CN103606686A - Air electrode for lithium air cells and preparation method of air electrode - Google Patents
Air electrode for lithium air cells and preparation method of air electrode Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8673—Electrically conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
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Abstract
The invention discloses an air electrode for lithium air cells and a preparation method of the air electrode. The air electrode possesses an ion conductive three-dimensional net and an electron conductive three-dimensional net at the same time, wherein the ion conductive three-dimensional net is formed by a room-temperature ionic liquid with catalytic characteristic, and the electron conductive three-dimensional net is formed by a conductive agent. The air electrode is prepared by uniformly mixing 10-40 parts by weight of the room-temperature ionic liquid and 60-90 parts by weight of the conductive agent and immobilizing on the surface of a porous current collector. Because the provided air electrode possesses double conductive nets, the three-phase reaction interface formed by electron conductive phase, ion conductive phase and oxygen and needed by electrode reaction is substantially enlarged, also the transportation speed of electrons and ions needed by the reaction is accelerated, and thus the voltage polarization is reduced, the air electrode shows excellent cell comprehensive performances when applied to the lithium air cells and has extremely good application prospect.
Description
Technical field
The present invention relates to the air electrode with two three-dimensional conductive networks based on liquid catalyst that a class can be used for lithium-air battery, belong to technical field of chemical power.
Background technology
Although business-like lithium ion battery is widely used at numerous areas such as various portable dams, digital product, Aero-Space at present, but because its energy density is subject to the restriction of insertion reaction mechanism, be difficult to meet electronic product progress miniaturization and electric automobile length apart from the instructions for use of driving, therefore, exploitation has the more secondary cell of high-energy-density becomes global study hotspot, and the research of lithium-air battery is arisen at the historic moment.
The basic functional principle of lithium-air battery is that in discharge process, lithium metal is oxidized at negative pole, then the surface to air electrode by electrolyte, with air electrode surface in porous be reduced from airborne combination with oxygen, to load, provide electric energy thus.The advantage of lithium-air battery maximum is just that positive active material is inexhaustible from airborne oxygen, and it does not need to be stored in inside battery, therefore lithium-air battery has the theoretical energy density of the superelevation of 13200Wh/Kg, almost can match in excellence or beauty with gasoline, become Mountain Everest of secondary cell.Although the actual energy density of the lithium-air battery of having reported at present obtains a very large progress, but unfortunately, because positive active material oxygen electrochemical redox dynamics slowly makes lithium-air battery invertibity poor, serious polarization, so lithium-air battery is realized practical application and is still faced with very large challenge.
In order to address these problems, researcher has done a lot of effort, comprise exploitation and prepare high performance catalyst (as various metal oxides, various carbon-based materials, noble metal catalyst and transition metal macrocyclic compound etc.) and the structural design of air electrode etc., and obtained certain achievement.But at present the catalyst of research is all in solid state, and traditional mode of preparing electrode makes be mingled with nonconducting binding agent between solid particle, and this just makes the inner network that is difficult to form three-dimensional conduction of air electrode.Known according to the reaction principle of air electrode, electrode reaction occurs in the three phase boundary of electronic conductor, ionic conductive agent and oxygen, therefore in air electrode inside, sets up the performance that three-dimensional conductive network will improve electrode greatly.
Up to now, electron conduction or ionic conductivity poor in existing design cause voltage polarizing and the poor invertibity that air electrode is high, therefore this area is in the urgent need to develop the air electrode structure of a kind of electron conduction that can guarantee and ionic conductivity simultaneously, to reduce the voltage polarizing of lithium-air battery, improve its invertibity, promote the realization of lithium-air battery practical application.
Summary of the invention
The problems referred to above that exist for prior art, the present invention aims to provide a kind of air electrode for lithium-air battery and preparation method thereof, to promote lithium-air battery to realize practical application.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of air electrode for lithium-air battery, there is ionic conduction three-dimensional network and electron conduction three-dimensional network simultaneously, described ionic conduction three-dimensional network is to be formed by the ionic liquid at room temperature with catalysis characteristics, and described electron conduction three-dimensional network is to be formed by conductive agent.
