CN112151920A - Solid-state lithium-air battery - Google Patents

Solid-state lithium-air battery Download PDF

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CN112151920A
CN112151920A CN201910571201.XA CN201910571201A CN112151920A CN 112151920 A CN112151920 A CN 112151920A CN 201910571201 A CN201910571201 A CN 201910571201A CN 112151920 A CN112151920 A CN 112151920A
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lithium
electrolyte
air battery
solid
air
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彭佳悦
黄杰
刘丹宪
俞会根
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Beijing WeLion New Energy Technology Co ltd
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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention provides a solid-state lithium-air battery, which comprises a lithium cathode, an electrolyte, an air anode and a packaging shell with an opening and closing function, wherein the electrolyte comprises an electrolyte with a curing function and a diaphragm, the lithium cathode, the diaphragm, the air anode and the packaging shell form a containing cavity for containing the electrolyte, the air anode is connected with the diaphragm, the diaphragm is a porous membrane, the electrolyte at least comprises a polymerized monomer and lithium salt, and the concentration of the lithium salt in the electrolyte is 0.2-7 mol/L; according to the invention, a polymer or a protective layer can be formed on the surface of the lithium cathode through in-situ solidification of the electrolyte, the protective layer can inhibit lithium dendrites and realize uniform deposition of lithium ions on the cathode, and simultaneously, the protective layer plays a role of a gas protective layer and isolates gases such as oxygen, water, carbon dioxide and the like from directly reacting with the lithium cathode; in addition, after the polymer is formed by in-situ polymerization of the electrolyte, the problem of electrolyte volatilization of a liquid system of the traditional lithium air battery can be solved, so that the service life of the lithium air battery is prolonged, and the use safety of the lithium air battery is improved.

Description

Solid-state lithium-air battery
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field related to lithium-air secondary batteries, and particularly relates to a solid-state lithium-air battery.
[ background of the invention ]
The lithium-air battery has 10 times higher theoretical energy density than the traditional lithium ion battery, and is the ultimate target of lithium battery development. Lithium-air batteries generally use metallic lithium or lithium-containing materials as a negative electrode, oxygen or air as a positive electrode, and nonaqueous organic electrolytes, aqueous electrolytes, polymer electrolytes and solid electrolytes as working electrolytes, and the electrolytes and the positive and negative electrodes may be mobile phases. The lithium air battery which is researched most widely and is not a nonaqueous organic electrolyte has the theoretical energy density of 3500Wh/kg which is far higher than that of any existing lithium ion battery system, even though only 1/4 of the theoretical energy density is exerted, the theoretical energy density is a considerable level, and the lithium air battery takes oxygen or air as working gas, is environment-friendly and has extremely high research value.
However, most of rechargeable and dischargeable secondary lithium-air batteries are button cell studies in laboratories so far, and the research and development and preparation of soft package-Ah grades are less. This is because although the lithium-air battery seems ideal theoretically, there are many problems, for example, the lithium-air battery uses metal lithium as a negative electrode, and the problems of dendrite, volume expansion, and the like of the conventional metal lithium negative electrode also exist in the lithium-air battery, and in addition, the lithium-air battery is an open/semi-open system, and the stability of the metal lithium under the working gas needs to be solved; for an open window at one side of the anode, the electrolyte can be gradually volatilized and consumed along with circulation, and the battery gradually loses efficacy; in addition, the performance of the lithium air battery is to be improved in various aspects such as cycle life, power density, energy efficiency, and the like.
The solid electrolyte has higher ionic conductivity at room temperature, does not have the volatilization problem of the electrolyte, has higher mechanical strength, can inhibit the growth of lithium dendrites, and is a better method for solving the practical application problem of the lithium-air battery. However, the positive electrode of the lithium-air battery is a three-phase interface formed by a gas channel, a lithium ion channel and an electronic channel, and the design of the positive electrode of the lithium-air battery system using inorganic ceramic as electrolyte is too complex, so that the three-phase interface is difficult to construct; and the use of the inorganic ceramic can greatly reduce the energy density of the lithium-air battery and exert the advantage of no lithium air.
