CN101114714A - Electro-catalyst of zinc-air battery and method for making same - Google Patents
Electro-catalyst of zinc-air battery and method for making same Download PDFInfo
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- CN101114714A CN101114714A CNA2007100288396A CN200710028839A CN101114714A CN 101114714 A CN101114714 A CN 101114714A CN A2007100288396 A CNA2007100288396 A CN A2007100288396A CN 200710028839 A CN200710028839 A CN 200710028839A CN 101114714 A CN101114714 A CN 101114714A
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Abstract
The invention discloses a clectrocatalyst for zinc-air batteries and a preparation method. The general formula of the clectrocatalyst is LiNixCoyFezMn2-x-y-zO4, wherein x is more than or equal to 0.10 and less than or equal to 0.50, y is more than or equal to 0 and less than or equal to 0.50, and z is more than or equal to 0 or less than or equal to 0.50. The crystalline structure of the clectrocatalyst is spinel-type crystalline structure. The clectrocatalyst of the invention has high electro-catalytic activity and good chemical stability, and the raw materials needed for the preparation of the clectrocatalyst has rich reserves and low prices; and the uniform doping of different metals in the clectrocatalyst outcome can be realized and an outcome with uniform structure at the molecular level can be obtained within a short time. The clectrocatalyst of the invention requires low heat treatment temperature and short heat treatment time, and the obtained outcome has high purity and narrow particle size distribution. And the reaction process and the microstructure of the sol-gel are easy to be controlled, resulting in little side effects, high outcome conversion rate, and thus having high outcome quality and production efficiency.
Description
Technical field
The present invention relates to technical field of chemical power, specifically be meant a kind of eelctro-catalyst that is used as zinc-air cell and preparation method thereof with spinel-type crystalline structure.
Background technology
Zinc-air cell has had the history in more than 100 year so far from coming out.It is to be positive active material with airborne oxygen, and metallic zinc is a negative electrode active material, issues biochemical reaction in the catalytic action of catalyst and produces a kind of chemical power source of electric current.As long as zinc electrode has not been consumed, oxygen just can arrive electrochemical reaction interface and zinc continuously by air diffusion electrode and react and constantly produce electric energy.This battery has advantages such as specific energy height, discharging voltage balance, raw material cheaply are easy to get, non-environmental-pollution, and wide application prospect is arranged.Yet the discharge current density of zinc-air cell is on the low side, can not satisfy the use needs than the home electronic appliance of high power discharge, thereby has limited its market and range of application.The method of taking to improve the air electrode air diffuser gross area can increase the discharging current of battery to a certain extent, but an alkali difficult problem is climbed in the leakage that but can aggravate zinc-air cell simultaneously.If the catalytic activity of catalyst in the raising course of reaction just can be quickened airborne oxygen and be adsorbed the inside that enters battery, improve the reaction rate of oxygen, thereby increase the discharging current of battery at the reaction interface place, promptly improve the power output of battery.As seen, the used eelctro-catalyst of the size of zinc-air cell discharge current density and its air diffusion electrode is closely related.
Activated carbon, electrolysis MnO that tradition adopts
2Catalytic activity Deng catalyst is lower, makes the reaction speed of oxygen on electrochemical interface slower, thereby has limited the discharge current density of zinc-air cell.This battery can only be applied to low power electronic and electrical equipments such as button cell.Afterwards, the someone adopted noble metal to replace active carbon or MnO
2Improve the catalytic activity of gas diffusion electrode of zinc-air battery as catalyst, but costing an arm and a leg of noble metal, and still do not satisfy the instructions for use of home electronic appliance as the current density of catalyst cell, thereby it is employed on a large scale with it.Spinel-type crystalline structure metal oxide is because advantage such as its electro catalytic activity height, good conductivity, raw material be cheap and easy to get is very promising novel electro-catalytic agent system.Employing sol-gal processes (ACP) such as N.LI have been prepared spinel-type LiCo
xM
2-xO
4[M=Co, Fe, (Co, Fe)] metal oxide is wherein with LiCo
0.6Mn
1.4O
4Metal oxide is that the air diffusion electrode of Preparation of Catalyst is separated out hydrogen reduction and oxygen under the Oxygen Flow condition and all shown higher electro catalytic activity.The method of employing Co element dopings such as Zhou Zhentao has prepared spinel-type LiCo
xMn
2-xO
4Metal oxide (seeing Chinese patent 01107488.4 for details), the optimal discharge current density of making the zinc-air cell of catalyst with this material can reach 150mA/cm
2More than, than with electrolysis MnO
2For the discharge current density of the zinc-air cell of catalyst (is about 30～50mA/cm
2) have increased significantly; Zhou Zhentao, Li Haibiao etc. disclose a kind of solwution method, adopt this method to prepare LiCo
xMn
2-xO
4Metal oxide (seeing Chinese patent application 200510032676.X for details) can be up to 258mA/cm in the optimum polarization current density the under-0.6V polarization potential with the zinc-air cell of the catalyst assembling of this method preparation
2Yet still there are the following problems for the above-mentioned background technology:
1, with spinel-type LiCo
xMn
2-xO
4Material is that the discharging current of zinc-air cell of Preparation of Catalyst is still on the low side, can not satisfy the use needs of some high-power electric appliances.
2, the price height of Co material, thus make that the business-like cost of its material is also higher.
3, in alkaline electrolyte, the chemical stability of metal Co element is relatively poor, becomes the useful life of battery thereby influenced it.