The preparation of air electrode of the present invention is the ionic liquid at room temperature of 10～40 weight portions to be mixed to rear be immobilizedly prepared from porous current collector surface with the conductive agent of 60～90 weight portions.
As a kind of preferred version, the preparation method of described air electrode, comprises the steps:
A) 10～40 weight portion ionic liquid at room temperature are mixed with 60～90 weight portion conductive agents;
B) mixed slurry step a) being obtained is immobilized on porous current collector, then dry at 50～100 ℃, then with the pressure of 6～10MPa, will conduct electricity active material and porous current collector and suppress solid;
C) by step b) electrode that obtains dry dewatering at 50～100 ℃, obtain described air electrode.
As a kind of preferred version, described porous current collector comprises metal porous collector and inorganic non-metallic porous current collector.
As further preferred version, described metal porous collector comprises nickel foam, porous aluminum and porous stainless steel; Described inorganic non-metallic porous current collector comprises porous carbon materials.
Described ionic liquid at room temperature includes nitrogen; fluorine; the elements such as boron also have the catalysis of reduction characteristic, recommend to be selected from least one in 1-ethyl-3-methylimidazole two (five fluoro-ethylsulfonyl) acid amides, two (trifluoromethyl sulfonyl) acid amides of 1-ethyl-3-methylimidazole, two (trifluoromethyl sulfonyl) acid amides of 1-methyl-3-octyl group imidazoles, 1-butyl-3-methylimidazole nine fluorine butyl sulfosalts, 1-ethyl-3-methylimidazole hexafluorophosphate.
As a kind of preferred version, described conductive agent is selected from least one in carbon-based conductive agent, conducting polymer agent and inorganic conductive agent.
As further preferred version, described carbon-based conductive agent is selected from least one in acetylene black, conductive carbon black, activated carbon, meso-porous carbon material, hollow carbon sphere, carbon fiber, carbon nano-tube; Described conducting polymer agent is selected from polypyrrole or polyaniline; Described inorganic conductive agent is conductive oxide, as SnO
2, perovskite-type compounds is as BaPbO
3, non-stoichiometric metal oxide is as Ti
4o
7deng.
As a kind of preferred version, described solid support method comprises infusion process, in situ deposition method and ultrasonic dispersion; Described infusion process is after adopting the method applying to be coated on collector conductive agent, vacuum impregnation in needed ionic liquid after pole drying, and the hole that allows ionic liquid enter electronic conductor forms three-dimensional ionic conduction network; Described in situ deposition method is also after the method that first conductive agent adopt applied is coated on collector, needed ionic liquid is dropped in to electrode surface and wait for a period of time and treat that ionic liquid is diffused into the hole of electronic conductor and forms three-dimensional ionic conduction network; Described ultrasonic dispersion is first conductive agent to be dispersed in needed ionic liquid, ultrasonic a period of time, make ionic liquid be coated on uniformly the surface of conductive agent, the method that then adopts traditional ball milling to apply is prepared into the air electrode with two three-dimensional conductive networks.
Principle of the present invention is: adopt the ionic liquid at room temperature with reduction characteristic as catalyst, on the one hand at the three-dimensional ionic conduction network of the inner formation of air electrode, adopt on the other hand same ionic liquid as electrolyte, between air electrode and electrolyte, form like this relation in total stream-tributary, electrolyte can enter into along with ionic liquid the various piece of electrode, thereby the ion that in electrode, reaction generates can directly enter in electrolyte and reduce the internal resistance of cell, is conducive to the raising of battery performance.In addition, ionic liquid in electrode also plays the effect of binding agent to a certain extent, even need in electrode, not add in addition binding agent, thereby can effectively reduce the weight of electrode, be conducive to improve the capacity density of electrode, can also avoid the problem declining at the unstable battery performance causing of discharge process performance due to conventional binders, be conducive to improve the combination property of battery simultaneously.
