CN113471450A - Flexible cathode based on ceramic solid electrolyte, preparation method thereof and battery - Google Patents
Flexible cathode based on ceramic solid electrolyte, preparation method thereof and battery Download PDFInfo
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- CN113471450A CN113471450A CN202110383933.3A CN202110383933A CN113471450A CN 113471450 A CN113471450 A CN 113471450A CN 202110383933 A CN202110383933 A CN 202110383933A CN 113471450 A CN113471450 A CN 113471450A
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
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Abstract
The invention provides a flexible cathode based on a ceramic solid electrolyte, a preparation method thereof and a battery. The preparation method comprises the following steps: coating the porous reticular matrix with the ceramic solid electrolyte; and then the carbon-based catalytic material is deposited on the surface of the porous reticular matrix coated with the ceramic solid electrolyte on a single side. The preparation method adopted by the flexible cathode provided by the invention can reduce the using amount of ceramic solid electrolyte, reduce the manufacturing cost, has lighter weight, can provide a porous structure with macropores and mesopores, and has the advantages of wider electrochemical stability window, high stability of a reaction interface, high catalytic activity, low polarization of a battery and the like. After the flexible cathode is subjected to photocuring bonding with the photocured gel polymer electrolyte and the lithium cathode, the flexible cathode can be prepared into an integrated solid-state lithium-air battery, and a new thought is provided for the design and preparation of the high-specific-energy solid-state lithium-air battery and the cathode thereof.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a flexible cathode based on a ceramic solid electrolyte, a preparation method thereof and a battery.
Background
The secondary lithium air battery adopts the metal lithium as the cathode, the required active substance is from the external oxygen, and the active substance does not need to be stored in the battery cathode material, so the secondary lithium air battery has ultrahigh theoretical energy density and is known as a final battery. However, the current secondary lithium-air battery adopting the organic system electrolyte has the problems of easy volatilization of organic solvents, poor chemical stability and electrochemical stability, easy occurrence of side reactions, easy flammability and the like, and inevitably limits the cycle performance of the lithium-air battery, thereby bringing safety hazards. The development of secondary lithium air batteries based on solid electrolytes having the advantages of non-volatility, non-flammability, wide electrochemical window, etc. can effectively improve the above problems. Wherein the oxide type solid electrolyte has an ion conductivity of 10 at room temperature-3S/cm (Solid State Commun.1993,86, 689) -693) and is stable to water and air, so that the Solid electrolyte is an ideal Solid electrolyte type for a semi-open system lithium-air battery, and the application of the Solid electrolyte type in the lithium-air battery becomes a research trend and a current research hotspot.
Regarding the application of oxide-type solid electrolyte in lithium air batteries, one of the technical solutions commonly adopted by researchers at present is to make the solid electrolyte into a "dense + porous" double-layer sheet structure, then inject 10% sucrose solution using water as solvent into the porous layer, dry and pyrolyze at high temperature, generate a layer of carbon simple substance in situ on the surface of the solid electrolyte as a storage location for catalyst and discharge product (j.mater.chem.a 2019, 7(7), 3150-; however, the carbon generated by this method may reduce the high valence ions in the solid electrolyte in contact with the carbon at high temperature, which causes structural damage on the surface of the solid electrolyte and accumulation of reduction byproducts, which affect the interfacial ionic conductivity and ultimately the performance of the battery. In addition, researchers have mixed solid electrolyte powder with carbon-based catalyst material and coated the mixture on a dense solid electrolyte sheet to apply the solid electrolyte in lithium air batteries (J.Mater.chem.A 2021, Advance arrow, doi:10.1039/D0TA12421D. ACS appl.Mater.Interfaces 2015,7(31):17307-17310.), but this method further reduces the ionic conductivity of the mixed electrode material, and has higher impedance, and in order to reduce the impedance and improve the cyclicity of the battery, the battery also needs to adopt a high-temperature working environment of about 60 ℃.
