CN111446454B - Application of electronic compound as lithium air battery anode catalyst material - Google Patents

Application of electronic compound as lithium air battery anode catalyst material Download PDF

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CN111446454B
CN111446454B CN202010314017.XA CN202010314017A CN111446454B CN 111446454 B CN111446454 B CN 111446454B CN 202010314017 A CN202010314017 A CN 202010314017A CN 111446454 B CN111446454 B CN 111446454B
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lithium
air battery
catalyst material
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CN111446454A (en
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原鲜霞
毛亚
王彦青
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Shanghai Jiaotong University
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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
    • H01M4/90—Selection of catalytic material
    • H01M4/9008—Organic or organo-metallic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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
    • H01M4/8668—Binders
    • 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
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention relates to an electron compoundThe molecular formula of the electronic compound is as follows: a. the x B y O z‑n :2ne ‑ Or C 2 N:e ‑ (ii) a Wherein A is low-valence large-radius cation, B is high-valence small-radius cation, and C is alkaline earth metal cation. The preparation method comprises a direct high-temperature reduction method, a metal steam reduction method and a hydrogen atmosphere reduction method. Compared with the prior art, the invention takes the electronic compound as the anode catalyst material of the lithium air battery, can provide electrons for reaction, has good bifunctional catalytic action on oxygen electrode reaction, and further can improve the discharge specific capacity of the battery, reduce the charge-discharge overpotential, and improve the rate capability and the cycle performance.

Description

Application of electronic compound as lithium air battery anode catalyst material
Technical Field
The invention belongs to the field of lithium air batteries, and particularly relates to an application method of an electronic compound as a lithium air battery anode catalyst material.
Background
In recent years, the energy density of the fuel cell has been ultrahigh (11400 Wh. kg) -1 ) And rechargeability, lithium-air batteries have received much attention as promising next-generation energy storage and conversion devices. The negative active material of the lithium-air battery is metallic lithium, and the positive active material is oxygen in the air. Its working principle is based on the oxidation/reduction reaction centered on metallic lithium on the negative electrode and the reduction/oxidation reaction of oxygen on the air electrode. During discharge, oxygen at the air electrode undergoes a reduction reaction (ORR) with electrons transferred through an external circuit and lithium ions transferred through the electrolyte/separator (the electrons and lithium ions are generated by oxidation of the metallic lithium at the negative electrode) to form lithium peroxide. During charging, lithium peroxide is decomposed on the air electrode to generate oxygen gas (OER), lithium ions and electrons, and the lithium ions are transferred to the negative electrode through the electrolyte/the diaphragm and combined with the electrons transferred through an external circuit to generate metal lithium.
Although the overall performance of the lithium air battery has been greatly improved in recent years, the current actual energy density of the lithium air battery is still far lower than the theoretical value, because the lithium air battery has some problems to be solved, mainly including negative electrode lithium dendrite, electrolyte instability, by-product generation, and the like. Among the key factors affecting the overall performance of lithium air batteries is that the kinetic rates of ORR and OER on the air positive electrode lag significantly behind the dissolution and deposition rates of metallic lithium on the negative electrode, which results in the polarization of lithium air batteries originating primarily from the air positive electrode. In actual work, in order to accelerate the ORR/OER rate to further improve the performance of the lithium air battery, a bifunctional catalyst having a catalytic effect on both ORR and OER is often used, and the currently used catalyst mainly includes carbon materials, noble metals and alloys thereof, transition metal oxides, transition metal sulfides, and the like. The carbon material is low in specific discharge capacity and poor in stability when being used as a positive electrode catalyst of the lithium air battery, is mainly used as a catalyst carrier at present, and forms a composite catalyst together with other catalyst materials; although the noble metal and alloy catalyst thereof have high activity, the cost is high and the resource is limited; the catalytic performance of transition metal oxides and sulfides is difficult to meet practical requirements. None of these catalyst materials simultaneously meets the requirements in terms of activity, stability, price etc. Therefore, the search for new high-efficiency catalyst materials is of great significance to the development and application of lithium air batteries.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an application of an electronic compound as a lithium air battery cathode catalyst material.
