CN101533935A - A high-energy safe rechargeable lithium-oxygen battery - Google Patents

A high-energy safe rechargeable lithium-oxygen battery Download PDF

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CN101533935A
CN101533935A CN200910301541A CN200910301541A CN101533935A CN 101533935 A CN101533935 A CN 101533935A CN 200910301541 A CN200910301541 A CN 200910301541A CN 200910301541 A CN200910301541 A CN 200910301541A CN 101533935 A CN101533935 A CN 101533935A
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lithium
battery
oxygen
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rechargeable lithium
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黄穗阳
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/10—Energy storage using batteries

Abstract

The embodiment of the present invention relates to a high-energy safe rechargeable lithium-oxygen battery, including an anode and a cathode, wherein, the reactant of the cathode adopts metal lithium, the reactant of the anode adopts oxygen and water, a solid electrolyte membrane is provided between the anode and cathode, and a charge electrode is provided in the anode. The high-energy safe rechargeable lithium-oxygen battery implementing the embodiment of the present invention can resolve low energy density, poor safety and reliability, low cycle life and high cost problems of the traditional lithium ion power cell, all can solve the complicated storage and transport, high cost of barrier diaphragm and catalyst, and high expenditure problems of the hydrogen fuel battery. The high-energy safe rechargeable lithium-oxygen battery can be widely used in various large-capacity high-capacity movable devices and mechanical devices, such as electric bicycles, electric motorcycle cars, electric vehicles, electric boats, electric aircraft, satellite communications machines, rocket launchers and submarines communications power supplies and so on.

Description

High-energy safe rechargeable lithium-oxygen battery
Technical field
The present invention relates to a kind of high-energy safe rechargeable lithium-oxygen battery, can be applicable to various large-capacity high-power mobile devices and mechanical device, for example electric bicycle, battery-operated motor cycle, electric automobile, electronic yacht, Electric aircraft, satellite communication machine, rocket launcher and submarine are with communication power supply etc.
Background technology
Current, the human main energy sources of using is an oil, yet use petroleum-based energy to bring the air pollution that is on the rise, greenhouse effect, problem of environmental pollution such as damage the ozone layer, and petroleum resources are also depleted day by day, therefore, development and development electric motor car or oil and electricity hybrid vehicle have become the industry that various countries, the world today first develop.
Electrokinetic cell is the core component of electric motor car.In various high-power motive-power batteries, large-scale lithium-ion-power cell is listed in the power set of pure electric vehicle first-selection under the prior art condition.Because superior more many than plumbic acid and Ni-MH battery on the technical performance, lithium-ion-power cell is one of selection of pure electric vehicle power supply under the prior art condition.But,, compare lithium-ion-power cell (LiCoO with reference to the data of following table 1, table 2 with petrol engine 2Electrokinetic cell, LiMnO 4Electrokinetic cell, LiFePO 4Electrokinetic cell etc.) there is following mortality shortcoming:
Table 1
Form of energy Energy density (Wh/kg) Energy density differs multiple Explanation
Gasoline 12,722 Benchmark Existing motor vehicle power resources
LiCoO 2Electrokinetic cell 150 85 Resource-constrained, poor stability can not be used for electric motor car
LiMn 2O 4Electrokinetic cell 95 134 Cycle life is low, hot properties is poor, can not be used for electric motor car
LiFePO 4Electrokinetic cell 75 170 Cycle life is better, fail safe is higher, can be used for electric motor car
Lead-acid battery 45 283 Fail safe is higher, can be used for electric motor car
Table 2
Distance travelled (km) 100 200 300 400
Gasoline consumption (kg) 7 15 22 29
LiCoO 2Electrokinetic cell demand weight (kg) 615 1230 1845 2460
LiMn 2O 4Electrokinetic cell demand weight (kg) 971 1942 2913 3884
LiFePO 4Electrokinetic cell demand weight (kg) 1230 2460 3689 4919
Lead-acid battery demand weight (kg) 2050 4099 6149 8199
There is following technical problem in lithium-ion-power cell:
One, energy density are very low, than low 85～170 times of gasoline.Usually, 400 kms that can travel continuously behind the automobile gases up, the gasoline that is consumed is 40 liters, 29 kilograms.In contrast to this, needing to use the weight of lithium-ion-power cell is 2.5～4.9 tons.Being about 1 ton car for a deadweight, loading the electrical source of power of weight like this, no matter from economy, technology equal angles, all is unacceptable;
