CN107591591A - Open half air fuel type faintly acid MH secondary battery - Google Patents

Abstract

The invention belongs to a kind of MH secondary battery of open replaceable battery liquid, there is application value in fields such as movable electrical appliances, portable electric appts, the vehicles.Its structure mainly includes zinc load, middle electrolyte layer, porous septum, anode, and outermost layer permeable porous film, battery cavities blow-by.Electrolyte is poured out when not in use and reduces zinc electrode corrosion；Electrolyte activated batteries are added when work uses.Battery can reclaim zinc with charging method, can also the work of air cell pattern, improve discharge capacity by supplementing electrolyte or changing zinc load.Anode is made up of doped conducting polymer, metal nitride, carbon material, and the electrode not only has electrochemical energy storage mechanism, while possesses superelevation specific discharge capacity with air oxidation circular regeneration in discharge process.Electrolyte is faintly acid electrolyte system, pH scopes 3 to 6, is made up of ammonium salt, organic acid, zinc salt, and has O_2 carrier such as hemoglobin, fluorocarbons.

Description

Open half air fuel type faintly acid MH secondary battery

Technical field：The invention belongs to the electrochemical energy storage technology that a kind of secondary cell and air cell merge, there is peace Entirely, environmental protection, advantage efficiently, inexpensive.In movable electrical appliances, portable wearing electronic equipment, the vehicles, intelligent grid, again The fields such as raw using energy source have significant application value.

Background technology：

Safe and environment-friendly, efficient, inexpensive electrochemical energy storage technology is in the vehicles, intelligent grid, utilization of regenerative energy There is significant application value Deng field.Lead-acid accumulator, nickel-cadmium cell, Ni-MH battery are widely used in secondary cell, by It is not high in aqueous systems electrolyte voltage reference terminal Finite System energy density；Using active metal lithium, sodium in non-aqueous no oxygen medium In may make up high specific energy batteries system, such as lithium ion battery, lithium-sulfur cell, sodium based battery.By the use of flow electrolyte as electricity The flow battery of chemical energy storage medium, because active material is stored in electrolyte, there is mobility, it is possible to achieve electrochemistry is anti- Place (electrode) and the separation of energy storage active substance spatially are answered, the power of battery is relatively independent with Capacity design, is adapted to great Rong Measure electric power storage energy storage demand, such as all-vanadium flow battery, sodium polysulfide/bromine redox flow cell, zinc/bromine flow battery.Full vanadium oxidation is also The research of stoste galvanic battery has had made great progress, but the application of its large-scale commercial also has some technology barriers, such as Battery lead plate inoxidizability and ion diaphragm acid resistance are improved, reduces production cost.Sodium polysulfide/bromine redox flow cell, zinc/bromine liquid stream Battery has advantage in cost than all-vanadium flow battery, but more bromide ions have strong corruption to ionic membrane and battery lead plate in positive pole liquid Corrosion, more bromide ion stabilizer costs are high.Conducting polymer is led as conjugated polymer polymer soft material in electrochemical energy storage There is significant application value in domain.Typical conducting polymer has polyacetylene, polyaniline, polypyrrole, polythiophene etc., particularly polyphenyl Amine, it not only has certain electric conductivity, and is readily synthesized and cost is low, electrochemical reversible is good, has Faradaic processes storage concurrently Can be with two kinds of mechanism of capacitance energy storage.Secondary cell can be assembled using Polyaniline Thin Film-Coated Electrode, such as zinc-Polyaniline Cell, lithium-poly- Aniline battery, ultracapacitor.Polyaniline theoretical capacity 294mAh/g (empirical value reaches as high as 100-140mAh/g), poly- pyrrole Cough up theoretical capacity 412mAh/g (empirical value is up to 82mAh/g).Due to depositing the thickness of conducting polymer thin film on a current collector Degree typically smaller than 20 microns (it is close with afflux body thickness, if can be produced when being worked using blocked up polymer film, electrode serious Polarization), the half of the actual specific capacity of overall electrode less than theoretical value；No matter aqueous systems or non-aqueous system conducting polymer it is thin The energy density of film battery is not high, restricts its business application.