The purpose of the invention can be realized by the following technical scheme: an application of an electronic compound as a catalyst material of a lithium-air battery anode.
Further, the molecular formula of the electronic compound is as follows: a. the x B y O z-n :2ne - Or C 2 N:e - (ii) a Wherein A is low-valence large-radius cation, B is high-valence small-radius cation, and C is alkaline earth metal cation.
Further, the low valence large radius cations include Ca 2+ 、Sr 2+ 、Ba 2+ 、La 3+ 、Eu 3+ 、Y 3+ 、Sn 2+ Or Cd 2 + The high valence small radius cation comprises Ti 4+ 、Si 4+ Or Al 3+ Said alkaline earth metal cation comprises Ca 2+ 、Sr 2+ Or Ba 2+ 。
Further, a is the same cation or the cation is substituted by one or more other cationic moieties, B is the same cation or the cation is substituted by one or more other cationic moieties, and C is the same cation or the cation is substituted by one or more other cationic moieties.
Further, the electronic compound is prepared from a precursor by a direct high-temperature reduction method, a metal vapor reduction method or a hydrogen atmosphere reduction method, wherein the precursor comprises an oxide (A) containing free oxygen x B y O z ) Or alkaline earth metal subnitrides (C) 3 N 2 )。
Further, the direct high temperature reduction method comprises the following steps: and (3) placing the precursor into a carbon crucible, and directly reducing at high temperature in an inert gas atmosphere to obtain the electronic compound, wherein the reduction temperature is 900-1500 ℃, the reduction time is 8-24 hours, and the inert gas is nitrogen or argon.
Further, the metal vapor reduction method comprises the following steps: placing the precursor in a quartz crucible, placing reducing agent metals at two ends of a tube furnace, and reducing under the atmosphere of metal steam generated by heating to obtain the electronic compound, wherein the reducing temperature is 700-1100 ℃, the reducing time is 24-240 h, and the reducing agent metals comprise: ca. Mg, Al or Ti.
Further, the hydrogen atmosphere reduction method comprises the following steps: the precursor was placed in a quartz crucible at 20% H 2 /80％N 2 Reducing the mixture in an atmosphere to obtain the electronic compound, wherein the reduction temperature is 1000-1500 ℃, and the reduction time is 2-10 h.
Among them, the direct high-temperature reduction method is preferable because the reduction of the precursor in a metal vapor atmosphere or a hydrogen atmosphere usually introduces impurities, the product has poor crystallinity, low electrical conductivity, and the reaction conditions are severe. The electronic compound obtained by the direct high-temperature reduction method has high purity, good crystallinity, high conductivity and higher electron concentration, has better catalytic effect on the electrochemical reaction of the oxygen electrode (anode) of the lithium air battery, has more advantages in experimental conditions and cost, and can better meet the actual production requirement.
Further, the specific application method comprises the following steps:
(1) the electronic compound is used as a positive electrode material, is dispersed in absolute ethyl alcohol together with a conductive agent and a binder, is uniformly stirred to prepare slurry, is sprayed on a substrate, and is dried to obtain a loading capacity of 0.5-10 mg-cm -2 The positive electrode sheet of (1).
(2) And (3) taking the positive plate as a positive electrode, the metal lithium plate as a negative electrode, the polyolefin porous membrane and the glass fiber membrane as diaphragms, adding electrolyte, and assembling into the lithium-air battery in an argon glove box.
Further, the mass ratio of the electronic compound to the conductive agent to the binder is 3:6:1, the conductive agent comprises Super P, Ketjen Balck (KB), Vulcan XC-72, Black Pearl (BP 2000) or CNT, and the binder comprises PTFE, PVDF or PVA.
Further, the substrate comprises foamed nickel, carbon paper, carbon cloth, a steel wire mesh or an aluminum mesh.