Its two, fail safe is relatively poor.As everyone knows, use organic liquid electrolyte and thin stephanoporate barrier film in the lithium-ion-power cell.Because the flash-point of liquid organic electrolyte is lower, poor stability, decomposes, catching fire easily.In battery charge and discharge process, the defective of inside battery or outside improper use, partial short-circuit can appear in the thin stephanoporate barrier film, to making battery overheated, emit a large amount of heats, liquid organic electrolyte at first decomposes and burns, and produces high interior pressure and causes battery to catch fire even explode, and the lithium-ion-power cell that usage quantity is huge in electric motor car will make fail safe and integrity problem become severe more;
Its three, cycle life is low, cost is high.In the process of charging repeatedly and discharging, structural change and performance degradation can appear in battery material, cause battery behavior change in recycling, and battery capacity occurs and descend, and internal resistance is risen, discharging current minimizing etc.Be generally 8 years the useful life of automobile, and the time of the battery of electric motor car about 1 year, degradation, even can not use, need more renew battery pack, increased the use cost of electric motor car greatly.The price of original electric vehicle power battery pack has accounted for about 50% of electric motor car car load price, if annual the needs changed battery pack, is equivalent to automobile and changes an engine every year, and no matter from which aspect and angle, all be unacceptable.
Hydrogen fuel cell is used in electric motor car, has more difficulty and obstacle equally, and its main cause is analyzed as follows:
One, as the hydrogen of gas form, at aspects such as storage and transportations, equipment is complicated and expense cost is higher.If the use liquified hydrogen, it preserves also very inconvenient, the hydrogen of gas form must be cooled to subzero 253 degrees centigrade and just can change liquified hydrogen into.In order to realize subzero 253 degrees centigrade liquified hydrogen condition, need the consume significant energy and use expensive equipment.With weight is the unit calculating energy, no matter the energy that gaseous state or liquified hydrogen had such as also has only at 1/4 of heavy petrol.In fact, Hydrogen Energy is not a kind of energy form, because we do not exploit out with it from rock, but must come the production Hydrogen Energy with electrolysis or the method for separating from natural gas.That is to say that Hydrogen Energy just shifts a kind of approach of the energy, itself is not a kind of energy;
Its two, proton exchange membrane of using in the hydrogen fuel cell and catalyst, not only cost costliness but also resource-constrained.The price of proton exchange membrane is 20 times of common lithium battery diaphragm.Use platinum or platinum alloy in the catalyst, platinum is a kind of rare metal also more expensive several times than gold, and the content in the ground spherical shell layer is 0.001ppm only, be 8,200 ten thousand of the content of aluminium in the ground spherical shell layer/.Material resources is rare and cost an arm and a leg, and causes hydrogen fuel cell can't realize the commercial applications of product in the commercial market.
Summary of the invention
Embodiment of the invention technical problem to be solved is, a kind of high-energy safe rechargeable lithium-oxygen battery is provided, can solve that traditional lithium-ion-power cell energy density is low, fail safe and poor reliability, the low and expensive problem of cycle life, can solve also that hydrogen fuel cell stores and transportation is complicated, barrier film and catalyst cost height, problem that expense is high, be a kind of high energy, safety, chargeable lithium-oxygen battery.
For solving the problems of the technologies described above, the embodiment of the invention adopts following technical scheme:
A kind of high-energy safe rechargeable lithium-oxygen battery comprises positive pole and negative pole, and the reactant of described negative pole adopts lithium metal, and the reactant of described positive pole adopts oxygen and water, is provided with solid electrolyte diaphragm between described positive pole and the negative pole; Be provided with charging electrode in the described positive pole.
The beneficial effect of the embodiment of the invention is:
By a kind of high-energy safe rechargeable lithium-oxygen battery is provided, comprise positive pole and negative pole, the reactant of described negative pole adopts lithium metal, and the reactant of described positive pole adopts oxygen and water, is provided with solid electrolyte diaphragm between described positive pole and the negative pole; Be provided with charging electrode in the described positive pole, can solve that traditional lithium-ion-power cell energy density is low, fail safe and poor reliability, the low and expensive problem of cycle life, can solve also that hydrogen fuel cell stores and transportation is complicated, barrier film and catalyst cost height, problem that expense is high, be a kind of high energy, safety and chargeable lithium-oxygen battery.
