CN114300789B - Preparation method of COF-based solid air positive electrode for solid lithium air battery - Google Patents
Preparation method of COF-based solid air positive electrode for solid lithium air battery Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 69
- 239000007787 solid Substances 0.000 title claims abstract description 54
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000006138 lithiation reaction Methods 0.000 claims description 10
- 238000011065 in-situ storage Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 8
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- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
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- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims 2
- 239000003792 electrolyte Substances 0.000 abstract description 37
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- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 29
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- 239000000463 material Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000002041 carbon nanotube Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
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- 238000011161 development Methods 0.000 description 4
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- 239000003960 organic solvent Substances 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
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- 239000011244 liquid electrolyte Substances 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 238000005498 polishing Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Hybrid Cells (AREA)
Abstract
The invention discloses a preparation method of a COF-based solid air positive electrode for a solid-state lithium air battery, which belongs to the technical field of metal air batteries, and solves the problems that the ion conductivity of the existing single polymer electrolyte is low at room temperature and the air stability of the inorganic solid-state electrolyte is poor, and the requirement of the solid-state lithium air battery on working at room temperature cannot be met, and the technical key points are that: the COF-based air anode has the advantages of high stability, high ionic and electronic conductivity and high porosity, so that the technical difficulty of difficult design of the existing solid-state air anode is solved, interface impedance is effectively reduced, reaction sites are increased, and the electrochemical performance of the solid-state lithium air battery is improved.
Description
Technical Field
The invention relates to the technical field of metal-air batteries, in particular to a preparation method of a COF-based solid-state air anode for a solid-state lithium-air battery.
Background
Energy conservation and environmental protection are two major topics of development in the world today, and efforts are continually being made to develop new energy sources and energy storage devices. New energy sources such as solar energy, wind energy, tidal energy and biological energy cannot be widely applied due to the influence of geographical and climate uncertainty factors. Emerging electrochemical energy storage devices are receiving a great deal of attention due to their stability and high storage capacity. Among them, secondary batteries having multiple energy conversions and high charge and discharge capacities are becoming research hotspots. The current commercial lithium ion battery also exposes a plurality of problems along with the rapid development of society, for example, the single trip distance of an electric automobile can not meet the travel distance requirement of people. Therefore, the development of energy storage devices with higher energy densities is of great strategic importance.
Lithium air batteries with ultra-high energy density (11140 Wh kg -1) are expected to meet the ever-increasing energy storage demands in the future. The actual energy density of the lithium air battery developed at present is already more than 1200Whkg -1, and the lithium air battery has great application prospect. But safety is a matter of concern before lithium air batteries can cross the threshold of application. Unlike the closed system of conventional lithium ion batteries, lithium air batteries are a unique open system, and volatilization of the liquid electrolyte is an unavoidable problem. In addition, the phenomena of organic electrolyte combustion, dendrite generation, pulverization and the like of lithium metal all lead to serious safety problems of the lithium air battery.
The solid-state lithium air battery using the solid-state electrolyte stably existing in the air to replace organic electrolyte is the most effective way to thoroughly solve the problems of safety and stability of the battery, and the characteristics of high compactness and high modulus of the battery enable the practical application of lithium metal to be possible, and the high energy density and the high safety are expected to be realized simultaneously. However, the research on lithium air batteries is still in the initial stage, and the lack of high-performance high-air-stability solid electrolyte and the complexity of solid air anode design are core technical problems to be solved urgently. The solid-state lithium-air battery mainly comprises a metal lithium cathode, a solid electrolyte layer and an air anode. Solid state electrolytes that have been used in lithium air batteries can be classified into inorganic solid state electrolytes and polymer electrolytes. Solid state positive electrodes are typically assembled cells by either selecting a method of mixing an inorganic solid state electrolyte with a catalytic material or directly stacking a polymer electrolyte with the positive electrode.
