CN101752629A - Rechargeable metal hydride air battery with auxiliary electrode - Google Patents
Rechargeable metal hydride air battery with auxiliary electrode Download PDFInfo
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Abstract
The invention relates to an air battery, and aims to provide a rechargeable metal hydride air battery provided with an auxiliary electrode. The transverse structure of the battery is as follows in sequence: an auxiliary electrode current collector with an oxygen discharge passage, a carrier coated with an auxiliary electrode catalyst, an auxiliary electrode diaphragm, a porous negative electrode, a diaphragm, a carrier coated with a positive electrode catalyst, and a positive electrode current collector with an air passage, and sealing is realized by a sealing ring; the porous negative electrode is loaded with hydrogen storage metal as a negative electrode material, and the electrolyte is absorbed in the porous negative electrode. The invention can avoid direct oxidation of the anode catalyst, maintain good hydrophobic performance of the anode, and is beneficial to oxygen in the air to smoothly diffuse to the anode catalyst layer through the carbon cloth or the carbon paper; the zinc electrode can be prevented from being deformed after the battery is short-circuited and is charged for many times due to dendritic crystal formation caused by the fact that zinc in the zinc-air battery serves as an energy storage medium, and the service life of the air battery is prolonged; can be used for manufacturing high-power air batteries to meet the requirement of serving as a power supply of an electric vehicle.
Description
Technical Field
The invention relates to an air battery, in particular to a rechargeable metal hydride air battery provided with an auxiliary electrode.
Background
The invention of air battery has been for hundreds of years history, and in 1878 french scientist l. Meixie first developed the technology of zinc-air battery by replacing manganese dioxide with platinum-containing porous carbon electrode in zinc-manganese battery. In 1917, a french scientist c replaces platinum with activated carbon to absorb oxygen, so that the zinc-air battery is put into practical use. Zinc-air batteries using alkaline electrolytes were published in 1932 by g.w. haize and e.a. sumachel. In the 60 s, the research on the oxygen electrode of the normal-temperature fuel cell for aerospace has been successful, and the development of the high-power zinc-air cell reaches the practical application stage. Miniature button zinc-air cells were developed in the mid 70 s. In 1995, israel Electric Fuel (Electric Fuel) limited used zinc-air batteries for Electric vehicles for the first time, so that the air batteries entered into practical use. The united states dreisback electrokinetic corporation and several countries in germany, france, sweden, the netherlands, finland, spain and south africa are also actively spreading zinc-air batteries on electric vehicles.
The zinc-air cell is a cell in which oxygen in the air is used as positive active material, and the electrode made of carrier active carbon and negative electrode using zinc as active material are reacted, and it uses KOH solution or NH 4 Cl is used as electrolyte. Oxygen in the air of the positive electrode reaches the reaction interface of the air electrode through diffusion to participate in electrochemical reaction to generate current, and after the oxygen is consumed, fresh oxygen is continuously absorbed from the air to continuously generate the current. As the oxygen of the anode reactive material is derived from air outside the battery body, is inexhaustible, the air anode can work continuously theoretically as long as sufficient zinc and electrolyte exist as cathode materials, and the characteristic of the zinc-air battery shows the advantage of high specific energy, thereby arousing great interest for a long time. With the gradual improvement of the zinc-air battery technology, the potential of the zinc-air battery is gradually developed, the application range is gradually expanded, and the zinc-air battery is not only applied to communication machines, navigation mark lamps, ocean buoys and other equipment, but also applied to the communication machines, the navigation mark lamps, the ocean buoys and other equipmentEnter everyday fields in large numbers, such as hearing aids, electronic watches, calculators, etc.
However, conventional air batteries such as zinc-air batteries all belong to primary batteries, and after discharge is finished, the air batteries cannot be reused without replacing cathode materials. Since the 60's of the 20 th century, many charging methods such as mechanical recharging, third electrode, mixed oxygen electrode, bifunctional oxygen electrode, and circulating active material and electrolyte have been explored, and no satisfactory results have been obtained. The third electrode charging method can directly charge the zinc electrode of the zinc-air battery by using the third electrode as an auxiliary electrode, but does not participate in discharging. The charging method can avoid different requirements of charging and discharging on the hydrophobicity of the electrode, but zinc dendrites generated when the zinc-air battery is charged easily cause short circuit of the battery and the zinc electrode deforms after multiple charging to reduce the use times of the air battery. In order to solve the above problems, it is necessary to use a negative electrode material that does not generate dendrites by increasing the number of times the air battery is used.
The hydrogen storage metal is a negative electrode material in a rechargeable nickel-metal hydride battery. It is a metal hydride which has high activity, can reduce hydrogen in water into hydrogen atoms under the action of electrons and stores the hydrogen atoms in a lattice of hydrogen storage metal to form. The nickel-hydrogen battery is composed of hydrogen storage metal as a negative electrode and nickel hydroxide as a positive electrode. During charging, electrochemical reactions occur in alkaline solutions:
negative electrode: m + xH 2 O+xe - →MH x +xOH - (1)
And (3) positive electrode: ni (OH) 2 +OH - →NiOOH+H 2 O+e - (2)
The battery reaction is as follows: m + xNi (OH) 2 →MHx+xNiOOH (3)
In the above reaction formula, M represents a hydrogen storage metal. The battery can store electric energy, and can convert chemical energy stored in the positive electrode and the negative electrode into electric energy to be released when needed through the reverse reaction of the reaction.
