | 2020-07-29 | Karlsruher Institut für Technologie | An electrochemical energy storage device and a method for producing an anode active material for the electrochemical energy storage device |
| CN111129507B (en) * | 2019-12-13 | 2021-02-02 | 同济大学 | Gas diffusion layer for fuel cell and preparation method and application thereof |
| CN112271302B (en) * | 2020-10-16 | 2021-08-03 | 成都新柯力化工科技有限公司 | Carbon fiber inlaid ceramic gas diffusion layer for fuel cell and preparation method |
| CN112563516B (en) * | 2020-12-28 | 2023-03-28 | 浙江唐锋能源科技有限公司 | Gas diffusion layer of environment-friendly fuel cell and preparation method thereof |
| CN114388813B (en) * | 2022-01-14 | 2023-07-04 | 中国科学技术大学先进技术研究院 | Current collector |
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