Zinc has the characteristics that electrochemical equivalent is low, electrode potential is relatively negative, cheap, aboundresources as electrode material, Have been widely used in one-shot battery, such as：Zinc-manganese battery, silver-zinc battery, zinc-mercuric oxide cell, zinc-air battery.Zinc Aqueous electrolyte secondary cell is also may make up as negative material, with security is good, environmental hazard is small, energy density compares lead The high advantage of sour battery, such as：Nickel-zinc battery, zinc-Zn-Br battery, zinc-conducting polymer battery.Zinc-air battery is a kind of high ratio Can battery system, its theoretical energy density is up to 1090Wh/kg, and with the spy such as safe, environment-friendly high-efficiency, cost be low Point, disposable galvanic cell can be both used as, but also as fuel cell, as long as constantly providing fuel zinc, it is possible to continuous output Electric energy, the electrochemical energy storage system (" zinc energy ") of zinc-air battery structure turn into current study hotspot.Although disposable micro The existing business application of zinc-air battery, but zinc-air battery is big in fields such as the vehicles, intelligent grid, renewable sources of energy energy storage Sizable application must also solve problems with：First, the self-corrosion problem of zinc electrode, due to zinc be in alkaline solution thermodynamics not Stable, therefore zinc can react while alkaline electro discharge in liquid along with a small amount of gas-evolving electrodes；Secondly, air electrode Carbonation problem, because battery works long hours, reaction product or alkaline electrolyte and extraneous CO₂Contact can produce a large amount of carbon It hydrochlorate, can be separated out when carbonate dissolves saturation on air electrode surface, cause air electrode to block and performance and energy occur Decay.

Air electrode is the core technology of zinc-air battery, and it is a kind of gas-permeable, liquid-impermeable, energy is conductive, has catalysis oxygen also The film of former activity, by oxygen and exuberant, the interlaced formation intercommunication between micropore of electrolyte in hydrophobic diffusion electrode micropore Network, thus form the gas, liquid, solid three phase boundary of Catalytic Layer.Oxygen in air first passes around waterproof when participating in reaction Air-permeable layer is diffused into up to the place of electrolyte infiltration, is then diffused in the liquid phase, finally on the three phase boundary of Catalytic Layer Participate in electrode catalyst oxygen reduction reaction.Researcher has pointed out many methods to improve its performance, for example with the more of N doping Hole carbon, perofskite type oxide, monoatomic layer platinum on graphene is deposited on, and uses CoO nitrogen-doped carbon nanometer pipes and Ni-Fe The carbon nano-tube modified bifunctional oxygen electrode for preparing of double-layered hydroxides realizes that electrochemistry can fill zinc-air battery.Air electrode Generally use porous carbon materials make electronic conductor, and its porosity is more big more is advantageous to material diffusion, but electric conductivity and anti-oxidant energy Power declines.Using nano material, Assembling of Nanoparticles prepares coating, catalytic activity, but complex process and cost height can be improved, is urged Change activity to be difficult to persistently.In a word, because the electrode process of oxygen on airwater mist cooling interface is sufficiently complex, oxygen reduction reaction is reversible Property is small, overpotential is high, and air electrode performance is influenceed by gas, liquid, solid three-phase many factors；In alkaline system metal-air battery Be also faced with for a long time using produce electrolyte carbonation problem, insoluble product to porous gas diffusive electrode duct block with And catalytic activity point covers and causes electrode activity to decline, the air electrode of high activity long-life is always study hotspot.