Disclosure of Invention
The invention aims to provide a rechargeable metal hydride air battery which has long service life and is provided with an auxiliary electrode.
In order to solve the technical problem, the rechargeable metal hydride air battery provided with the auxiliary electrode is provided with the auxiliary electrode, wherein a cation exchange membrane, an anion exchange membrane or a polypropylene membrane is used as a diaphragm to separate a negative electrode and a positive electrode.
The transverse structure of the air battery is as follows in sequence: an auxiliary electrode current collector with an oxygen discharge passage, a carrier coated with an auxiliary electrode catalyst, an auxiliary electrode diaphragm, a porous negative electrode, a diaphragm, a carrier coated with a positive electrode catalyst, and a positive electrode current collector with an air passage, and sealing is realized by a sealing ring; the positive terminal of the air battery is led out by the positive current collector, the negative terminal is led out by the porous negative electrode, and the auxiliary electrode is led out by the auxiliary current collector; loading hydrogen storage metal in the porous negative electrode as a negative electrode material, taking ammonium chloride aqueous solution, KOH solution, naOH solution or chloroalkylimidazole ionic liquid as electrolyte, wherein the concentration of the electrolyte is 1-6 mol/L, and the electrolyte is absorbed in the porous negative electrode;
the current collector is used for connecting a positive electrode terminal or a negative electrode terminal of a battery when the battery is used, and is made of a conductive material such as a metal or a carbon material, and plays a role in conducting current.
The general formula of the hydrogen storage metal used as the negative electrode material is Zr 1-y Ti y Ni 2-a-b M a N b Wherein: m is transition metal V, cr, mn, fe or Co; n is an additive element Al or Si; a ranges from 0 to 1, b ranges from 0 to 1, y ranges from 0 to 0.5;
the porous negative electrode is prepared by the following method: preparing a slurry from powdered hydrogen storage metal and 5wt.% of sodium carboxymethyl cellulose solution or 5wt.% of polyvinyl alcohol solution according to the mass ratio of 1: 1-3, filling the slurry into a negative electrode base material, drying at room temperature, and pressing into a porous negative electrode; the negative electrode substrate is a porous metal material or a porous material made of conductive fibers; in the prepared porous negative electrode, the mass ratio of the hydrogen storage metal to the negative electrode base material is 1: 0.05-0.5;
the air battery takes at least one of polypyrrole-modified carbon-supported noble metal catalysts as a positive electrode catalyst, and the noble metal is Pt, pd, au or Ag;
the support coated with the positive electrode catalyst is prepared by the following method:
(1) Preparing polypyrrole-modified carbon-supported noble metal:
dispersing carbon black into water, methanol or chloroform to prepare suspension with the mass ratio of 1: 15; adding glacial acetic acid or hydrochloric acid to adjust the pH value to 2.5-3, and stirring for 10-30 min at room temperature; adding pyrrole according to the mass ratio of carbon black to pyrrole of 1: 0.05-0.3, stirring for 5-10 min, then adding 1 g of noble metal chloride or mixture thereof, and then adding 0.05-0.1 g of H 2 O 2 (ii) a Stirring at room temperature for 3-10 h, and heating to 70-90 ℃; slowly adding 300ML of 0.1ML -1 After the reducing agent is alkaline sodium borohydride solution, stirring vigorously for 30-60 min, and naturally cooling; washing and filtering with deionized water, drying at 70-90 deg.C for 6-12 h, and adding Ar or N 2 And then heat treatment is carried out for 1-5 h at 300-600 ℃ under inert atmosphere to prepare the corresponding polypyrrole modified carbon-supported noble metal catalyst.
(2) Mixing polypyrrole-modified carbon-supported noble metal catalyst, water, 5wt.% polytetrafluoroethylene suspension and absolute ethyl alcohol according to the mass ratio of 1: 3: 2-7: 3-6 to prepare slurry, coating the slurry on hydrophobic carbon paper or carbon cloth, and naturally airing the hydrophobic carbon paper or carbon cloth x H y The mass ratio of the catalyst to the carbon paper or the carbon cloth is 1: 10-100;
the auxiliary electrode of the air battery is prepared by the following steps:
mixing polypyrrole-modified carbon-supported noble metal catalyst, water, 5wt.% of polyvinyl alcohol solution and absolute ethyl alcohol or polypyrrole-modified carbon-supported noble metal catalyst, water, 5wt.% of sodium carboxymethyl cellulose solution and absolute ethyl alcohol according to the mass ratio of 1: 3: 2-7: 3-6 to prepare slurry, coating the slurry on hydrophobic carbon paper or carbon cloth, and naturally airing the hydrophobic carbon paper or carbon cloth to obtain the polypyrrole-modified carbon-supported noble metal catalyst and the carbon paper or the carbon cloth, wherein the mass ratio of the polypyrrole-modified carbon-supported noble metal catalyst to the carbon paper or the carbon cloth is 1: 10-100.
