CN114639856B - Composite gel polymer electrolyte for lithium-air battery, preparation method of composite gel polymer electrolyte and lithium-air battery - Google Patents
Composite gel polymer electrolyte for lithium-air battery, preparation method of composite gel polymer electrolyte and lithium-air battery Download PDFInfo
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 69
- 239000011159 matrix material Substances 0.000 claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 43
- 239000003792 electrolyte Substances 0.000 claims abstract description 35
- 239000000945 filler Substances 0.000 claims abstract description 23
- 239000004964 aerogel Substances 0.000 claims abstract description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- 239000003960 organic solvent Substances 0.000 claims description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims description 16
- 159000000002 lithium salts Chemical class 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- -1 polypropylene Polymers 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 230000008961 swelling Effects 0.000 claims description 8
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- 150000003949 imides Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 abstract description 6
- 125000006575 electron-withdrawing group Chemical group 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 6
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002001 electrolyte material Substances 0.000 abstract description 2
- 229920005597 polymer membrane Polymers 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012456 homogeneous solution Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910006715 Li—O Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
-
- 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
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Composite Materials (AREA)
- Secondary Cells (AREA)
- Hybrid Cells (AREA)
Abstract
The invention provides a composite gel polymer electrolyte for a lithium air battery, which comprises the following components: a battery separator; the lithium polymer matrix is compounded on the surface of the battery diaphragm, the nano aerogel inert filler is dispersed in the polymer matrix, and the polymer in the polymer matrix meets the following two points: (I) The polymer has no strong electron-withdrawing functional group on the side chain; (II) when the polymer main chain is an aliphatic main chain, no hydrogen atom having an electron withdrawing group of alpha or beta is present on the main chain. The electrolyte material for the lithium-air battery can meet the requirement of the lithium-air battery at room temperature, and can promote the stability of the electrolyte for the lithium-air battery in resisting lithium peroxide and lithium.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a composite gel polymer electrolyte for a lithium air battery and a preparation method thereof.
Background
In the past decades, lithium ion batteries have been widely used in the energy storage fields of portable electronic products, communication and the like due to the advantages of high energy density, long cycle life, no memory effect and the like, but commercial lithium ion batteries are mainly based on cradle mechanisms of lithium ion intercalation compounds, and positive electrode materials become the limitation of the energy density of the lithium ion batteries and are difficult to meet the requirements of energy storage equipment with higher energy density.
Lithium air batteries using metallic lithium as the negative electrode are receiving attention because of their ultra-high theoretical specific capacity. Through theoretical calculation, the theoretical specific capacity density is as high as 11140Wh/Kg, which is about 10 times of that of the lithium ion battery. The cathode active material of the lithium-air battery is derived from oxygen in air, and the metal lithium is taken as an anode, so that the lithium-air battery has the advantages of environmental friendliness and low material cost, and is considered to be a very promising next-generation energy storage system. However, the conventional liquid lithium-air battery contains a large amount of electrolyte, and lithium dendrite growth is difficult to be suppressed. In the open system of lithium-air batteries, the electrolyte is very volatile, leaks and burns, creating a series of safety issues. In addition, lithium peroxide and lithium superoxide are generated during the battery charging process, and these products undergo nucleophilic reaction with the electrolyte or electrolyte to generate irreversible byproducts, thereby reducing the capacity and cycle stability of the battery.
In contrast to liquid electrolytes, polymer electrolytes are a class of battery separators that are capable of transporting lithium ions and effectively isolating positive and negative electrode contact shorts. Polymer electrolytes can be divided into two broad categories depending on composition and morphology, one being solid polymer electrolytes and the other being gel polymer electrolytes. The ionic conductivity of the former room temperature is still very low compared with that of the liquid electrolyte, and the high interface impedance and compatibility of the solid electrolyte and the anode and cathode interface are also needed to be solved; the latter is mainly composed of a polymer matrix, lithium salt and a plasticizer, combines the high room temperature ionic conductivity of liquid electrolyte and the high safety of solid polymer electrolyte, and is hopeful to become a main stream material system of a high-energy lithium battery.
Some reports based on a certain polymer matrix are reported, but the effect of polymers of different monomer structures on the stability in lithium-air batteries has not been studied in depth. The choice of a suitable polymer matrix is therefore critical for resistance to superoxide radical stabilization and for lithium stabilization in lithium-air batteries.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a composite gel polymer electrolyte for a lithium air battery and a preparation method thereof.