[ summary of the invention ]
Aiming at the technical problems in the prior art, the invention adopts the electrolyte capable of in-situ polymerization to polymerize on the surface of the lithium cathode to form the solid/semi-solid polymer electrolyte, which can inhibit the growth of lithium dendrites on the cathode, solve the problem of easy volatilization of the electrolyte, improve the safety and the cycle life of the lithium-air battery, and in order to realize the aim, the technical scheme of the invention is as follows:
the utility model provides a solid-state lithium-air battery, includes lithium negative pole, electrolyte, air positive pole and has the encapsulation shell of switching function, the electrolyte includes the diaphragm and has the electrolyte of solidification function, lithium negative pole, diaphragm, air electrode and encapsulation shell constitute and hold the chamber that holds of electrolyte, air positive pole with the diaphragm is connected and is located the diaphragm is kept away from the one side of lithium negative pole, the diaphragm is the porous membrane, electrolyte includes polymerization monomer and lithium salt at least, in the electrolyte the concentration of lithium salt is 0.2-7 mol/L.
Further, the polymerized monomer is an olefin containing at least one oxygen atom or a cyclic olefin containing at least one oxygen atom.
Further, the electrolyte also comprises an organic solvent, and the volume of the organic solvent accounts for 10-90% of the total volume of the electrolyte; the volume of the polymerized monomer accounts for 10-90% of the total volume of the electrolyte.
The diaphragm is one or more of a polyethylene film, a polypropylene film, a polyvinyl chloride film, a polyvinylidene fluoride-hexafluoropropylene film, a polyimide film, a polycarbonate film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyether acetone film, a polyisophthaloyl metaphenylene diamine film and a cellulose film which are laminated and combined.
Further, the lithium salt is any one of lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonate) imide, lithium bis (fluorosulfonyl) imide, lithium bis (oxalato) borate, lithium difluorooxalato borate, lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate, lithium perchlorate, lithium bromide, lithium iodide, lithium difluorophosphate, and lithium nitrate, or a mixture of two or more thereof.
Further, the organic solvent comprises any one or a mixture of more than two of ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethyl sulfoxide, dimethylformamide, acetonitrile, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, vinylene carbonate, ethylene carbonate, fluoroethylene carbonate and ionic liquid.
Further, the lithium negative electrode is metallic lithium, a lithium alloy, or a composite containing metallic lithium.
Further, the air positive electrode includes a porous conductive material, a catalyst, a binder, and a conductive current collector that allows gas to pass through.
Further, the working gas of the solid-state lithium air battery comprises one of oxygen, carbon dioxide and sulfur dioxide, or a mixed gas containing oxygen, or a mixed gas containing carbon dioxide or a mixed gas containing sulfur dioxide.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, through in-situ polymerization of the electrolyte, on one hand, a polymer or gel protective layer can be formed on the surface of the lithium cathode, and the protective layer can inhibit lithium dendrites and realize uniform deposition of lithium ions on the cathode, and also can play a role of a gas protective layer to isolate gases such as oxygen, water and carbon dioxide from directly reacting with the metal lithium cathode; on the other hand, after the polymer is formed by in-situ polymerization of the electrolyte, the problem of electrolyte volatilization of a liquid system of the traditional lithium air battery can be solved, so that the service life of the lithium air battery is prolonged, the safety of the lithium air battery is improved, and the cycle life of the lithium air battery is prolonged.
[ description of the drawings ]
FIG. 1 is a charge-discharge curve of a lithium-air battery using a control electrolyte at 1 week and 31 week with a capacity limit of 1000 mAh/g;
FIG. 2 is a charge-discharge curve at week 1 and week 100 in a state of capacity limit of 1000mAh/g for a lithium-air battery using the electrolyte of example 1;
fig. 3 is a schematic view of the structure of the lithium-air battery prepared in example 1.
[ detailed description ] embodiments
The invention aims to provide a solid-state lithium-air battery, which comprises a lithium cathode, an electrolyte, an air cathode and a packaging shell with an opening and closing function, wherein the electrolyte comprises a diaphragm and an electrolyte with a curing function, the lithium cathode, the diaphragm, the air cathode and the packaging shell form a first accommodating cavity for accommodating the electrolyte, the air cathode is connected with the diaphragm and is arranged on one surface of the diaphragm, which is far away from the lithium cathode, the diaphragm is a porous membrane, the electrolyte at least comprises a polymerized monomer and a lithium salt, and the concentration of the lithium salt in the electrolyte is 0.2-7 mol/L; more preferably, the concentration of the lithium salt in the electrolyte is 0.8-6.0 mol/L; further, the polymerized monomer is an olefin containing at least one oxygen atom or a cyclic olefin containing at least one oxygen atom, including but not limited to 1, 3-dioxolane, 1, 4-dioxane, trioxymethylene, oxetane, tetrahydrofuran or a mixture of one or more of 1, 3-dioxolane substituted with a group, 1, 4-dioxane, ethylene oxide, oxetane and tetrahydrofuran; wherein, the group is selected from one of alkyl, cycloalkyl, carboxyl, hydroxyl, aryl, amino, halogen, acyl, aldehyde group, alkoxy and ester group.