Chinese patent CN2485806Y is related to a kind of zinc-air battery.By High Efficiency Air-Electrode, imbibition felt, electrolyte, Mercury-free zinc electrode, negative cover component units battery.Chinese patent CN102509806A, one kind is new to fill metal-air battery oxygen Electrode and preparation method thereof, reaction terminating caused by deposition of the oxidation product in gas circuit during in order to eliminate metal discharge, The oxygen electrode reaction efficiency and cyclical stability of metal-air battery can be filled by effectively improving, and reduce three-phase reaction interface area, be reduced Murder by poisoning of the moisture to electrode reaction in air and the corrosion to electrode.Moisture in air is reduced using gas microchannel, used Gas distribution grid improves direction and the gas distribution of air-flow, and hole carbon material is combined to the efficiently three-dimensional electricity of composition with array material Pole.CN103560256A is related to a kind of lithium air battery positive electrode containing new catalyst and preparation method thereof.Positive electrode is to urge Composite of agent metal nanoparticle (20-60nm) high dispersive on micron-sized carbon plate, the metal nanoparticle are Cobalt, nickel, copper, zinc, manganese, chromium, molybdenum, vanadium or yttrium.Carbon material includes acetylene black, superconduction carbon black, carbon fiber, graphene, superconduction carbon black It is one or two kinds of.CN103387229A is related to the preparation method of porous graphene and the preparation side of graphene-based aluminium-air cell Method, using graphite oxide as presoma, high-temperature heat treatment is carried out to it in Muffle furnace, is then dispersed in ethanol, at ultrasonic wave Reason prepares graphen catalyst.Preparation of the preparation method of the graphene-based aluminium-air cell including air electrode diffusion layer, The preparation of graphene catalyst layer, the step of assembling three of air electrode.A kind of polymer membrane fuel of CN1355573A disclosure of the invention The composite-layer bipolar plate and its manufacture method of battery.The bipolar plate features are：Overall structure is made up of graphite worm, outside it Surface is polypyrrole or polyaniline film layer, and polypyrrole either polyaniline Internet is admixed among wooden partition graphite worm layer, or Person is the folder adhesion metal thin plate among wooden partition graphite worm layer.Manufacture method uses die pressing, and its step is in upper and lower mould In fill up graphite worm, and sheet metal is placed among graphite worm, then pressure forming, or filled up in upper and lower mould Graphite worm, then pressure forming, exist after shaping in polar board surface coating or electro synthesis polypyrrole or polyaniline film layer, its feature In：With 10~80MPa forming under the pressure, polypyrrole or polyaniline Internet is made in electrosynthesis inside wooden partition graphite worm. A kind of preparation method of carbon-silver-bearing copper-polyaniline composite electrocatalysts for fuel cell oxygen reduction reaction of CN102784665A, With use ethanol as solvent and reducing agent, using hydro-thermal method, silver and copper nano particles are deposited in carbon particle simultaneously, form carbon The silver-bearing copper bielement nano metallic catalyst of load, the catalyst particle surface is then used by Polyaniline-modified by chemical method again again, So as to obtain carbon-silver-bearing copper-polyaniline composite electrocatalyst.Absolute ethyl alcohol and Nafion solution are added, ultrasonic disperse forms pasty state Glassy carbon electrode surface is pasted on after thing corresponding carbon-silver-bearing copper-polyaniline composite electrocatalyst electrode is made.CN104979568A is sent out Bright to provide a kind of fuel battery cathod catalyst and preparation method thereof, the catalyst is expressed as：N/CNTs, it is receiving for N doping Rice network structure.The catalyst is polyaniline (PANI) and melamine for carrier with moderate oxidation CNT (moCNTs) (Mela) it is nitrogen source, ferric trichloride is raw material, first prepares moCNTs/PANI/Mela-Fe compounds, then obtain through high-temperature roasting Arrive.CN102064287A inventions are related to a kind of inner core replaceable alkaline battery, and it includes being provided with the hollow cylinder shape with top The box hat of structure, the inner core being placed in box hat and the closure located at box hat openend, described closure are provided with current collection Copper pin, it is characterised in that：Connected between the box hat and closure with dismountable structure.

The content of the invention：

In order to develop safe and environment-friendly, efficient, inexpensive electrochemical energy storage technology, the present invention is based on metal-air battery With the fusion of metal-conducting polymer battery advantage, a kind of air catalytic oxidation regenerative conducting polymer composite material is proposed Positive pole system, the bifunctional electrodes not only have electrochemical energy storage mechanism, while are regenerated in discharge process with air oxidation Process is recycled, superelevation specific discharge capacity can be possessed.The invention discloses a kind of zinc two of open replaceable battery liquid Primary cell, its structure mainly include zinc load, middle electrolyte layer, porous septum, anode, and outermost layer porous breathable Film.Battery zinc load theoretical capacity is 5 to 20 times of the theoretical capacity of polymer composite anode.In occupation mode, battery uses Intermittent operation mode, electrolyte is poured out when not in use, reduce the corrosion of zinc electrode；Activated batteries during work：During use Add electrolyte.Battery can reclaim zinc with charging method, can also the work of air cell pattern, by supplementing electrolyte or more Zinc load is changed to improve discharge capacity, is used in the case of no external power supply.