In addition, when the thickness of the oxide solid electrolyte sheet used is large, the inhibition of the transmission of lithium ions is increased, and thus high polarization is caused; and the thin sheet has poor mechanical toughness and is fragile and inconvenient to produce and apply. In addition, the prepared slice has the problems of heavier mass, higher manufacturing cost and the like, restricts the exertion of the energy density of the high specific energy lithium-air battery, and is not beneficial to the market popularization of the technical product in the future. Therefore, a new preparation process needs to be explored to solve the problems of poor mechanical properties, heavy weight and the like of the ceramic solid electrolyte, and the ceramic solid electrolyte is applied to the lithium-air battery in a better mode (such as light weight, certain flexibility and the like) to exert respective advantages and improve the performance of the battery.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The embodiment of the invention provides a lithium air battery with a flexible cathode based on a ceramic solid electrolyte, which aims to solve the problems that the ceramic solid electrolyte is easy to be fragile and has heavier mass in the prior art.
The embodiment of the invention provides a preparation method of a flexible cathode based on a ceramic solid electrolyte, which comprises the following steps: coating the porous reticular matrix with the ceramic solid electrolyte; and then the carbon-based catalytic material is deposited on the surface of the porous reticular matrix coated with the ceramic solid electrolyte on a single side. The preparation method of the flexible cathode can reduce the using amount of the ceramic solid electrolyte, reduce the manufacturing cost, has lighter weight, can provide a porous structure with macropores and mesopores, and has the advantages of wider electrochemical stability window, high stability of a reaction interface, high catalytic activity, low polarization of a battery and the like. After the flexible cathode is subjected to photocuring bonding with the photocured gel polymer electrolyte and the lithium cathode, the flexible cathode can be prepared into an integrated solid-state lithium-air battery, and a new thought is provided for the design and preparation of the high-specific-energy solid-state lithium-air battery and the cathode thereof.
According to the invention, the carbon-based catalytic material is selected to have oxygen reduction or oxygen evolution catalytic properties.
According to the preparation method of the flexible cathode based on the ceramic solid electrolyte provided by the embodiment of the invention, the ceramic solid electrolyte is selected from one or more of LAGP, LATP, LLTO, LZGO, LLZO, LGPS and LLZTO; and/or, the porous reticular substrate is selected from one or more of an aluminum mesh, a nickel foam, a carbon cloth and a stainless steel mesh; and/or the carbon-based catalytic material is selected from one or more of carbon material, N-doped carbon material, metal/N-doped carbon material and composite metal oxide-doped carbon material; the carbon material is conductive carbon black (Super P, Ketjin black or XC72), a carbon nano tube, a carbon nano fiber, graphene oxide or reduced graphene oxide. According to the invention, by adopting the ceramic solid electrolyte, the porous reticular matrix and the carbon-based catalytic material, the consumption of the ceramic solid electrolyte can be greatly reduced, the manufacturing cost is reduced, and particularly, the coated porous reticular matrix has certain flexibility, so that the ceramic solid electrolyte with poor machining performance is endowed with flexibility, the porous reticular matrix does not need to have electronic conductivity, a high polymer material with lighter weight can be used, and the surface of the porous reticular matrix has an open structure, so that the deposition and the attachment of a catalyst can be facilitated, the efficient transmission of oxygen to a catalytic reaction site can be better realized, the reaction kinetics is improved, and the reduction of polarization and the improvement of cycle performance of a battery are facilitated.
According to the preparation method of the flexible cathode based on the ceramic solid electrolyte, provided by the embodiment of the invention, the deposition is selected from one or more of a spin coating method, a blade coating method, a spray coating method and a gas phase deposition method.