The electrolyte may include an organic solvent, preferably selected from one or a mixture of two or more of glyme (DME), triglyme (G3), tetraglyme (G4), dimethyl sulfoxide (DMSO), Dimethylformamide (DMF), Acetonitrile (ACN), Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), Propylene Carbonate (PC), Vinylene Carbonate (VC), ethylene carbonate (VEC), fluoroethylene carbonate (FEC), ionic liquid, in addition to the polymerized monomer and lithium salt; in the electrolyte containing the organic solvent, the volume of the polymerized monomer accounts for 10-90 percent of the total volume of the electrolyte, and preferably 30-80 percent; the volume of the organic solvent accounts for 10-90%, preferably 20-70% of the total volume of the electrolyte.
In the technical scheme, the diaphragm is one or more than two of a polyethylene film, a polypropylene film, a polyvinyl chloride film, a polyvinylidene fluoride-hexafluoropropylene film, a polyimide film, a polycarbonate film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyether acetone film, a polyisophthaloyl metaphenylene diamine film and a cellulose film; preferably, the membrane has a thickness of 0.1 to 50 μm.
In the above technical scheme, the lithium salt is lithium trifluoromethanesulfonate (LiCF)3SO3) Lithium bis (trifluoromethanesulfonate) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (lidob), lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) Lithium bromide (LiBr), lithium iodide (LiI), lithium difluorophosphate (LiPO)2F2) Lithium nitrate (LiNO)3) One or a mixture of two or more of (a); preferably, the lithium salt is selected from lithium hexafluorophosphate (LiPF)6) One or a mixture of two or more of lithium bis (fluorosulfonyl) imide (LiFSI) and lithium difluorooxalato borate (liddob); wherein, LiCF3SO3And LiDFOB mixture, LiTFSI and LiFSI mixture, LiTFSI and LiBF4Mixture, LiTFSI and LiPF6Mixture, LiCF3SO3And LiFSI mixture is a more preferred lithium salt, wherein LiCF3SO3The molar concentration of LiTFSI is 0.5-3.0mol/L, and the molar concentration of LiDFOB and LiFSI is 0.5-6 mol/L.
In the above technical scheme, the lithium negative electrode is metallic lithium, a lithium alloy or a compound containing metallic lithium; wherein, the lithium content in the lithium alloy is not less than 30 percent, and the lithium alloy also comprises any one or more than two of aluminum, magnesium, boron, silicon, tin, calcium, gallium and germanium; the lithium-containing compound comprises a physical mixture of lithium metal and carbon, silicon, aluminum, copper and tin, and copper nitride, lithium copper nitrogen, lithium iron nitrogen, lithium manganese nitrogen, lithium cobalt nitrogen and Li7MP3(M ═ Ti, V, Mn), wherein the content of metallic lithium is not less than 30%.
The air anode is used forThe porous conductive material comprises any one or a mixture of more than two of carbon nano tubes, carbon fibers, porous carbon, acetylene black, graphite, graphene oxide and nitrogen-doped carbon; the catalyst comprises any one or a mixture of more than two of transition metal oxide, transition metal nitride, ruthenium (Ru), platinum (Pt), palladium (Pd) and gold (Au), wherein the transition metal oxide is preferably manganese oxide, manganous oxide, ferric oxide, nickel oxide, cobalt oxide, ruthenium oxide, iridium oxide, molybdenum oxide and cerium oxide; the transition metal nitride is preferably manganese nitride, iron nitride, nickel nitride, titanium nitride, or cobalt nitride, and the catalyst may be LixMaOzWherein M is Ti, Cu, Mn, Fe, Co, Ni, Zn, Ag, Zr, Nb, Mo or W, x is 0-4, a is 0.5-3, and z is 0.5-5; the binder comprises one or a mixture of more than two of polytetrafluoroethylene, polyvinylidene fluoride, polyamide-imide, polyimide, sodium alginate and carboxymethyl cellulose; the conductive current collector comprises one or a mixture of more than two of porous aluminum foil, aluminum mesh, stainless steel mesh, foamed nickel, carbon paper and carbon cloth.