The invention provides a composite gel polymer electrolyte for a lithium air battery, which comprises the following components:
A battery separator;
the lithium polymer matrix is compounded on the surface of the battery diaphragm, the nano aerogel inert filler is dispersed in the polymer matrix, and the polymer in the polymer matrix meets the following two points:
(I) The polymer has no strong electron-withdrawing functional group on the side chain;
(II) when the polymer main chain is an aliphatic main chain, no hydrogen atom having an electron withdrawing group of alpha or beta is present on the main chain.
Preferably, the strong electron withdrawing functionality is selected from one or more of-C.ident.N, -X, -NO 2、-CF3, the group-X is selected from-F and/or-Cl.
Preferably, the polymer matrix is selected from one or more of polymethyl methacrylate, polyurethane, polystyrene and polytetrafluoroethylene;
preferably, the thickness of the single-sided polymeric matrix is 10 to 45 microns.
Preferably, the nano aerogel inert filler is one or more of nano titanium dioxide, nano silicon dioxide and nano aluminum oxide; the grain diameter is 7-40 nanometers; the mass of the nano aerogel inert filler accounts for 5-20wt% of the mass of the polymer matrix.
Preferably, the battery separator is selected from a polypropylene separator, a polyethylene separator or a glass fiber separator, and the thickness of the battery separator is 15-30 micrometers.
The invention also provides a preparation method of the composite gel polymer electrolyte, which comprises the following steps:
a) Dissolving a polymer matrix in an organic solvent to obtain a gel solution;
b) Dispersing the nano aerogel inert filler in the gel solution to obtain a mixed gel solution;
c) Immersing the battery diaphragm into the mixed gel solution, and taking out and drying the battery diaphragm to obtain the battery diaphragm with the surface composited with the polymer matrix;
D) And (3) placing the battery diaphragm with the polymer matrix on the surface in a liquid lithium salt ether electrolyte for swelling, lithiating, taking out, and drying to obtain the composite gel polymer electrolyte.
Preferably, the organic solvent is one or more of tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, acetonitrile and the like;
the concentration of the mixed gel solution polymer is 3-30wt%.
Preferably, the liquid lithium salt ether electrolyte comprises a lithium salt and an ether organic solvent, wherein the lithium salt is selected from lithium bistrifluoromethylsulfonyl imide, and the ether organic solvent is selected from one or more of tetraethylene glycol dimethyl ether, ethylene glycol dimethyl ether and dimethyl ether; the concentration of the lithium bistrifluoromethylsulfonyl imide in the liquid lithium salt ether electrolyte is 0.5M-2M.
Preferably, in the step C), the drying condition is 50-100 ℃, and the vacuum drying is carried out for 24-48 hours;
In the step D), the swelling time is 8-12 h.
The invention also provides a lithium-air battery comprising the composite gel polymer electrolyte.
Compared with the prior art, the invention provides a composite gel polymer electrolyte for a lithium air battery, which comprises the following components: a battery separator; the lithium polymer matrix is compounded on the surface of the battery diaphragm, the nano aerogel inert filler is dispersed in the polymer matrix, and the polymer in the polymer matrix meets the following two points: (I) The polymer has no strong electron-withdrawing functional group on the side chain; (II) when the polymer main chain is an aliphatic main chain, no hydrogen atom having an electron withdrawing group of alpha or beta is present on the main chain. The electrolyte material for the lithium-air battery can meet the requirement of the lithium-air battery at room temperature, and can promote the stability of the electrolyte for the lithium-air battery in resisting lithium peroxide and lithium.
Drawings
FIG. 1 is an SEM image of a polymer membrane prepared according to example 2;
FIG. 2 is an SEM image of a polymer membrane prepared according to example 2 after swelling;
FIG. 3 is an intercalation-deintercalation curve at 0.25mA/cm 2 for the assembled lithium-air symmetric cell of example 2;
Fig. 4 is a first-turn charge-discharge curve of the assembled lithium-air battery of example 2;
fig. 5 is a constant current charge and discharge curve at 0.5mA/cm 2 for the assembled lithium-air battery of example 2.