According to the invention, the knife coating preferably comprises: mixing and dispersing the carbon-based catalytic material, a binder and a dispersion liquid, and then blade-coating the mixture on a porous reticular matrix coated with a ceramic solid electrolyte to form a flexible cathode; preferably, the binder is polytetrafluoroethylene or polyvinylidene fluoride, and the dispersion liquid is water, n-methyl pyrrolidone, acetone or ethanol; preferably, a small amount of surfactant is added to the mixture. The spraying method comprises the following steps: mixing and dispersing the carbon-based catalytic material, a binder and a dispersion liquid, and spraying the mixture onto a porous mesh substrate coated with a ceramic solid electrolyte to form the flexible cathode; preferably, the binder is polytetrafluoroethylene or polyvinylidene fluoride, and the dispersion liquid is water, n-methyl pyrrolidone, acetone or ethanol; preferably, a small amount of surfactant is added to the mixture. The vapor deposition method comprises the step of taking hydrocarbon organic matter vapor as a carbon source, and directly depositing on the surface of a porous reticular matrix coated with a solid electrolyte by heating under the conditions of isolating oxygen and having hydrogen and argon to form the flexible cathode. In the invention, by adopting the method for depositing the carbon-based catalytic material with the catalytic characteristic of oxygen reduction or oxygen precipitation on the porous reticular matrix, the catalyst and the ceramic solid electrolyte coated on the porous reticular matrix can be combined and coated more conveniently, and particularly for the catalyst which is difficult to dissolve into a uniform solution, the coating of the catalyst material on the surface of the solid electrolyte can be better realized.
The embodiment of the invention also provides a flexible cathode based on the ceramic solid electrolyte, which is obtained by the preparation method of the flexible cathode based on the ceramic solid electrolyte. According to the invention, the flexible cathode based on the ceramic solid electrolyte has certain toughness, is not fragile, has light weight, can reduce the manufacturing cost, and avoids the problems that interface high valence state ions are reduced and the like.
An embodiment of the present invention further provides a lithium air battery, including: the flexible cathode is obtained by the preparation method of the flexible cathode based on the ceramic solid electrolyte.
According to the lithium air battery provided by the embodiment of the invention, the working gas of the lithium air battery is oxygen, carbon dioxide, sulfur dioxide, a mixed gas containing oxygen, a mixed gas containing carbon dioxide or a mixed gas containing sulfur dioxide.
The embodiment of the present invention further provides a method for preparing the lithium-air battery, wherein the flexible cathode based on the ceramic solid electrolyte preferably includes: coating part of gel polymer electrolyte precursor solution on the surface of a lithium cathode, irradiating for 2-100 s by ultraviolet light, and curing to form a curing film A; coating the residual gel polymer electrolyte precursor solution on the surface of the curing film A to form a gel liquid film B; and then, enabling one surface of the flexible cathode, on which the carbon-based catalytic material is not deposited, to be in contact with the gel liquid film B, suspending the flexible cathode on the surface of the gel liquid film B, and irradiating for 2-100 seconds by adopting ultraviolet light. According to the invention, the preparation process of the lithium-air battery can avoid direct contact between the solid electrolyte and the metal lithium, and particularly, the gel electrolyte film layer with higher stability to the metal lithium can better realize adhesion between the gel electrolyte film layer and the metal lithium electrode and a flexible solid electrolyte cathode in the photocuring process, so that the preparation process has a better effect on reducing large polarization caused by solid-solid contact of the pure solid battery.
According to the preparation method of the lithium-air battery provided by the embodiment of the invention, the preparation of the photopolymerization gel precursor liquid comprises the following steps: polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), inorganic filler powder, lithium salt, a photopolymerization agent, a photoinitiator and an organic electrolyte solvent are mixed to obtain a photopolymerization gel precursor liquid. In the invention, the in-situ cured gel electrolyte can be conveniently and rapidly prepared by adopting the photopolymerization gel precursor liquid, and particularly, the crystallinity of a polymer matrix can be better reduced, the dissociation of lithium salt is promoted, the number of free lithium ions and a rapid transmission channel of the lithium ions are increased by adding the inorganic filler powder, so that the ionic conductivity is improved.
According to the preparation method of the lithium-air battery provided by the embodiment of the invention, the inorganic filler powder is selected from Al2O3、SiO2、TiO2One or more of LAGP, LATP, LLTO, LZGO, LLZO, LGPS and LLZTO; and/or, the lithium salt is selected from LiTFSI and LiFSI、LiTF、LiNO3、LiClO4、LiPF6、LiBF4One or more of LiBOB; and/or the organic electrolyte solvent is selected from one or more of dimethyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and dimethyl sulfoxide; and/or the photopolymerization agent is ethoxylated trimethylolpropane triacrylate (ETPTA), and the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone (HMPP); preferably, the mass ratio of ETPTA to PVDF-HFP is 2-6: 1, the addition amount of HMPP is 0.1-3% of the mass of ETPTA, and the mass ratio of the inorganic filler powder to PVDF-HFP is 0.5-3: 1; the concentration of the lithium salt in the organic electrolyte solvent is 0.2-6 mol/L. In the invention, the inorganic filler powder LAGP, LATP and other solid electrolyte materials are adopted, and the mass ratio of the solid electrolyte powder to PVDF-HFP is preferably 0.5-3: 1 can directly participate in the transportation of lithium ions, provide a lithium source and better improve the ionic conductivity of the gel layer.