In the preparation process of the porous negative electrode, polypyrrole-modified carbon black is added as an additive of the negative electrode during preparation of slurry, namely powdery hydrogen storage metal, polypyrrole-modified carbon black and 5wt.% of sodium carboxymethyl cellulose solution or 5wt.% of polyvinyl alcohol solution are prepared into slurry according to the mass ratio of 1: 0-0.5: 1-3;
the polypyrrole-modified carbon black is prepared by the following steps: dispersing carbon black into water, methanol or chloroform to prepare suspension with the mass ratio of 1: 15; adding glacial acetic acid or hydrochloric acid to adjust the pH value to 2.5-3, and stirring for 10-30 min at room temperature; adding pyrrole according to the mass ratio of carbon black to pyrrole of 1: 0.05-0.3, stirring for 5-10 min, and then adding H with the mass of 0.05-0.1 g 2 O 2 As an initiator of the polymerization reaction, stirring for 3-10 h at room temperature; washing the product with warm deionized water, and drying in vacuum to obtain the polypyrrole-modified carbon black.
In the invention, the porous metal material is foamed nickel or foamed copper, and the porous material made of the conductive fibers is a porous material made of nickel fibers, nickel-plated metal fibers or carbon fibers.
In the invention, the preparation of the hydrogen storage metal as the anode material comprises the following steps:
(1) The substituting elements M and N of the zirconium, the titanium, the nickel and the nickel are (1-y) to y to (2-a-b) to a to b according to the atomic ratio, and the using amounts of the substituting elements M and N of the zirconium, the titanium, the nickel and the nickel are determined; melting in an electromagnetic induction furnace or an arc furnace under the protection of argon, cooling to obtain Zr blocks 1-y Ti y Ni 2-a-b M a N b Alloying;
(2) Crushing the obtained hydrogen storage metal into particles with particle diameter below 2 mm by a mechanical method, placing the particles in a stainless steel reactor, and vacuumizing at room temperature until the pressure of the reactor is less than 10 -3 Torr, then hydrogenation is carried out, and the pressure is increased to 20 atmospheric pressure for hydrogenation; heating and cooling for 1-10 times at room temperature-100 deg.C to obtainThe purpose of hydrogen releasing and absorbing circulation is achieved, and the hydrogen storage metal powder is obtained.
In the invention, the auxiliary electrode diaphragm is a cation exchange membrane, an anion exchange membrane or a polypropylene membrane.
In the invention, when the air battery is charged, 1.5-2V voltage is applied between the auxiliary electrode and the negative electrode, electrochemical oxidation is generated on the auxiliary electrode to generate oxygen, and electrochemical hydrogen charging of hydrogen storage metal is generated on the negative electrode to form metal hydride. Charging ends when all of the hydrogen storage metal is converted to a metal hydride. When the load is connected to the positive and negative electrodes of the air battery, hydrogen in the metal hydride at the negative electrode is electrochemically oxidized to form water, and oxygen is electrochemically reduced at the positive electrode. Taking a rechargeable air battery formed by taking an anionic electrolyte membrane as an isolated negative electrode, a positive electrode and an auxiliary electrode as an example, the working principle of the rechargeable air battery is as follows:
applying a voltage of 1.5-2V between the auxiliary electrode and the negative electrode to charge the air battery, generating electrochemical oxidation on the auxiliary electrode to generate oxygen,
4OH - →O 2 +2H 2 O+4e - (4)
OH - ions are derived from the alkaline solution added in the negative electrode and diffused to the carbon-supported catalyst of the auxiliary electrode through the anion exchange membrane. Electrons generated by electrochemical oxidation reaction on the auxiliary electrode flow to the negative electrode through an external circuit, water in the solution is electrochemically reduced on the hydrogen storage metal negative electrode to generate atomic hydrogen, and the atomic hydrogen enters the hydrogen storage metal lattice to form metal hydride:
M+xH 2 O+xe - →MH x +xOH - (5)
OH - ions are diffused to the auxiliary electrode for supplying, and the sodium carboxymethyl cellulose and the polyvinyl alcohol play roles in absorbing and storing alkaliThe action of the liquid. Thus, the combined reactions (4) and (5), which occur when the air battery is charged, are:
4M+2xH 2 O→4MH x +xO 2 (6)
when the load is connected to the positive and negative electrodes of the air battery, hydrogen in the metal hydride of the negative electrode is electrochemically oxidized to form water,
MH x +xOH - →M+xH 2 O+xe - (7)
electrons released by the cathode do work outwards when passing through the load, and the electrons flow to the anode to electrochemically reduce oxygen to generate OH - The ions are selected from the group consisting of,
O 2 +2H 2 O+4e - →4OH - (8)
OH - the ions return to the cathode by diffusion through the anion exchange membrane. Thus, the combined reactions (7) and (8), which occur when the air battery is discharged, are:
4MH x +xO 2 →4M+2xH 2 O (9)
and the reaction (9) is the reverse reaction of the reaction (6), thereby realizing reversible charge and discharge of the air battery.