The present invention is to reach above-mentioned purpose technical scheme to be：

The technology of preparing route of anode composite material：With nano metal nitride such as zirconium nitride, yttrium nitride, tantalum nitride, nitrogen Change cerium, nitridation lanthanum, vanadium nitride, silicon nitride, titanium nitride, aluminium nitride, nitrogenized manganese, vanadium nitride, chromium nitride, and carbon material particles are such as Acetylene black, superconduction carbon black, carbon fiber, graphene, superconduction carbon black, Ketjen black etc. are the core of complex microsphere, metal nitride and carbon Quality of materials ratio is 1: 1, and grain diameter is controlled below 1 micron.Above-mentioned nanoparticle is dispersed in 0.05-0.5M conducting polymers In the acid solution that thing monomer and 0.0005-0.01M water solubilitys quinones are formed, weigh a certain amount of ammonium persulfate and be dissolved in water In solution, reaction system is placed under ul-trasonic irradiation, ammonium persulfate solution is slowly dropped to by control temperature at 20~23 DEG C Conducting polymer monomer (aniline or pyrroles)/and into the solution of karyomicrosome mix suspending solution, after reaction terminates, to reaction product Filtered, washed, remove water-solubility impurity.First suction filtration is washed with ethanol solution once, then wash suction filtration once with hydrochloric acid solution. By above-mentioned same method, respectively by other various inorganic (hydrochloric acid, sulfuric acid, phosphoric acid) or organic acid (p-methyl benzenesulfonic acid, dodecane Base benzene sulfonic acid, camphorsulfonic acid) polyaniline or polypyrrole are doped, can obtain inorganic acid and organic acid doped polyaniline or The composite of polypyrrole parcel.Conducting polymer wraps up composite size controlling at 3 microns to 10 microns in preparation process Between, optimized particle size value is 6 microns.Quality forms conducting polymer: metal nitride: carbon particle 8 in anode composite material: 1∶1。

Conducting polymer mainly includes polyaniline, polypyrrole, polythiophene, poly- to benzene, polyacene, polyethylene ferrocene, poly- Naphthols, polyamino anthaquinone and their derivative, can by chemical oxidizing agent such as persulfate (potassium peroxydisulfate, ammonium persulfate), The oxidative synthesis such as potassium permanganate, iron chloride, hydrogen peroxide, it can also be synthesized by electrochemical oxidation method.

The synthesis specific method of polyaniline and derivative is as follows：By a certain amount of aniline monomer and inorganic acid such as hydrochloric acid, it is made into Aniline solution；Weigh a certain amount of ammonium persulfate to be dissolved in the aqueous solution, reaction system is placed under ul-trasonic irradiation, control temperature exists 20~23 DEG C, ammonium persulfate solution is slowly dropped in the solution of aniline, after reaction terminates, reaction product filtered, Washing, remove water-solubility impurity.First suction filtration is washed with ethanol solution once, then wash suction filtration once with hydrochloric acid solution.By above-mentioned same The method of sample, respectively by other various inorganic (hydrochloric acid, sulfuric acid, phosphoric acid) or organic acid (p-methyl benzenesulfonic acid, detergent alkylate sulphur Acid, camphorsulfonic acid) aniline is doped, it can obtain inorganic acid and organic acid doped polyaniline.It is prepared by polyaniline derivative Method is identical with polyaniline.

The synthesis specific method of polypyrrole and derivative is as follows：By a certain amount of pyrrole monomer and inorganic acid such as hydrochloric acid, it is made into Chromium solution；Weigh a certain amount of ammonium persulfate to be dissolved in the aqueous solution, control temperature enters N at 20~23 DEG C₂By persulfuric acid under protection Ammonium salt solution is slowly dropped in chromium solution, and after reaction terminates, reaction product is filtered, will precipitation successively with largely going Ionized water, methanol and ether washing.Products therefrom is dried in vacuo 24h at 60 DEG C, polished to obtain black polypyrrole powder. Polypyrrole derivatives preparation method is identical with polypyrrole.

The synthesis specific method of poly- 3 methyl thiophene is as follows：A certain amount of 3 methyl thiophene is dissolved in chloroform, enters N2 It will be added in liquor ferri trichloridi under protection, after reaction terminates, reaction product will be filtered, precipitation is used into methanol and second successively Ether washs.Products therefrom is dried in vacuo 24h at 60 DEG C, polished to obtain poly- 3 methyl thiophene.Other conducting polymers Prepared using above-mentioned similar approach.