Summary of the invention
At the existing problem of above-mentioned existing zinc-air cell technology, primary and foremost purpose of the present invention is to provide the eelctro-catalyst of the zinc-air cell that a kind of prices of raw and semifnished materials are cheap, catalytic activity is high.Zinc-air cell eelctro-catalyst of the present invention is that the salt with transition metals such as Mn, Ni, Fe, Co is a base-material, is to adopt Prepared by Sol Gel Method to go out to have the composite oxide of metal eelctro-catalyst LiNi of spinel-type crystalline structure
xCo
yFe
zMn
2-x-y-zO
4.
Another object of the present invention is the preparation method who is to provide above-mentioned zinc-air cell eelctro-catalyst.
Purpose of the present invention realizes by following technical proposals: the eelctro-catalyst of zinc-air cell of the present invention, general formula are LiNi
xCo
yFe
zMn
2-x-y-zO
4, in the formula, 0.10≤x≤0.50,0≤y≤0.50,0≤z≤0.50.The crystalline structure of this eelctro-catalyst is the spinel-type crystalline structure.
The preparation method of above-mentioned zinc-air cell eelctro-catalyst comprises the steps:
The first step is according to spinel-type crystalline structure LiNi
xCo
yFe
zMn
2-x-y-zO
4The stoichiometry mol ratio Li of composite oxide of metal: Ni: Co: Fe: Mn=1.00: 0.1 0～0.50: 0～0.50: 0～0.50: 0.50～1.90 takes by weighing each slaine, adds distilled water and makes it be made into saturated aqueous solution.
Second step added citric acid and ethylene glycol in above-mentioned reaction system, the pH of conditioned reaction system is 4.5～7.0; Wherein, citric acid: ethylene glycol: the mol ratio of metal ion summation is 2.0～3.5: 3.5～5.0: 1.0.
The 3rd step, above-mentioned reaction system is placed in the water bath with thermostatic control makes water evaporates obtain transparent colloidal sol gradually in 50～90 ℃ of following heating, continue dehydration and formed wet gel in 2～6 hours, under 100～160 ℃, wet gel was carried out heat drying 3～16 hours then, obtain cellular xerogel, in air atmosphere, under 400～900 ℃, xerogel was heat-treated 1～16 hour at last, be cooled to room temperature then, promptly obtain the eelctro-catalyst of zinc-air cell.
In order to realize the present invention better, described slaine comprises one or more the mixture in nitrate, acetate or the oxalates of each metallic element.
Described nitrate comprises LiNO
3, Ni (NO
3)
26H
2O, Co (NO
3)
26H
2O, Mn (NO
3)
2Or Fe (NO
3)
29H
2O; Described acetate comprises Ni (CH
3COO)
24H
2O, Mn (CH
3COO)
24H
2O or Co (CH
3COO)
2Described oxalates comprises CoC
2O
42H
2O.
The pH of conditioned reaction system is 4.5～7.0th in second step, regulates with ammoniacal liquor.
Structural analysis: the X Pert Pro type X-ray diffractometer that adopts Dutch PANalytical company to produce is analyzed graphite monochromator filtering, copper target K to the crystalline structure of product
α 1Radiation, operating voltage are 40kV, operating current 40mA, and the scanning angle scope is 2 θ=10 °～70 °.Analysis result shows that the serial eelctro-catalyst of gained all has the spinel-type crystalline structure.
The preparation of air diffusion electrode: acetylene black and pore creating material ammonium oxalate are mixed with alcohol, dropwise add in the ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains waterproof ventilated membrane repeatedly after cohesion; Catalyst, active carbon that the present invention is prepared mix with an amount of alcohol, add ptfe emulsion, constantly stir, and make it to be uniformly dispersed, and roll-in obtains catalytic membrane repeatedly after cohesion.Waterproof ventilated membrane, catalytic membrane and metal collector (nickel screen etc.) be superimposed carry out roll-forming, just obtain air diffusion electrode.Wherein the set of dispense of waterproof ventilated membrane is than being acetylene black: PTFE: pore creating material=40wt%: 40wt%: 20wt%; The set of dispense ratio of catalytic membrane is: active carbon: pore creating material: PTFE: catalyst=35wt%: 15wt%: 20wt%: 50wt%.
The test of steady-state current-voltage polarizing curve: the method for steady-state current-voltage polarizing curve by the test air diffusion electrode is measured the electro catalytic activity of eelctro-catalyst.Under the room temperature normal pressure, the CHI660b electrochemical workstation of marine products in the employing, with the air diffusion electrode is work electrode, the Hg/HgO electrode is a reference electrode, nickel screen is to electrode, the KOH aqueous solution of 6mol/L is electrolyte, with three electrode test system air diffusion electrodes the catalytic activity of eelctro-catalyst is carried out steady-state current-voltage polarizing curve test.
Zinc-air cell of the present invention composite oxide of metal eelctro-catalyst of spinel-type crystalline structure and preparation method thereof compared with prior art has following advantage and beneficial effect:
1, the electro catalytic activity height of gained eelctro-catalyst of the present invention, chemical stability are good.
2, to prepare the required raw material reserves of eelctro-catalyst abundant, cheap in the present invention.
3, preparation method of the present invention can realize the even doping of trace element in the eelctro-catalyst product, obtains the product of even structure unanimity on molecular level in the short period of time.