Below in conjunction with accompanying drawing the embodiment of the invention is described in further detail.
Description of drawings
Fig. 1 is the specific embodiment schematic diagram of high-energy safe rechargeable lithium-oxygen battery of the present invention;
Fig. 2 is the discharging structure schematic diagram of the high-energy safe rechargeable lithium-oxygen battery of the embodiment of the invention;
Fig. 3 is that the high-energy safe rechargeable lithium-oxygen battery of the embodiment of the invention at room temperature carries out the discharge curve schematic diagram that discharge test is obtained;
Fig. 4 is the charging structure schematic diagram of the high-energy safe rechargeable lithium-oxygen battery of the embodiment of the invention;
Fig. 5 is that the high-energy safe rechargeable lithium-oxygen battery of the embodiment of the invention at room temperature discharges and recharges the charging and discharging curve schematic diagram that experiment obtains.
Embodiment
The embodiment of the invention provides a kind of high-energy safe rechargeable lithium-oxygen battery, comprises positive pole and negative pole, and the reactant of described negative pole adopts lithium metal, and the reactant of described positive pole adopts oxygen and water, is provided with solid electrolyte diaphragm between described positive pole and the negative pole; Be provided with charging electrode in the described positive pole, it is low to solve traditional lithium-ion-power cell energy density, fail safe and poor reliability, low and the expensive problem of cycle life, also can solve hydrogen fuel cell stores and transports complicated, barrier film and catalyst cost height, the problem that expense is high, be a kind of high energy, safety, chargeable lithium-oxygen battery, can be widely used in various large-capacity high-power mobile devices and mechanical device, for example electric bicycle, battery-operated motor cycle, electric automobile, electronic yacht, Electric aircraft, the satellite communication machine, rocket launcher and submarine are with communication power supply etc.
Below by specific embodiment high-energy safe rechargeable lithium-oxygen battery of the present invention is described.
Fig. 1 is the specific embodiment schematic diagram of high-energy safe rechargeable lithium-oxygen battery of the present invention, and with reference to this figure, the cathode reactant of this battery is lithium metal (Li), and anode reactant is oxygen (O 2) and water (H 2O), the direction of this battery from the negative pole to the positive pole comprises successively:
Negative current collector 101, negative current collector 101 adopts nickel foil, Copper Foil, stainless steel foil or its alloy foil, and perhaps, negative current collector 101 adopts nickel, copper, stainless steel or its alloy network material, perhaps, negative current collector 101 adopts nickel plating steel mesh or perforation nickel strap etc.;
Lithium metal 102, can be pure lithium or lithium alloy, in following table 3, can see, in all metals, lithium metal 102 has the highest energy density 13000Wh/kg, and is suitable with the gasoline energy density 12722Wh/kg that lists in the table 1, that is to say, compare with using the travel automobile of 400 kms of 40 liters of (29 kilograms) gasoline, use the electric motor car of the battery that the is equipped with 28 kilograms of lithium metals same mileage that also can travel; In addition, owing to adopt lithium metal 102, its storage, transportation and use are all very convenient and simple;
Table 3
Metal/oxygen electricity is to (negative pole/positive pole) Metal gram volume (Ah/g) Theoretical energy density (Wh/kg) Electricity price Theoretical voltage (V) Virtual voltage (V)
Li/O 2 3.86 13,000 1 3.4 2.4～3.0
Al/O 2 2.98 8,100 3 2.7 1.1～1.4
Mg/O 2 2.20 6,800 2 3.1 1.2～1.4
Ca/O 2 1.34 4,600 2 3.4 2.0
Na/O 2 1.17 3,500 1 3.1 2.2～2.9
Zn/O 2 0.82 1,300 2 1.6 1.0～1.2
Fe/O 2 0.96 1,200 2 1.3 1.0
Negative pole electrolyte 103, lithium metal 102 and solid electrolyte diaphragm 104 all are rigid solids, the surface contact is bad, interface resistance is higher, negative pole electrolyte 103 promptly can be the organic electrolyte that comprises electrolytic salt, organic solvent, thereby can reduce lithium metal 102 and solid electrolyte diaphragm 104 interface resistances, promotes the operating voltage and the power of battery, avoid the corrosion and the oxidation of aqueous electrolysis confrontation lithium metal 102 simultaneously, electrolytic salt is lithium hexafluoro phosphate (LiPF 6), LiBF4 (LiBF 4) and/or dioxalic acid close lithium borate (LiBOB), organic solvent is ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), methyl ethyl carbonate fat (EMC) and/or carbonic acid diethyl ester (DEC), and the concentration span of electrolytic salt in organic solvent is 0.8 mol to 1.5 mol;