Compared with prior art, air electrode provided by the invention has following significant characteristics:
1) using itself there is reproducibility ionic liquid as catalyst, saved the problems such as unstable chemcial property of preparing the step of solid catalyst complexity and having avoided solid catalyst itself to have;
2) compound with the ionic liquid of liquid and the conductive agent of solid, thereby can realize, liquid is multi-faceted to be contacted with solid conduction agent, compound than the very large solid catalyst of interface energy and solid conduction agent, greatly reduce the interface energy that two kinds of materials contact, be conducive to the carrying out of electrode reaction;
3) using same ionic liquid as electrolyte simultaneously as catalyst, thereby guaranteed that ion migration has unobstructed passage, reduced the internal resistance of ion migration, be conducive to the raising of battery performance;
4) the three-dimensional conductive network forming with ionic liquid at room temperature is than the three-dimensional ionic conduction network that adopts original position generating mode to form, and preparation method is easier, has more the continuity of ionic conductivity;
5) due to the liquid condition of ionic liquid, make when forming the three-dimensional conductive network of ionic liquid, being in contact with one another of solid conduction agent is not interrupted, can form the three-dimensional network of electron conduction;
6) formation of two conductive networks in electrode, greatly increased the needed electron conduction of electrode reaction, the three-phase reaction interface that ionic conduction and oxygen form, accelerated to react the transmission speed of needed electronics and ion simultaneously, thereby can promote greatly the carrying out of electrode reaction, reduce voltage polarizing;
7) in electrode material, can not use binding agent, can effectively reduce the weight of electrode material, be conducive to improve the capacity density of battery, avoid the decline of the battery performance that causes because binding agent is unstable, thereby be conducive to the raising of battery combination property.
Compare with the preparation method of existing various air electrodes, preparation method's tool of the present invention has the following advantages:
1, preparation method is simple;
2, can not use special binding agent, avoid the battery performance causing because binding agent is unstable to decline, reduce the weight of electrode simultaneously, be conducive to improve the performance of electrode;
3, pollution-free, environmental protection, utilizes simple ball milling method just can realize the combination of ionic liquid and conductive agent, forms three-dimensional electron conduction network when forming three-dimensional ionic conduction network;
4, the abundant species of ionic liquid at room temperature and conductive agent, can obtain the air electrode with different qualities by different combinations, thereby it is adjustable to realize the characteristic of air electrode;
5, raw material sources are abundant, and preparation cost is low.
Accompanying drawing explanation
Fig. 1 is the structural representation of lithium-air battery provided by the invention;
Fig. 2 is the timing charging and discharging curve of the lithium-air battery of air electrode described in use embodiment 3.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.
Fig. 1 is the structural representation that utilizes lithium-air battery prepared by air electrode provided by the invention, wherein: 1 is lithium metal anode, 2 is organic electrolyte, and 3 is solid electrolyte, and 4 is air electrode provided by the invention (comprising ionic liquid at room temperature 41 and solid conduction agent 42).
Comparative example 1
Employing acetylene black is conductive agent, PVDF is binding agent, the two weight ratio with 8:2 adds NMP mixing and ball milling, then the slurry drying after ball milling is coated on nickel foam collector to a certain extent afterwards, then on forcing press, the pressure with 8MPa is suppressed, electrode after compacting is placed on 80 ℃ of dry 12h in vacuum drying chamber, to get rid of the moisture in electrode.Then by electrode assembling in lithium-air battery, lithium-air battery adopts metal Li//1M LiPF
6be dissolved in the structure of 1-butyl-3-methyl imidazolium tetrafluoroborate // air electrode of two (trimethyl fluoride sulfonyl) imine lithium of EC/DMC (1:1) //LATP//dissolved 0.5M.Then the battery assembling is carried out to electrochemical property test and comprise regularly charge-discharge test, volume test.As can be seen from Table 1, the discharge voltage of battery is lower, is 2.73V, and charging voltage is 4.2V, and coulomb efficiency only has 65%, and first discharge specific capacity only has 171.5mAh/g.
Comparative example 2
Employing acetylene black is conductive agent, manganese dioxide is catalyst, to be binding agent three add ball milling after NMP with the weight ratio of 6:2:2 to PVDF, prepare the mode of electrode identical with comparative example 1 with the mode of battery assembling, then the battery assembling is carried out to electrochemical property test and comprise regularly charge-discharge test and volume test.Data by table 1 can find out, the discharge voltage first of battery is lower, and coulomb efficiency only has 66%, and capacity is 1193mAh/g.