4, preparation method of the present invention makes the chemical reaction in the reaction system carry out easily, and the heat treatment temperature of eelctro-catalyst is lower, heat treatment time is shorter, higher, the narrower particle size distribution of the purity of products therefrom; The microstructure of course of reaction and collosol and gel all is easy to control, and side reaction is less, and the conversion ratio of product is higher, thereby makes the quality of product and production efficiency all higher.
Description of drawings
Fig. 1 is the comparison diagram of the steady-state current-voltage polarizing curve of the obtained air diffusion electrode of eelctro-catalyst of eelctro-catalyst of the present invention and existing background technology.
Fig. 2 analyzes collection of illustrative plates for the X-ray diffraction (XRD) of gained eelctro-catalyst of the present invention.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment one
The preparation method of zinc-air cell eelctro-catalyst comprises the steps:
The first step is according to stoichiometry mol ratio Li: Ni: Mn=1.00: take by weighing LiNO at 0.20: 1.80
3, Ni (CH
3COO)
24H
2O and weight percent concentration are the Mn (NO of 50wt%
3)
2Solution adds distilled water and is made into saturated aqueous solution.
Second step added citric acid and ethylene glycol in above-mentioned reaction system, be 5.0 with the pH of ammoniacal liquor conditioned reaction system.Wherein, citric acid: ethylene glycol: the mol ratio of metal ion summation is 3.0: 4.0: 1.0.
The 3rd step, reaction system is placed in the water bath with thermostatic control makes water evaporates obtain vitreosol gradually in 80 ℃ of following heating, continue dehydration and formed wet gel in 4 hours, under 120 ℃, wet gel was carried out heat drying 12 hours then, obtain cellular xerogel, in air atmosphere, under 500 ℃, xerogel was heat-treated 6 hours at last, cool to room temperature then with the furnace, just obtain having the LiNi of spinel-type crystalline structure
0.2Mn
1.8O
4Eelctro-catalyst.As shown in Figure 2, be gained LiNi of the present invention
0.2Mn
1.8O
4The X-ray diffraction of eelctro-catalyst (XRD) is analyzed collection of illustrative plates.Check the standard spectrogram through retrieval and prove that the crystal structure of gained eelctro-catalyst is the spinel-type crystalline structure.
The preparation of air diffusion electrode: acetylene black and pore creating material ammonium oxalate are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains waterproof ventilated membrane repeatedly after cohesion; Catalyst, pore creating material, active carbon and acetylene black are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains catalytic membrane repeatedly after cohesion.Waterproof ventilated membrane, catalytic membrane and collector (nickel screen) be superimposed carry out roll-forming and just obtain air diffusion electrode.Wherein the set of dispense of waterproof ventilated membrane is than being acetylene black: PTFE: pore creating material=40wt%: 40wt%: 20wt%; The set of dispense ratio of catalytic membrane is: active carbon: pore creating material: PTFE: catalyst=35wt%: 15wt%: 20wt%: 50wt%.
The test of steady-state current-voltage polarizing curve: the steady-state current-voltage polarizing curve by the test air diffusion electrode is measured the electro catalytic activity of eelctro-catalyst.Under the room temperature normal pressure, the CHI660b electrochemical workstation of marine products in the employing, with the air diffusion electrode is work electrode, the Hg/HgO electrode is a reference electrode, nickel screen is to electrode, the KOH aqueous solution of 6mol/L is electrolyte, with three electrode test systems the electro catalytic activity of air diffusion electrode eelctro-catalyst is carried out steady-state current-voltage polarizing curve test.Test result shows, its current density under-0.6V (Hg/HgO is a reference electrode) polarization potential reaches 265mA/cm
2
As the comparison diagram of Fig. 1 for the steady-state current-voltage polarizing curve of the obtained air diffusion electrode of eelctro-catalyst of the present invention and existing background technology.The meaning of respectively numbering representative among the figure is as follows: a---with the prepared spinel-type LiNi of sol-gal process of the present invention
0.2Mn
1.8O
4Composite oxide of metal is the steady-state current-voltage polarizing curve of the air diffusion electrode of eelctro-catalyst; B---with the spinel-type LiMn of background technology
1.5Co
0.5O
4Composite oxide of metal is the steady-state current-voltage polarizing curve of the air diffusion electrode of eelctro-catalyst; C---with the electrolytic manganese dioxide is the steady-state current-voltage polarizing curve of the air diffusion electrode of eelctro-catalyst.This comparison diagram explanation has higher polarized current density with Preparation of Catalyst air diffusion electrode of the present invention under the equipolarization current potential.Polarized current density is big more, and then the activity of eelctro-catalyst is high more.
Embodiment two
The preparation method of zinc-air cell eelctro-catalyst comprises the steps:
The first step is according to stoichiometry mol ratio Li: Ni: Mn=1.00: take by weighing LiNO at 0.10: 1.90
3, Ni (CH
3COO)
24H
2O and weight percent concentration are the Mn (NO of 50wt%
3)
2Solution adds distilled water and is made into saturated aqueous solution.
Second step added citric acid and ethylene glycol in above-mentioned reaction system, be 5.0 with the pH of ammoniacal liquor conditioned reaction system.Wherein, citric acid: ethylene glycol: the mol ratio of metal ion summation is 3.0: 4.0: 1.0.
