CN1540777A - Metal box for fuel cell - Google Patents

Abstract

Metal box for fuel cell is composed of metal fuel, negative or positive pole plates, electrolyte, and carrying case or container case for fuel cell. The metal box is a common turning over set for supplying and replacing fuel cell in electric motor car quickly.

Description

Metal fuel cell box

The invention relates to a metal fuel cell box which can be used for public circulation, in particular to a metal fuel cell box which can be used for public circulation of various electric vehicles, can be used for quickly replacing a cell box and quickly supplementing electric energy and uses movable metal as cell fuel, and a manufacturing method thereof.

The structure of various fuel cells in the prior art, such as alkaline hydrogen-oxygen fuel cell, phosphoric acid hydrogen-oxygen fuel cell and proton exchange membrane hydrogen-oxygen fuel cell, is characterized in that electrodes, diaphragms, current collecting plates and electrocatalyst layers are made of various composite materials, because the fuel cells need to continuously feed fuel and oxidant into the electrode plate flow field with complex structure in the cells and timely remove water as a reaction product when working, the traditional technology requires that the fuel and oxidant used by the fuel cells are all fluid, namely gas and liquid, the most common fuel is pure hydrogen, various gases rich in hydrogen (such as reformed gas) and some liquid (such as methanol aqueous solution), the most common oxidant is pure oxygen, purified air and the like and some liquid (such as aqueous solution of hydrogen peroxide and nitric acid), and because the cell structure is complex, the hydrogen production cost is high, and the manufacturing of the electrode plates and the electrode plates leads to highoverall cost of the fuel cell, when the hydrogen storage tank is applied to the electric vehicle, the hydrogen storage tank carried along with the vehicle has certain danger, and huge investment is needed for building and supplementing hydrogen stations along the road, so the development and popularization of the hydrogen-oxygen fuel cell are restricted, and other various batteries need to be charged for a long time after electric energy is exhausted, and when the hydrogen storage tank is applied to the electric vehicle, the batteries and the electric vehicle are tightly installed and are inconvenient to replace, so that great inconvenience is brought to users.

The invention aims to overcome the defects of the prior art, and on the basis of fully understanding, analyzing and recognizing the structural characteristics of a fuel cell and restricting the fundamental reasons of research, development and practicability of the fuel cell and an electric vehicle thereof, the essence of the electrochemical reaction of the fuel cell is that the energy level of fuel oxidation (losing electrons) is greatly reduced and the energy level of oxidant (such as oxygen) reduction (obtaining electrons) is slightly increased, wherein the energy level difference performs external work and is released in the form of heat energy, based on the recognition, the invention changes the technical requirement of the traditional fuel cell on fuel requirement as fluid, proposes to adopt solid substances, particularly active metal in the solid substances as the fuel of the fuel cell, adopt alkaline or acidic liquid or salt solution as electrolyte, pure oxygen or purified air or common air or certain liquids (such as aqueous solution of hydrogen peroxide and nitric acid) as oxidant, the metal fuel cell is a novel fuel cell which is easy to prepare, store, replace at regular intervals, transport safely, popularize, practicalize and industrialize. The metal fuel cell and the hydrogen-oxygen fuel cell are essentially the same, and are all fuel oxidation (losing electrons), the energy level of the fuel is reduced, and one part of the reduced energy level is used for electric power to do work outwards, and the other part generates chemical reaction heat energy, and the corresponding reverse reaction is that when producing the fuel, for example, electrolyzing water to obtain hydrogen gas, the electric energy is consumed to increase the energy level of hydrogen ions to obtain high-level hydrogen molecules, or electrolyzing metal compounds, and the energy level of metal ions is increased (reduced) to obtain high-level metal atoms or metal simple substances, and the two reverse reactions, namely the redox reaction and the electrolysis reaction, follow the principle of energy conservation, wherein the high-level hydrogen molecules and the metal atoms are essentially substance carriers of the electric energy and are both supply substances of the electric energy of the fuel cell, however, because the movable metal has more stable performance and can be safely stored and transported, and is in negative, The anode plate does not need to be provided with flow field grooves with various shapes, the flow field reaction site is simple, fuel is easy to add, the manufacturing cost is low, and the like, compared with hydrogen, the anode plate has the advantages that the anode plate has more advantages, the hydrogen is more excellent, therefore, from the aspects of reducing social cost and industrialization, movable metal can be judiciously selected to be used as electric fuel of a fuel cell, and metal fuel and reaction products in the fuel cell can be replaced regularly. In order to make the metal fuel cell can supply power for the electric vehicle for a long time and shorten the time for supplementing electric energy to the battery as much as possible, the metal fuel cell is made into an integrated box-type structure from the viewpoint of system integration toform a metal fuel cell box which comprises a metal fuel cell container and a metal fuel cell suitcase, the metal fuel cell box can be quickly replaced after the electric energy of the metal fuel cell box is exhausted, so that the electric vehicle can be supplemented with the electric energy in time, the metal fuel cell box is formed by combining a box body or a metal fuel cell pack in the box body, a cathode electrode plate, an anode electrode plate, a diaphragm, electrolyte, metal fuel and an oxidant, wherein the metal fuel is selected from magnesium, aluminum, manganese, zinc, chromium, iron, nickel, tin, lead, copper and other movable metals or alloys thereof in a metal activity sequence table, the electrodes are formed by composite materials, and the cathode is formed by a chemically stable electrode plate carbon electrode or a graphite electrode or a, The aluminum surface is plated with nickel and gold to form electrode plate or can be oxidized to form metal fuel electrode plate, and the anode is formed by gas diffusion electrode.