Anode composite material grinds system after can also being mixed with conducting polymer with nano metal nitride, carbon material particles It is standby.Nano metal nitride is mainly zirconium nitride, yttrium nitride, tantalum nitride, cerium nitride, nitridation lanthanum, vanadium nitride, silicon nitride, nitridation One or both of titanium, aluminium nitride, nitrogenized manganese, vanadium nitride, chromium nitride, carbon material particles be mainly acetylene black, superconduction carbon black, One or both of carbon fiber, graphene, superconduction carbon black, Ketjen black, quality forms conducting polymer in anode composite material: Metal nitride: carbon particle 8: 1: 1.

Anode is made up of conducting polymer composite material and porous carbon fiber net collector.Using binding agent by conduction Polymer composites and porous carbon fiber net collector constituting membrane electrode compressed together.Also emulsus Flow-through electrode work can be used Operation mode, there are redox characteristic conducting polymer or their microballoons with composite material of inorganic matter to be dispersed in electrolyte solution The middle emulsus electrode solution for forming flow battery, emulsus liquid stream electroactive polymer positive pole is collectively forming with solid netted collector, In charge and discharge process positive pole emulsion with the type of flow by cathode chamber, for forming flow battery system.Positive pole (cathode chamber) Simultaneously contact solution another side uses teflon-coated ingress of air, forms half air-fuel battery.

GND is by zinc or kirsite, such as zinc-manganese, zinc-magnesium, zinc-aluminium, zinc-tin, zinc bismuth, zinc antimony alloy etc..

The chemical composition of electrolyte is faintly acid electrolyte system, Acidity Range pH 3-6, by ammonium salt, organic acid, zinc salt Form.Ammonium salt has ammonium chloride, ammonium bromide, ammonium fluoride, ammonium fluoroborate, ammonium sulfate, thiosulfonic acid ammonium, pyrovinic acid ammonium, ammonium perchlorate, Ammonium phosphate, one or more of fractions formed in electrolyte in them, mainly with ammonium chloride, ammonium sulfate, pyrovinic acid ammonium Based on.

Organic acid mainly have formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, capric acid, stearic acid, palmitic acid, acrylic acid, Octanoic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, citric acid, maleic acid, tartaric acid, benzoic acid, phenylacetic acid, phthalic acid, Terephthalic acid (TPA), EDTA, wherein based on citric acid, oxalic acid and their sodium salt, sylvite.

Electrolyte conditions can be solid sheet, add the aqueous solution after being filled into electrolyte cavities, the aqueous solution can be pure Water purification, running water, tea, urine etc.；Also the electrolyte solution prepared can be used, is directly filled during use.

Contain O_2 carrier such as hemoglobin, bilirubin in electrolyte, fluorocarbons includes perfluoro-n-butyl group furans, complete Fluorine tri-n-butylamine, the high E4 of fluorine row, perfluorodecalin, perfluoromethyidecalin, perfluamine, sulfur hexafluoride etc., its content are overall electricity Between solve liquid quality 1% to 20%.

Perforated membrane is used between cathode chamber and anode chamber in the system of assembled battery, its material can use nylon cloth, gather Propylene, polyethene microporous membrane, optimum aperture are controlled at 2 microns, and too big aperture, short grained conductive polymer microspheres may Microporous barrier can add the resistance of film during through micropore, too small-bore.

Embodiment：

Embodiment 1

Zinc/polyaniline composite material secondary cell

The negative pole of battery uses 1mm thickness zine plates, and plus plate current-collecting body uses graphite felt, and the composition of anode composite material is nitridation Yttrium, acetylene black, polyaniline, mass ratio 1: 1: 8, Polyaniline Doped agent are camphorsulfonic acid.

Battery electrolyte composition 2mol/L ZnCl₂、2mol/L NH₄Cl.The barrier film of both positive and negative polarity is using the poly- of 0.6 millimeters thick Vinyl film.Battery open circuit voltage is 1.5 volts, battery charging voltage scope 0.8V-1.8V, cell discharge voltage scope 1.8V- 0.8V, charging and discharging currents density 2mA/cm², coulombic efficiency 93%, battery energy density is 40m Wh/g (zinc electrode capacity mistakes It is surplus, do not count).

Embodiment 2

The air secondary battery of zinc/polyaniline composite material half

The negative pole of battery uses 1mm thickness zine plates, and plus plate current-collecting body uses graphite felt, and the composition of anode composite material is nitridation Cerium, superconduction carbon black, polyaniline, mass ratio 1: 1: 8, Polyaniline Doped agent are camphorsulfonic acid.Positive pole one side uses polytetrafluoroethyl-ne Alkene perforated membrane wraps up ingress of air, forms half air-fuel battery.