In the above technical solution, the packaging case with an opening and closing function has a two-layer or multi-layer structure, wherein the inner layer is a single-layer air-permeable layer, the air-permeable layer is made of a material including but not limited to Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), Polyaniline (PAN), polyethylene terephthalate (PET), or one of polytetrafluoroethylene-coated glass fibers (TCFC) or a derivative thereof, and the thickness of the air-permeable layer is preferably 10-400 μm; the outer layer is a removable sealing layer, and comprises a laminated structure formed by combining one or more than two of aluminum plastic film, polypropylene film (PP) and polyethylene terephthalate (PET) film.
In the above technical solution, the working gas of the solid-state lithium-air battery is one of oxygen, carbon dioxide and sulfur dioxide, or a mixed gas containing oxygen (such as air or other mixed gas containing oxygen), or a mixed gas containing carbon dioxide or a mixed gas containing sulfur dioxide.
The invention also provides a preparation method of the solid-state lithium-air battery, which comprises the following steps: arranging a lithium cathode, a diaphragm and an air anode in an inner layer of a packaging shell to assemble the battery in an inert atmosphere or a dry atmosphere, wherein the lithium cathode, the diaphragm, the air anode and the packaging shell form a containing cavity capable of containing electrolyte; the air anode is connected with the diaphragm and arranged on one surface of the diaphragm, which is far away from the lithium cathode, electrolyte is injected into the accommodating cavity to package the battery, and the battery does not contact air after being packaged; standing for a period of time, and polymerizing the electrolyte to obtain the solid lithium-air battery; and then opening a sealing window or an air passage opening on the air positive electrode side, connecting working air, and charging and discharging the solid-state lithium-air battery in an open environment.
Further, the time required by the electrolyte polymerization is 1-100h, preferably 3-24 h; the reaction temperature during polymerization is 10 to 50 ℃ and preferably 15 to 35 ℃.
The working temperature of the solid-state lithium-air battery provided by the invention is 0-150 ℃, and preferably 20-90 ℃.
It should be noted that the assembly and structure of the lithium-air battery are in the prior art, and will not be described in detail here.
The solid-state lithium-air battery provided by the invention can form a polymer or gel protective layer on the surface of a lithium cathode based on in-situ polymerization of electrolyte, and the protective layer can inhibit lithium dendrite and realize uniform deposition of lithium ions on the cathode, and can also play a role of a gas protective layer to isolate direct reaction of gases such as oxygen, water, carbon dioxide and the like with a metal lithium cathode; in addition, after the polymer is formed by in-situ polymerization of the electrolyte, the problem of electrolyte volatilization of a liquid system of the traditional lithium air battery can be solved, so that the service life of the lithium air battery is prolonged, the safety of the lithium air battery is improved, and the cycle life of the lithium air battery is prolonged.
The solid-state lithium-air battery provided by the invention is simple in preparation process and easy for industrial production.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A solid-state lithium-air battery comprises an air positive electrode, an electrolyte, a lithium negative electrode and a packaging shell with an opening and closing function, and the preparation method comprises the following steps:
s1: preparing an air positive electrode: weighing Carbon Nano Tube (CNT) and Polytetrafluoroethylene (PTFE) binder according to the mass percent of 95:5, taking deionized water as a dispersing agent, and uniformly stirring; uniformly spraying the slurry to a current collector aluminum mesh by a spraying method, and drying in a 55 ℃ oven; then transferring the mixture into a vacuum oven at the temperature of 110 ℃ for 12 hours to completely volatilize the dispersing agent;
s2: preparing an electrolyte: the polymerization monomer is 1, 3-Dioxolane (DOL), the volume of the polymerization monomer accounts for 50% of the total volume of the electrolyte, the organic solvent is tetraethylene glycol dimethyl ether (G4), the organic solvent accounts for 50% of the total volume of the solution, and the lithium salt is 1mol/L of lithium bis (trifluoromethanesulfonate) imide (LiTFSI) and 3mol/L of lithium bis (fluorosulfonyl) imide (LiFSI);
s3: assembling the lithium-air battery: assembling a negative electrode 1, an electrolyte 2 (comprising a diaphragm and electrolyte), an air positive electrode 3 and a packaging shell (comprising a breathable layer 4, a removable packaging layer 5 and a battery shell 6) into a battery in a dry atmosphere or a glove box filled with argon, wherein the battery structure is shown in FIG. 3;
s4: and injecting the electrolyte prepared in the S2, communicating the working gas 7 after the polymerization is finished, and performing a discharge charge test on the battery by taking oxygen as the working gas.