The metal fuel cell battery is composed of a box body and a metal fuel cell battery group in the box body, and is characterized in that the box body is composed of a suitcase structure with a locker or a locking hole and one or two handles or a container structure with a hoisting hole and the locker or the locking hole.

The invention is described in further detail below with reference to the figures and the specific embodiments

Fig. 1 is a schematic structural diagram of a metal fuel cell box with a cell slot of a battery pack.

Fig. 2 is a schematic structural view of a metal fuel cell case having a cell separator inside the case.

Fig. 1 is a schematic structural diagram of a metal fuel cell box with a cell slot of a battery pack, wherein 1 is a metal fuel cell box body, (2) is a hoisting hole, (3) is a support leg at the bottom of the metal fuel cell box, (4) is a single metal fuel cell pack with a cell slot, and (5) is a power supply socket.

FIG. 2 is a schematic structural diagram of a metal fuel cell case, in which (1) the metal fuel cell case body, the cell set and the cell tank are in a cuboid, cube or columnar structure, the cell set and the case body are in a separable sealing installation structure or a fastening sealing installation structure, (2) the hoisting hole, (6) the cell case cover, (7) the cathode plate, (8) the anode plate, one cathode plate surface and one anode plate surface are placed in parallel to form a single cell, a plurality of cathode plates and a plurality of anode plates are arranged in parallel and spaced to form a cathode and anode plate cluster to form a multi-segment cell, and the multi-segment cell is assembled to be vertically or parallelly installed in each cell tank in the case body to form the metal fuel cell case, (9) the metal fuel cavity between the cathode plate and the anode plate, (10) the metal fuel is granular metal fuel, and the metal is mainly magnesium in a metal activity order table, The metal particles are mainly short columnar, flaky, ellipsoidal and spherical structures, particularly metal fuel particles with spherical structures, and are the preferred shape structure of the metal particles of the metal fuel cell because the surfaces of the spherical particles are smooth, the mutual obstruction is small, the surface area is large, the density of the particles after filling is large, and the fuel can be quickly filled, the electrolyte is composed of alkaline electrolyte potassium hydroxide, sodium hydroxide or solution of hydrochloric acid, sulfuric acid or phosphoric acid and salt of acidic electrolyte, a movable quick-detachable structure is arranged between the cell box cover (6) and the cell boxbody (1), and an acid-resistant and alkali-resistant sealing gasket is arranged between the cell box cover and the cell box body.