Covalent organic framework materials (COFs) have wide application prospects in the fields of gas separation, energy storage, sensing, catalysis and the like due to the advantages of high specific surface area, high porosity, regular open pore channels, high thermal stability and the like. The COF is applied to the field of solid electrolyte of lithium air batteries, and has the advantages that 1, the COF material is insulated and cannot cause short circuit together with the positive electrode and the negative electrode; 2. the long-range ordered arrangement in two-dimensional and three-dimensional directions can be realized, and a unique condition is created for filling lithium salt into the holes; 3. the structure unit can be precisely controlled, the interaction of a host and a guest can be regulated and controlled by adjusting the environment in the COF hole, and the open pore canal is beneficial to lithium ion transmission, so that the conductivity and the migration number of the electrolyte are effectively improved; 4. the components and the structure can be accurately regulated and controlled, the stability of the air components is improved, and the method is suitable for the environment in which the battery operates in the air; 5. is easy to synthesize in situ on the surface of the catalytic material, and is beneficial to constructing an integrated air anode.
Disclosure of Invention
Aiming at the defects existing in the prior art, the embodiment of the invention aims to provide a preparation method of a COF-based solid air positive electrode for a solid lithium air battery, which aims to solve the problems in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
A preparation method of a COF-based solid air positive electrode for a solid lithium air battery, which is a preparation method of CD-COF-Li solid electrolyte powder and an integrated COF-based solid air positive electrode, comprises the following steps:
Step 1: adding gamma-cyclodextrin, lithium hydroxide, trimethyl borate, super-dry mesitylene and super-dry N, N-dimethylformamide into a reaction kettle, heating by microwaves to obtain turbid liquid, centrifugally collecting solid, washing with the N, N-dimethylformamide and acetone, and activating in vacuum to obtain CD-COF-Li;
Step 2: adding the obtained CD-COF-Li powder into a lithiation solution, standing in a glove box filled with argon, and removing the solvent under the condition of vacuum drying to obtain CD-COF-Li (Li) powder with ion conduction capability;
step 3: pressing the obtained CD-COF-Li (Li) powder into a sheet to obtain a solid electrolyte sheet;
step 4: firstly growing CNTs in situ on a substrate;
Step 5: adding the CNT electrode obtained in the step (4) into the step (1), and obtaining a CD-COF-Li (Li) -CNT integrated anode in situ by a microwave hydrothermal method; and
Step 6: and (3) repeating the operation process of the step (2) on the electrode-electrolyte integrated material obtained in the step (5).
As a further scheme of the invention, the microwave heating time is 4-6h.
As a further scheme of the invention, the vacuum activation time is 8-16h.
As a further scheme of the invention, the lithiation solution is 0.1-1M, and the lithiation time is 6-12h.
As a further aspect of the present invention, the lithiation solution comprises a lithium salt and an organic solvent, the lithium salt comprising one or more of lithium hexafluorophosphate, lithium perchlorate, lithium trifluoromethanesulfonyl imide and lithium trifluoromethanesulfonate.
As a further aspect of the present invention, the organic solvent includes one or more of ethylene carbonate, dimethyl sulfoxide and tetraethylene glycol dimethyl ether.
As a further aspect of the present invention, the substrate comprises a stainless steel mesh, a carbon cloth, a carbon paper, and a nickel mesh.
In summary, compared with the prior art, the embodiment of the invention has the following beneficial effects:
(1) The COF-based solid electrolyte material has high flame retardance, high ionic conductivity and high air stability, is applied to a lithium air battery, can be used as a solid electrolyte interlayer to effectively protect a negative electrode from corrosion, and can effectively reduce interface impedance between the electrolyte interlayer and a positive electrode/negative electrode.
(2) The COF-based solid air anode provided by the invention has the advantages that the nano holes rich in carbon nano tubes can still not obstruct the diffusion of gas after being in close contact with the solid electrolyte, more porous structures can be provided for the anode to ensure the flow of oxygen, and the solid electrolyte material and the conductive material are tightly combined to form continuous ion and electron conduction, so that a large number of three-phase reaction interfaces are constructed to generate redox reaction of the battery. The anode has excellent stability and can be still maintained in the multi-cycle process; the problems of large interface impedance and few three-phase interfaces of the positive electrode of the existing solid-state lithium air battery are solved.