According to the preparation method of the lithium-air battery provided by the embodiment of the invention, the gel polymer electrolyte precursor solution is coated on the surface of the lithium negative electrode by a spin coating method, a blade coating method, a spraying method or a vapor deposition method.
According to the preparation method of the lithium-air battery provided by the embodiment of the invention, the preparation steps of the lithium-air battery are preferably as follows:
(1) dissolving polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), inorganic filler powder, a photopolymerization agent, a photoinitiator and lithium salt into an organic electrolyte solvent to prepare a photopolymerization gel precursor liquid,
(2) coating a ceramic solid electrolyte on a porous reticular matrix, and then depositing a carbon-based catalytic material with oxygen reduction or oxygen precipitation catalytic characteristics on one surface of the porous reticular matrix to prepare a ceramic solid electrolyte flexible cathode;
(3) and coating the photo-polymerization gel precursor solution on the lithium cathode under the condition of dark light, curing for 2-100 seconds by illumination to form a cured film A, coating a small amount of the gel polymer electrolyte precursor solution on the surface of the film A to form a gel liquid film B, suspending the flexible cathode of the ceramic solid electrolyte on the surface of the gel liquid film B, directly contacting the side, not deposited with the carbon-based catalytic material, of the flexible cathode with the gel liquid film B, and curing for 2-100 seconds by adopting an ultraviolet polymerization method to form the lithium-air battery with the flexible cathode based on the ceramic solid electrolyte.
The invention has the beneficial effects that: the lithium air battery with the flexible cathode based on the ceramic solid electrolyte has the advantages of obviously reduced quality, low brittleness and excellent machining performance, can provide a porous structure with macropores and mesopores, an open interface of the lithium air battery can improve the efficient transmission and reaction kinetics of O2, is beneficial to reducing the polarization of reaction, has a wider electrochemical stability window, high stability of the reaction interface, high catalytic activity, low polarization of the battery and the like, can effectively improve the energy density and the application form of the solid lithium air battery, greatly reduces the manufacturing and processing cost of the battery based on the technology, and has attractive application prospects.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic diagram of the process for preparing a flexible cathode based on a ceramic solid electrolyte according to the present invention and the structure of a corresponding lithium-air battery;
Fig. 2 is a lithium air battery cycle performance curve (a) and a change graph of charge and discharge capacity with cycle times of the flexible cathode based on the ceramic solid electrolyte (b): the cutoff voltage of 2.2V-4.5V is adopted, the current density is 100mA/g of catalyst, the first three weeks are according to 500mAh/g of catalyst, the subsequent circulation is according to the constant volume circulation of 1000mAh/g of catalyst, and the battery can stably circulate for 102 weeks;
FIG. 3 is a graph (a) showing the variation of constant current charge and discharge curve and the variation of charge and discharge capacity with cycle times of a liquid organic lithium air battery assembled by a comparative experiment at a cut-off voltage of 2.2V to 4.5V, a charge and discharge depth of 500mAh/g catalyst and a current density of 50mA/g catalyst;
fig. 4 is a schematic diagram (a) of the charging and discharging curve of the lithium-air battery based on the liquid organic system and the variation of the charging and discharging voltage of the battery with the cycle number in the cycle process according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications.
In the present invention, the instruments and the like used are conventional products which are purchased from regular vendors, not indicated by manufacturers. The process is conventional unless otherwise specified, and the starting materials are commercially available from the open literature. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications.