A gas diffusion electrode plate of metal fuel cell is prepared from water-proof air-permeable layer, catalytic layer and electric conducting net through heating, pressing to obtain PTFE-type electrode, wetting the water-proof layer with activated carbon and teflon emulsion, mixing with alcohol and water, rolling, drying in air, cutting to obtain water-proof layer, preparing catalytic layer, and preparing anode plateThe catalyst layer is prepared by coating 2 mol of silver nitrate and 1 mol of mercuric nitrate solution on the surface of a cut polytetrafluoroethylene electrode plate, mixing and airing, adding 40% hydrazine hydrate at the temperature of zero ℃ for reduction reaction, and reactingAir drying, wherein the conductive skeleton is prepared by annealing copper foil with thickness of 0.1mm in hydrogen furnace, punching, welding silver foil with thickness of 0.2mm on copper net in spot welder, pressing, electroplating silver, and the process for preparing anode of gas diffusion electrode of metal fuel cell comprises placing glycerin-free cellophane in tabletting mold, sequentially placing waterproof film, conductive skeleton, waterproof film, catalytic film, covering cellophane on catalytic film, closing cover, heating at 50-60 deg.C, and pressurizing (8-10 MP)_a) The metal fuel is prepared by uniformly mixing massive, columnar and spherical particles of active metals such as magnesium, aluminum, manganese, zinc, chromium, iron, nickel (for acid batteries), tin, lead, copper and the like in the metal activity sequence table, or blocky, columnar and spherical particles prepared by mixing metal powder, metal oxide corresponding to the metal, inorganic and/or organic corrosion inhibitor, binder, plant fiber with the mass of 2 percent, PFTE emulsion with the mass of 0.5 to 1 percent, PFTE emulsion and powder, Granulating, oven drying to obtain massive or columnar or spherical metal fuel particles or plates, or adding inorganic and/or organic corrosion inhibitor into the metal powder or pure metal, molding with a molding press or hot melting, casting into massive or columnar or spherical metal fuel particles, filling the metal fuel particles into a metal fuel cavity (9), wrapping the gas diffusion electrode plate, i.e. anode plate with an insulating material to prepare porous gas-conducting and ion-conducting diaphragm such as asbestos film (paper), silicon carbide film or lithium meta-aluminate film or cellulose acetate paper or cellulose hydrate film or superfine glass fiberThe metal fuel in the metal fuel cavity can be regarded as an extended cathode electrode in the metal fuel cavity, and the metal fuel regarded as the extended cathode electrode can be continuously oxidized and can be repeatedly replaced, metal atoms in the metal fuel particles lose electrons in the oxidation process, the metal ions are changed into metal ions to enter the electrolyte, and the current conduction between the metal fuel particles and the cathode electrode plate and an external circuit form current to do work outwards, and the electrons can flow through a current loop lead of an electric appliance, The oxygen molecules flowing to the anode undergo a reduction reaction with the oxygen molecules at the anode, the energy level of the oxygen molecules is slightly increased, and hydroxyl protons are generated, and the general chemical reaction formula is as follows:

[O]represents an oxidizing agent [ R]Represents a reducing agent, P represents the reaction product e^-Representing electrons, the bivalent active metal fuel separation and combination reaction is as follows:

[R]→[R]²⁺+2e

the separation and combination reaction of the trivalent movable metal is as follows:

the electrochemical formula of the metal fuel cell is listed below by taking metal zinc as a reducing agent and oxygen as an oxidizing agent as examples and selecting potassium hydroxide as an electrolyte:

(-)Zn|KOH|O₂(C)(+)

negative electrode:

and (3) positive electrode:

metal fuel cell reaction:

the electromotive force of the metal fuel cell is

$E={{\mathrm{\φ}}^{*}}_{O_2/O_{H^{-}}}-{{\mathrm{\φ}}^{*}}_{\mathrm{ZnO}/\mathrm{Zn}}+\frac{2.303\mathrm{RT}}{\mathrm{\ηF}}{{\log \mathrm{po}}_2}^{1/2}$

$=0.404-(-1.245)+\frac{0.059}{2}\·{{\log o}_2}^{1/2}$

$=1.646+\frac{0.059}{2}{{\log \mathrm{po}}_2}^{1/2}$

When the positive electrode active material is pure oxygen, Po₂＝p⁰o₂When the active property of the positive electrode is air, the partial pressure of oxygen is 21% of the atmospheric pressure, so that the value of E is 0.401+ 1.245-1.646V:

$E=1.646+\frac{0.059}{2}{{\log \mathrm{po}}_2}^{1/2}=1.646+0.0295\log {\left(0.21\right)}^{1/2}=1.636V$

in order to reduce the self-discharge of the metal fuel particles, a small amount of corrosion inhibitors such as Pb (Ac) and the like can also be added into the electrolyte, or no corrosion inhibitor is added into the electrolyte, the corrosion inhibitors added into the metal fuel or the electrolyte are divided into inorganic corrosion inhibitors and organic corrosion inhibitors, the inorganic corrosion inhibitors are composed of indium or tin or aluminum or silver or lead or calcium or mercury oxide, and the organic corrosion inhibitors are composed of 8-nitroquinoline and/or 8-chloroquinoline and/or 4-biphenylcarboxylic acid and/or benzyl tert-butanol and/or 4-biphenyl and/or N-N-diethyl carbobenzamide and/or P-dicycloethylbenzene, triphenylchloromethane and/or saturated or unsaturated monocarboxylic acid containing ethanolamine groups.