Solid electrolyte diaphragm 104, solid electrolyte film 104 can adopt the material with following characteristic:
A, high electronic isolation, anticathode and the anodal electronics of implementing completely cut off, and force electronics to pass through the external circuit acting of battery;
B, high-lithium ion conductivity to the efficient conducting of lithium ion, make its smooth and easy shuttling back and forth between negative pole and positive pole between negative pole and positive pole;
C, when battery charge, suppress the growth of dendritic lithium metal crystallization, prevent that it from penetrating solid electrolyte diaphragm 104 and causing internal short-circuit;
D, the organic electrolyte of separating negative pole and anodal alkaline aqueous solution make two kinds of mutual indiffusion of electrolyte and infiltration, particularly stop hydrone to enter organic electrolyte and corroding metal lithium 102;
E, have better machinery and chemical strength, under the negative potential and high normal potential condition of exoelectrical reaction and charging reaction, opposing electrochemical corrosion and oxidation keep superperformance;
Distinguish from material, solid electrolyte diaphragm 104 can be divided into organic (macromolecule) class and mineral-type, organic class can be selected based on the anionic single ionomer pectination side chain polyelectrolyte of trifluoromethyl sulfonymethyl, sulfonate, fluoroalkyl sulfate or acid imide, mineral-type comprise simple substance solid electrolyte diaphragm and composite solid electrolyte barrier film etc., the simple substance solid electrolyte diaphragm can be selected LiPON (LiPON), and its lithium ion conductivity is about 10 -5S/cm, the composite solid electrolyte barrier film comprises kernel and external coating, can adopt the lithium ion conductivity height (to be about 10 -3S/cm) but relatively poor oxide, sulfide, selenides, nitride and the phosphide of chemical stability as kernel, the wide oxide material of chemical stability height, electrochemical window is as coating layer, inner nuclear material can be selected lithium sulfate (LiSO for use 4), lithium metasilicate (LiSiO 4), lithium phosphate (γ-Li 3PO 4), the perovskite solid solution (Li of A position defective 3xLa (2/3)-x (1/3)-2xTiO 3(0≤x≤1)), lithium sulfide (Li 2S), germanium lithium (Li 2Ge) and/or phosphoric sulfide (P 2S 5) etc., the external coating material can be selected for use and mix titanium phosphate lithium Li 1+xTi 2-xM x(PO 4) 3(M=Al, Ga, In, Sc) etc., composite solid electrolyte barrier film compatibility the requirement of high-lithium ion conductivity and high chemical stability, be the material of the preferred solid electrolyte diaphragm 104 of the embodiment of the invention;
The anodal electrolyte 105 of water is provided, anodal electrolyte 105 is alkaline aqueous solution, as lithium hydroxide (LiOH) aqueous solution etc., when exoelectrical reaction, lithium ion enters organic electrolyte from the negative terminal surface dissolving, enter positive pole by solid electrolyte diaphragm 104 again, with oxygen generation electrochemical reaction, if the electrochemical reaction product is to form Li 2The O solid powder substance, will stop up anodal reaction channel, make follow-up electrochemical reaction be obstructed, slow down even stop, in order to guarantee constantly and normally carrying out of electrochemical reaction, the product of the exoelectrical reaction of lithium metal must be liquid or gaseous state, and therefore, the embodiment of the invention preferably adopts alkaline aqueous solution, the electrochemical reaction product is LiOH, with Li +And OH -Form is present among the alkaline aqueous solution, makes anodal reaction channel unblocked, and air flows into smoothly, brings necessary oxygen into;
Porous carbon 106, porous carbon 106 adopts activated carbon, mesoporous carbon, graphite, acetylene black, middle phase microballoon or carbon nano-tube;