Comparative example 3
Employing acetylene black is conductive agent, adopt ionic liquid 1-carboxymethyl-3-methylimidazole villaumite without reproducibility dissolve 0.5mol/L two (trimethyl fluoride sulfonyl) imine lithium be additive, the two prepares the mode of electrode identical with comparative example 1 with the mode of battery assembling with the weight ratio mixing and ball milling of 8:2.Then the battery assembling is carried out to electrochemical property test and comprise charge-discharge test and volume test.Data by table 1 can find out, the discharge voltage first of battery is very low, illustrates that the reduction of ionic liquid is more weak, and charging voltage is very high, and coulomb efficiency only has 67%, and capacity is 1265mAh/g.
Embodiment 1
Employing acetylene black is conductive agent, the 1-ethyl-3-methylimidazole tetrafluoroborate that is dissolved with two (trimethyl fluoride sulfonyl) imine lithium of 0.5mol/L is catalyst, conductive agent and catalyst are with the weight ratio mixing and ball milling of 8:2, then the slurry drying after ball milling is coated on nickel foam collector to a certain extent afterwards, then on forcing press, the pressure with 8MPa is suppressed, electrode after compacting is placed on 80 ℃ of dry 12h in vacuum drying chamber, to get rid of the moisture in electrode.By electrode assembling, in lithium-air battery, lithium-air battery adopts metal Li//1M LiPF
6two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI) that is dissolved in EC/DMC (1:1) //LATP//0.5mol/L is dissolved in the structure of 1-butyl-3-methyl imidazolium tetrafluoroborate // air electrode, then the battery assembling is carried out to electrochemical property test and comprise regularly charge-discharge test, volume test.Acquired results is as shown in table 1, can find out with comparative example contrast, discharge voltage improves a lot first, for 2.82V, charging voltage obviously reduces, and is 3.95V, coulomb efficiency reaches 71.4%, capacity also increases, and is 1500mAh/g, illustrates that the air electrode of this kind of two conductive network structures can effectively improve battery polarization and improve battery specific capacity.
Employing acetylene black is conductive agent, the 1-ethyl-3-methylimidazole tetrafluoroborate that has dissolved two (trimethyl fluoride sulfonyl) imine lithium of 0.5mol/L is catalyst, conductive agent and catalyst be with the weight ratio mixing and ball milling of 9:1, identical with embodiment 1 of preparation process and condition.Then by electrode assembling in lithium-air battery, lithium-air battery adopts metal Li//1M LiPF
6be dissolved in the structure of 1-ethyl-3-methylimidazole tetrafluoroborate // air electrode of two (trimethyl fluoride sulfonyl) imine lithium of EC/DMC (1:1) //LATP//dissolved 0.5mol/L, then the battery assembling is carried out to electrochemical property test, comprise regularly charge-discharge test and volume test, test result is as shown in table 1, compare with comparative example, voltage polarizing and capacity all increase, but compare with embodiment 1, the polarization performance of battery and capacity are all bad, trace it to its cause is because the minimizing of ionic liquid at room temperature in electrode, thereby more illustrated that the ionic liquid at room temperature in electrode has played key effect in the performance that improves battery.
Employing acetylene black is conductive agent, the 1-ethyl-3-methylimidazole tetrafluoroborate that has dissolved two (trimethyl fluoride sulfonyl) imine lithium of 0.5mol/L is catalyst, conductive agent and catalyst be with the weight ratio mixing and ball milling of 6:4, identical with embodiment 1 of preparation process and condition.Then by electrode assembling in lithium-air battery, lithium-air battery adopts metal Li//1M LiPF
6be dissolved in the structure of 1-ethyl-3-methylimidazole tetrafluoroborate // air electrode of two (trimethyl fluoride sulfonyl) imine lithium of EC/DMC (1:1) //LATP//dissolved 0.5mol/L, then the battery assembling is carried out to electrochemical property test and comprise regularly charge-discharge test, volume test.As shown in Figure 2, discharge voltage is 2.89V to the timing charging and discharging curve in its first five week first, initial charge voltage 3.57V, and corresponding coulomb cycle efficieny 81%, demonstrates good polarization performance.It is not very greatly that five weeks rear charging/discharging voltages of battery timing circulation simultaneously change, and illustrates that it has good cyclical stability.Battery is carried out to volumetric properties test simultaneously, can obtain the discharge capacity first of 2396mAh/g.With each comparative example data described in table 1, compare, the lithium-air battery that the air electrode being comprised of this kind forms demonstrates good battery polarization performance and volumetric properties, thereby the air electrode that has further proved this kind of two conductive network structures is in the advantage improving aspect battery combination property.