Of course, in the metal fuel cell stack of the metal fuel cell case, the cathode electrode plate and the metal fuel can be integrated into a whole, the metal fuel can be made into a detachable and replaceable metal fuel cathode plate by compression molding, and the metal fuel cell case can be combined with the gas diffusion anode electrode plate, the electrolyte and the cell case to form the metal fuel cell case.

The metal fuel of the metal fuel cell can be completely recycled after being used, so that the metal fuel cell is environment-friendly, and the recycling electrochemical formula of the metal fuel zinc is as follows, taking the metal fuel zinc as an example:

in the metal fuel cell box, the metal fuel cell group is directly installed in the cell box body with the cell group groove clapboard inside to form the metal fuel cell box or the cell group is provided with the cell groove and is placed in the cell box body to form the metal fuel cell box, the anode and the cathode of the cell box are respectively connected with the anode (anode) and the cathode (cathode) of the cell group in the box body, the anode and the cathode of the cell box outside the box body are respectively connected with the lead wire with two cores and/or multi-core socket-plug, the inner wall of the cell box is a smooth structural plate or the two opposite side surfaces are provided with mutually parallel vertical grooves for fixing the electrode plate cluster, the cathode and the anode electrode plates can be respectively and independently inserted into the box wall grooves, or the electrode connecting and fixing base strips (12, 13) which are installed at the two ends of the top of the cathode and anode electrode plate cluster can be integrally inserted into the box body or the box wall grooves, or lifted out of the box body or the groove thereof, the metal fuel particles (10) and electrolyte solution can be directly filled into the metal fuel cavity (9) between the cathode electrode plate and the anode electrode plate, or the metal fuel cathode electrode plate, the anode electrode plate, the diaphragm and the electrolyte can be arranged in the cell. Corresponding to the structure, the cover of the metal fuel cell box is of a cover structure with an air inlet or a pipe (15) as a whole and is directly installed and sealed on the metal fuel cell box, and the battery cover (3) and the outer wall of the box body (1) are locked and sealed through a movable locking clamp or a movable locking pin (clamp) or locking quick release or a screw.

The cathode electrode plate cluster binding post (17) and the anode electrode plate cluster binding post (16) which is connected with the cathode electrode plate cluster binding post in series in another battery cell are movable detachable binding posts and are connected through a detachable metal connecting strip (11) in the box or outside the box cover to form a metal fuel battery box with detachable and replaceable electrode plates.

One of the best embodiments of the invention is a metal fuel cell container which is provided with a hoisting hole (2) at the outer top of a container body and a battery pack groove clapboard in the container body and uses a metal fuel cathode electrode plate, the metal fuel cathode electrode plate is a detachable replaceable electrode plate, the anode is a gas diffusion electrode plate, a diaphragm between a cathode electrode plate and an anode electrode plate adopts a asbestos film soaked in alkali liquor, the electrolyte is potassium hydroxide solution, binding posts (16) and (17) of the cathode electrode plate and the anode electrode plate are connected through detachable metal connecting strips, and a frame type locker is adopted between a metal fuel container body and a container placing bin on an electric vehicle to lock the container body.

The second best embodiment of the invention is that the fuel cavity with battery groove clapboard inside the box body with lifting hole (2) outside the box body is filled with metal fuel particles (10) and potassium hydroxide solution electrolyte, the cathode is a chemically stable carbon electrode plate or graphite electrode plate (7), the anode is a gas diffusion electrode plate (8), the cathode and anode electrode plate binding posts (16), (17) are connected by a detachable metal connecting strip (11), and the locking device adopts a frame locking device between the box body and the container placing bin.

Claims (9)

1. A metallic fuel cell box is composed of a box body and a cell set in it, and features that the box body is composed of a suitcase with one or two handles and a lock or a locking hole and a common circulation structure or a container with a lifting hole and a lock or a locking hole, the metallic fuel cell set in the box body is composed of a cell container with a cell container or a metal fuel cell set in the box body, the cell set and the cell container, and the cell set and the box body are in separable sealed installation structure or fastened sealed installation structure.

2. A metallic fuel cell case according to claim 1, wherein the inner wall of the metallic fuel cell case has a smooth plate structure or has vertical grooves formed on opposite sides thereof in parallel for fixing electrode plate clusters, the cathode electrode plates of the stack in the metallic fuel cell case are made of carbon, graphite, nickel plates, or magnesium or aluminum plates plated with nickel or gold on the surface, the anode is a gas diffusion electrode plate, and the filling chamber is filled with replaceable electrolyte and metallic fuel particles.