The 3rd step, reaction system is placed in the water bath with thermostatic control makes water evaporates obtain vitreosol gradually in 80 ℃ of following heating, continue dehydration and formed wet gel in 3 hours, under 120 ℃, wet gel was carried out heat drying 12 hours then, obtain cellular xerogel, in air atmosphere, under 500 ℃, xerogel was heat-treated 6 hours at last, cool to room temperature then with the furnace, just obtain having the LiNi of spinel-type crystalline structure
0.2Mn
1.8O
4Eelctro-catalyst.
The preparation of air diffusion electrode: acetylene black and pore creating material ammonium oxalate are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains waterproof ventilated membrane repeatedly after cohesion; Catalyst, pore creating material, active carbon and acetylene black are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains catalytic membrane repeatedly after cohesion.Waterproof ventilated membrane, catalytic membrane and collector (nickel screen) be superimposed carry out roll-forming and just obtain air diffusion electrode.Wherein the set of dispense of waterproof ventilated membrane is than being acetylene black: PTFE: pore creating material=40wt%: 40wt%: 20wt%; The set of dispense ratio of catalytic membrane is: active carbon: pore creating material: PTFE: catalyst=35wt%: 15wt%: 20wt%: 50wt%.
The test of steady-state current-voltage polarizing curve: the steady-state current-voltage polarizing curve by the test air diffusion electrode is measured the electro catalytic activity of eelctro-catalyst.Under the room temperature normal pressure, the CHI660b electrochemical workstation of marine products in the employing, with the air diffusion electrode is work electrode, the Hg/HgO electrode is a reference electrode, nickel screen is to electrode, the KOH aqueous solution of 6mol/L is electrolyte, with three electrode test systems the electro catalytic activity of air diffusion electrode eelctro-catalyst is carried out steady-state current-voltage polarizing curve test.Test result shows, its current density under-0.6V (Hg/HgO is a reference electrode) polarization potential is 223mA/cm
2
Embodiment three
The preparation method of zinc-air cell eelctro-catalyst comprises the steps:
The first step is according to stoichiometry mol ratio Li: Ni: Mn=1.00: take by weighing LiNO at 0.50: 1.50
3, NiC
2O
42H
2O and weight percent concentration are the Mn (NO of 50wt%
3)
2Solution adds distilled water and is made into saturated aqueous solution.
Second step added citric acid and ethylene glycol in above-mentioned reaction system, be 5.5 with the pH of ammoniacal liquor conditioned reaction system.Wherein, citric acid: ethylene glycol: the mol ratio of metal ion summation is 2.0: 3.5: 1.0.
The 3rd step, reaction system is placed in the water bath with thermostatic control makes water evaporates obtain vitreosol gradually in 90 ℃ of following heating, continue dehydration and formed wet gel in 2 hours, under 100 ℃, wet gel was carried out heat drying 16 hours then, obtain cellular xerogel, in air atmosphere, under 900 ℃, xerogel was heat-treated 1 hour at last, cool to room temperature then with the furnace, just obtain having the LiNi of spinel-type crystalline structure
0.5Mn
1.5O
4Eelctro-catalyst.
The preparation of air diffusion electrode: acetylene black and pore creating material ammonium oxalate are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains waterproof ventilated membrane repeatedly after cohesion; Catalyst, pore creating material, active carbon and acetylene black are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains catalytic membrane repeatedly after cohesion.Waterproof ventilated membrane, catalytic membrane and collector (nickel screen) be superimposed carry out roll-forming and just obtain air diffusion electrode.Wherein the set of dispense of waterproof ventilated membrane is than being acetylene black: PTFE: pore creating material=40wt%: 40wt%: 20wt%; The set of dispense ratio of catalytic membrane is: active carbon: pore creating material: PTFE: catalyst=35wt%: 15wt%: 20wt%: 50wt%.
The test of steady-state current-voltage polarizing curve: the steady-state current-voltage polarizing curve by the test air diffusion electrode is measured the electro catalytic activity of eelctro-catalyst.Under the room temperature normal pressure, the CHI660b electrochemical workstation of marine products in the employing, with the air diffusion electrode is work electrode, the Hg/HgO electrode is a reference electrode, nickel screen is to electrode, the KOH aqueous solution of 6mol/L is electrolyte, with three electrode test systems the electro catalytic activity of air diffusion electrode eelctro-catalyst is carried out steady-state current-voltage polarizing curve test.Test result shows, its current density under-0.6V (Hg/HgO is a reference electrode) polarization potential is 214mA/cm
2
Embodiment four
The preparation method of zinc-air cell eelctro-catalyst comprises the steps:
The first step, according to stoichiometry mol ratio Li: Ni: Co: Fe: Mn=1.00: 0.10: 0.20: 0.50: 1.20 take by weighing LiNO
3, Ni (NO
3)
26H
2O, Co (NO
3)
26H
2O, Fe (NO
3)
29H
2O and Mn (CH
3COO)
24H
2O adds distilled water and is made into saturated aqueous solution.
Second step added citric acid and ethylene glycol in above-mentioned reaction system, be 6.0 with the pH of ammoniacal liquor conditioned reaction system.Wherein, citric acid: ethylene glycol: the mol ratio of metal ion summation is 2.5: 5.0: 1.0.
The 3rd step, reaction system is placed in the water bath with thermostatic control makes water evaporates obtain vitreosol gradually in 70 ℃ of following heating, continue dehydration and formed wet gel in 6 hours, under 160 ℃, wet gel was carried out heat drying 3 hours then, obtain cellular xerogel, in air atmosphere, under 700 ℃, xerogel was heat-treated 8 hours at last, cool to room temperature then with the furnace, just obtain having the LiNi of spinel-type crystalline structure
0.1Co
0.2Fe
0.5Mn
1.2O
4Eelctro-catalyst.