Detailed Description
The invention provides a composite gel polymer electrolyte for a lithium air battery, which comprises the following components:
A battery separator;
the lithium polymer matrix is compounded on the surface of the battery diaphragm, the nano aerogel inert filler is dispersed in the polymer matrix, and the polymer in the polymer matrix meets the following two points:
(I) The polymer has no strong electron-withdrawing functional group on the side chain;
(II) when the polymer main chain is an aliphatic main chain, no hydrogen atom having an electron withdrawing group of alpha or beta is present on the main chain.
The composite gel polymer electrolyte for the lithium air battery comprises a battery diaphragm. The battery separator is selected from a polypropylene separator, a polyethylene separator or a glass fiber separator, and the thickness of the battery separator is 15-30 microns, preferably 20-25 microns.
The composite gel polymer electrolyte for the lithium air battery also comprises a lithiated polymer matrix which is compounded on the surface of the battery diaphragm, wherein the inside of the polymer matrix is dispersed with nano aerogel inert filler.
In the present invention, the polymer in the polymer matrix satisfies the following two points:
(I) The polymer has no strong electron-withdrawing functional group on the side chain;
(II) when the polymer main chain is an aliphatic main chain, no hydrogen atom having an electron withdrawing group of alpha or beta is present on the main chain.
Wherein the strong electron withdrawing functional group is selected from one or more of-C.ident.N, -X, -NO 2、-CF3, and-X is selected from-F and/or-Cl.
In some embodiments of the invention, the polymer in the polymer matrix satisfies the following two points: (I) The polymer has no strong electron-withdrawing functional group on the side chain; (II) when the polymer main chain is an aliphatic main chain, no hydrogen atom having an electron withdrawing group of alpha or beta is present on the main chain. Thus, the lithium peroxide resistance of the electrolyte for the lithium-air battery can be improved, and the polymer matrix is stable to lithium. Preferably one or more of polymethyl methacrylate, polyurethane, polystyrene and polytetrafluoroethylene.
In the invention, the polymer matrix is internally dispersed with nano aerogel inert filler, and one or more of nano titanium dioxide, nano silicon dioxide and nano aluminum oxide serving as the nano aerogel inert filler; particle size of 7 to 40 nm, preferably 10 to 35 nm, and more preferably 20to 25 nm; the mass of the nano aerogel inert filler accounts for 5-20wt%, preferably 10-15wt%, of the mass of the polymer matrix.
The polymer matrix in the composite gel polymer electrolyte is subjected to pre-lithiation and is compounded on the surface of the battery diaphragm. Wherein the thickness of the single-sided polymer matrix is 10-45 micrometers.
The invention also provides a preparation method of the composite gel polymer electrolyte, which comprises the following steps:
a) Dissolving a polymer matrix in an organic solvent to obtain a gel solution;
b) Dispersing the nano aerogel inert filler in the gel solution to obtain a mixed gel solution;
c) Immersing the battery diaphragm into the mixed gel solution, and taking out and drying the battery diaphragm to obtain the battery diaphragm with the surface composited with the polymer matrix;
D) And (3) placing the battery diaphragm with the polymer matrix on the surface in a liquid lithium salt ether electrolyte for swelling, lithiating, taking out, and drying to obtain the composite gel polymer electrolyte.
The invention firstly dissolves the polymer matrix in the organic solvent to obtain the gel solution.
The organic solvent is one or more of tetrahydrofuran, N-methyl pyrrolidone, dimethylformamide, acetonitrile and the like.
And then dispersing the nano aerogel inert filler in the gel solution to obtain a mixed gel solution. The method for dispersing the nano aerogel inert filler in the gel solution is not particularly limited, and the nano aerogel inert filler can be dispersed in an ultrasonic dispersion and magnetic stirring mode.
The concentration of the mixed gel solution polymer is 3-30wt%, preferably 5-25wt%.
And immersing the battery diaphragm into the mixed gel solution, taking out and drying to obtain the battery diaphragm with the surface composited with the polymer matrix.
Specifically, the battery diaphragm is immersed in the mixed gel solution for 1-5 h. Then taking out, putting into deionized water for reverse extraction to extract an organic solvent phase, repeatedly flushing for 3-4 times, and soaking in the deionized water for 2h. Finally, the polymer separator is removed and dried. The drying condition is 50-100 ℃ and the vacuum drying is carried out for 24-48 hours.
And finally, placing the battery diaphragm with the polymer matrix compounded on the surface into a liquid lithium salt ether electrolyte for swelling, taking out and drying after lithiation, thus obtaining the composite gel polymer electrolyte.