The catalyst layer of the anode is hydrophobic, which is favorable for air diffusion, and the catalyst layer of the auxiliary electrode is hydrophilic, which is favorable for OH - The diffusion of ions avoids different requirements on the hydrophobicity and the hydrophilicity of the anode of the air battery in the charging and discharging processes.
The invention has the beneficial effects that:
(1) The auxiliary electrode directly charges the hydrogen storage metal of the air battery, but does not participate in discharging. The charging method can avoid direct oxidation of the anode catalyst, maintain good hydrophobic performance of the anode, and is beneficial to oxygen in the air to smoothly diffuse to the anode catalyst layer through carbon cloth or carbon paper.
(2) The hydrogen storage metal is used as the cathode material of the air battery, the energy storage is realized by utilizing the chemical valence state change of hydrogen, the short circuit of the battery and the deformation of a zinc electrode after multiple charging caused by the formation of dendrite caused by the zinc in the zinc-air battery as an energy storage medium can be avoided, thereby increasing the use times of the air battery and prolonging the service life of the air battery.
(3) The method can be used for manufacturing a high-power air battery to meet the requirement of serving as a power supply of an electric vehicle, reduces air pollution and has higher social benefit and economic benefit.
Drawings
Fig. 1 shows the structure of a metal hydride air battery provided with an auxiliary electrode.
Fig. 2 is a comparison of the cycle characteristics of the air cell described in example 3 with a conventional zinc-air cell.
The reference numbers in the figures are:
an auxiliary electrode seal 201, an auxiliary electrode separator 202, an auxiliary electrode current collector 203, an oxygen gas discharge passage 204, an auxiliary electrode catalyst carrier 205, an auxiliary electrode catalyst 206, an auxiliary electrode seal 207, a negative electrode seal 208, a porous negative electrode 209 having absorbed an electrolyte, a positive electrode seal 211, a positive electrode catalyst 212, a positive electrode catalyst carrier 213, an air passage 214, a positive electrode current collector 215, a positive electrode seal 216, a separator 217, a negative electrode seal 218, a negative electrode terminal 219, an auxiliary electrode terminal 220, and a positive electrode terminal 221.
Detailed Description
The hydrogen storage metal (AB 2 type) of the negative electrode material of the invention has the general formula of Zr i-y Ti y Ni 2-a-b M a N b In the formula: m is transition metal V, cr, mn, fe, co; n is additive elements Al and Si, and the range of a is 0-1.5; b ranges from 0 to 0.5; y ranges from 0 to 1.
A method of making a hydrogen storage metal comprising the steps of:
(1) Determining the use amounts of the substitutional elements M and N of the zirconium, the titanium, the nickel and the nickel according to the atomic ratio of (1-y) to y to (2-a-b) to a to b; melting the Zr in an electromagnetic induction furnace or an electric arc furnace under the protection of argon, and cooling to form the Zr blocks respectively 1-y Ti y Ni 2-a-b M a N b And (3) alloying.
(2) Crushing the obtained hydrogen storage metal into particles with the particle size of below 2 mm by a mechanical method, placing the particles in a stainless steel reactor, vacuumizing the reactor at room temperature until the pressure of the reactor is less than 10-3Torr, and then adding hydrogen and increasing the pressure to 20 atmospheric pressure for hydrogenation; heating and cooling for 1-10 times at room temperature-100 deg.c to reach the aim of hydrogen releasing and absorbing circulation to obtain hydrogen storing metal powder.
The present invention is described in further detail below with reference to specific embodiments:
the first embodiment is as follows: with TiNi 0.5 Mn 1.5 Rechargeable air battery as negative electrode material
Sieving TiNi with particle size less than 10 microns 0.5 Mn 1.5 Pulverizing TiNi 0.5 Mn 1.5 Mixing the fine powder with binder carboxymethylcellulose sodium solution (5 wt.%) to obtain slurry, coating the slurry onto foamed nickel, drying at room temperature, and press-forming to obtain TiNi 0.5 Mn 1.5 Negative electrode of air cell. TiNi 0.5 Mn 1.5 The mass ratio of the nickel foam to the nickel foam is 1: 0.5.
Dispersing carbon black into water to prepare suspension, wherein the mass ratio of the suspension to the carbon black is 1: 15; adding glacial acetic acid to adjust pH to 2.5, and stirring at room temperature for 30min; adding pyrrole at a mass ratio of carbon black to pyrrole of 1: 0.3, stirring for 5min, adding platinum chloride at a mass ratio of carbon black to platinum chloride of 1: 0.1, adding 10 ml hydrogen peroxide (with a concentration of 0.5 wt.%) to carry out pyrrole polymerization reaction, stirring for 10h at room temperature, and heating to 90 ℃; slowly adding 300ML of 0.1ML -1 After the reducing agent is alkaline with the sodium borohydride solution, stirring vigorously for 60min, and naturally cooling; washing and filtering with deionized water, drying at 90 ℃ in vacuum for 6h, and then preserving heat at 300 ℃ in Ar atmosphere for 5h for heat treatment to prepare the polypyrrole modified carbon-supported platinum catalyst. Mixing a catalyst, water, a polytetrafluoroethylene suspension (5 wt.%) and absolute ethyl alcohol according to a mass ratio of 1: 3: 2: 3to prepare a slurry, coating the slurry on hydrophobic carbon cloth, and naturally airing to obtain the anode. The mass ratio of the polypyrrole modified carbon-supported platinum to the carbon cloth is 1: 100. Mixing a catalyst, water, a PVA solution (5 wt.%) and absolute ethyl alcohol according to the mass ratio of 1: 3: 2: 3to prepare a slurry, coating the slurry on hydrophobic carbon cloth, and naturally airing to obtain the auxiliary electrode. Polypyrrole modified carbon supported platinum and carbonThe mass ratio of the cloth is 1: 100.