(II) in-situ polymerization electrochemical performance test of chargeable and dischargeable solid-state lithium air battery
The constant current charge and discharge mode test was performed using a charge and discharge instrument, model CT2001A, purchased from wuhan blue electronics, inc, at a test temperature of 25 c, with the test results shown in table 1.
Voltage-limiting discharge test: and carrying out charge and discharge tests at the current of 100mA/g, discharging the battery firstly, wherein the charge and discharge voltage range is 2.0-4.5V, and then repeating the process.
Capacity-limited cycle testing: the two processes are firstly discharged for 5 hours at the current of 200mA/g and then charged for 5 hours at the current of 200mA/g (capacity limit is 1000mAh/g), and then the two processes are sequentially repeated, and the curve of the charging and discharging specific capacity to the voltage is shown in figure 2. It can be seen that the battery provided by the embodiment has two obvious platforms in the discharging and charging processes, the midpoint of the discharging platform is located at 2.7V, the midpoint of the charging platform is located at 4.0V, and the difference between the charging and discharging platforms is about 1.3V. During the first five cycles, the voltage difference did not change significantly, nor did the specific capacity decrease significantly, indicating that the cell was capable of operation and had excellent cycling performance.
The cycle is the cycle when the discharge termination potential is greater than 2.0V
Comparative example
The other conditions were the same as in example 1 except that S2) used a general electrolyte that could not be polymerized in situ, and the specific formulation was such that 1mol/L LiTFSI was dissolved in G4 solvent and, after complete dissolution, it was used by injection.
The lithium-air battery prepared by the comparative example is subjected to electrochemical performance test, the test content and the test method are the same as those of the example 1, and the curve of the charge-discharge specific capacity to the voltage is shown in figure 1; the results of the relevant performance tests are shown in table 1.
Example 2
The other conditions were the same as example 1 except for S1) preparation of an air positive electrode, and the preparation method of example 2 was: weighing Keqin carbon black (KB) and polyvinylidene fluoride (PVDF) binder in a mass ratio of 92:8, taking N-methyl pyrrolidone (NMP) as a dispersing agent, and uniformly stirring to prepare slurry; uniformly spraying the slurry on the current collector carbon paper by a spraying method, and drying in a 55 ℃ oven; and then transferred to a vacuum oven at 110 ℃ for 12 hours to completely volatilize the dispersing agent.
Example 3
The other conditions were the same as in example 1 except that S2) the in-situ polymerizable electrolyte solution contained 40% of the polymerized monomer and 60% of the solvent by volume.
Example 4
The other conditions were the same as in example 1 except that S2) the monomer polymerizable in situ in the electrolyte was 1, 4-dioxane.
Example 5
The other conditions were the same as in example 1 except that S2) the monomer polymerizable in situ in the electrolyte was tetrahydrofuran.
Example 6
The other conditions were the same as in example 1 except that S2) the monomer polymerizable in situ in the electrolyte was trioxymethylene.
Example 7
The other conditions were the same as in example 1 except that S2) the monomer polymerizable in situ in the electrolyte was propylene oxide.
Example 8
The other conditions were the same as example 1 except that S2) the lithium salt in the in-situ polymerizable electrolyte was LiCF3SO3 at 1mol/L and LiFSI at 2 mol/L.
Example 9
The other conditions were the same as in example 1 except that S2) the lithium salt in the in-situ polymerizable electrolyte was LiCF3SO3 at 1mol/L and LiDFOB at 3 mol/L.
Example 10
The other conditions were the same as in example 1 except that S2) the lithium salt in the in-situ polymerizable electrolyte was 1mol/L of LiTFSI and 3mol/L of LiDFOB.