The liquid lithium salt ether electrolyte comprises lithium salt and ether organic solvent, wherein the lithium salt is selected from lithium bistrifluoromethylsulfonyl imide, and the ether organic solvent is selected from one or more of tetraethylene glycol dimethyl ether, ethylene glycol dimethyl ether and dimethyl ether; the concentration of the lithium bistrifluoromethylsulfonyl imide in the liquid lithium salt ether electrolyte is 0.5M-2M, preferably 1.0M-1.5M.
The swelling time is 8-12 h.
And after the polymer membrane is fully swelled, wiping off the electrolyte on the surface of the polymer membrane to obtain the composite gel polymer electrolyte.
The invention also provides a lithium-air battery comprising the composite gel polymer electrolyte.
Specifically, the lithium-air battery includes a positive electrode, a negative electrode, and the composite gel polymer electrolyte.
In some embodiments of the invention, the air electrode is carbon paper loaded with multiwall carbon nanotubes and the negative electrode is a metallic lithium foil.
Compared with the prior art, the invention has the beneficial effects that:
the composite gel polymer electrolyte has low raw material cost, simple preparation process and environment friendliness, and is expected to be practically applied.
The composite gel polymer electrolyte can inhibit the growth of lithium dendrites, and has obviously better performance than the traditional electrolyte.
The electrochemical window of the composite gel polymer electrolyte is more than 4.5V, and the chemical stability requirement of the electrolyte for the lithium-air battery can be met.
The composite gel polymer electrolyte for lithium-air batteries of the present invention has stability to lithium peroxide.
The experimental results show that: at room temperature, the composite gel polymer electrolyte can be cycled for 1200 times under the current density of 0.25mA/cm 2, and still shows lower polarization; the capacity fade occurs after the Li-O 2 battery is cycled 120 times under the current density of 0.5mA/cm 2, and the first-ring discharge capacity is 6.8mAh/cm 2.
In order to further understand the present invention, the composite gel polymer electrolyte for lithium air battery, the preparation method thereof and the lithium-air battery provided by the present invention are described below with reference to examples, and the scope of the present invention is not limited by the following examples.
Example 1
(1) 0.08G of multi-walled carbon nanotubes was dispersed in 1g of a 2% polyvinylidene fluoride solution to prepare a slurry, which was scraped onto a carbon paper current collector with a doctor blade having a blade coating thickness of 200. Mu.m. Drying in an electric blast oven at 80 ℃ for 10 hours, transferring to a vacuum drying oven, and drying in vacuum at 110 ℃ for 12 hours. Finally, the mixture is placed in a glove box with O 2<0.1ppm,H2 O less than 0.1ppm, namely the air electrode.
(2) 1M lithium bistrifluoromethylsulfonylimide is weighed in a glove box with O 2<0.1ppm,H2 O less than 0.1ppm and added into 20mL of tetraethylene glycol dimethyl ether solvent, and the mixture is stirred at room temperature for 12 hours until a homogeneous solution is formed, namely the electrolyte of the lithium battery.
Example 2
0.4G of polymethyl methacrylate as a polymer matrix is added into 10mL of dimethylformamide as an organic solvent, and the mixture is stirred at room temperature for 10h until the mixture is completely dissolved to form a homogeneous solution; adding 0.04g of inert filler nano aerogel titanium dioxide into the solution, performing ultrasonic dispersion, and magnetically stirring for a period of time to form a homogeneous solution; and then immersing the membrane polypropylene of the commercial battery of the support membrane into the solution for 2 hours, taking out, putting into deionized water for inverting, extracting an organic solvent phase, repeatedly flushing for 3-4 times, and immersing in the deionized water for 2 hours. Finally, the polymer membrane was removed, dried in vacuo at 50℃for 36h and placed in a glove box with O 2<0.1ppm,H2 O <0.1ppm for use. And (3) placing the standby polymer membrane in the electrolyte of the lithium battery prepared in the embodiment (1) for 12 hours, and wiping off the electrolyte on the surface of the polymer membrane after the polymer membrane is fully swelled, thus obtaining the composite gel polymer electrolyte.