3. A metallic fuel cell case as defined in claim 1, wherein the inner wall of the metallic fuel cell case is of a smooth plate structure or has vertical grooves formed on opposite sides thereof in parallel for fixing electrode clusters, the cathode electrode plate of the cell stack in the metallic fuel cell case is made of metallic fuel by die-pressing or spreading the plate, the anode electrode plate is a gas diffusion electrode plate, and the filling cavity is filled with an electrolyte and/or an asbestos felt membrane or an ultra-fine glass fiber felt membrane.

4. The metal fuel cell case according to claim 1 or 2, wherein the gas diffusion electrode plate anode plate of the metal fuel cell case is formed by combining a water-proof layer, a catalyst layer, and a conductive mesh, the water-proof layer is formed by wetting and stirring activated carbon, polytetrafluoroethylene and ethanol, and waterThe catalyst layer is prepared by brushing mixed liquid of silver nitrate and mercury nitrate on the surface of a cut plate obtained in the same step as the waterproof layer, drying, carrying out reduction reaction with hydrazine hydrate, and drying to prepare the catalyst layer, the conductive net is prepared by copper foil through annealing, net punching, silver foil spot welding, punching and silver plating, the gas diffusion electrode anode of the metal fuel cell is prepared by sequentially stacking glycerin-free glass movable paper, a waterproof film, the conductive net, the waterproof film, the catalytic film and glass paper into a tabletting mold, closing a film cover, heating at 50-60 ℃ and pressurizing (8-10MPa) for molding; or the gas diffusion electrode plate is composed of lithiated porous nickel electrode plate or is prepared by carrying out high-temperature heat treatment on graphite powder and resin or is prepared by bonding platinum/carbon (0.25 mg/cm) with polytetrafluoroethylene²) And carbon paper treated by polytetrafluoroethylene.

5. The metal fuel cell box according to claim 1 or 2, wherein themetal fuel in the metal fuel cell box is prepared by mixing metal powder of zinc, magnesium, aluminum, manganese, chromium, nickel, iron, aluminum or copper, metal oxide corresponding to the metal, inorganic corrosion inhibitor or organic corrosion inhibitor, binder, plant fiber with the mass of 2% and PTFE emulsion with the mass of 0.5% -1%, uniformly mixing, granulating, drying, forming, washing, drying to prepare blocky, columnar or spherical metal fuel particles or metal fuel cathode electrode plates, or preparing blocky, columnar or spherical metal fuel particles by only using the metal powder or pure metal simple substance or alloy, or adding inorganic corrosion inhibitor or organic corrosion inhibitor into pure metal or alloy thereof, especially preparing spherical metal fuel particles or metal fuel cathode electrode plates.

6. A metal fuel cell container according to claim 1 or 2, wherein the cathode plate cluster terminal (16) is removably connected to a set of anode plate cluster terminals (17) in series with the cathode plate cluster terminal in another cell, the terminals being connected by a metal connecting strip (11).

7. A metal fuel cell case according to claim 1, 3 or 6, wherein fixing base strips and handles (12), (13) for fixing the parallel metal fuel cathode electrode plates are provided at both ends of the top of the metal fuel cathode electrode plate and/or anode electrode plate cluster.

8. A metal fuel cell box according to claim 1 or 2 or 3, characterized in that the body of the metal fuel cell box is formed by a structure of a suitcase with a locker or a locking hole and with one or two handles or by a structure of a container with a lifting hole (16) or a supporting leg (14) and a locker or a locking hole, the metal fuel cellset is directly placed in the body with a battery compartment divider inside to form the metal fuel cell box or the battery set is placed in the body to form the metal fuel cell box, the positive pole and the negative pole of the battery box in the body are respectively connected with the positive pole (positive pole) and the negative pole (negative pole) of the battery set, the positive pole and the negative pole of the battery box are respectively connected with a lead wire with two-core and/or multi-core socket-plug outside the body, the lifting hole (or ear) (2) is positioned at the four corners and/or the middle part of the top of the body, the four corners and/or the middle part of the bottom of the box body are provided with convex or flat or concave supporting legs (3) or locking holes, the metal fuel cell box cover is a detachable peripheral sealing box cover with an air inlet or an air inlet pipe (15) and/or an electrode column hole, and a movable locking clamp or a movable locking groove or a movable locking pin or a locking quick-release or screw is arranged between the outer wall of the box body and the box cover.

9. A metal fuel cell case according to claim 1, 2 or 3, wherein the insulating acid or alkali or salt resistant metal fuel cell case is surrounded by a metal case housing.