Porous carbon 106 is provided with catalyst 107, in order to improve anodal reaction efficiency, improve the polarization of electrode characteristic, improve the operating voltage and the open circuit voltage of battery, can use catalyst 107 on anodal surface, usually, catalyst 107 can be platinum, rhodium, gold, noble metal or precious metal alloys such as silver, its good catalytic activity, perhaps, in order to reduce cost, catalyst 107 can be aboundresources, cheap transition metal oxide and/or rare-earth oxide, wherein, transition metal can be from manganese, vanadium, iron, cobalt, nickel, copper, molybdenum, chromium, titanium, silver, select in gold and the tungsten, rare earth metal can be from cerium, praseodymium, selecting in samarium and the terbium, is example with the manganese catalyst series, can adopt manganese dioxide (MnO 2), manganese sesquioxide managnic oxide (Mn 2O 3), mangano-manganic oxide (Mn 3O 4), alkali formula manganese oxide (MnOOH) etc., it has low price, high efficiency catalysis characteristics;
In addition, in embodiments of the present invention, can with an amount of porous carbon, conductive agent, bonding agent, catalyst by mix, mode such as roll extrusion makes anodal layer, is compressed on the anode collection surface then;
Plus plate current-collecting body 108, plus plate current-collecting body is provided with the path 10 9 that is used to import oxygen, plus plate current-collecting body 108 adopts nickel, nickel foam, aluminium, stainless steel or its alloy network material, perhaps, plus plate current-collecting body 108 adopts nickel plating steel mesh or perforation nickel strap, oxygen has stronger electrochemical reaction ability and high energy density, therefore preferred with the reactant of oxygen as positive pole, from last table 3, can also see, the electricity of lithium metal and oxygen is that all metals and oxygen electricity centering are the highest to voltage, in actual battery, also has the highest operating voltage, not only improved the energy density of battery, and reduced battery pack and need the series connected battery number, promoted the reliability of battery pack, reduce the cost of battery protection and control circuit device, because, the electric motor car required voltage is up to tens volts even the hundreds of volt, if single battery has higher operating voltage, battery pack needs the series connected battery number to reduce relatively; In all positive electrode materials, the oxygen that obtains from air is the most cheap, relaxed and easily, therefore is provided with the above-mentioned path 10 9 that is used to import oxygen;
In addition, the independently charging electrode 110 that in the positive pole of battery, can be provided with, special supply battery charge is used, its effect is, if use porous carbon 106 to charge, anodal charging reaction and relevant electrochemical reaction thereof, to itself produce oxidations to porous carbon 106 with catalyst 107, corrosion and side effect such as poison, thereby destroy the composition of porous carbon 106 itself and catalyst 107, structure and characteristic thereof, so in circulation discharge process next time, anodal discharge performance will be subjected to seriously influencing very much, adopt independently charging electrode 110 can avoid this point;
(1) below with reference to Fig. 2 the discharge process of high-energy safe rechargeable lithium-oxygen battery is described, structure when Fig. 2 shows the high-energy safe rechargeable lithium-oxygen battery discharge, the high-energy safe rechargeable lithium-oxygen battery that Fig. 3 shows the embodiment of the invention at room temperature carries out the discharge curve that discharge test is obtained, and discharging current is 0.1mA/cm 2, the supercharging air machine 202 that reacts is provided better comprising external discharge load 201 and with airborne oxygen:
In the above-mentioned battery, the exoelectrical reaction of the reactant lithium of negative pole can be as shown in the formula shown in (1):
Li→Li ++e -　　　　(1)
At inside battery, lithium metal enters organic electrolyte with the form of lithium ion from surface dissolution, enters alkaline aqueous solution in the positive pole by solid electrolyte diaphragm 104 again, forms LiOH as the electrochemical reaction product, is present in the alkaline aqueous solution; At outside batteries, the lithium metal dissolving enters the electronics of emitting when organic electrolyte forms lithium ion, arrives in the anodal alkaline aqueous solution by the outside batteries circuit;
In battery discharge procedure, lithium concentration progressively raises in the alkaline aqueous solution;
Be soaked in the positive pole in the alkaline aqueous solution, be made up of porous carbon 106, catalyst 107, oxygen and plus plate current-collecting body 108, the anodal reactants water and the exoelectrical reaction of oxygen are as shown in the formula shown in (2):