Select concentration of 1ML -1 The aqueous ammonium chloride solution was used as an electrolyte, and the negative electrode was separated from the positive electrode and the auxiliary electrode by an anion exchange membrane, and an air battery was assembled as shown in fig. 1.
Example two: with Zr 0.8 Ti 0.2 Ni 1.3 Co 0.3 Si 0.2 Air battery as negative electrode material
Zr with grain diameter more than 10 mu m and less than 100 mu m 0.8 Ti 0.2 Ni 1.3 Co 0.3 Si 0.2 And mixing the fine powder and a PVA solution (5 wt.%) according to the mass ratio of 1: 0.3: 2 to prepare a slurry, coating the slurry into the foam copper, drying at room temperature, and then pressing and forming to obtain the negative electrode used as the air battery. With Zr 0.8 Ti 0.2 Ni 1.3 Co 0.3 Si 0.2 The mass ratio of the copper foam to the copper foam is 1: 10.
Dispersing carbon black into methanol to prepare suspension with the mass ratio of 1: 15, adding hydrochloric acid to adjust the pH value to 3, and stirring at room temperature for 20min; adding pyrrole and stirring for 10min, then adding palladium chloride, wherein the mass ratio of carbon black to pyrrole is 1: 0.05, adding 15 ml of hydrogen peroxide (with the concentration of 0.5 wt.%) to perform pyrrole polymerization reaction, stirring for 3h at room temperature, and heating to 70 ℃; slowly adding a reducing agent alkaline sodium borohydride solution, violently stirring for 60min, and naturally cooling; washing and filtering with deionized water, drying at 80 ℃ for 12h in vacuum, and then preserving heat at 400 ℃ for 1h under nitrogen atmosphere for heat treatment to prepare the polypyrrole-modified carbon-supported palladium catalyst. Mixing a catalyst, water, a polytetrafluoroethylene suspension (5 wt.%) and absolute ethyl alcohol according to a mass ratio of 1: 3: 7: 6 to prepare a slurry, coating the slurry on hydrophobic carbon paper, and naturally airing to obtain the anode. The mass ratio of the polypyrrole-modified carbon-supported palladium to the carbon paper is 1: 5. Mixing a catalyst, water, a CMC solution (5 wt.%) and absolute ethyl alcohol according to the mass ratio of 1: 3: 7: 6 to prepare a slurry, coating the slurry on hydrophobic carbon paper, and naturally airing to obtain the auxiliary electrode. The mass ratio of the polypyrrole-modified palladium-on-carbon to the carbon paper is 1: 5.
Selection of concentrationIs 1ML -1 The negative electrode was separated from the positive electrode and the auxiliary electrode by a cation exchange membrane using the ammonium chloride aqueous solution as an electrolyte, and an air battery was assembled as shown in fig. 1.
Example three: with ZrNi 1.5 Cr 0.25 Al 0.25 Air battery as negative electrode material
ZrNi 1.5 Cr 0.25 Al 0.25 Mixing the fine powder (less than 100 microns) and PVA aqueous solution (5 wt.%) according to the mass ratio of 1: 0.5: 3to prepare slurry, coating the slurry into a carbon fiber felt, drying at room temperature, and then performing compression molding to obtain the ZrNi serving as the negative electrode of the air battery 1.5 Cr 0.25 Al 0.25 The mass ratio of the carbon fiber felt to the carbon fiber felt is 1: 0.05.
Dispersing carbon black into chloroform to prepare a suspension with the mass ratio of 1: 15, adding hydrochloric acid to adjust the pH value to 3, and stirring at room temperature for 10min; adding pyrrole at the mass ratio of carbon black to pyrrole of 1: 0.1, stirring for 5min, adding gold chloride and platinum chloride at the mass ratio of carbon black to gold chloride to platinum chloride of 1: 2.5, adding 20 ml hydrogen peroxide (with the concentration of 0.5 wt.%) to perform pyrrole polymerization reaction, stirring for 5h at room temperature, and heating to 80 ℃; slowly adding a reducing agent alkaline sodium borohydride solution, violently stirring for 60min, and naturally cooling; washing and filtering with deionized water, and drying at 70 ℃ for 10h in vacuum to obtain the polypyrrole modified carbon-supported platinum catalyst. Mixing a catalyst, water, a polytetrafluoroethylene suspension (5 wt.%) and absolute ethyl alcohol according to a mass ratio of 1: 3: 4 to prepare a slurry, coating the slurry on hydrophobic carbon paper, and naturally airing to obtain the anode. The mass ratio of the polypyrrole modified carbon-supported platinum to the carbon paper is 1: 10. Mixing a catalyst, water, a CMC solution (5 wt.%) and absolute ethyl alcohol according to the mass ratio of 1: 3: 4 to prepare a slurry, coating the slurry on hydrophobic carbon paper, and naturally airing to obtain the auxiliary electrode. The mass ratio of the polypyrrole modified carbon-supported platinum to the carbon paper is 1: 10.