The preparation of air diffusion electrode: acetylene black and pore creating material ammonium oxalate are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains waterproof ventilated membrane repeatedly after cohesion; Catalyst, pore creating material, active carbon and acetylene black are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains catalytic membrane repeatedly after cohesion.Waterproof ventilated membrane, catalytic membrane and collector (nickel screen) be superimposed carry out roll-forming and just obtain air diffusion electrode.Wherein the set of dispense of waterproof ventilated membrane is than being acetylene black: PTFE: pore creating material=40wt%: 40wt%: 20wt%; The set of dispense ratio of catalytic membrane is: active carbon: pore creating material: PTFE: catalyst=35wt%: 1 5wt%: 20wt%: 50wt%.
The test of steady-state current-voltage polarizing curve: the steady-state current-voltage polarizing curve by the test air diffusion electrode is measured the electro catalytic activity of eelctro-catalyst.Under the room temperature normal pressure, the CHI660b electrochemical workstation of marine products in the employing, with the air diffusion electrode is work electrode, the Hg/HgO electrode is a reference electrode, nickel screen is to electrode, the KOH aqueous solution of 6mol/L is electrolyte, with three electrode test systems the electro catalytic activity of air diffusion electrode eelctro-catalyst is carried out steady-state current-voltage polarizing curve test.Test result shows, its current density under-0.6V (Hg/HgO is a reference electrode) polarization potential is 232mA/cm
2
Embodiment five
The preparation method of zinc-air cell eelctro-catalyst comprises the steps:
The first step, according to stoichiometry mol ratio Li: Ni: Co: Fe: Mn=1.00: 0.10: 0.50: 0.10: 1.30 take by weighing LiNO
3, Ni (NO
3)
26H
2O, Co (CH
3COO)
2, Fe (NO
3)
29H
2O and weight percent concentration are the Mn (NO of 50wt%
3)
2Solution adds distilled water and is made into saturated aqueous solution.
Second step added citric acid and ethylene glycol in above-mentioned reaction system, be 7.0 with the pH of ammoniacal liquor conditioned reaction system.Wherein, citric acid: ethylene glycol: the mol ratio of metal ion summation is 3.5: 5.0: 1.0.
The 3rd step, reaction system is placed in the water bath with thermostatic control makes water evaporates obtain vitreosol gradually in 75 ℃ of following heating, continue dehydration and formed wet gel in 3 hours, under 120 ℃, wet gel was carried out heat drying 7 hours then, obtain cellular xerogel, in air atmosphere, under 650 ℃, xerogel was heat-treated 9 hours at last, cool to room temperature then with the furnace, just obtain having the LiNi of spinel-type crystalline structure
0.1Co
0.5Fe
0.1Mn
1.3O
4Eelctro-catalyst.
The preparation of air diffusion electrode: acetylene black and pore creating material ammonium oxalate are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains waterproof ventilated membrane repeatedly after cohesion; Catalyst, pore creating material, active carbon and acetylene black are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains catalytic membrane repeatedly after cohesion.Waterproof ventilated membrane, catalytic membrane and collector (nickel screen) be superimposed carry out roll-forming and just obtain air diffusion electrode.Wherein the set of dispense of waterproof ventilated membrane is than being acetylene black: PTFE: pore creating material=40wt%: 40wt%: 20wt%; The set of dispense ratio of catalytic membrane is: active carbon: pore creating material: PTFE: catalyst=35wt%: 15wt%: 20wt%: 50wt%.
The test of steady-state current-voltage polarizing curve: the steady-state current-voltage polarizing curve by the test air diffusion electrode is measured the electro catalytic activity of eelctro-catalyst.Under the room temperature normal pressure, the CHI660b electrochemical workstation of marine products in the employing, with the air diffusion electrode is work electrode, the Hg/HgO electrode is a reference electrode, nickel screen is to electrode, the KOH aqueous solution of 6mol/L is electrolyte, with three electrode test systems the electro catalytic activity of air diffusion electrode eelctro-catalyst is carried out steady-state current-voltage polarizing curve test.Test result shows, its current density under-0.6V (Hg/HgO is a reference electrode) polarization potential is 245mA/cm
2
Embodiment six
The preparation method of zinc-air cell eelctro-catalyst comprises the steps:
The first step is according to stoichiometry mol ratio Li: Ni: Co: Mn=1.00: take by weighing LiNO at 0.20: 0.2: 1.60
3, Ni (CH
3COO)
24H
2O, Co (NO
3)
26H
2O and weight percent concentration are the Mn (NO of 50wt%
3)
2Solution adds distilled water and is made into saturated aqueous solution.
Second step added citric acid and ethylene glycol in above-mentioned reaction system, be 6.0 with the pH of ammoniacal liquor conditioned reaction system.Wherein, citric acid: ethylene glycol: the mol ratio of metal ion summation is 2.5: 4.0: 1.0.
The 3rd step, reaction system is placed in the water bath with thermostatic control makes water evaporates obtain vitreosol gradually in 85 ℃ of following heating, continue dehydration and formed wet gel in 3 hours, under 140 ℃, wet gel was carried out heat drying 10 hours then, obtain cellular xerogel, in air atmosphere, under 400 ℃, xerogel was heat-treated 16 hours at last, cool to room temperature then with the furnace, just obtain having the LiNi of spinel-type crystalline structure
0.2Co
0.2Mn
1.6O
4Eelctro-catalyst.