In the following examples, the specific information of the raw materials used is as follows: LAGP (Shenzhen Kanjin, particle size of 500 nm), 60% PTFE emulsion (Japan Dajin, D210C), o-phenanthroline (Shanghai Michelin Biochemical Co., Ltd., analytical purity, 97%), ferrous acetate tetrahydrate (Shanghai Michelin Biochemical Co., Ltd., analytical purity, 95%), 2-hydroxy-2-methyl propiophenone (abbreviated as HMPP, Aladdin, 97%), trimethylolpropane ethoxylate triacrylate (abbreviated as ETPTA, Sigma-Aldrich, averge Mn-428), ruthenium trichloride hydrate (Aladdin, molecular weight: 207.43, 35.0-42.0% Ru basis), poly (vinylidene fluoride-co-hexafluoropropylene) (abbreviated as PVDF-HFP, Aladdin, Melindex: 9-15 g/10 min; Tm: 132-136 ℃)
Example 1
As shown in fig. 1, this embodiment provides a flexible cathode based on ceramic solid electrolyte and a lithium air battery thereof, and the preparation method thereof is as follows:
(1) mixing ceramic solid electrolyte Li1.5Al0.5Ge1.5P3O12Adding a proper amount of surfactant and deionized water into the (LAGP) and 60% PTFE emulsion according to the mass ratio of 80: 7, homogenizing for 0.5 hour by a homogenizer, quickly spraying the obtained slurry on one surface of an aluminum net by a spray gun, horizontally placing the aluminum net on a heating table top at 80 ℃, evaporating the volatile solvent, and then spraying the slurry on the other surface of the aluminum net by the spray gun until the aluminum net is completely coated by the LAGP, thus obtaining the aluminum net matrix based on the ceramic solid electrolyte.
(2) Mixing ferrous acetate tetrahydrate, o-phenanthroline and CNT in a mass ratio of 10: 22: 205 in ethanol by sol-gel method, heating and stirring at 100 deg.C, evaporating to dryness to obtain uniformly mixed powder, grinding in agate mortar, sieving with 400 mesh stainless steel screen, placing the sieved powder in ceramic boat, and filling with N2Heating the temperature to 700 ℃ from room temperature at the speed of 5 ℃/min in a tubular furnace with protective atmosphere, preserving the temperature for 30min, cooling the temperature to room temperature along with the furnace, and taking out the cooled temperature to obtain the Fe/N @ CNT catalyst;
Mixing the prepared Fe/N @ CNT catalyst powder with ruthenium trichloride hydrate (the mass ratio of Ru is 35-42%), CNT and 60% PTFE emulsion according to the mass ratio of 540: 651-780: 100: 375 in an aqueous solution added with a proper amount of surfactant, homogenizing by a homogenizer, spraying the obtained slurry A on the aluminum mesh substrate coated with the ceramic solid electrolyte obtained in example 1 by a spray gun on one side, and controlling the loading amount to 0.1-15mg/cm2Filling the sprayed substrate with N2Raising the temperature from room temperature to 350 ℃ in a tubular furnace with protective atmosphere at the speed of 5 ℃/min, preserving the heat for 20min, then cooling the temperature to room temperature along with the furnace, and taking out the cooled temperature to obtain the Fe/N @ CNT carried composite RuO2A flexible cathode based on a ceramic solid electrolyte of a catalyst;
(3) the polymer PVDF-HFP was mixed with ETPTA (containing 1 wt% HMPP), and the mixture was mixed with 1.1 times the mass of Al in the polymer mixture2O3And 2.8 times of 1M LiTFSI/TEGDME solution by using a homogenizerHomogenizing to obtain gel precursor solution;
(4) under a dark light environment, firstly placing a metal lithium cathode with the diameter of 16mm in a cathode shell of a CR2032 button cell, spin-coating the gel precursor solution obtained in the step (3) on the surface of the metal lithium cathode, carrying out ultraviolet curing for 20s to form a gel film A, then taking 15uL of the gel precursor solution to spin-coat on the surface of the gel film A, soaking the surface of the flexible cathode which is prepared in the step (2) and is not coated with the catalyst and the uncured gel film, then carrying out ultraviolet curing for 20s, covering a positive shell with holes, and pressing to obtain the lithium-air cell of the flexible cathode based on the ceramic solid electrolyte.