Example 11
The other conditions were the same as in example 1 except that S2) the lithium salt in the in-situ polymerizable electrolyte was LiTFSI at 1mol/L and LiPF6 at 1 mol/L.
Example 12
The other conditions were the same as in example 1 except that S2) the lithium salt in the in-situ polymerizable electrolyte was 1mol/L LiTFSI and 1mol/L LiBF 4.
Example 13
The other conditions were the same as in example 1 except that S2) the lithium salt in the in-situ polymerizable electrolyte was 1mol/L LiTFSI, 0.05mol/L LiI, and 2mol/L LiFSI.
Example 14
The other conditions were the same as in example 1 except that S4) the working gas was air.
Example 15
The other conditions were the same as in example 1 except that S4) the working gas was a mixed gas of oxygen and carbon dioxide in a volume ratio of 1: 2.
Example 16
The other conditions were the same as in example 1 except that S4) the working gas was carbon dioxide.
Example 17
The other conditions were the same as in example 1 except that S2) the polymerizable electrolyte contained only a lithium salt and a polymerization monomer, and no other solvent, and the lithium salt used was LiFSI of 3 mol/L.
The electrochemical performance tests of the examples 2 to 17 are carried out, and the test contents and the test method are the same as those of the example 1; wherein, the testing temperature of the lithium air battery prepared in the examples 2 to 16 is the same as that of the example 1; the lithium air battery prepared in example 17 was tested at 60 ℃.
TABLE 1 test results of electrochemical properties of control and lithium air batteries prepared in examples 1 to 17
Figure BDA0002110932750000131
Figure BDA0002110932750000141
As can be seen from the test results in table 1, the lithium-air battery can be cycled for only 30 weeks using the control electrolyte, and the discharge capacity and the charge capacity in the first week are low, and the metallic lithium negative electrode also has dendrite formation. The solid-state lithium air battery capable of in-situ polymerization designed by the invention shows very high cycle life and charge-discharge capacity, and no lithium dendrite is formed on the negative electrode. Comparing the charge-discharge curves of the control group in fig. 1 and the example 1 in fig. 2, the discharge voltage of the control group decays rapidly to below 2.0V in cycle 31, while the discharge plateau of the battery in example 1 is maintained above 2.5V in cycle 300, the charge-discharge polarization is about 1.5V, and the polarization is about the same as the first cycle of the control group; examples 14-16 show that the lithium-air battery provided by the invention has better performance under different working gases and temperatures.
The foregoing is a more detailed description of the present invention in connection with specific preferred embodiments and is not intended to limit the practice of the invention to these embodiments. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (9)

1. The utility model provides a solid-state lithium-air battery, includes lithium negative pole, electrolyte, air positive pole and has the encapsulation shell of switching function, its characterized in that, the electrolyte includes diaphragm and the electrolyte that has the solidification function, lithium negative pole, diaphragm, air positive pole and encapsulation shell constitute and hold the chamber that holds of electrolyte, air positive pole with the diaphragm is connected and is located the diaphragm is kept away from the one side of lithium negative pole, the diaphragm is the porous membrane, electrolyte includes polymerization monomer and lithium salt at least, in the electrolyte the concentration of lithium salt is 0.2-7 mol/L.
2. The solid-state lithium-air battery according to claim 1, wherein the polymerized monomer is an olefin containing at least one oxygen atom or a cyclic olefin containing at least one oxygen atom.
3. The solid-state lithium-air battery according to claim 1, wherein the electrolyte further comprises an organic solvent, the volume of the organic solvent accounts for 10-90% of the total volume of the electrolyte; the volume of the polymerized monomer accounts for 10-90% of the total volume of the electrolyte.
4. The solid-state lithium air battery according to any one of claims 1 to 3, wherein the separator is one or a stacked combination of two or more of a polyethylene film, a polypropylene film, a polyvinyl chloride film, a polyvinylidene fluoride-hexafluoropropylene film, a polyimide film, a polycarbonate film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyether acetone film, a polymetaphenylene isophthalamide film, and a cellulose film.
5. The solid-state lithium air battery according to any one of claims 1 to 3, wherein the lithium salt is lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonate) imide, lithium bis (fluorosulfonyl) imide, lithium bis (oxalato) borate, lithium difluorooxalato borate, lithium hexafluorophosphate (LiPF)6) Any one or a mixture of more than two of lithium tetrafluoroborate, lithium perchlorate, lithium bromide, lithium iodide, lithium difluorophosphate and lithium nitrate.