The preparation of air diffusion electrode: acetylene black and pore creating material ammonium oxalate are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains waterproof ventilated membrane repeatedly after cohesion; Catalyst, pore creating material, active carbon and acetylene black are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains catalytic membrane repeatedly after cohesion.Waterproof ventilated membrane, catalytic membrane and collector (nickel screen) be superimposed carry out roll-forming and just obtain air diffusion electrode.Wherein the set of dispense of waterproof ventilated membrane is than being acetylene black: PTFE: pore creating material=40wt%: 40wt%: 20wt%; The set of dispense ratio of catalytic membrane is: active carbon: pore creating material: PTFE: catalyst=35wt%: 15wt%: 20wt%: 50wt%.
The test of steady-state current-voltage polarizing curve: the steady-state current-voltage polarizing curve by the test air diffusion electrode is measured the electro catalytic activity of eelctro-catalyst.Under the room temperature normal pressure, the CHI660b electrochemical workstation of marine products in the employing, with the air diffusion electrode is work electrode, the Hg/HgO electrode is a reference electrode, nickel screen is to electrode, the KOH aqueous solution of 6mol/L is electrolyte, with three electrode test systems the electro catalytic activity of air diffusion electrode eelctro-catalyst is carried out steady-state current-voltage polarizing curve test.Test result shows, its current density under-0.6V (Hg/HgO is a reference electrode) polarization potential is 253mA/cm
2
Embodiment seven
The preparation method of zinc-air cell eelctro-catalyst comprises the steps:
The first step is according to stoichiometry mol ratio Li: Ni: Fe: Mn=1.00: take by weighing LiNO at 0.20: 0.20: 1.60
3, Ni (CH
3COO)
24H
2O, Fe (NO
3)
29H
2O and weight percent concentration are the Mn (NO of 50wt%
3)
2Solution adds distilled water and is made into saturated aqueous solution.
Second step added citric acid and ethylene glycol in above-mentioned reaction system, be 6.0 with the pH of ammoniacal liquor conditioned reaction system.Wherein, citric acid: ethylene glycol: the mol ratio of metal ion summation is 3.0: 4.5: 1.0.
The 3rd step, reaction system is placed in the water bath with thermostatic control makes water evaporates obtain vitreosol gradually in 50 ℃ of following heating, continue dehydration and formed wet gel in 4 hours, under 140 ℃, wet gel was carried out heat drying 3 hours then, obtain cellular xerogel, in air atmosphere, under 550 ℃, xerogel was heat-treated 5 hours at last, cool to room temperature then with the furnace, just obtain having the LiNi of spinel-type crystalline structure
0.2Fe
0.2Mn
1.6O
4Eelctro-catalyst.
The preparation of air diffusion electrode: acetylene black and pore creating material ammonium oxalate are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains waterproof ventilated membrane repeatedly after cohesion; Catalyst, pore creating material, active carbon and acetylene black are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains catalytic membrane repeatedly after cohesion.Waterproof ventilated membrane, catalytic membrane and collector (nickel screen) be superimposed carry out roll-forming and just obtain air diffusion electrode.Wherein the set of dispense of waterproof ventilated membrane is than being acetylene black: PTFE: pore creating material=40wt%: 40wt%: 20wt%; The set of dispense ratio of catalytic membrane is: active carbon: pore creating material: PTFE: catalyst=35wt%: 15wt%: 20wt%: 50wt%.
The test of steady-state current-voltage polarizing curve: the steady-state current-voltage polarizing curve by the test air diffusion electrode is measured the electro catalytic activity of eelctro-catalyst.Under the room temperature normal pressure, the CHI660b electrochemical workstation of marine products in the employing, with the diffusing electrode of air is work electrode, the Hg/HgO electrode is a reference electrode, nickel screen is to electrode, the KOH aqueous solution of 6mol/L is electrolyte, with three electrode test systems the electro catalytic activity of air diffusion electrode eelctro-catalyst is carried out steady-state current-voltage polarizing curve test.Test result shows, its current density under-0.6V (Hg/HgO is a reference electrode) polarization potential is 237mA/cm
2
Embodiment eight
The preparation method of zinc-air cell eelctro-catalyst comprises the steps:
The first step, according to stoichiometry mol ratio Li: Ni: Co: Fe: Mn=1.00: 0.20: 0.20: 0.20: 1.40 take by weighing LiNO
3, Ni (NO
3)
26H
2O, CoC
2O
42H
2O, Fe (NO
3)
29H
2O and weight percent concentration are the Mn (NO of 50wt%
3)
2Solution adds distilled water and is made into saturated aqueous solution.
Second step added citric acid and ethylene glycol in above-mentioned reaction system, be 6.0 with the pH of ammoniacal liquor conditioned reaction system.Wherein, citric acid: ethylene glycol: the mol ratio of metal ion summation is 2.5: 4.5: 1.0.
The 3rd step, reaction system is placed in the water bath with thermostatic control makes water evaporates obtain vitreosol gradually in 80 ℃ of following heating, continue dehydration and formed wet gel in 3 hours, under 140 ℃, wet gel was carried out heat drying 3 hours then, obtain cellular xerogel, in air atmosphere, under 700 ℃, xerogel was heat-treated 8 hours at last, cool to room temperature then with the furnace, just obtain having the LiNi of spinel-type crystalline structure
0.2Co
0.2Fe
0.2Mn
1.4O
4Eelctro-catalyst.