Selecting 3ML -1 The negative electrode was separated from the positive electrode and the auxiliary electrode by a polypropylene nonwoven fabric using NaOH as an electrolyte, and an air battery was assembled as shown in FIG. 1. Fig. 2 is a comparison of the cycle characteristics of the battery with that of a conventional zinc-air battery.
Example four: with Zr 0.5 Ti 0.5 Ni 1.5 V 0.5 Air battery as negative electrode material
Adding Zr 0.5 Ti 0.5 Ni 1.5 V 0.5 And mixing the fine powder and a PVA solution (5 wt.%) according to a mass ratio of 1: 3to prepare a slurry, coating the slurry into foamed nickel, drying at room temperature, and then performing compression molding to obtain the negative electrode used as the air battery.
Dispersing carbon black into chloroform to prepare suspension with the mass ratio of 1: 15, adding hydrochloric acid to adjust the pH value to 3, and stirring at room temperature for 30min; adding pyrrole and silver chloride at a mass ratio of carbon black to pyrrole of 1: 0.2, stirring for 8min, adding silver chloride at a mass ratio of carbon black to silver chloride of 1: 2.5, stirring for 3h at room temperature, adding 20 ml hydrogen peroxide (with a concentration of 0.5 wt.%) to perform pyrrole polymerization reaction, stirring for 5h at room temperature, and heating to 80 ℃; slowly adding a reducing agent alkaline sodium borohydride solution, violently stirring for 60min, and naturally cooling; washing and filtering with deionized water, drying at 90 ℃ in vacuum for 8h, and then preserving heat at 600 ℃ in nitrogen atmosphere for 1h for heat treatment to prepare the polypyrrole modified carbon-supported silver catalyst. Mixing a catalyst, water, a polytetrafluoroethylene suspension (5 wt.%) and absolute ethyl alcohol according to a mass ratio of 1: 3: 5: 6 to prepare a slurry, coating the slurry on hydrophobic carbon paper, and naturally airing to obtain the anode. The mass ratio of the polypyrrole modified carbon-supported silver catalyst to the carbon paper is 1: 20. Mixing a catalyst, water, a PVA solution (5 wt.%) and absolute ethyl alcohol according to the mass ratio of 1: 3: 5: 6 to prepare a slurry, coating the slurry on hydrophobic carbon paper, and naturally airing to obtain the auxiliary electrode. The mass ratio of the polypyrrole modified carbon-supported silver catalyst to the carbon paper is 1: 20.
The selected concentration is 6ML -1 The negative electrode was separated from the positive electrode and the auxiliary electrode by a polypropylene nonwoven fabric, and the air battery was assembled as shown in fig. 1.
Example five: with Zr 0.2 Ti 0.8 Ni 1.3 Fe 0.2 Al 0.5 Air battery as negative electrode material
Dispersing carbon black into water to prepare suspension with the mass ratio of 1: 15, adding glacial acetic acid to adjust the pH value to 2.5, and stirring at room temperature for 30min; the mass ratio of the carbon black to the pyrrole is 1: 0.25, the pyrrole is added and stirred for 10min, then 10 ml of hydrogen peroxide (with the concentration of 0.5 wt.%) is added and used as an initiator of polymerization reaction, the mixture is stirred for 3h at room temperature and then filtered, and the mixture is washed and filtered by deionized water and then dried for 12h at 90 ℃ in vacuum to prepare the polypyrrole modified carbon black.
Zr (B) is added 0.2 Ti 0.8 Ni 1.5 Fe 0.5 Mixing the fine powder, the polypyrrole-modified carbon black and a CMC solution (5 wt.%) according to a mass ratio of 1: 0.3: 3to prepare a slurry, coating the slurry on a nickel-plated fiber felt, drying at room temperature, and then performing compression molding to obtain the negative electrode used as an air battery.