Fig. 1 is an SEM image of a polymer separator prepared in example 2, which exhibits a uniform honeycomb structure with a pore size of 1-3 microns. Fig. 2 is an SEM image of the composite gel polymer electrolyte prepared in example 2, and it can be seen from fig. 2 that pores of the composite gel polymer electrolyte are almost disappeared, forming a uniform gel electrolyte structure. The composite gel polymer electrolyte is used as electrolyte for lithium-air battery, and electrochemical performance test is carried out under room temperature condition to test the battery performance. As can be seen from fig. 3, 4, and 5, the symmetrical cell still exhibits lower polarization at 1500 cycles at a current density of 0.25mA/cm 2 at room temperature; the capacity decay occurs after the Li-O 2 battery is cycled for 120 times under the current density of 6.8mAh/cm 2;0.5mA/cm2 at the first-cycle discharge capacity.
Example 2
0.4G of polyurethane is added into 10mL of organic solvent N-methyl pyrrolidone, and stirred at room temperature for 10h until the polyurethane is completely dissolved, so as to form a homogeneous solution; adding 0.04g of inert filler nano aerogel silicon dioxide into the solution, performing ultrasonic dispersion, and magnetically stirring for a period of time to form a homogeneous solution; and then immersing the membrane polypropylene of the commercial battery of the support membrane into the solution for 2 hours, taking out, putting into deionized water for inverting, extracting an organic solvent phase, repeatedly flushing for 3-4 times, and immersing in the deionized water for 2 hours. Finally, the polymer membrane was removed, dried in vacuo at 50℃for 36h and placed in a glove box with O 2<0.1ppm,H2 O <0.1ppm for use. And (3) placing the standby polymer membrane in the electrolyte of the lithium battery prepared in the embodiment (1) for 12 hours, and wiping off the electrolyte on the surface of the polymer membrane after the polymer membrane is fully swelled, thus obtaining the composite gel polymer electrolyte.
The composite gel polymer electrolyte is used as electrolyte for lithium-air battery, and electrochemical performance test is carried out under room temperature condition to test the battery performance. At room temperature, the symmetrical battery still shows lower polarization after 470 times of circulation under the current density of 0.5mA/cm 2; the capacity fade occurs after the Li-O 2 battery is cycled 115 times at the current density of 0.5mA/cm 2, and the first-cycle discharge capacity is 6.3mAh/cm 2.
Example 3
0.4G of polystyrene is added into 10mL of organic solvent tetrahydrofuran, and stirred at room temperature for 10h until the polystyrene is completely dissolved, so as to form a homogeneous solution; adding 0.04g of inert filler nano aluminum oxide into the solution, performing ultrasonic dispersion, and magnetically stirring for a period of time to form a homogeneous solution; and then immersing the membrane polypropylene of the commercial battery of the support membrane into the solution for 2 hours, taking out, putting into deionized water for inverting, extracting an organic solvent phase, repeatedly flushing for 3-4 times, and immersing in the deionized water for 2 hours. Finally, the polymer membrane was removed, dried in vacuo at 50℃for 36h and placed in a glove box with O 2<0.1ppm,H2 O <0.1ppm for use. And (3) placing the standby polymer membrane in the electrolyte of the lithium battery prepared in the embodiment (1) for 12 hours, and wiping off the electrolyte on the surface of the polymer membrane after the polymer membrane is fully swelled, thus obtaining the composite gel polymer electrolyte.
The composite gel polymer electrolyte is used as electrolyte for lithium-air battery, and electrochemical performance test is carried out under room temperature condition to test the battery performance. At room temperature, the symmetrical battery still shows lower polarization after 256 times of circulation under the current density of 1mA/cm < 2 >; the capacity decay occurs after 107 cycles of the Li-O 2 battery at a current density of 0.5 mAh/cm2, and the first-cycle discharge capacity is 5.9mAh/cm2.
Comparative example 1
Comparative example the comparative example was different from example 2 in that the comparative example directly uses a commercial battery separator polypropylene as a separator for a lithium-air battery. After the commercial battery separator is dried for 36 hours under vacuum at 50 ℃, the commercial battery separator is transferred into a glove box with O 2<0.1ppm,H2 O <0.1ppm, swelled for 12 hours in the electrolyte of the lithium battery prepared in the step (2) of the example 1, and the electrolyte on the surface of the lithium ion battery separator is wiped off; the lithium-air battery was assembled in a glove box with O 2<0.1ppm,H2 O <0.1 ppm. The negative electrode is lithium foil, and one surface of the negative electrode is tightly pressed on the stainless steel plate; the positive electrode is an air electrode, and electrolyte-positive electrode-foam nickel of a lithium ion battery diaphragm Celgard2400+60 microliter after negative electrode-swelling is packaged in a lithium-air battery shell in sequence.