O 2+2H 2O+4e -→4OH - (2)
The middle lithium metal of exoelectrical reaction (1) that the anodal required electronics of exoelectrical reaction (2) comes from negative pole dissolves the electronics of emitting when entering organic electrolyte, and the external circuit by battery arrives in the anodal alkaline aqueous solution, be supplied to anodal exoelectrical reaction to use, meanwhile, the exoelectrical reaction of negative pole (1) electrochemical reaction product Li +Enter in the anodal alkaline aqueous solution by solid electrolyte diaphragm 104, make the elecrtonegativity of the middle electrochemical reaction product that produces of anodal exoelectrical reaction (2) obtain neutralization, the electric neutrality that has kept anodal alkaline aqueous solution, in other words, the electrochemical reaction product Li of the exoelectrical reaction of negative pole (1) +Enter the alkaline aqueous solution of positive pole by solid electrolyte diaphragm 104 after, do not generate/separate out Li 2Solid matters such as O stop up anodal reaction channel (as the carbon micropore in the porous carbon, be used to import the path 10 9 of oxygen etc.), but be present in the anodal alkaline aqueous solution with water-soluble products LiOH, make anodal reaction channel unblocked, thereby the electrochemical reaction of battery can be carried out continuously;
In conjunction with (1), (2), the net reaction of exoelectrical reaction can be as shown in the formula shown in (3):
4Li+O 2+2H 2O+4e -→4Li ++4OH - (3)
After discharge was finished, high-energy safe rechargeable lithium-oxygen battery can carry out following charging process;
(2) below with reference to Fig. 4 the charging process of high-energy safe rechargeable lithium-oxygen battery is described, structure when Fig. 4 shows the high-energy safe rechargeable lithium-oxygen battery charging, the high-energy safe rechargeable lithium-oxygen battery that Fig. 5 shows the embodiment of the invention at room temperature discharges and recharges the charging and discharging curve figure that experiment obtains, and (wherein dotted line is represented charging curve, solid line is represented discharge curve), charging current is 0.05mA/cm 2, comprising the charger 401 that external electric energy is provided:
First kind of charging modes, can charge by the electric power mode, with lithium ion in the alkaline aqueous solution is that power is separated from solution with the external electric energy, enter by solid electrolyte diaphragm 104 in the organic electrolyte of negative pole, then in the crystallization again of negative current collector 101 surfaces, form new negative pole, charging reaction can be as shown in the formula shown in (4):
Li ++e -→Li (4)
The required electronics of above-mentioned charging reaction is provided by charger 301, arrives negative current collector 101 by lead, and lithium ion is reduced into lithium metal behind the negative pole electron gain;
And the charging of the positive pole in when charging reaction can be as shown in the formula shown in (5):
4OH -→O 2+2H 2O+4e - (5)
Carbon micropore by the porous carbon of positive pole of the oxygen that produces in the charging of the above-mentioned positive pole reaction (5), form that can oxygen, path 10 9 etc. are discharged in the atmosphere; The electronics that produces in the anodal charging reaction (5) is transported in the charger 401 by the independently charging electrode 110 that is provided with in the positive pole of battery, is transported to negative pole, the lithium ion Li in the organic electrolyte of negative pole by charging 401 again +Behind the negative terminal surface electron gain, be reduced into lithium metal, shown in following formula (4);
In conjunction with (4), (5), the net reaction of charging reaction can be as shown in the formula shown in (6):
4Li ++4OH -→4Li+O 2+2H 2O+4e -　　　(6)
Second kind of charging modes, can use mechanical system, lithium can adopt the changeable type structure to be arranged in the high-energy safe rechargeable lithium-oxygen battery, the changeable type structure can be the cartridge mode, be about to use the lithium metal cartridge of the empty negative pole in back to extract, insert new lithium metal cartridge, finish after this operation, battery is full of new fuel, can continue discharge and use.
Describe following preferred embodiment in detail, will understand the superiority of the high-energy safe rechargeable lithium-oxygen battery of the embodiment of the invention better.