Employing activated carbon is conductive agent, the 1-ethyl-3-methylimidazole tetrafluoroborate that has dissolved two (trimethyl fluoride sulfonyl) imine lithium of 0.5mol/L is catalyst, conductive agent and catalyst be with the weight ratio mixing and ball milling of 8:2, identical with embodiment 1 of preparation process and condition.Then by electrode assembling in lithium-air battery, lithium-air battery adopts metal Li//1M LiPF
6be dissolved in the structure of 1-ethyl-3-methylimidazole tetrafluoroborate // air electrode of two (trimethyl fluoride sulfonyl) imine lithium of EC/DMC (1:1) //LATP//dissolved 0.5mol/L, then the battery assembling is carried out to electrochemical property test and comprise regularly charge-discharge test and volume test, obtained good result.
Embodiment 5
Employing mesoporous carbon CMK-3 is conductive agent, the 1-ethyl-3-methylimidazole tetrafluoroborate that has dissolved two (trimethyl fluoride sulfonyl) imine lithium of 0.5mol/L is catalyst, conductive agent and catalyst be with the weight ratio mixing and ball milling of 8:2, identical with embodiment 1 of preparation process and condition.Then by electrode assembling in lithium-air battery, lithium-air battery adopts metal Li//1MLiPF
6be dissolved in the structure of 1-ethyl-3-methylimidazole tetrafluoroborate // air electrode of two (trimethyl fluoride sulfonyl) imine lithium of EC/DMC (1:1) //LATP//dissolved 0.5mol/L, then the battery assembling carried out to electrochemical property test.Result demonstration, the electrode of preparation has higher discharge voltage first and lower charging voltage, corresponding higher coulomb efficiency first.First discharge specific capacity is also high a lot of than traditional comparative example.
Embodiment 6
Adopt acetylene black conductor, the 1-ethyl-3-methylimidazole tetrafluoroborate that has dissolved two (trimethyl fluoride sulfonyl) imine lithium of 0.5mol/L is catalyst, conductive agent and catalyst be with the weight ratio mixing and ball milling of 8:2, identical with embodiment 1 of preparation process and condition.Then by electrode assembling in lithium-air battery, lithium-air battery adopts metal Li//1M LiPF
6be dissolved in EC/DMC (1:1) //LATP//dissolved the structure of two (trifluoromethyl sulfonyl) acid amides // air electrodes of 1-ethyl-3-methylimidazole of two (trimethyl fluoride sulfonyl) imine lithium of 0.5mol/L; then the battery assembling is carried out to electrochemical property test and comprise regularly charge-discharge test, volume test.The electrode of preparing with conventional method is as comparing in comparative example 1, battery has higher discharge voltage and lower charging voltage, corresponding higher coulomb efficiency first, but adopt the battery of same ionic liquid to compare with catalyst in embodiment 5 with air electrode one side electrolyte, it is good that battery polarization performance is not so good as embodiment 5.Infer that reason is that the pore passage structure of CMK-3 has also increased the wetting passage of electrolyte simultaneously, is therefore conducive to the raising of battery performance owing to adopting the battery of same ionic liquid to have good electrode wetability.