Further, the electrolyte comprises LiTFSI/TEGDME and LiCF 3 SO 3 /TEGDME、LiTFSI/DMSO、LiClO 4 DMSO or LiPF 6 /EC:DMC[1:1(v/v)]The concentration of the electrolyte is 0.1-10M.
Compared with the prior art, the invention has the beneficial effects that:
the invention selects an electronic compound as a positive electrode catalyst material of the lithium air battery, wherein the electronic compound is an ionic compound rich in valence electrons, and redundant electrons do not occupy an atom orbit but serve as anions and are localized in a lattice gap. The general method for synthesizing electronic compounds is to further reduce on the basis of precursors, so that the precursor oxide A x B y O z The composition (A) contains free oxygen ions (O) which are easily reduced 2- ). The free oxygen ions are linked to the weakly ionic A site ions and not to the strongly covalent B site ions, so that A is a low-valent large-radius cation and B is a high-valent small-radius cation (the smaller the ionic radius, the stronger the covalent property; the larger the ionic radius, the more the ionic radius, the lower the ionic radius, the more the ionic radius, the less the ionic radius, the more the ionic radius, and the ionic radius, and the ionic radius are in aThe weaker the ionic nature; the less the number of charges carried by the ion, the less ionic). The surplus electrons in the electronic compound move freely in the framework structure gap formed by the cations and can provide electrons for the reaction, so that the electronic compound has a good promotion effect on the electrode reaction.
The electronic compound material is used as a positive electrode catalyst material of the lithium air battery, can provide electrons for electrode reaction, and accelerates oxygen electrode reaction kinetics, thereby increasing the discharge specific capacity of the battery, reducing the overvoltage of the battery, and improving the rate capability and the cycling stability of the battery.
Drawings
FIG. 1: [ Ca ] prepared in example 1 24 Al 28 O 64 ] 4+ :4e - SEM images of electronic compounds;
FIG. 2: [ Ca ] prepared in example 1 24 Al 28 O 64 ] 4+ :4e - An XRD pattern of the electronic compound;
FIG. 3: comparative battery performance when the electronic compounds prepared in examples 1 to 4 and comparative examples 1 to 2 were used as a positive electrode catalyst material for a lithium air battery.
Detailed Description
The following examples are given for the detailed implementation and the specific operation procedures, but the scope of the present invention is not limited to the following examples.
Example 1: [ Ca ] 24 Al 28 O 64 ] 4+ :4e - Use of electronic compounds in lithium air batteries
Weighing 200mg Ca 24 Al 28 O 66 Placing in a carbon crucible, placing the carbon crucible in a high-temperature tube furnace, vacuumizing to negative pressure, continuously introducing argon, calcining under the protection of argon, wherein the calcining temperature is 1350 ℃, the heating rate is 5 ℃/min, the calcining time is 24h, and cooling along with the furnace after calcining to obtain [ Ca ℃ 24 Al 28 O 64 ] 4+ :4e - An electronic compound. FIG. 1 and FIG. 2 are SEM photograph and XRD spectrum of the electronic compound, respectively。
[Ca 24 Al 28 O 64 ] 4+ :4e - Electronic compound powder is used as a positive electrode catalyst material, Super P is used as a conductive agent, PTFE is used as a binder, the Super P is dispersed in absolute ethyl alcohol according to the mass ratio of the catalyst to the conductive agent to the binder of 3:6:1, the catalyst slurry is obtained by magnetic stirring until the catalyst slurry is uniformly dispersed, the catalyst slurry is uniformly sprayed on a foam nickel substrate by a spray gun, and the foam nickel substrate is dried overnight in vacuum at 60 ℃ to obtain the catalyst slurry with the loading capacity of 0.5 mg-cm -2 The positive electrode sheet of (1).
An improved Swagelock die is adopted, a positive plate is used as a positive electrode, a metal lithium plate is used as a negative electrode, a polyolefin porous membrane and a glass fiber membrane are double-layer diaphragms, 0.1M LiTFSI/TEGDME is used as electrolyte, and the lithium-air battery is assembled in an argon glove box.