The preparation of air diffusion electrode: acetylene black and pore creating material ammonium oxalate are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains waterproof ventilated membrane repeatedly after cohesion; Catalyst, pore creating material, active carbon and acetylene black are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains catalytic membrane repeatedly after cohesion.Waterproof ventilated membrane, catalytic membrane and collector (nickel screen) be superimposed carry out roll-forming and just obtain air diffusion electrode.Wherein the set of dispense of waterproof ventilated membrane is than being acetylene black: PTFE: pore creating material=40wt%: 40wt%: 20wt%; The set of dispense ratio of catalytic membrane is: active carbon: pore creating material: PTFE: catalyst=35wt%: 15wt%: 20wt%: 50wt%.
The test of steady-state current-voltage polarizing curve: the steady-state current-voltage polarizing curve by the test air diffusion electrode is measured the electro catalytic activity of eelctro-catalyst.Under the room temperature normal pressure, the CHI660b electrochemical workstation of marine products in the employing, with the air diffusion electrode is work electrode, the Hg/HgO electrode is a reference electrode, nickel screen is to electrode, the KOH aqueous solution of 6mol/L is electrolyte, with three electrode test systems the electro catalytic activity of air diffusion electrode eelctro-catalyst is carried out steady-state current-voltage polarizing curve test.Test result shows, its current density under-0.6V (Hg/HgO is a reference electrode) polarization potential is 251mA/cm
2
Embodiment nine
The preparation method of zinc-air cell eelctro-catalyst comprises the steps:
The first step, according to stoichiometry mol ratio Li: Ni: Co: Fe: Mn=1.00: 0.10: 0.10: 0.10: 1.70 take by weighing LiNO
3, Ni (NO
3)
26H
2O, Co (NO
3)
26H
2O, Fe (NO
3)
29H
2O and weight percent concentration are the Mn (NO of 50wt%
3)
2Solution adds distilled water and is made into saturated aqueous solution.
Second step added citric acid and ethylene glycol in above-mentioned reaction system, be 7.0 with the pH of ammoniacal liquor conditioned reaction system.Wherein, citric acid: ethylene glycol: the mol ratio of metal ion summation is 2.5: 4.0: 1.0;
The 3rd step, reaction system is placed in the water bath with thermostatic control makes water evaporates obtain vitreosol gradually in 65 ℃ of following heating, continue dehydration and formed wet gel in 5 hours, under 130 ℃, wet gel was carried out heat drying 7 hours then, obtain cellular xerogel, in air atmosphere, under 600 ℃, xerogel was heat-treated 12 hours at last, cool to room temperature then with the furnace, just obtain having the LiNi of spinel-type crystalline structure
0.1Co
0.1Fe
0.1Mn
1.7O
4Eelctro-catalyst.
The preparation of air diffusion electrode: acetylene black and pore creating material ammonium oxalate are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains waterproof ventilated membrane repeatedly after cohesion; Catalyst, pore creating material, active carbon and acetylene black are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains catalytic membrane repeatedly after cohesion.Waterproof ventilated membrane, catalytic membrane and collector (nickel screen) be superimposed carry out roll-forming and just obtain air diffusion electrode.Wherein the set of dispense of waterproof ventilated membrane is than being acetylene black: PTFE: pore creating material=40wt%: 40wt%: 20wt%; The set of dispense ratio of catalytic membrane is: active carbon: pore creating material: PTFE: catalyst=35wt%: 15wt%: 20wt%: 50wt%.
The test of steady-state current-voltage polarizing curve: the steady-state current-voltage polarizing curve by the test air diffusion electrode is measured the electro catalytic activity of eelctro-catalyst.Under the room temperature normal pressure, the CHI660b electrochemical workstation of marine products in the employing, with the air diffusion electrode is work electrode, the Hg/HgO electrode is a reference electrode, nickel screen is to electrode, the KOH aqueous solution of 6Mol/L is electrolyte, with three electrode test systems the electro catalytic activity of air diffusion electrode eelctro-catalyst is carried out steady-state current-voltage polarizing curve test.Test result shows, its current density under-0.6V (Hg/HgO is a reference electrode) polarization potential is 245mA/cm
2
Embodiment ten
The preparation method of zinc-air cell eelctro-catalyst comprises the steps:
The first step, according to stoichiometry mol ratio Li: Ni: Co: Fe: Mn=1.00: 0.50: 0.50: 0.50: 0.50 takes by weighing LiNO
3, Ni (NO
3)
26H
2O, Co (NO
3)
26H
2O, Fe (NO
3)
29H
2O and weight percent concentration are the Mn (NO of 50wt%
3)
2Solution adds distilled water and is made into saturated aqueous solution.
Second step added citric acid and ethylene glycol in above-mentioned reaction system, be 7.0 with the pH of ammoniacal liquor conditioned reaction system.Wherein, citric acid: ethylene glycol: the mol ratio of metal ion summation is 2.5: 4.0: 1.0.
The 3rd step, reaction system is placed in the water bath with thermostatic control makes water evaporates obtain vitreosol gradually in 75 ℃ of following heating, continue dehydration and formed wet gel in 3 hours, under 130 ℃, wet gel was carried out heat drying 7 hours then, obtain cellular xerogel, in air atmosphere, under 600 ℃, xerogel was heat-treated 12 hours at last, cool to room temperature then with the furnace, just obtain having the LiNi of spinel-type crystalline structure
0.1Co
0.1Fe
0.1Mn
1.7O
4Eelctro-catalyst.