(3) The COF-based solid state lithium air battery of the present invention exhibits high specific capacity, low overpotential and good cycling stability. Compared with the existing PEO polymer electrolyte and LAGP solid electrolyte, the PEO polymer electrolyte has excellent electrochemical performance.
(4) The preparation method provided by the invention is simple, controllable and efficient, opens up a new direction for the design and development of a novel solid-state lithium air battery, and expands the application prospect of a solid-state energy storage system.
In order to more clearly illustrate the structural features and efficacy of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is a graph showing the thickness of a COF solid electrolyte sheet in example 1 of the present invention;
FIG. 2 is an electrochemical impedance spectrum of a COF solid electrolyte sheet in example 1 of the present invention;
FIG. 3 is a flame retardancy test of a COF solid-state electrolyte sheet in example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of the positive electrode of COF-based air in example 2 of the present invention;
fig. 5 is a first-cycle deep charge-discharge curve of the solid-state lithium oxygen battery of example 3 and comparative examples 1 and 2 of the present invention;
FIG. 6 is a cycle curve of the solid state lithium oxygen cells of example 3 and comparative examples 1 and 2 of the present invention;
Fig. 7 is a magnification curve of solid lithium metal batteries in example 4 and comparative examples 1 and 2 according to the present invention;
Fig. 8 is a cycle curve of solid lithium metal batteries of example 4 and comparative examples 1 and 2 of the present invention;
FIG. 9 is a morphology characterization of PEO polymer electrolyte of comparative example 1 of the present invention;
FIG. 10 is an electrochemical impedance spectrum of PEO polymer electrolyte according to comparative example 1 of the present invention;
FIG. 11 is a morphology characterization of the LAGP electrodeless ceramic electrolyte of comparative example 2 of the present invention;
FIG. 12 is an electrochemical impedance spectrum of the LAGP electrodeless ceramic electrolyte of comparative example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Specific implementations of the invention are described in detail below in connection with specific embodiments.
In one embodiment, a method for preparing a COF-based solid air positive electrode for a solid-state lithium air battery, a method for preparing a CD-COF-Li solid-state electrolyte powder and an integrated COF-based solid air positive electrode, comprises the following steps:
Step 1: adding gamma-cyclodextrin, lithium hydroxide, trimethyl borate, super-dry mesitylene and super-dry N, N-dimethylformamide into a reaction kettle, heating by microwaves to obtain turbid liquid, centrifugally collecting solid, washing with the N, N-dimethylformamide and acetone, and activating in vacuum to obtain CD-COF-Li;
Step 2: adding the obtained CD-COF-Li powder into a lithiation solution, standing in a glove box filled with argon, and removing the solvent under the condition of vacuum drying to obtain CD-COF-Li (Li) powder with ion conduction capability;
step 3: pressing the obtained CD-COF-Li (Li) powder into a sheet to obtain a solid electrolyte sheet;
step 4: firstly growing CNTs in situ on a substrate;
Step 5: adding the CNT electrode obtained in the step (4) into the step (1), and obtaining a CD-COF-Li (Li) -CNT integrated anode in situ by a microwave hydrothermal method; and
Step 6: and (3) repeating the operation process of the step (2) on the electrode-electrolyte integrated material obtained in the step (5).
In this embodiment, the first aspect provides a COF-based solid air anode and a preparation method thereof, where a solid electrolyte material is grown on the surface of an active material of the anode in situ, so as to obtain the integrated COF-based solid air anode;
The COF-based solid electrolyte comprises CD-COF-Li solid electrolyte powder;
The air positive electrode active material includes: carbon Nanotubes (CNT), graphene, activated carbon, superP, etc.;
preferably, CNT with high specific surface area is used as an active material of the air positive electrode;
preferably, the microwave heating time is 4-6 hours;
Preferably, the vacuum activation time is 8-16 hours;
Preferably, the lithiation solution is 0.1-1M;
preferably, the lithiation time is 6-12 hours;
Preferably, the lithiation solution comprises a lithium salt and an organic solvent;
Preferably, the lithium salt comprises one or more of lithium hexafluorophosphate, lithium perchlorate, lithium trifluoromethanesulfonyl imide, and lithium trifluoromethanesulfonate;
Preferably, the organic solvent comprises one or more of ethylene carbonate, dimethyl sulfoxide and tetraethylene glycol dimethyl ether;
the substrate comprises a stainless steel net, carbon cloth, carbon paper and a nickel net;
the second aspect of the invention provides a COF-based solid-state lithium air battery, comprising an electrode-electrolyte integrated material and a metallic lithium negative electrode;
the electrode-electrolyte integrated material is the CD-COF-Li (Li) -CNT electrode-electrolyte integrated material;
The assembly mode is a lamination method.