The lithium air battery charging and discharging performance test is carried out on LAND battery test equipment (Wuhan blue electronic Co., Ltd.), the battery is placed in an oxygen glove box with the water content lower than 0.1ppm, the battery is kept still for 2 hours in the oxygen atmosphere before the test, the discharging cut-off voltage of the battery is 2.0V, and the current density is 100 mA.g -1 And after the discharge is finished, charging with equal capacity is carried out at the same current density, and a battery charge-discharge curve is obtained. The specific discharge capacity is limited to 500 mAh.g -1 The current density is 100mA · g -1 And the discharge cutoff voltage is 2.0V, so that a cycle performance curve is obtained. The specific discharge capacity, overpotential and cycle count of this cell are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery reaches 6064mAh g -1 The overpotential is 1.28V, and the cycle life is 205 cycles. Super P and Ca compared to comparative examples 1 and 2, respectively 24 Al 28 O 66 Based on [ Ca 24 Al 28 O 64 ] 4+ :4e - The lithium air battery made of the material has larger specific discharge capacity, lower overpotential and more cycle numbers, which shows that the [ Ca ] prepared by the invention 24 Al 28 O 64 ] 4+ :4e - The material has excellent catalytic performance, has a bifunctional catalytic action on ORR/OER, and greatly improves the specific capacity and the cycle performance of the battery.
Example 2: [ Ca ] 2 N] + :e - Use of electronic compounds in lithium air batteries
Weighing 150mg Ca 3 N 2 Placing the carbon crucible into a carbon crucible, placing the carbon crucible into a high-temperature tube furnace, vacuumizing to negative pressure, continuously introducing argon, calcining under the protection of argon, wherein the calcining temperature is 900 ℃, the heating rate is 5 ℃/min, the calcining time is 12h, and cooling along with the furnace after calcining to obtain [ Ca ] 2 N] + :e - An electronic compound. A positive electrode sheet was prepared, a lithium air battery was assembled, and an electrochemical test was performed in the same manner as in example 1. The specific discharge capacity, overpotential, and number of cycles of the cell are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery reaches 5631 mAh.g -1 The overpotential is 1.32V, and the cycle life is 186 cycles. Super P and Ca compared to comparative examples 1 and 2, respectively 24 Al 28 O 66 Based on [ Ca 2 N] + :e - The lithium air battery made of the material has larger specific discharge capacity, lower overpotential and more cycle numbers, which shows that the [ Ca ] prepared by the invention 2 N] + :e - The material has excellent catalytic performance, has bifunctional catalytic action on ORR/OER, and greatly improves the specific capacity and the cycle performance of the battery.
Example 3: [ Ca ] 24 Al 24 Sn 4 O 64 ] 4+ :4e - Use of electronic compounds in lithium air batteries
Weighing 300mg of Ca 24 Al 24 Sn 4 O 66 Placing the precursor in a carbon crucible, placing the carbon crucible in a high-temperature tube furnace, vacuumizing to negative pressure, continuously introducing argon, calcining under the protection of argon, wherein the calcining temperature is 1500 ℃, the heating rate is 5 ℃/min, the calcining time is 8h, and cooling along with the furnace after calcining is finished to obtain [ Ca ] 24 Al 24 Sn 4 O 64 ] 4+ :4e - An electronic compound. A positive electrode sheet was prepared, a lithium air battery was assembled, and electrochemical tests were performed in the same manner as in example 1. The specific discharge capacity, overpotential and cycle count of this cell are shown in fig. 3, from which it can be seen that: lithium air batteryThe specific discharge capacity reaches 8258 mAh.g -1 The overpotential is 0.95V, and the cycle life is 290 circles. These properties are not only superior to the data of comparative examples 1 and 2, but also to [ Ca ] prepared in example 1 24 Al 28 O 64 ] 4+ :4e - Based on [ Ca 24 Al 24 Sn 4 O 64 ] 4+ :4e - The lithium-air battery has larger specific discharge capacity, lower overpotential and more cycle number, and the doping of the A site or the B site of the electronic compound can improve the catalytic performance of the material.