The commercial battery separator is used as the separator of a lithium-air battery, and electrochemical performance test is carried out under the room temperature condition to test the battery performance. The polarization voltage increases significantly after 640 cycles at a current density of 0.25mA/cm 2 at room temperature.
Comparative example 2
Comparative example the comparative example was different from example 2 in that the polymer matrix used was polyacrylonitrile as a film for lithium-air battery. The prepared polyacrylonitrile membrane is dried for 36 hours at 50 ℃ in vacuum and then is transferred into a glove box with O 2<0.1ppm,H2 O <0.1ppm, and is swelled for 12 hours in the electrolyte of the lithium battery prepared in the step (2) of the example 1, and the electrolyte on the surface of the lithium ion battery membrane is wiped off; the lithium-air battery was assembled in a glove box with O 2<0.1ppm,H2 O <0.1 ppm. The negative electrode is lithium foil, and one surface of the negative electrode is tightly pressed on the stainless steel plate; the positive electrode is an air electrode, and the negative electrode, the swelled polyacrylonitrile diaphragm, the positive electrode and the foam nickel are packaged in a lithium-air battery shell in sequence.
The polyacrylonitrile diaphragm is used as the diaphragm of the lithium-air battery, and the electrochemical performance test is carried out under the room temperature condition to test the battery performance. The capacity fade occurs after 60 cycles of the Li-O 2 battery at a current density of 0.5mA/cm 2, and the first-cycle discharge capacity is 2.2mAh/cm 2.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A composite gel polymer electrolyte for a lithium air battery, comprising:
A battery separator;
The lithium-treated polymer matrix is compounded on the surface of the battery diaphragm, nano aerogel inert filler is dispersed in the polymer matrix, the polymer matrix is selected from polymethyl methacrylate, and the nano aerogel inert filler is selected from nano titanium dioxide.
2. The composite gel polymer electrolyte of claim 1, wherein the polymer matrix has a single-sided thickness of 10-45 microns.
3. The composite gel polymer electrolyte of claim 1, wherein the particle size of the nano aerogel inert filler is 7-40 nanometers; the mass of the nano aerogel inert filler accounts for 5-20wt% of the mass of the polymer matrix.
4. The composite gel polymer electrolyte according to claim 1, wherein the battery separator is selected from a polypropylene separator, a polyethylene separator or a glass fiber separator, and the thickness of the battery separator is 15-30 micrometers.
5. A method for preparing the composite gel polymer electrolyte according to any one of claims 1 to 4, comprising the steps of:
A) Dissolving a polymer matrix in an organic solvent to obtain a gel solution;
b) Dispersing the nano aerogel inert filler in the gel solution to obtain a mixed gel solution;
C) Immersing the battery diaphragm into the mixed gel solution, and taking out and drying the battery diaphragm to obtain the battery diaphragm with the surface composited with the polymer matrix;
D) And (3) placing the battery diaphragm with the polymer matrix on the surface in a liquid lithium salt ether electrolyte for swelling, lithiating, taking out, and drying to obtain the composite gel polymer electrolyte.
6. The preparation method according to claim 5, wherein the organic solvent is one or more of tetrahydrofuran, N-methylpyrrolidone, dimethylformamide and acetonitrile;
the concentration of the mixed gel solution polymer is 3-30wt%.
7. The method according to claim 5, wherein the liquid lithium salt ether-based electrolyte comprises a lithium salt selected from lithium bistrifluoromethylsulfonylimide and an ether-based organic solvent selected from one or more of tetraethyleneglycol dimethyl ether, ethyleneglycol dimethyl ether, and dimethyl ether; the concentration of the lithium bistrifluoromethylsulfonyl imide in the liquid lithium salt ether electrolyte is 0.5-2M.
8. The method according to claim 5, wherein in the step C), the drying condition is 50 ℃ to 100 ℃, and the drying is performed for 24 to 48 hours in vacuum;
In the step D), the swelling time is 8-12 h.
9. A lithium-air battery comprising the composite gel polymer electrolyte of any one of claims 1-4.
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