Dispersing carbon black into water to prepare suspension with the mass ratio of 1: 15, adding glacial acetic acid to adjust the pH value to 2.5, and stirring at room temperature for 30min; adding pyrrole at the mass ratio of carbon black to pyrrole of 1: 0.25, stirring for 10min, adding gold chloride at the mass ratio of carbon black to gold chloride of 1: 5, adding 10 ml hydrogen peroxide (with the concentration of 0.5 wt.%) to perform pyrrole polymerization reaction, stirring for 3h at room temperature, and heating to 90 ℃; slowly adding alkaline sodium borohydride solution serving as a reducing agent, violently stirring for 60min, and naturally cooling; washing and filtering with deionized water, and drying at 90 ℃ in vacuum for 12h to obtain the polypyrrole modified carbon-supported gold catalyst. Mixing a catalyst, water, a polytetrafluoroethylene suspension (5 wt.%) and absolute ethyl alcohol according to a mass ratio of 1: 3: 2: 3to prepare a slurry, coating the slurry on hydrophobic carbon cloth, and naturally airing to obtain the anode. The mass ratio of the polypyrrole modified carbon-supported gold to the carbon cloth is 1: 100. Mixing a catalyst, water, a CMC solution (5 wt.%) and absolute ethyl alcohol according to the mass ratio of 1: 3: 2: 3to prepare a slurry, coating the slurry on hydrophobic carbon cloth, and naturally airing to obtain the auxiliary electrode. The mass ratio of the polypyrrole modified carbon-supported gold to the carbon cloth is 1: 100.
The selected concentration is 6ML -1 The negative electrode was separated from the positive electrode and the auxiliary electrode by a polypropylene nonwoven fabric, and the air battery was assembled as shown in fig. 1.
Finally, it is also noted that the above-mentioned publications only illustrate specific embodiments of the present invention. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (5)
1. A rechargeable metal hydride air battery with an auxiliary electrode takes a cation exchange membrane, an anion exchange membrane or a polypropylene membrane as a diaphragm to separate a negative electrode and a positive electrode, and is characterized by also being provided with the auxiliary electrode; the transverse structure of the air battery is as follows in sequence: an auxiliary electrode current collector with an oxygen discharge passage, a carrier coated with an auxiliary electrode catalyst, an auxiliary electrode diaphragm, a porous negative electrode, a diaphragm, a carrier coated with a positive electrode catalyst, and a positive electrode current collector with an air passage, and sealing is realized by a sealing ring; the positive terminal of the air battery is led out by a positive current collector, the negative terminal is led out by a porous negative electrode, and the auxiliary electrode is led out by an auxiliary electrode current collector; loading hydrogen storage metal in the porous negative electrode as a negative electrode material, taking ammonium chloride aqueous solution, KOH solution, naOH solution or chloroalkylimidazole ionic liquid as electrolyte, wherein the concentration of the electrolyte is 1-6 mol/L, and the electrolyte is absorbed in the porous negative electrode;
the general formula of the hydrogen storage metal used as the negative electrode material is Zr 1-y Ti y Ni 2-a-b M a N b Wherein: m is transition metal V, cr, mn, fe or Co; n is additive element Al or Si; a ranges from 0 to 1, b ranges from 0 to 1, y ranges from 0 to 0.5;
the porous negative electrode is prepared by the following method: preparing a slurry from powdered hydrogen storage metal and 5wt.% of sodium carboxymethyl cellulose solution or 5wt.% of polyvinyl alcohol solution according to the mass ratio of 1: 1-3, filling the slurry into a negative electrode base material, drying at room temperature, and pressing into a porous negative electrode; the negative electrode substrate is a porous metal material or a porous material made of conductive fibers; in the prepared porous negative electrode, the mass ratio of the hydrogen storage metal to the negative electrode base material is 1: 0.05-0.5;
the air battery takes at least one of polypyrrole-modified carbon-supported noble metal catalysts as a positive electrode catalyst, and the noble metal is Pt, pd, au or Ag;
the support coated with the positive electrode catalyst is prepared by the following method:
(1) Preparing polypyrrole-modified carbon-supported noble metal:
dispersing carbon black into water, methanol or chloroform to prepare suspension with the mass ratio of 1: 15; adding glacial acetic acid or hydrochloric acid to adjust the pH value to 2.5-3, and stirring for 10-30 min at room temperature; adding pyrrole and stirring for 5-10 min according to the mass ratio of the carbon material to the pyrrole of 1: 0.05-0.3, and then adding 1 g of noble metal chloride or a mixture thereof; then adding H with the mass of 0.05-0.1 g 2 O 2 (ii) a Stirring at room temperature for 3-10 h, and heating to 70-90 ℃; slowly adding 300ML of alkaline sodium borohydride solution of reducing agent with the concentration of 0.1ML-1, violently stirring for 30-60 min, and naturally cooling; washing and filtering with deionized water, drying at 70-90 deg.C for 6-12 h, and adding Ar or N 2 The temperature is kept at 300-600 ℃ for 1-5 h under the inert atmosphere for heat treatment to prepare the corresponding polypyrrole modified carbon-supported noble metal catalyst;
(2) Mixing polypyrrole-modified carbon-supported noble metal catalyst, water, 5wt.% polytetrafluoroethylene suspension and absolute ethyl alcohol according to the mass ratio of 1: 3: 2-7: 3-6 to prepare slurry, coating the slurry on hydrophobic carbon paper or carbon cloth, and naturally airing the hydrophobic carbon paper or carbon cloth, wherein the mass ratio of the polypyrrole-modified carbon-supported noble metal catalyst to the carbon paper or the carbon cloth is 1: 10-100;
the auxiliary electrode of the air battery is prepared by the following steps:
mixing polypyrrole-modified carbon-supported noble metal catalyst, water, 5wt.% of polyvinyl alcohol solution and absolute ethyl alcohol or mixing polypyrrole-modified carbon-supported noble metal catalyst, water, 5wt.% of sodium carboxymethyl cellulose solution and absolute ethyl alcohol according to the mass ratio of 1: 3: 2-7: 3-6 to prepare slurry, coating the slurry on hydrophobic carbon paper or carbon cloth, and naturally airing the hydrophobic carbon paper or carbon cloth, wherein the mass ratio of the polypyrrole-modified carbon-supported noble metal catalyst to the carbon paper or the carbon cloth is 1: 10-100.