Example 4: [ Ba ] 2 N] + :e - Use of electronic compounds in lithium air batteries
Weighing 200mg of Ba 3 N 2 Placing the mixture into a carbon crucible, placing the carbon crucible into a high-temperature tube furnace, vacuumizing to negative pressure, continuously introducing argon, calcining under the protection of argon, wherein the calcining temperature is 1300 ℃, the heating rate is 5 ℃/min, the calcining time is 15h, and cooling along with the furnace after calcining is carried out to obtain [ Ba 2 N] + :e - An electronic compound. A positive electrode sheet was prepared, a lithium air battery was assembled, and electrochemical tests were performed in the same manner as in example 1. The specific discharge capacity, overpotential and cycle count of this cell are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery reaches 4870 mAh.g -1 The overpotential is 1.5V, and the cycle life is 147 circles. Super P and Ca compared to comparative examples 1 and 2, respectively 24 Al 28 O 66 Based on [ Ba 2 N] + :e - The lithium air battery made of the material has larger specific discharge capacity, lower overpotential and more cycle numbers, which shows that the [ Ba ] prepared by the invention 2 N] + :e - The material has excellent catalytic performance, has a bifunctional catalytic action on ORR/OER, and greatly improves the specific capacity and the cycle performance of the battery.
Example 5: [ Ca ] 20 Cd 4 Al 28 O 64 ] 4+ :4e - Use of electronic compounds in lithium air batteries
Weighing 200mg of Ca 20 Cd 4 Al 28 O 66 Placing in quartz crucible, weighing 200mg metal Ca particles simultaneously, placing at two ends of high temperature tube furnace, vacuumizing to negative pressure, heating to 700 deg.C, maintaining for 240 hr at a heating rate of 5 deg.C/min, and cooling with the furnace after calcining to obtain [ Ca ] 20 Cd 4 Al 28 O 64 ] 4+ :4e - An electronic compound.
[Ca 20 Cd 4 Al 28 O 64 ] 4+ :4e - Electronic compound powder is a positive electrode catalyst material, KB is used as a conductive agent, PVDF is used as a binder, the KB, the conductive agent and the binder are dispersed in absolute ethyl alcohol according to the mass ratio of 3:6:1, the catalyst, the conductive agent and the binder are magnetically stirred until the catalyst, the conductive agent and the binder are uniformly dispersed to obtain catalyst slurry, the catalyst slurry is uniformly sprayed on a carbon paper substrate by a spray gun, and the carbon paper substrate is dried in vacuum at 60 ℃ overnight to obtain the catalyst slurry with the loading capacity of 10 mg-cm -2 The positive electrode sheet of (1).
Adopting an improved Swagelock die, taking a positive plate as a positive electrode, a metal lithium plate as a negative electrode, a polyolefin porous membrane and a glass fiber membrane as double-layer diaphragms, and 2M LiCF 3 SO 3 the/TEGDME was an electrolyte and the lithium air cell was assembled in an argon glove box.
The lithium air battery is placed in an oxygen glove box with the water content lower than 0.1ppm, and is kept stand for 2 hours in an oxygen atmosphere before the test, the discharge cut-off voltage of the battery is 2.0V, and the current density is 200 mA.g -1 After the discharge, the battery is charged with the same capacity at the same current density, and a battery charge-discharge curve is obtained. The specific discharge capacity is limited to 1000 mAh.g -1 The current density is 200 mA.g -1 And the discharge cut-off voltage is 2.0V, so that a cycle performance curve is obtained. Based on [ Ca 20 Cd 4 Al 28 O 64 ] 4+ :4e - The specific discharge capacity of the lithium-air battery of the material reaches 4538mAh & g -1 The overpotential is 1.57V, and the cycle life is 120 circles.