In one embodiment 1, one COF material is three-dimensional CD-COF-Li, and the preparation method comprises the following steps:
step 1: adding 0.1373g of gamma-cyclodextrin, 0.0132g of lithium hydroxide, 0.5mL of trimethyl borate, 7mL of super-dry mesitylene and 8mL of super-dry N, N-dimethylformamide into a reaction kettle, carrying out microwave heating reaction for 4 hours at 120 ℃ to obtain a turbid liquid, centrifugally collecting a solid, washing with N, N-dimethylformamide and acetone, and carrying out vacuum activation at 100 ℃ for 12 hours to obtain CD-COF-Li;
Step 2: adding the obtained CD-COF-Li powder into a 1M LiPF 6/TEGDME lithiation solution, standing for 12h in a glove box filled with argon, and removing the solvent under vacuum drying conditions to obtain CD-COF-Li (Li) powder with ion conduction capability; and
Step 3: the obtained CD-COF-Li (Li) powder was pressed into a sheet under a pressure of 5MPa for 180 seconds to obtain a solid electrolyte sheet.
In this example, referring to FIG. 1, the thickness of the CD-COF-Li (Li) electrolyte sheet obtained in example 1 was measured, and as shown in FIG. 1, the thickness of the CD-COF-Li (Li) electrolyte sheet obtained in example 1 was 0.55mm, and referring to FIG. 2, the electrochemical impedance spectrum of the CD-COF-Li (Li) electrolyte sheet obtained in example 1 was measured;
As shown in FIG. 2, the ionic conductivity of the CD-COF-Li (Li) electrolyte sheet obtained in example 1 was calculated to be 2.7mScm -1, indicating that the CD-COF-Li (Li) electrolyte has an ideal ionic conductivity.
Referring to FIG. 3, the CD-COF-Li (Li) electrolyte sheet obtained in example 1 was tested for flame retardancy;
As shown in fig. 3, the CD-COF-Li (Li) electrolyte sheet obtained in example 1 can remain stable after being placed on the flame of the alcohol lamp for 60 seconds, and cannot be ignited, which indicates that the CD-COF-Li (Li) electrolyte sheet has ideal flame retardant capability, and solves the problems of leakage and combustion of liquid electrolyte.
In one example 2, in one example 1, a COF-based solid air positive electrode with rich reaction interface and a method for preparing the same, the steps are as follows:
Step 1: firstly, pretreating carbon cloth, and soaking the carbon cloth in concentrated nitric acid for 1h;
step 2: heating the treated carbon cloth for 30min under inert gas, introducing a mixed gas of acetylene and hydrogen, closing a gas path after 30min, and then cooling under inert protection to obtain CNT-carbon cloth; and
Step 3: adding CNT-carbon cloth into the solution in the step 1 of the example 1, and in-situ growing to obtain the integrated material of the CD-COF-Li/CD-COF-Li-CNT electrode and electrolyte.
In this example, referring to fig. 4, the morphology of the integrated material of CD-COF-Li/CD-COF-Li-CNT electrode-electrolyte obtained in example 2 was characterized;
As shown in fig. 4, the CD-COF-Li/CD-COF-Li-CNT electrode-electrolyte integrated material obtained in example 2 had continuous ion, electron and gas transport channels.
In one example 3, a COF-based solid-state lithium air battery was fabricated by cutting the CD-COF-Li/CD-COF-Li-CNT electrode-electrolyte integrated material prepared in example 2 into a 16mm diameter disc, using a 14mm diameter lithium sheet as the negative electrode of the solid-state lithium air battery, using a 2025 type button cell case as the negative electrode case and positive electrode case of the solid-state lithium air battery, and sequentially stacking the electrode-electrolyte integrated material and the negative electrode.