2. The rechargeable metal hydride air battery with the auxiliary electrode as claimed in claim 1, wherein during the preparation of the porous negative electrode of the air battery, polypyrrole-modified carbon black is added as a negative electrode additive during the preparation of slurry, i.e. powdered hydrogen storage metal, polypyrrole-modified carbon black, and 5wt.% sodium carboxymethyl cellulose solution or 5wt.% polyvinyl alcohol solution are mixed to form slurry according to the mass ratio of 1: 0-0.5: 1-3;
the polypyrrole-modified carbon black is prepared by the following method: dispersing carbon black into water, methanol or chloroform to prepare suspension with the mass ratio of 1: 15; adding glacial acetic acid or hydrochloric acid to adjust the pH value to 2.5-3, and stirring for 10-30 min at room temperature;adding pyrrole according to the mass ratio of carbon black to pyrrole of 1: 0.05-0.3, stirring for 5-10 min, and then adding H with the mass of 0.05-0.1 g 2 O 2 As an initiator of the polymerization reaction, stirring for 3-10 h at room temperature; washing the product with warm deionized water, and drying in vacuum to obtain the polypyrrole-modified carbon black.
3. A rechargeable metal hydride air battery with an auxiliary electrode according to any of claims 1 to 3, characterized in that the porous metal material is nickel foam or copper foam and the porous material made of conductive fibers is a porous material made of nickel fibers, nickel-plated metal fibers or carbon fibers.
4. A rechargeable metal hydride air battery provided with an auxiliary electrode according to any of claims 1 to 3, characterized in that the preparation of the hydrogen storage metal as negative electrode material comprises the following steps:
(1) Determining the use amounts of the substitutional elements M and N of the zirconium, the titanium, the nickel and the nickel according to the atomic ratio of (1-y) to y to (2-a-b) to a to b; melting in an electromagnetic induction furnace or an arc furnace under the protection of argon, cooling to obtain Zr blocks 1-y Ti y Ni 2-a-b M a N b Alloying;
(2) Crushing the obtained hydrogen storage metal into particles with the particle size of below 2 mm by a mechanical method, placing the particles in a stainless steel reactor,vacuumizing at room temperature until the pressure of the reactor is less than 10 -3 Torr, then hydrogenation is carried out, and the pressure is increased to 20 atmospheric pressure for hydrogenation; heating and cooling for 1-10 times at room temperature-100 deg.c to reach the aim of hydrogen releasing and absorbing circulation to obtain hydrogen storing metal powder.
5. A rechargeable metal hydride air battery as claimed in any of claims 1 to 3 provided with an auxiliary electrode, wherein the auxiliary electrode diaphragm is a cation exchange membrane, an anion exchange membrane or a polypropylene nonwoven fabric.
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| CN102181682A (en) * | 2011-04-13 | 2011-09-14 | 河北师范大学 | Preparation method of high-capacity porous metal alloy block serving as hydrogen storage material |
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| CN102181682A (en) * | 2011-04-13 | 2011-09-14 | 河北师范大学 | Preparation method of high-capacity porous metal alloy block serving as hydrogen storage material |
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| US10547046B2 (en) | 2011-11-30 | 2020-01-28 | Lawrence Livermore National Security, Llc | High energy/power density nickel oxide/hydroxide materials and nickel cobalt oxide/hydroxide materials and production thereof |
| CN107959056A (en) * | 2016-10-17 | 2018-04-24 | 通用汽车环球科技运作有限责任公司 | Battery is tested in three poles |
| CN106784764A (en) * | 2016-12-10 | 2017-05-31 | 浙江大学 | Lithium-oxygen battery with nitrogenous carbon-supported nanometer boron lithium alloy as anode material |
| CN106784764B (en) * | 2016-12-10 | 2019-04-02 | 浙江大学 | Using nitrogenous carbon-supported nanometer boron lithium alloy as the lithium-oxygen battery of anode material |
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| CN113140840A (en) * | 2021-05-18 | 2021-07-20 | 中国科学技术大学 | Aqueous conductive polymer-hydrogen secondary battery |
| CN114883582A (en) * | 2022-05-10 | 2022-08-09 | 吉林大学 | Photo-thermal coupling bifunctional catalyst for metal-air battery and application thereof |
| CN114883582B (en) * | 2022-05-10 | 2023-08-22 | 吉林大学 | Photo-thermal coupling dual-function catalyst for metal-air battery and application thereof |
| CN115609989A (en) * | 2022-12-20 | 2023-01-17 | 四川省众望科希盟科技有限公司 | Polytetrafluoroethylene sealing material with low friction coefficient and low wear |
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