Example 6: [ Sr ] 2 N] + :e - Use of electronic compounds in lithium air batteries
Weighing 300mg of Sr 3 N 2 Is placed on the stoneSimultaneously weighing 300mg of metal Ti particles in an British crucible, placing the metal Ti particles at two ends of a high-temperature tube furnace, vacuumizing to negative pressure, heating to 1100 ℃, keeping the temperature for 24 hours at the heating rate of 5 ℃/min, and cooling along with the furnace after calcining to obtain [ Sr ] 2 N] + :e - An electronic compound.
[Sr 2 N] + :e - The electronic compound powder is used as a positive electrode catalyst material, CNT is used as a conductive agent, PVA is used as a binder, the CNT is dispersed in absolute ethyl alcohol according to the mass ratio of 3:6:1 of the catalyst, the conductive agent and the binder, the catalyst is magnetically stirred until the catalyst is uniformly dispersed to obtain catalyst slurry, the catalyst slurry is uniformly sprayed on a carbon cloth substrate by a spray gun, and the catalyst slurry is dried in vacuum at 60 ℃ overnight to obtain the catalyst slurry with the loading capacity of 5mg cm -2 The positive electrode sheet of (1).
An improved Swagelock die is adopted, a positive plate is used as a positive electrode, a metal lithium plate is used as a negative electrode, a polyolefin porous membrane and a glass fiber membrane are double-layer diaphragms, 10M LiTFSI/TEGDME is used as electrolyte, and the lithium-air battery is assembled in an argon glove box.
The lithium air battery is placed in an oxygen glove box with the water content lower than 0.1ppm, and is kept stand for 2 hours in an oxygen atmosphere before the test, the discharge cut-off voltage of the battery is 2.0V, and the current density is 300 mA.g -1 After the discharge, the battery is charged with the same capacity at the same current density, and a battery charge-discharge curve is obtained. The specific discharge capacity is limited to 1000 mAh.g -1 The current density is 100 mA.g -1 And the discharge cut-off voltage is 2.0V, so that a cycle performance curve is obtained. Based on [ Sr 2 N] + :e - The specific discharge capacity of the lithium-air battery of the material reaches 4285 mAh.g -1 The overpotential is 1.64V, and the cycle life is 134 circles.
Example 7: [ Y ] 2 Ti 2 O 6 ] + :2e - Use of electronic compounds in lithium air batteries
Weighing 400mg of Y 2 Ti 2 O 7 Placing in a quartz crucible, placing in a high temperature tube furnace, vacuumizing to negative pressure, and continuously introducing 20% H 2 /80％N 2 Heating the mixed gas to 1500 ℃, preserving the heat for 2 hours, and raising the temperature rateAt 5 deg.C/min, and furnace cooling after calcining to obtain [ Y ] 2 Ti 2 O 6 ] + :2e - An electronic compound.
[Y 2 Ti 2 O 6 ] + :2e - Electronic compound powder is used as a positive electrode catalyst material, Super P is used as a conductive agent, PVDF is used as a binder, the Super P is dispersed in absolute ethyl alcohol according to the mass ratio of the catalyst to the conductive agent to the binder of 3:6:1, the catalyst slurry is obtained by magnetic stirring till the catalyst slurry is uniformly dispersed, the slurry is uniformly sprayed on a foam nickel substrate by a spray gun, and the foam nickel substrate is dried in vacuum at 60 ℃ overnight to obtain the catalyst slurry with the loading capacity of 2mg cm -2 The positive electrode sheet of (1).
An improved Swagelock die is adopted, a positive plate is used as a positive electrode, a metal lithium plate is used as a negative electrode, a polyolefin porous membrane and a glass fiber membrane are double-layer diaphragms, 2M LiTFSI/TEGDME is used as electrolyte, and the lithium-air battery is assembled in an argon glove box.