The prepared lithium-air battery is placed in a sealed glass container filled with high-purity oxygen, on a blue-ray device, according to a cut-off voltage of 2.2V-4.5V, the previous three weeks are circulated according to a constant volume of 500mAh/g of catalyst, the later circulation is circulated according to a constant volume of 1000mAh/g of catalyst, and according to a current density of 100mA/g of catalyst, a constant-current charge-discharge test is carried out, and as shown in figure 2, the battery can be stably circulated for 102 weeks.
Example 2
Using the Fe/N @ CNT catalyst powder obtained in step (2) of example 1, 5% PVDF (solvent NMP) binder, NMP solvent were added as follows: 20: 500 to prepare a slurry, spraying the slurry on one surface of the aluminum mesh substrate coated with the LAGP in the step (1) in the example 1 by using a spray gun, preparing the lithium air battery based on the ceramic solid electrolyte flexible cathode in the step (4) in the example 1 by using the gel precursor solution obtained in the step (3) in the example 1, placing the lithium air battery in a sealed glass container filled with high-purity oxygen, and performing a constant-volume circulation constant-current charge and discharge test on a blue-ray device according to the cut-off voltage of 2.2V-4.9V, the current density of 100mA/g of the catalyst and the capacity of 1000mAh/g of the catalyst, wherein the battery can stably circulate for 56 weeks as shown in fig. 3.
Comparative example 1
The slurry A containing the mixture of Fe/N @ CNT and ruthenium trichloride hydrate obtained in the step (2) of the example 1 is sprayed on an aluminum mesh substrate by a spray gun on one side, and the loading capacity is controlled to be 0.1-15mg/cm2Filling the sprayed substrate with N2Raising the temperature from room temperature to 350 ℃ in a tubular furnace with protective atmosphere at the speed of 5 ℃/min, preserving the heat for 20min, then cooling the temperature to room temperature along with the furnace, and taking out the cooled temperature to obtain the Fe/N @ CNT carried composite RuO2An electrode for a catalyst; diameter of the steel pipe
The lithium metal cathode is placed in the cathode shell of the CR2032 button cell, and the diameter is adjusted
The glass fiber diaphragm is put on a metal lithium cathode, 200 mu L of 1M LiTFSI/TEGDME electrolyte is dripped, and then
Fe/N @ CNT composite RuO2The electrode plate is stacked on the diaphragm, so that the surface containing the catalyst faces the diaphragm, the bare and leaked aluminum mesh substrate faces external oxygen, and the anode shell with holes is covered and compressed to obtain the liquid organic system lithium-air battery;
placing the liquid organic system lithium-air battery in a sealed glass container filled with high-purity oxygen, and performing constant-current charge-discharge test on a blue-ray device according to a cut-off voltage of 2.2-4.5V, a charge-discharge depth of 500mAh/g of catalyst and a current density of 50mA/g of catalyst; as shown in fig. 4, compared to the lithium-air battery with the flexible cathode based on the ceramic solid electrolyte in example 2, the liquid organic system lithium-air battery stably cycles for 56 weeks under the condition of lower charge-discharge capacity and lower current density by using the same catalyst, the battery firstly shows an increase in charge polarization in the following 57-80 weeks, reaches the set charge capacity at 4.5V and reaches the charge cut-off under the voltage protection condition, and the discharge capacity also sharply decreases after 79 weeks, and the battery completely fails at 80 weeks; therefore, the prepared lithium air battery with the flexible cathode based on the ceramic solid electrolyte has more stable cycle performance and longer cycle life compared with a liquid system lithium air battery.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a flexible cathode based on a ceramic solid electrolyte is characterized by comprising the following steps: coating the porous reticular matrix with the ceramic solid electrolyte; and then the carbon-based catalytic material is deposited on the surface of the porous reticular matrix coated with the ceramic solid electrolyte on a single side.