The preparation of air diffusion electrode: acetylene black and pore creating material ammonium oxalate are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains waterproof ventilated membrane repeatedly after cohesion; Catalyst, pore creating material, active carbon and acetylene black are mixed with alcohol, add ptfe emulsion, constantly stir, make it to be uniformly dispersed, roll-in obtains catalytic membrane repeatedly after cohesion.Waterproof ventilated membrane, catalytic membrane and collector (nickel screen) be superimposed carry out roll-forming and just obtain air diffusion electrode.Wherein the set of dispense of waterproof ventilated membrane is than being acetylene black: PTFE: pore creating material=40wt%: 40wt%: 20wt%; The set of dispense ratio of catalytic membrane is: active carbon: pore creating material: PTFE: catalyst=35wt%: 15wt%: 20wt%: 50wt%.
The test of steady-state current-voltage polarizing curve: the steady-state current-voltage polarizing curve by the test air diffusion electrode is measured the electro catalytic activity of eelctro-catalyst.Under the room temperature normal pressure, the CHI660b electrochemical workstation of marine products in the employing, with the air diffusion electrode is work electrode, the Hg/HgO electrode is a reference electrode, nickel screen is to electrode, the KOH aqueous solution of 6Mol/L is electrolyte, with three electrode test systems the electro catalytic activity of air diffusion electrode eelctro-catalyst is carried out steady-state current-voltage polarizing curve test.Test result shows, its current density under-0.6V (Hg/HgO is a reference electrode) polarization potential is 202mA/cm
2
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (5)
1. the eelctro-catalyst of a zinc-air cell is characterized in that, the general formula of described eelctro-catalyst is LiNi
xCo
yFe
zMn
2-x-y-zO
4, wherein, 0.10≤x≤0.50,0≤y≤0.50,0≤z≤0.50; The crystalline structure of described eelctro-catalyst is the spinel-type crystalline structure.
2. the preparation method of the described zinc-air cell eelctro-catalyst of claim 1 is characterized in that comprising the steps:
The first step is according to spinel-type crystalline structure LiNi
xCo
yFe
zMn
2-x-y-zO
4The stoichiometry mol ratio Li of composite oxide of metal: Ni: Co: Fe: Mn=1.00: 0.10～0.50: 0～0.50: 0～0.50: 0.50～1.90 takes by weighing each slaine, adds distilled water and is made into saturated aqueous solution;
Second step added citric acid and ethylene glycol in above-mentioned reaction system, be 4.5～7.0 with the pH of ammoniacal liquor conditioned reaction system; Wherein, citric acid: ethylene glycol: the mol ratio of metal ion summation is 2.0～3.5: 3.5～5.0: 1.0;
The 3rd step, above-mentioned reaction system is placed in the water bath with thermostatic control makes water evaporates obtain vitreosol gradually in 50～90 ℃ of following heating, continue dehydration and formed wet gel in 2～6 hours, under 100～160 ℃, wet gel was carried out heat drying 3～16 hours then, obtain xerogel, in air atmosphere, under 400～900 ℃, xerogel was heat-treated 1～16 hour at last, be cooled to room temperature then, just obtain the eelctro-catalyst of zinc-air cell; Described eelctro-catalyst has the spinel-type crystalline structure.
3. the preparation method of zinc-air cell eelctro-catalyst according to claim 2 is characterized in that,, described slaine comprises one or more the mixture in nitrate, acetate or the oxalates of each metallic element.
4. the preparation method of zinc-air cell eelctro-catalyst according to claim 3 is characterized in that, described nitrate comprises LiNO
3, Ni (NO
3)
26H
2O, Co (NO
3)
26H
2O, Mn (NO
3)
2Or Fe (NO
3)
29H
2O; Described acetate comprises Ni (CH
3COO)
24H
2O, Mn (CH
3COO)
24H
2O or Co (CH
3COO)
2Described oxalates comprises CoC
2O
42H
2O.
5. the preparation method of zinc-air cell eelctro-catalyst according to claim 2 is characterized in that, the pH of conditioned reaction system is 4.5～7.0th in second step, regulates with ammoniacal liquor.
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| CNB2007100288396A CN100490229C (en) | 2007-06-26 | 2007-06-26 | Electro-catalyst of zinc-air battery and method for making same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102005578A (en) * | 2010-10-15 | 2011-04-06 | 南开大学 | Cylindrical film air electrode and application thereof in zinc-air battery |
| CN112382766A (en) * | 2020-08-26 | 2021-02-19 | 哈尔滨工业大学（深圳） | Catalyst, method for preparing the same, and secondary battery comprising the same |
| CN112758996A (en) * | 2020-12-14 | 2021-05-07 | 清华大学 | Bifunctional oxygen electrocatalyst and preparation and application thereof |
-
2007
- 2007-06-26 CN CNB2007100288396A patent/CN100490229C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102005578A (en) * | 2010-10-15 | 2011-04-06 | 南开大学 | Cylindrical film air electrode and application thereof in zinc-air battery |
| CN112382766A (en) * | 2020-08-26 | 2021-02-19 | 哈尔滨工业大学（深圳） | Catalyst, method for preparing the same, and secondary battery comprising the same |
| CN112758996A (en) * | 2020-12-14 | 2021-05-07 | 清华大学 | Bifunctional oxygen electrocatalyst and preparation and application thereof |
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|---|---|
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