The lithium air battery is tested on LAND battery test equipment, the battery is placed in an oxygen glove box with the water content lower than 0.1ppm and is kept stand for 2 hours in an oxygen atmosphere before the test, the discharge cut-off voltage of the battery is 2.0V, and the current density is 400 mA.g -1 After the discharge, the battery is charged with the same capacity at the same current density, and a battery charge-discharge curve is obtained. The specific discharge capacity is 2000mAh g -1 The current density is 400mA · g -1 And the discharge cutoff voltage is 2.0V, so that a cycle performance curve is obtained. Based on [ Y 2 Ti 2 O 6 ] + :2e - The specific discharge capacity of the lithium-air battery of the material reaches 3847 mAh.g -1 The overpotential is 1.73V, and the cycle life is 98 circles.
Example 8: [ YEuTi ] 2 O 6 ] + :2e - Use of electronic compounds in lithium air batteries
Weighing 400mg YEuTi 2 O 7 Placing in a quartz crucible, placing in a high temperature tube furnace, vacuumizing to negative pressure, and continuously introducing 20% H 2 /80％N 2 Heating the mixed gas to 1000 ℃, keeping the temperature for 10h, keeping the heating rate at 5 ℃/min, and cooling the calcined gas along with the furnace to obtain [ YEuTi ] 2 O 6 ] + :2e - An electronic compound.
[YEuTi 2 O 6 ] + :2e - Electronic compound powder is used as a positive electrode catalyst material, BP 2000 is used as a conductive agent, PTFE is used as a binder, the catalyst, the conductive agent and the binder are dispersed in absolute ethyl alcohol according to the mass ratio of 3:6:1, the catalyst, the conductive agent and the binder are magnetically stirred until the catalyst and the binder are uniformly dispersed to obtain catalyst slurry, the catalyst slurry is uniformly sprayed on an aluminum mesh substrate by a spray gun, and the catalyst slurry is dried in vacuum at 60 ℃ overnight to obtain the catalyst slurry with the loading capacity of 4mg cm -2 The positive electrode sheet of (1).
An improved Swagelock die is adopted, a positive plate is used as a positive electrode, a metal lithium plate is used as a negative electrode, a polyolefin porous membrane and a glass fiber membrane are double-layer diaphragms, 1M LiTFSI/DMSO is used as electrolyte, and the lithium-air battery is assembled in an argon glove box.
The lithium air battery is placed in an oxygen glove box with the water content lower than 0.1ppm, and is kept stand for 2 hours in an oxygen atmosphere before the test, the discharge cut-off voltage of the battery is 2.0V, and the current density is 150 mA.g -1 And after the discharge is finished, charging with equal capacity is carried out at the same current density, and a battery charge-discharge curve is obtained. The specific discharge capacity is limited to 900 mAh.g -1 The current density is 100mA · g -1 Discharge cutoff voltage of 2.0V, a cycle performance curve based on [ YEuTi 2 O 6 ] + :2e - The specific discharge capacity of the lithium-air battery of the material reaches 4756 mAh.g -1 The overpotential is 1.52V, and the cycle life is 129 cycles.
Comparative example 1: application of Super P in lithium-air battery
A positive electrode sheet was prepared by replacing the positive electrode catalyst material of example 1 with Super P in the same manner as in example 1, and a lithium air battery was assembled and subjected to electrochemical testing in the same manner as in example 1. The specific discharge capacity, overpotential and cycle count of this cell are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery is 1868 mAh.g -1 The overpotential is 1.89V, and the cycle life is 45 circles.
Comparative example 2: ca 24 Al 28 O 66 Application in lithium air battery
Ca 24 Al 28 O 66 The powder was used as a positive electrode catalyst material, and a positive electrode sheet was prepared, assembled with a lithium air battery, and subjected to electrochemical testing in the same manner as in example 1. The specific discharge capacity, overpotential, and number of cycles of the cell are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery is 1354mAh & g -1 The overpotential is 1.94V, and the cycle life is 21 cycles.
It should be noted that the present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the protection scope of the present invention.