2. The method of claim 1, wherein the ceramic solid electrolyte is selected from one or more of LAGP, LATP, LLTO, LZGO, LLZO, LGPS, and LLZTO; and/or, the porous reticular substrate is selected from one or more of an aluminum mesh, a nickel foam, a carbon cloth and a stainless steel mesh; and/or the carbon-based catalytic material is selected from one or more of carbon material, N-doped carbon material, metal/N-doped carbon material and composite metal oxide-doped carbon material; the carbon material is conductive carbon black, a carbon nanotube, a carbon nanofiber, graphene oxide or reduced graphene oxide.
3. The method for preparing a flexible cathode based on a ceramic solid electrolyte according to claim 1 or 2, wherein the deposition is selected from one or more of a spin coating method, a doctor blade method, a spray coating method and a vapor deposition method.
4. A flexible cathode based on a ceramic solid-state electrolyte, characterized in that it is obtained by the process for the preparation of a flexible cathode based on a ceramic solid-state electrolyte according to any one of claims 1 to 3.
5. A lithium-air battery, comprising: the flexible cathode, the photocured gel polymer electrolyte, the lithium cathode and the packaging shell with the opening and closing functions are obtained by the preparation method of the flexible cathode based on the ceramic solid electrolyte in any one of claims 1 to 3.
6. The lithium-air battery according to claim 5, wherein the working gas of the lithium-air battery is oxygen, carbon dioxide, sulfur dioxide, a mixed gas containing oxygen, a mixed gas containing carbon dioxide, or a mixed gas containing sulfur dioxide.
7. A method for manufacturing a lithium-air battery, characterized in that a flexible cathode based on a ceramic solid-state electrolyte according to any one of claims 1 to 3 is used, preferably comprising: coating part of gel polymer electrolyte precursor solution on the surface of a lithium cathode, irradiating for 2-100 s by ultraviolet light, and curing to form a curing film A; coating the residual gel polymer electrolyte precursor solution on the surface of the curing film A to form a gel liquid film B; and then, enabling one surface of the flexible cathode, on which the carbon-based catalytic material is not deposited, to be in contact with the gel liquid film B, suspending the flexible cathode on the surface of the gel liquid film B, and irradiating for 2-100 seconds by adopting ultraviolet light.
8. The method of manufacturing a lithium-air battery according to claim 7, wherein the preparing of the photo-polymerizable gel precursor liquid includes: polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), inorganic filler powder, lithium salt, a photopolymerization agent, a photoinitiator and an organic electrolyte solvent are mixed to obtain a photopolymerization gel precursor liquid.
9. The method of claim 8, wherein the inorganic filler powder is selected from Al2O3、SiO2、TiO2One or more of LAGP, LATP, LLTO, LZGO, LLZO, LGPS and LLZTO; and/or, the lithium salt is selected from the group consisting of LiTFSI, LiFSI, LiTF, LiNO3、LiClO4、LiPF6、LiBF4One or more of LiBOB; and/or, the organic electrolyte solventOne or more selected from dimethyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and dimethyl sulfoxide; and/or the photopolymerization agent is ethoxylated trimethylolpropane triacrylate (ETPTA), and the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone (HMPP); preferably, the mass ratio of ETPTA to PVDF-HFP is 2-6: 1, the addition amount of HMPP is 0.1-3% of the mass of ETPTA, and the mass ratio of the inorganic filler powder to PVDF-HFP is 0.5-3: 1; the concentration of the lithium salt in the organic electrolyte solvent is 0.2-6 mol/L.
10. The method for preparing a lithium-air battery according to any one of claims 7 to 9, wherein the gel polymer electrolyte precursor solution is coated on the surface of the lithium negative electrode by a spin coating method, a doctor blade method, a spray coating method or a vapor deposition method.
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| CN110407577A (en) * | 2019-07-26 | 2019-11-05 | 惠州市富济电子材料有限公司 | Ceramic membrane material, catalysis electrode and its preparation method and application |
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| CN107851840A (en) * | 2015-06-01 | 2018-03-27 | 气动覆层科技有责任限公司 | The manufacture method of battery for the nanometer engineering coating of active material of positive electrode, active material of cathode and solid electrolyte and comprising nanometer engineering coating |
| CN110407577A (en) * | 2019-07-26 | 2019-11-05 | 惠州市富济电子材料有限公司 | Ceramic membrane material, catalysis electrode and its preparation method and application |
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