CN113258172A - Solid electrolyte suitable for room-temperature all-solid-state zinc-air battery and preparation method thereof - Google Patents
Solid electrolyte suitable for room-temperature all-solid-state zinc-air battery and preparation method thereof Download PDFInfo
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- CN113258172A CN113258172A CN202110417001.6A CN202110417001A CN113258172A CN 113258172 A CN113258172 A CN 113258172A CN 202110417001 A CN202110417001 A CN 202110417001A CN 113258172 A CN113258172 A CN 113258172A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 36
- 239000011701 zinc Substances 0.000 claims abstract description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 23
- 239000004033 plastic Substances 0.000 claims abstract description 12
- 150000003751 zinc Chemical class 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 13
- -1 1-methyl-1-ethyl pyrrolidinium bis (trifluoromethyl sulfonyl) imide salt Chemical class 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 4
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical group [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000557 Nafion® Polymers 0.000 claims description 2
- IAHFWCOBPZCAEA-CQDYUVAPSA-N butanedinitrile Chemical group N#[13C]CC[13C]#N IAHFWCOBPZCAEA-CQDYUVAPSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 9
- 230000002441 reversible effect Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 239000010416 ion conductor Substances 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 2
- YKODOXARRQIKIP-UHFFFAOYSA-N FC(F)(F)S(=O)(=O)[Zn]S(=O)(=O)C(F)(F)F Chemical compound FC(F)(F)S(=O)(=O)[Zn]S(=O)(=O)C(F)(F)F YKODOXARRQIKIP-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
Abstract
The invention belongs to the field of metal-air batteries, and particularly relates to a solid electrolyte suitable for a room-temperature all-solid-state zinc-air battery and a preparation method thereof. The solid electrolyte consists of a plastic crystal micromolecule matrix, anhydrous zinc salt and inert inorganic nano-filler; the electrolyte is solid at room temperature and has an ionic conductivity of up to 10‑4S/cm, and acts as both an ion conductor and a battery separator between the air positive electrode and the metallic zinc negative electrode. The solid zinc ion electrolyte has the advantages of simple preparation, good plasticity and high ionic conductivity, can realize reversible deposition/dissolution reaction of a zinc electrode, and increases the safety and the service life of the battery. The prepared solid electrolyte is arranged between a zinc sheet electrode and a catalyst coated carbon paper electrode, and the assembled all-solid-state zinc-air battery has longer cycle stability and higher energy density.
Description
Technical Field
The invention belongs to the field of metal-air batteries, and particularly relates to a solid electrolyte suitable for a room-temperature all-solid-state zinc-air battery and a preparation method thereof.
Background
Zinc is one of the most abundant metal elements in the earth's crust, and in addition, it possesses many special advantages: (1) the reduction potential of zinc is low (-0.76V vs. SHE); (2) the zinc element is non-toxic and stable, and has high biocompatibility; (3) the zinc metal and the electrode can stably exist in oxygen and humid environments, and the operation cost is low; (4) the price is low. Therefore, the metal zinc is widely applied to various energy storage devices. Among them, the zinc-air battery has the characteristics of high energy density, green, no pollution, good safety, abundant resources, low cost and the like, and is considered to be one of the most promising battery technologies. However, the zinc-air battery currently commercialized generally uses a high-concentration alkaline electrolyte, and thus there is a safety risk due to leakage of the electrolyte, which results in a large limitation in the application field of such a battery. On the other hand, carbon dioxide in the air is liable to react with the electrolyte of the aqueous rechargeable zinc-air battery, resulting in a decrease in the stability of the rechargeable battery. To solve this problem, an electrolyte circulation system and a carbon dioxide blocking system are required to be added to the rechargeable zinc-air battery, which makes the design of the battery system very complicated, and further increases the cost of the battery. The all-solid-state zinc-air battery can thoroughly solve two problems of electrolyte leakage and carbon dioxide corrosion, and becomes a research hotspot of the zinc-air battery in recent years.