Embodiment 7
Employing acetylene black is conductive agent, the 1-ethyl-3-methylimidazole tetrafluoroborate that has dissolved two (trimethyl fluoride sulfonyl) imine lithium of 0.5mol/L is catalyst, conductive agent and catalyst be with the weight ratio mixing and ball milling of 8:2, identical with embodiment 1 of preparation process and condition.Then by electrode assembling in lithium-air battery, lithium-air battery adopts metal Li//1M LiPF
6be dissolved in the structure of 1-ethyl-3-methylimidazole hexafluorophosphate // air electrode of two (trimethyl fluoride sulfonyl) imine lithium of EC/DMC (1:1) //LATP//dissolved 0.5mol/L, then the battery assembling is carried out to electrochemical property test and comprise regularly charge-discharge test, volume test.Result shows that battery demonstrates good volumetric properties and polarization performance.
Embodiment 8
Employing acetylene black is conductive agent; two (trifluoromethyl sulfonyl) acid amides of 1-ethyl-3-methylimidazole that dissolved two (trimethyl fluoride sulfonyl) imine lithium of 0.5mol/L are catalyst; conductive agent and catalyst be with the weight ratio mixing and ball milling of 8:2, identical with embodiment 1 of preparation process and condition.Then by electrode assembling in lithium-air battery, lithium-air battery adopts metal Li//1M LiPF
6be dissolved in the structure of two (trifluoromethyl sulfonyl) acid amides // air electrodes of 1-ethyl-3-methylimidazole of two (trimethyl fluoride sulfonyl) imine lithium of EC/DMC (1:1) //LATP//dissolved 0.5mol/L, then the battery assembling carried out to electrochemical property test.Result shows that this battery has good polarization performance, better than battery polarization performance in embodiment 5.Infer that reason is owing to not only there being fluorine atom in used ionic liquid, and have sulphur atom, nitrogen-atoms etc., are conducive to the raising of its catalytic performance, so battery has good polarization performance.
Embodiment 9
Employing acetylene black is conductive agent; 1-ethyl-3-methylimidazole two (the five fluoro-ethylsulfonyl) acid amides that has dissolved two (trimethyl fluoride sulfonyl) imine lithium of 0.5mol/L is catalyst; conductive agent and catalyst be with the weight ratio mixing and ball milling of 8:2, identical with embodiment 1 of preparation process and condition.Then by electrode assembling in lithium-air battery, lithium-air battery adopts metal Li//1M LiPF
6be dissolved in the structure of 1-ethyl-3-methylimidazole two (five fluoro-ethylsulfonyl) acid amides // air electrode of two (trimethyl fluoride sulfonyl) imine lithium of EC/DMC (1:1) //LATP//dissolved 0.5mol/L; then the battery assembling is carried out to electrochemical property test and comprise regularly charge-discharge test, volume test.Result shows that battery demonstrates good volumetric properties and polarization performance.
Employing mesoporous carbon CMK-3 is conductive agent; two (trifluoromethyl sulfonyl) acid amides of 1-methyl-3-octyl group imidazoles that dissolved two (trimethyl fluoride sulfonyl) imine lithium of 0.5mol/L are catalyst; conductive agent and catalyst be with the weight ratio mixing and ball milling of 8:2, identical with embodiment 1 of preparation process and condition.Then by electrode assembling in lithium-air battery, lithium-air battery adopts metal Li//1M LiPF
6be dissolved in the structure of two (trifluoromethyl sulfonyl) acid amides // air electrodes of 1-methyl-3-octyl group imidazoles of two (trimethyl fluoride sulfonyl) imine lithium of EC/DMC (1:1) //LATP//dissolved 0.5mol/L, then the battery assembling carried out to electrochemical property test.Result demonstration, the electrode of preparation has higher discharge voltage first and lower charging voltage, corresponding higher coulomb efficiency first.First discharge specific capacity is also high a lot of than traditional comparative example.
Embodiment 11
Employing activated carbon is conductive agent, 1-butyl-3-methylimidazole nine fluorine the butyl sulfosalts that dissolved two (trimethyl fluoride sulfonyl) imine lithium of 0.5mol/L are catalyst, conductive agent and catalyst be with the weight ratio mixing and ball milling of 8:2, identical with embodiment 1 of preparation process and condition.Then by electrode assembling in lithium-air battery, lithium-air battery adopts metal Li//1MLiPF
6be dissolved in the structure of 1-butyl-3-methylimidazole nine fluorine butyl sulfosalt // air electrodes of two (trimethyl fluoride sulfonyl) imine lithium of EC/DMC (1:1) //LATP//dissolved 0.5mol/L, then the battery assembling is carried out to electrochemical property test and comprise regularly charge-discharge test and volume test, obtained good result.