In this example, referring to fig. 5, the deep charge and discharge capacity test was performed on the solid lithium air battery obtained in example 3;
As shown in fig. 5, the solid lithium air battery obtained in example 3 has a discharge cutoff voltage of 2V and a charge cutoff voltage of 4.5V at a current density of 100mAg -1, and the discharge capacity can reach 9340mAhg -1 and a charge capacity of 8200mAhg -1.
Referring to fig. 6, the cycle performance test was performed on the solid lithium air battery obtained in example 3;
As shown in fig. 6, the solid-state lithium air battery obtained in example 3 can stably operate after 100 cycles under the condition that the current density of 200mAg -1 and the limiting capacity of 500mAhg -1.
In one example 4, a COF-based solid lithium metal battery was fabricated by cutting the CD-COF-Li (Li) electrolyte sheet prepared in example 1 into a 16mm diameter disc, taking a 14mm diameter lithium iron phosphate electrode as a positive electrode, taking a 14mm diameter lithium sheet as a negative electrode of a solid lithium air battery, taking a 2032 model button battery case as a negative electrode case and a positive electrode case of the solid lithium metal battery, and stacking the negative electrode case, the elastic sheet, the gasket, the negative electrode, the electrolyte sheet, the positive electrode and the positive electrode case in this order.
In this example, referring to fig. 7, there is a rate performance test performed on the solid lithium metal battery obtained in example 4; as shown in fig. 7, the solid lithium metal battery obtained in example 4 was discharged at a current density of 0.1C, 0.2C, 0.5C, 1C and 2C, and the discharge capacity could still reach 125mAhg -1.
Referring to fig. 8, the cycle performance test was performed on the solid lithium metal battery obtained in example 4; as shown in fig. 8, the solid-state lithium air battery obtained in example 4 can still have a very good capacity retention after 100 cycles at a current density of 0.1C.
In one embodiment, a PEO polymer electrolyte is prepared and a solid state lithium air battery is prepared as follows:
Step 1: liTFSI ([ E 0]:[Li+ ] =10:1) was dissolved in acetonitrile and a homogeneous solution was formed by stirring at 55 ℃ for 12 h. The slurry was then cast onto horizontal polytetrafluoroethylene plates and dried in a vacuum oven at 50 ℃ for 24h to remove most of the acetonitrile solvent. Cutting into electrolyte wafers with the diameter of 16mm;
Step 2: liTFSI ([ E 0]:[Li+ ] =10:1) was dissolved in acetonitrile and a homogeneous solution was formed by stirring at 55 ℃ for 12 h. CNT powder was weighed into the above solution, stirred for 2 hours to form a uniform solution, and then the slurry was cast onto a horizontal teflon plate and dried in a vacuum oven at 50 ℃ for 24 hours to remove most of the acetonitrile solvent. Cutting into electrode-electrolyte discs with the diameter of 16 mm;
step 3: assembling the electrode-electrolyte sheet with a metallic lithium negative laminate to form a solid state lithium air battery; and
Step 4: and assembling the electrolyte sheet, the lithium iron phosphate anode and the metal lithium cathode lamination into a solid lithium metal battery.
In this example, as comparative example 1, see fig. 9, which is a morphology characterization of the PEO polymer electrolyte of comparative example 1; as shown in fig. 9, the PEO polymer electrolyte of comparative example 1 was in the form of a film with rough particles on the surface.
Referring to fig. 10, there is an electrochemical impedance spectroscopy test of the PEO polymer electrolyte of comparative example 1;
As shown in fig. 10, the ionic conductivity of the PEO polymer electrolyte in comparative example 1 was calculated to be 1.05×10 -6Scm-1.
Referring to fig. 5, a deep charge and discharge capacity test curve of the solid lithium air battery of comparative example 2;
As shown in fig. 5, the solid lithium air battery of comparative example 2 has a discharge cut-off voltage of 2V and a charge cut-off voltage of 4.5V at a current density of 100mah -1, and can reach a discharge capacity of 2100mah -1 and a charge capacity of 1200mah -1. The problem of relatively low ionic conductivity at room temperature of PEO polymer electrolytes is illustrated.