One of the core components of an all-solid zinc-air battery is an all-solid zinc ion electrolyte. In order to meet the performance requirements of all-solid zinc-air batteries, all-solid zinc ion electrolytes need to have the following characteristics: higher ionic conductivity, wider electrochemical window and better chemical compatibility. However, all-solid-state zinc ion electrolytes having high conductivity at room temperature are very rare, and the corresponding electrode utilization rate is low, so that stable operation of a room-temperature zinc-air battery cannot be realized.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a solid electrolyte suitable for room temperature all-solid-state zinc-air battery and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a solid electrolyte suitable for room temperature all-solid-state zinc-air batteries is composed of a plastic crystal micromolecule matrix, anhydrous zinc salt and inert inorganic nano-fillers; wherein, the anhydrous zinc salt accounts for 1-20% of the total mass of the solid electrolyte, and the inert inorganic nano filler accounts for 2-10% of the total mass of the solid electrolyte.
Furthermore, a plastic crystal material is adopted as a matrix of the solid electrolyte, anhydrous zinc salt is used for doping, zinc ions are introduced, and meanwhile, inert nano inorganic filler is added to stabilize the system, so that the electrolyte system which has higher ionic conductivity and keeps the scale stability of the solid system is realized.
Preferably, the anhydrous zinc salt accounts for 10-20% of the total mass of the solid electrolyte, and the inert inorganic nano filler accounts for 4-8% of the total mass of the solid electrolyte.
The plastic crystal micromolecule matrix is butanedinitrile or 1-methyl-1-ethyl pyrrolidinium bis (trifluoromethyl sulfonyl) imide salt; the zinc salt is zinc trifluoromethanesulfonate or bis (trifluoromethanesulfonyl) zinc imide; the inert inorganic nano filler is one or more of nano silicon dioxide, nano titanium dioxide and nano aluminum oxide, and the particle size is 10-50 nm.
A process for preparing solid electrolyte includes heating the plastic crystal of small molecular matrix at 80-90 deg.C to smelt, proportionally adding anhydrous zinc salt and inertial inorganic nano filler to the plastic crystal, and cooling to room temp.
Use of a solid-state electrolyte for the manufacture of an all-solid-state zinc-air battery.
The all-solid-state zinc-air battery consists of electrolyte, air anode, metal zinc cathode and battery shell, and is of sandwich structure, the sandwich layer is the solid-state electrolyte, and the two sides are respectively zinc cathode and air anode.
The air anode is prepared by dispersing a Pt-containing catalyst into a mixed solution of a Nafion solution and absolute ethyl alcohol to obtain a dispersion liquid, and then dripping the dispersion liquid on carbon cloth or carbon paper to dry at room temperature; the metal zinc cathode is one or more of a zinc sheet, a zinc foil, a porous zinc net, foamed zinc and zinc powder.
In a further aspect of the present invention,
A. pressing the solid electrolyte to obtain a solid electrolyte sheet;
B. obtaining an air anode according to the records for later use;
C. polishing the metal zinc cathode; or, mixing and pressing zinc powder and conductive carbon material for standby;
D. and C, forming a sandwich structure by the solid electrolyte sheet obtained in the step A, the positive plate obtained in the step B and the metal zinc negative electrode obtained in the step C, wherein the sandwich layer is the solid electrolyte sheet, then placing the solid electrolyte sheet into a battery mould shell, and pressurizing to obtain the all-solid-state zinc-air battery.
The invention has the following technical advantages:
1. the solid electrolyte has simple preparation process, easy batch production and good repeatability;
2. the solid electrolyte has the advantages of good electrochemical stability, high zinc ion conductivity and the like;
3. instability of solid-solid interfacial contact between the solid electrolyte and the electrode is a recognized bottleneck problem for solid-state battery applications. The solid electrolyte disclosed by the invention is subjected to continuous heating and cooling experiments, and is found to have the thermoreversible characteristic, and reversible conversion between a high-temperature (>50 ℃) flow state and a solid state (<50 ℃) is controlled through simple temperature adjustment, so that high affinity with an electrode material can be realized, and the interface stability and the long cycle performance are improved. In the circulation process, once the solid-solid interface loss phenomenon occurs, the surface of the electrode can be infiltrated again through simple temperature rise, and the performance of the battery can be recovered in situ.
4. The solid electrolyte can keep the dimension of a solid system stable at room temperature, so that the solid electrolyte can prevent the occurrence of battery leakage in a zinc-air battery.
5. The solid electrolyte provided by the invention can ensure that the room-temperature all-solid-state zinc-air battery can stably operate, and the battery has longer cycle stability and higher energy density.
6. The invention has guiding significance for the development of all-solid-state metal-air batteries.
Drawings
Fig. 1 is a digital photograph of a solid electrolyte provided by the present invention.