The preferred embodiment of high-energy safe rechargeable lithium-oxygen battery of the present invention comprises:
Negative current collector 101 adopts nickel screen;
Solid-state lithium 102 adopts pour lithium slice;
Negative pole electrolyte 103 adopts organic electrolyte, and its electrolytic salt is lithium hexafluoro phosphate (LiPF 6), its organic solvent adopts the ternary organic solvent of ethylene carbonate (EC), propene carbonate (PC) and dimethyl carbonate (DMC), and the concentration of electrolytic salt in organic solvent is 1.2 mol, and the volume ratio of each component is 1:1:1 in the organic solvent;
Solid electrolyte diaphragm 104 adopts the composite solid electrolyte barrier film of mineral-type, and its inner nuclear material is selected the Li that contains amorphous silicon oxidation thing grain boundary layer for use 1/8La 5/8 1/4TiO 3, granularity is about 10～30 μ m; External coating material selection Li 1.5Ti 1.5Al 0.5(PO 4) 3, thickness is 1～5 μ m; The composite solid electrolyte powder is 130 Xie through the thickness of suppressing the composite solid electrolyte barrier film that forms thus, and lithium ion conductivity is 10 -4S/cm, electrochemical window is greater than 5V;
Anodal electrolyte 105 adopts alkaline aqueous solution, lithium hydroxide (LiOH) aqueous solution, and its initial concentration is 0.02 mol, along with the exoelectrical reaction process of battery, the lithium hydroxide concentration in the alkaline aqueous solution progressively raises, and reaches as high as 5.8 mol;
Charging electrode 110 adopts stainless (steel) wire;
Plus plate current-collecting body 108 adopts nickel foam;
Porous carbon 106 adopts activated carbon;
Catalyst 107 adopts the mangano-manganic oxide of load 20wt%;
Correspondingly, conductive agent is an acetylene black, and binding agent is a polytetrafluoroethylene (PTFE), prescription is that the ratio of conductive agent, binding agent, activated carbon is 5:12:88 in detail, make slurry according to this ratio, apply roll extrusion then, make positive pole after the baking drying on plus plate current-collecting body 108 surfaces;
The initial open circuit voltage of battery is 3.2V, connects after the external discharge load 201, and voltage instantaneous descends, and in the oxide layer course of dissolution on lithium surface, discharging current fluctuates up and down, voltage bounce, and electric current progressively is stabilized in 0.1mA/cm then 2, average voltage is 2.6V, finishes when discharging into 1V, total discharge capacity is 8.1 ampere-hours;
Still use the high-energy safe rechargeable lithium-oxygen battery of preferred embodiment of the battery of the invention described above, after its discharge finishes, use charging electrode 110, at 0.05mA/cm 2With constant-current supply battery is carried out constant current charge under the charging current, total charging capacity is 9.3 ampere-hours, and charging not stopped one hour after finishing, and changes the Constant Current Load discharge then over to, and continuous current is 0.1mA/cm 2, finishing when discharging into 1V, total discharge capacity is 7.9 ampere-hours.
The above is the specific embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also are considered as protection scope of the present invention.

Claims (8)

  1. [claim 1] a kind of high-energy safe rechargeable lithium-oxygen battery comprises positive pole and negative pole, it is characterized in that, the reactant of described negative pole adopts lithium metal; The reactant of described positive pole adopts oxygen and water; Be provided with solid electrolyte diaphragm between described positive pole and the negative pole; Be provided with charging electrode in the described positive pole.
  2. [claim 2] high-energy safe rechargeable lithium-oxygen battery as claimed in claim 1 is characterized in that, is provided with successively to described positive extreme direction from described negative pole:
    Negative current collector, described lithium metal, negative pole electrolyte, described solid electrolyte diaphragm, provide anodal electrolyte, porous carbon, the plus plate current-collecting body of described water, described plus plate current-collecting body is provided with the passage that is used to import described oxygen.
  3. [claim 3] high-energy safe rechargeable lithium-oxygen battery as claimed in claim 2, it is characterized in that described porous carbon is provided with catalyst, described catalyst is noble metal or precious metal alloys, perhaps, described catalyst is transition metal oxide and/or rare-earth oxide.
  4. [claim 4] high-energy safe rechargeable lithium-oxygen battery as claimed in claim 2, it is characterized in that, described solid electrolyte film is based on the anionic single ionomer pectination side chain polyelectrolyte of trifluoromethyl sulfonymethyl, sulfonate, fluoroalkyl sulfate or acid imide, perhaps, described solid electrolyte film is the composite solid electrolyte film that comprises kernel and external coating, described kernel adopts perovskite solid solution, lithium sulfide, germanium lithium and/or the phosphoric sulfide of lithium sulfate, lithium metasilicate, lithium phosphate, A position defective, and described external coating adopts and mixes the titanium phosphate lithium.