Table 1
From table 1, air electrode provided by the present invention, increase along with ionic liquid at room temperature addition in air electrode, the polarization performance of battery and capacity have all obtained increasing substantially, thereby illustrated that ionic liquid at room temperature in the air electrode of this kind of two conductive network structures has played the effect of catalyst and ionic conduction really, has the advantage that can obviously improve battery combination property really.
Finally be necessary described herein: above embodiment is only for being described in more detail technical scheme of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (10)
1. the air electrode for lithium-air battery, it is characterized in that: described air electrode has ionic conduction three-dimensional network and electron conduction three-dimensional network simultaneously, described ionic conduction three-dimensional network is to be formed by the ionic liquid at room temperature with catalysis characteristics, and described electron conduction three-dimensional network is to be formed by conductive agent.
2. a method of preparing air electrode described in claim 1, is characterized in that: be the ionic liquid at room temperature of 10～40 weight portions to be mixed to rear be immobilizedly prepared from porous current collector surface with the conductive agent of 60～90 weight portions.
3. method as claimed in claim 2, is characterized in that, comprises the steps:
A) 10～40 weight portion ionic liquid at room temperature are mixed with 60～90 weight portion conductive agents;
B) mixed slurry step a) being obtained is immobilized on porous current collector, then dry at 50～100 ℃, then with the pressure of 6～10MPa, will conduct electricity active material and porous current collector and suppress solid;
C) by step b) electrode that obtains dry dewatering at 50～100 ℃, obtain described air electrode.
4. method as claimed in claim 2 or claim 3, is characterized in that: described porous current collector comprises metal porous collector and inorganic non-metallic porous current collector.
5. method as claimed in claim 4, is characterized in that: described metal porous collector comprises nickel foam, porous aluminum and porous stainless steel.
6. method as claimed in claim 4, is characterized in that: described inorganic non-metallic porous current collector comprises porous carbon materials.
7. method as claimed in claim 2 or claim 3, is characterized in that: described ionic liquid at room temperature is selected from least one in 1-ethyl-3-methylimidazole two (five fluoro-ethylsulfonyl) acid amides, two (trifluoromethyl sulfonyl) acid amides of 1-ethyl-3-methylimidazole, two (trifluoromethyl sulfonyl) acid amides of 1-methyl-3-octyl group imidazoles, 1-butyl-3-methylimidazole nine fluorine butyl sulfosalts, 1-ethyl-3-methylimidazole hexafluorophosphate.
8. method as claimed in claim 2 or claim 3, is characterized in that: described conductive agent is selected from least one in carbon-based conductive agent, conducting polymer agent and inorganic conductive agent.
9. method as claimed in claim 8, is characterized in that: described carbon-based conductive agent is selected from least one in acetylene black, conductive carbon black, activated carbon, meso-porous carbon material, hollow carbon sphere, carbon fiber, carbon nano-tube; Described conducting polymer agent is selected from polypyrrole or polyaniline; Described inorganic conductive agent is conductive oxide.
10. method as claimed in claim 2 or claim 3, is characterized in that: described solid support method comprises infusion process, in situ deposition method and ultrasonic dispersion.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN106463803A (en) * | 2014-05-15 | 2017-02-22 | 宝马股份公司 | Lithium-air battery |
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| CN109065832B (en) * | 2018-06-25 | 2021-07-09 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Method for growing protective layer on surface of metal negative electrode of secondary lithium battery |
| CN109786661A (en) * | 2019-01-14 | 2019-05-21 | 天能电池集团有限公司 | A kind of lithium battery pole slice and its preparation method and application of full-filling conductive agent |
| CN111710875A (en) * | 2019-03-18 | 2020-09-25 | 现代自动车株式会社 | Anode for lithium-air battery with improved stability, method of manufacturing the same, and lithium-air battery including the same |
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