Battery electrolyte composition 1mol/L ZnCl₂、4mol/L NH₄Cl, O_2 carrier content of hemoglobin are 10g/L.Just The barrier film of negative pole uses the polyethylene film of 0.6 millimeters thick.Battery open circuit voltage is 1.3 volts, battery charging voltage scope 0.8V- 1.6V, cell discharge voltage scope 1.4V-0.8V, the discharge energy density of battery for 500m Wh/g (zinc electrode capacity excess, Do not count).

Embodiment 3

Zinc/Pt/Polypyrrole composite material secondary cell

The negative pole of battery uses 1mm thickness zine plates, and plus plate current-collecting body uses graphite felt, and the composition of anode composite material is nitridation Yttrium, acetylene black, polypyrrole, mass ratio 1: 1: 8, doped polypyrrole agent are camphorsulfonic acid.

Battery electrolyte composition 2mol/L ZnCl₂、2mol/L NH₄Cl.The barrier film of both positive and negative polarity is using the poly- of 0.6 millimeters thick Vinyl film.Battery open circuit voltage is 1.3 volts, battery charging voltage scope 0.8V-1.6V, cell discharge voltage scope 1.4V- 0.8V, charging and discharging currents density 2mA/cm², coulombic efficiency 99%, battery energy density is 35m Wh/g (zinc electrode capacity mistakes It is surplus, do not count).

Embodiment 4

The air secondary battery of zinc/Pt/Polypyrrole composite material half

The negative pole of battery uses 1mm thickness zine plates, and plus plate current-collecting body uses graphite felt, and the composition of anode composite material is nitridation Cerium, superconduction carbon black, polypyrrole, mass ratio 1: 1: 8, doped polypyrrole agent are camphorsulfonic acid.Positive pole one side uses polytetrafluoroethyl-ne Alkene perforated membrane wraps up ingress of air, forms half air-fuel battery.

Battery electrolyte composition 1mol/L ZnCl₂、4mol/L NH₄Cl, O_2 carrier content of hemoglobin are 10g/L.Just The barrier film of negative pole uses the polyethylene film of 0.6 millimeters thick.Battery open circuit voltage is 1.3 volts, battery charging voltage scope 0.8V- 1.6V, cell discharge voltage scope 1.3V-0.8V, for 650m Wh/g, (zinc electrode capacity excess, is not counted the discharge energy of battery Including calculation).

Embodiment 5

The air secondary battery of manganese alloy/Pt/Polypyrrole composite material half

The negative pole of battery uses 1mm thickness manganese alloy plates, manganese content 5%, and plus plate current-collecting body uses graphite felt, and positive pole is compound The composition of material is nitridation lanthanum, superconduction carbon black, polypyrrole, and mass ratio 1: 1: 8, doped polypyrrole agent is camphorsulfonic acid.Positive pole Simultaneously using polytetrafluoroethylporous porous membrane parcel ingress of air, half air-fuel battery is formed.

Battery electrolyte composition 0.5mol/L sodium citrates, 4mol/L NH₄Cl, O_2 carrier 10g/L fluorine normal-butyl furans Emulsion.The barrier film of both positive and negative polarity uses the polyethylene film of 0.6 millimeters thick.Battery open circuit voltage is 1.6 volts, battery charging voltage model 0.9V-1.8V is enclosed, cell discharge voltage scope 1.6V-0.9V, the discharge energy of battery is 800m Wh/g (zinc electrode capacity mistakes It is surplus, do not count).

Embodiment 6

The air secondary battery of zinc/Pt/Polypyrrole composite material half

The negative pole of battery uses 1mm thickness zine plates, and plus plate current-collecting body uses graphite felt, and the composition of anode composite material is nitridation Cerium, superconduction carbon black, polypyrrole, mass ratio 1: 1: 8, doped polypyrrole agent are camphorsulfonic acid.Positive pole one side uses polytetrafluoroethyl-ne Alkene perforated membrane wraps up ingress of air, forms half air-fuel battery.