Claims (8)

1. The application of an electronic compound as a lithium-air battery anode catalyst material;
the molecular formula of the electronic compound is as follows: a. the x B y O z-n :2ne - Or C 2 N:e - (ii) a Wherein A is low-valence large-radius cation, B is high-valence small-radius cation, and C is alkaline earth metal cation;
the low valence large radius cation comprises Ca 2+ 、Sr 2+ 、Ba 2+ 、La 3+ 、Eu 3+ 、Y 3+ 、Sn 2+ Or Cd 2+ The high valence small radius cation comprises Ti 4+ 、Si 4+ Or Al 3+ Said alkaline earth metal cation comprises Ca 2+ 、Sr 2+ Or Ba 2+ The electronic compound is used as a bifunctional catalyst material of an ORR and an OER of a lithium air battery.
2. The use of the electronic compound of claim 1 as a lithium air battery positive electrode catalyst material, wherein a is the same cation or the cation is substituted with one or more other cation moieties, B is the same cation or the cation is substituted with one or more other cation moieties, and C is the same cation or the cation is substituted with one or more other cation moieties.
3. The use of the electronic compound according to claim 1 or 2 as a lithium air battery positive electrode catalyst material, wherein the electronic compound is prepared from a precursor by a direct high temperature reduction process, a metal vapor reduction process or a hydrogen atmosphere reduction process, wherein the precursor comprises an oxide containing free oxygen or an alkaline earth metal subnitride.
4. The use of the electronic compound of claim 3 as a positive electrode catalyst material for a lithium air battery, wherein the direct high temperature reduction process comprises the steps of: and (3) placing the precursor into a carbon crucible, and directly reducing the precursor at high temperature under the inert gas atmosphere to obtain the electronic compound, wherein the reduction temperature is 900-1500 ℃, the reduction time is 8-24 h, and the inert gas is nitrogen or argon.
5. The use of the electronic compound of claim 3 as a lithium-air battery positive electrode catalyst material, wherein the metal vapor reduction process comprises the steps of: placing the precursor in a quartz crucible, placing reducing agent metals at two ends of a tube furnace, and reducing under the atmosphere of metal steam generated by heating to obtain the electronic compound, wherein the reducing temperature is 700-1100 ℃, the reducing time is 24-240 h, and the reducing agent metals comprise: ca. Mg, Al or Ti.
6. The use of the electronic compound according to claim 3 as a catalyst material for a positive electrode of a lithium air battery, wherein the hydrogen atmosphere reduction method comprises the steps of: the precursor was placed in a quartz crucible at 20% H 2 /80% N 2 And reducing under the atmosphere to obtain the electronic compound, wherein the reduction temperature is 1000-1500 ℃, and the reduction time is 2-10 h.
7. The application of the electronic compound as the lithium-air battery positive electrode catalyst material according to claim 1 is characterized in that the specific application method is as follows:
(1) the electronic compound is used as a positive electrode catalyst material, the electronic compound, a conductive agent and a binder are dispersed in absolute ethyl alcohol together, the mixture is uniformly stirred to prepare slurry, then the slurry is sprayed on a substrate, and the substrate is dried to obtain the loading capacity of 0.5-10 mg-cm -2 The positive electrode sheet of (1);
(2) and (3) adding electrolyte into the lithium air battery by taking the positive plate as a positive electrode, the metal lithium plate as a negative electrode and the polyolefin porous membrane and the glass fiber membrane as diaphragms, and assembling the lithium air battery in an argon glove box.
8. The use of the electronic compound as a lithium-air battery cathode catalyst material according to claim 7, wherein the mass ratio of the electronic compound to the conductive agent to the binder is 3:6:1, the conductive agent comprises Super P, Ketjen Balck, Vulcan XC-72, Black Pearl or CNT, and the binder comprises PTFE, PVDF or PVA; the substrate comprises foamed nickel, carbon paper, carbon cloth, a steel wire mesh or an aluminum mesh; the electrolyte comprises LiTFSI/TEGDME and LiCF 3 SO 3 /TEGDME、LiTFSI/DMSO、LiClO 4 DMSO or LiPF 6 /EC:DMC [1:1 (v/v)]The concentration of the electrolyte is 0.1-10M.
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