Referring to fig. 7, a rate performance test curve of the solid lithium metal battery of comparative example 1, at a large current, capacity was drastically attenuated;
As shown in fig. 8, the solid lithium metal battery of comparative example 1 had only 50 cycles, and the capacity had decayed rapidly.
In one embodiment, a preparation of a LAGP electrodeless ceramic electrolyte and a solid state lithium air battery are provided, comprising the following steps:
step 1: powder of CeO 2、Li2CO3、Al2O3、NH4H2PO4 is prepared according to the mass ratio of 0.7:0.3:1.8:4, mixing, repeatedly ball milling for three times and annealing, pressing the obtained powder into a solid electrolyte wafer with the diameter of 16mm, annealing the electrolyte wafer at 900 ℃ for 2 hours, and polishing;
step 2: CNT, LAGP and PVDF were mixed according to 7:2:1, adding N-methyl pyrrolidone solution for dispersion, and spin-coating the solution on an electrolyte sheet after ultrasonic uniform dispersion to obtain an electrode-electrolyte integrated material;
step 3: assembling the electrode-electrolyte sheet with a metallic lithium negative laminate to form a solid state lithium air battery; and
Step 4: and assembling the electrolyte sheet, the lithium iron phosphate anode and the metal lithium cathode lamination into a solid lithium metal battery.
In this example, as comparative example 1, see fig. 11, which is a characterization of the LAGP solid electrolyte of comparative example 2; as shown in fig. 11, the LAGP solid electrolyte of comparative example 2 is formed by tightly connecting square particles, but is inferior in compactness due to large grain boundary resistance.
Referring to fig. 6, there is a cycle performance test curve of the solid lithium air battery of comparative example 2; as shown in fig. 6, the number of cycles of the solid state lithium air battery of comparative example 1 was only 38 times, and the number of cycles of the solid state lithium air battery of comparative example 2 was only 50 times;
Referring to fig. 12, an electrochemical impedance spectroscopy test of the LAGP solid electrolyte of comparative example 2; as shown in fig. 12, the ion conductivity of the LAGP solid electrolyte in comparative example 2 was calculated to be 4.15×10 -1Scm-5;
Referring to fig. 5, a deep charge and discharge capacity test curve of the solid lithium air battery of comparative example 2; as shown in fig. 5, the solid lithium air battery of comparative example 2 has a discharge cut-off voltage of 2V and a charge cut-off voltage of 4.5V at a current density of 100 mah -1, and can reach a discharge capacity of 5040mah -1 and a charge capacity of 4020mah -1. The problem that the interface of the electrodeless ceramic electrolyte is relatively large is solved.
Referring to fig. 7, a rate performance test curve of the solid lithium metal battery of comparative example 2, at a large current, capacity was drastically attenuated;
As shown in fig. 8, the solid lithium metal battery of comparative example 2 had only 76 cycles, and the capacity had decayed rapidly.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (1)
1. The preparation method of the COF-based solid air positive electrode for the solid lithium air battery is characterized by comprising the following steps of:
step 1: firstly growing CNT on a substrate in situ, wherein the substrate comprises a stainless steel mesh, carbon cloth, carbon paper and nickel mesh;
step 2: adding gamma-cyclodextrin, lithium hydroxide, trimethyl borate, super-dry mesitylene and super-dry N, N-dimethylformamide into a reaction kettle, heating by microwaves to obtain turbid liquid, centrifugally collecting solids, washing with the N, N-dimethylformamide and acetone, activating in vacuum to obtain a CD-COF-Li integrated anode, adding the CNT electrode obtained in the step 1, and obtaining the CD-COF-Li-CNT integrated anode in situ by a microwave hydrothermal method; and
Step 3: and (3) adding the CD-COF-Li-CNT integrated cathode material obtained in the step (2) into a lithiation solution, standing in a glove box filled with argon, and removing the solvent under the condition of vacuum drying to obtain the CD-COF-Li (Li) -CNT integrated cathode material with ion conduction capability.
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