Battery electrolyte composition 0.5mol/L sodium citrates, 2mol/L citric acids, O_2 carrier perfluamine content are 10g/L.The barrier film of both positive and negative polarity uses the polyethylene film of 0.6 millimeters thick.Battery open circuit voltage is 1.5 volts, battery charging voltage model 0.8V-1.8V is enclosed, cell discharge voltage scope 1.5V-0.8V, the discharge energy of battery is 680m Wh/g (zinc electrode capacity mistakes It is surplus, do not count).

Claims (9)

1. the invention discloses a kind of MH secondary battery of open replaceable battery liquid, its structure mainly include zinc load, in Between electrolyte layer, porous septum, anode, and outermost layer permeable porous film, battery cavities blow-by.Battery zinc load is theoretical Capacity is 5 to 20 times of the theoretical capacity of polymer composite anode.In occupation mode, battery uses intermittent operation mode, no Electrolyte is poured out during use, reduces the corrosion of zinc electrode；Electrolyte activated batteries are added when work uses.Battery can charge Method reclaims zinc, can also the work of air cell pattern, improve discharge capacity by supplementing electrolyte or changing zinc load, Used in the case of no external power supply.

2. a kind of air catalytic oxidation regenerative conducting polymer composite material not only has electrochemistry storage as positive pole, the electrode Energy mechanism, while can possess superelevation specific discharge capacity with air oxidation recycling utilization process in discharge process.

3. as claimed in claim 2, conducting polymer composite material is by conducting polymer, nano metal nitride, carbon material group Into conducting polymer: metal nitride: carbon particle mass ratio is 8: 1: 1.

4. conducting polymer as claimed in claim 2 is polyaniline, polypyrrole, the poly- thiophene for adulterating quinones or anthraquinone analog compound Fen, gather to benzene, polyacene, polyethylene ferrocene, poly- naphthols and their derivative.

5. nano metal nitride described in claim 3 is mainly zirconium nitride, yttrium nitride, tantalum nitride, cerium nitride, nitridation lanthanum, nitrogen Change one or both of vanadium, silicon nitride, titanium nitride, aluminium nitride, nitrogenized manganese, vanadium nitride, chromium nitride, carbon material particles are mainly One or both of acetylene black, superconduction carbon black, carbon fiber, graphene, superconduction carbon black, Ketjen black.

Add when being used 6. MH secondary battery as claimed in claim 1 is a kind of battery of blow-by replaceable battery liquid, during work Enter electrolyte activated batteries, deposit pours out electrolyte when not in use.Battery can reclaim zinc by charging method, can also be empty Pneumoelectric pool mode works, and discharge capacity is improved by supplementing electrolyte or changing zinc load, in the case of no external power supply Use.

7. MH secondary battery as claimed in claim 1, GND is by zinc or kirsite, mainly including zinc-manganese, zinc-magnesium, zinc-aluminium, Zinc-tin, zinc bismuth, zinc antimony alloy etc..

8. MH secondary battery as claimed in claim 1, the chemical composition of electrolyte is faintly acid electrolyte system, and pH scopes 3 arrive 6, it is made up of ammonium salt, organic acid, zinc salt.Ammonium salt has ammonium chloride, ammonium bromide, ammonium fluoride, ammonium fluoroborate, ammonium sulfate, thiosulfonic acid ammonium, Pyrovinic acid ammonium, ammonium perchlorate, ammonium phosphate, one or more of fractions formed in electrolyte in them, mainly with chlorination Ammonium, ammonium sulfate, based on pyrovinic acid ammonium.Organic acid mainly has formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, capric acid, tristearin Acid, palmitic acid, acrylic acid, octanoic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, citric acid, maleic acid, tartaric acid, benzoic acid, Phenylacetic acid, phthalic acid, terephthalic acid (TPA), EDTA, wherein based on citric acid, oxalic acid and their sodium salt, sylvite.Electricity It can be solid sheet to solve matter state, and the aqueous solution is added after being filled into electrolyte cavities, and the aqueous solution can be pure water, originally Water, tea, urine etc.；Also the electrolyte solution prepared can be used, is directly filled during use.

It is red containing O_2 carrier such as hemoglobin, courage in electrolyte 9. the faintly acid electrolyte of zinc battery as claimed in claim 7 One or more in element, ferriporphyrin, fluorocarbons, between its content is 1% to the 20% of overall electrolyte quality.Fluorine carbon Compound includes perfluoro-n-butyl group furans, perfluorotributylamine, the high E4 of fluorine row, perfluorodecalin, perfluoromethyidecalin, perfluor 3 third Amine, sulfur hexafluoride etc..