  5. [claim 5] high-energy safe rechargeable lithium-oxygen battery as claimed in claim 2, it is characterized in that, described negative pole electrolyte is the organic electrolyte that comprises electrolytic salt, organic solvent, described electrolytic salt is that lithium hexafluoro phosphate, LiBF4 and/or dioxalic acid close lithium borate, described organic solvent is ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate fat and/or carbonic acid diethyl ester, and the concentration span of described electrolytic salt in described organic solvent is 0.8 grams per liter to 1.5 grams per liter.
  6. [claim 6] high-energy safe rechargeable lithium-oxygen battery as claimed in claim 2 is characterized in that, described anodal electrolyte is alkaline aqueous solution.
  7. [claim 7] high-energy safe rechargeable lithium-oxygen battery as claimed in claim 2, it is characterized in that, described negative current collector adopts nickel foil, Copper Foil, stainless steel foil or its alloy foil, perhaps, described negative current collector adopts nickel, copper, stainless steel or its alloy network material, perhaps, described negative current collector adopts nickel plating steel mesh or perforation nickel strap; Described plus plate current-collecting body adopts nickel, nickel foam, aluminium, stainless steel or its alloy network material, and perhaps, described plus plate current-collecting body adopts nickel plating steel mesh or perforation nickel strap; Described porous carbon adopts activated carbon, mesoporous carbon, graphite, acetylene black, middle phase microballoon or carbon nano-tube.
  8. [claim 8] is characterized in that as each described high-energy safe rechargeable lithium-oxygen battery in the claim 1 to 7, and described lithium metal adopts the changeable type structure to be arranged in the described high-energy safe rechargeable lithium-oxygen battery.
CN200910301541A 2009-04-14 2009-04-14 A high-energy safe rechargeable lithium-oxygen battery Pending CN101533935A (en)

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CN102687324B (en) * 2009-12-28 2016-01-13 Posco公司 A kind of composite ceramic material and preparation method thereof
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CN102687324A (en) * 2009-12-28 2012-09-19 Posco公司 Composite ceramic material and method for manufacturing the same
CN102948005A (en) * 2010-06-22 2013-02-27 巴斯夫欧洲公司 Electrodes and production and use thereof
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CN103415953A (en) * 2010-12-01 2013-11-27 魁北克电力公司 Lithium-air battery
CN103415953B (en) * 2010-12-01 2016-07-06 魁北克电力公司 Lithium-air battery
CN103000971A (en) * 2011-09-15 2013-03-27 北汽福田汽车股份有限公司 Lithium air battery and production method thereof
CN103943880A (en) * 2013-01-22 2014-07-23 华为技术有限公司 Sulphur-based glass ceramic electrolyte, preparation method thereof, all-solid-state lithium battery and preparation method of the all-solid-state lithium battery
CN104393310A (en) * 2014-10-20 2015-03-04 上海空间电源研究所 Air electrode material of high-activity lithium air battery and preparation method of nano-composite catalyst material
CN105845847A (en) * 2016-03-25 2016-08-10 渤海大学 Lithium-oxygen battery having controllable-composite anode structure
CN105845847B (en) * 2016-03-25 2018-05-25 渤海大学 A kind of controllable composite anode structure lithium-oxygen battery
CN107591529A (en) * 2017-10-10 2018-01-16 中南大学 A kind of titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material and preparation method thereof
DE102018100765A1 (en) * 2018-01-15 2019-07-18 Atlas Elektronik Gmbh Underwater device for use under water with an energy generating device
CN111269509A (en) * 2020-02-14 2020-06-12 中国科学院长春应用化学研究所 Porous plastic crystal electrolyte for all-solid-state metal-air battery, preparation method of porous plastic crystal electrolyte and all-solid-state metal-air battery
CN111269509B (en) * 2020-02-14 2021-09-21 中国科学院长春应用化学研究所 Porous plastic crystal electrolyte for all-solid-state metal-air battery, preparation method of porous plastic crystal electrolyte and all-solid-state metal-air battery
CN112421031A (en) * 2020-11-24 2021-02-26 宁德新能源科技有限公司 Electrochemical device and electronic device
CN112421031B (en) * 2020-11-24 2022-04-05 宁德新能源科技有限公司 Electrochemical device and electronic device
CN114944493A (en) * 2022-05-05 2022-08-26 青岛大学 Lithium ion lithium oxygen hybrid battery and preparation method thereof
CN114944493B (en) * 2022-05-05 2024-02-06 青岛大学 Lithium ion lithium oxygen hybrid battery and preparation method thereof

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