6. The solid-state lithium air battery according to claim 3, wherein the organic solvent includes one or a mixture of two or more of ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethyl sulfoxide, dimethylformamide, acetonitrile, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, and an ionic liquid.
7. The solid-state lithium air battery according to claim 1, wherein the lithium negative electrode is metallic lithium, a lithium alloy, or a composite containing metallic lithium.
8. The solid state lithium air battery of claim 1, wherein the air positive electrode comprises a porous conductive material, a catalyst, a binder, and a conductive current collector that allows gas to pass through.
9. The solid-state lithium air battery according to claim 8, wherein the working gas of the solid-state lithium air battery comprises one of oxygen, carbon dioxide, and sulfur dioxide, or a mixed gas containing oxygen, or a mixed gas containing carbon dioxide, or a mixed gas containing sulfur dioxide.
CN201910571201.XA 2019-06-28 2019-06-28 Solid-state lithium-air battery Pending CN112151920A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2763037C1 (en) * 2021-06-09 2021-12-27 Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук (ИФХЭ РАН) Solid polymer electrolyte lithium oxygen battery
CN114204167A (en) * 2021-12-10 2022-03-18 辽宁大学 Preparation method of rechargeable iron or zinc-air battery based on hydrogel electrolyte
CN114512717A (en) * 2022-01-25 2022-05-17 五邑大学 Gel polymer electrolyte for lithium salt in-situ initiated polymerization, and preparation method and application thereof
CN114695901A (en) * 2020-12-31 2022-07-01 北京卫蓝新能源科技有限公司 Lithium air battery gel air anode, preparation method and lithium air battery
CN117691131A (en) * 2024-02-01 2024-03-12 新乡学院 MoO for lithium air battery 2 /CeO 2 Nanosphere composite material and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110014522A1 (en) * 2004-02-06 2011-01-20 Polyplus Battery Company Protected active metal electrode and battery cell with ionically conductive preotective architecture
CN103570873A (en) * 2013-10-23 2014-02-12 深圳新宙邦科技股份有限公司 Composition for gel polymer electrolyte, gel polymer electrolyte and electrochemical device
US20140045078A1 (en) * 2011-04-26 2014-02-13 Solvay Sa Lithium air battery cell
US20140255800A1 (en) * 2013-03-08 2014-09-11 Samsung Sdi Co., Ltd. Positive electrode for lithium air battery, method of preparing same, and lithium air battery including same
CN109103517A (en) * 2017-06-20 2018-12-28 中国科学院化学研究所 A kind of method and its application of polymer protection metal secondary batteries cathode

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110014522A1 (en) * 2004-02-06 2011-01-20 Polyplus Battery Company Protected active metal electrode and battery cell with ionically conductive preotective architecture
US20140045078A1 (en) * 2011-04-26 2014-02-13 Solvay Sa Lithium air battery cell
US20140255800A1 (en) * 2013-03-08 2014-09-11 Samsung Sdi Co., Ltd. Positive electrode for lithium air battery, method of preparing same, and lithium air battery including same
CN103570873A (en) * 2013-10-23 2014-02-12 深圳新宙邦科技股份有限公司 Composition for gel polymer electrolyte, gel polymer electrolyte and electrochemical device
CN109103517A (en) * 2017-06-20 2018-12-28 中国科学院化学研究所 A kind of method and its application of polymer protection metal secondary batteries cathode

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114695901A (en) * 2020-12-31 2022-07-01 北京卫蓝新能源科技有限公司 Lithium air battery gel air anode, preparation method and lithium air battery
RU2763037C1 (en) * 2021-06-09 2021-12-27 Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук (ИФХЭ РАН) Solid polymer electrolyte lithium oxygen battery
CN114204167A (en) * 2021-12-10 2022-03-18 辽宁大学 Preparation method of rechargeable iron or zinc-air battery based on hydrogel electrolyte
CN114512717A (en) * 2022-01-25 2022-05-17 五邑大学 Gel polymer electrolyte for lithium salt in-situ initiated polymerization, and preparation method and application thereof
CN117691131A (en) * 2024-02-01 2024-03-12 新乡学院 MoO for lithium air battery 2 /CeO 2 Nanosphere composite material and preparation method thereof

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