Fig. 2 is an electrochemical ac impedance diagram of the solid electrolyte provided by the present invention at room temperature.
FIG. 3 is a representation of the thermal reversibility of a solid state electrolyte provided by the present invention.
FIG. 4 is a cyclic voltammogram of an asymmetric zinc-titanium cell of the invention at a test condition of 0.5 mV/s.
FIG. 5 shows the present invention at 0.05mA/cm2Under the test condition, a constant current polarization curve diagram of the zinc-zinc symmetrical battery is shown.
FIG. 6 shows the present invention at 0.1mA/cm2And (3) under the test condition, a charge-discharge curve diagram of the all-solid-state zinc-air battery.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
The solid electrolyte of the invention adds soluble anhydrous zinc salt and inert nano inorganic filler into a plastic crystal material matrix to form a stable solid electrolyte system, the preparation is simple, the electrolyte is solid at room temperature, and the ionic conductivity of the electrolyte can reach as high as 10-4S/cm, and acts as both an ion conductor and a battery separator between the air positive electrode and the metallic zinc negative electrode. The solid zinc ion electrolyte has the advantages of simple preparation, good plasticity and high ionic conductivity, can realize reversible deposition/dissolution reaction of a zinc electrode, and increases the safety and the service life of the battery. The obtained solid electrolyte has high ionic conductivity, and simultaneously maintains an electrolyte system with a stable solid system size, so that the all-solid zinc-air battery can stably operate at room temperature. The prepared solid electrolyte is arranged between a zinc sheet electrode and a catalyst coated carbon paper electrode, and the assembled all-solid-state zinc-air battery has longer cycle stability and higher energy density.
Example 1
The solid electrolyte consists of succinonitrile matrix, zinc trifluoromethanesulfonate and gas-phase nano silicon dioxide. Heating succinonitrile to be molten at 80 ℃, adding 15% of zinc trifluoromethanesulfonate and 5% of fumed nano-silica into the molten succinonitrile melt by mass percent, and cooling to room temperature to obtain a waxy solid electrolyte, wherein a digital photograph of the electrolyte is shown in figure 1; as can be seen from fig. 1, the electrolyte of the present invention maintains a dimensionally stable solid system at room temperature, which can substantially prevent the occurrence of liquid leakage of the metal-air battery device.
The conductivity was measured by electrochemical AC impedance technique, as shown in FIG. 2, and the conductivity at room temperature was 10 from the conductivity formula-4Of the order of S/cm.
The solid electrolyte is heated to more than 50 ℃ for 5 minutes at the temperature of 45 ℃ to melt the electrolyte, and then the solid electrolyte is recovered after being cooled to the room temperature, and can be repeated for a plurality of times, as shown in fig. 3, so that the solid electrolyte has the thermal reversible characteristic, and reversible conversion between flow dynamics and solid state can be controlled through simple temperature regulation.
Therefore, the electrolyte provided by the invention can keep the solid system stable in scale at room temperature, and has the advantages of simple preparation process, high zinc ion conductivity, good thermal reversible property and the like.
Example 2
Pressing the solid electrolyte of example 1 into a circular sheet with a diameter of 10mm to obtain a solid electrolyte sheet; cutting a titanium foil with the thickness of 0.1mm serving as a working electrode into a circular sheet with the diameter of 10 mm; and taking a zinc sheet with the thickness of 0.15mm as a counter electrode, polishing the zinc sheet, cutting the polished zinc sheet into a circular sheet with the diameter of 10mm, forming a sandwich structure by the solid electrolyte sheet, the working electrode and the counter electrode, wherein the sandwich layer is the solid electrolyte sheet, and then putting the solid electrolyte sheet into a shell of a button cell die to assemble the asymmetric zinc-titanium cell. The assembled cell was then subjected to cyclic voltammetry at a sweep rate of 0.5mV/s, as shown in FIG. 4. As can be seen from fig. 4, the solid electrolyte of the present invention can achieve reversible deposition/dissolution reactions of the zinc electrode.
Example 3
The solid electrolyte sheet of example 2 and two zinc sheet electrodes of example 2 were combined into a sandwich structure, the sandwich was a solid electrolyte sheet, which was then placed into a button cell mold housing to assemble a symmetrical zinc-zinc cell, and the assembled cell was then charged to 0.05mA/cm2It was subjected to a constant current polarization test at a current density as shown in fig. 5. It can be seen from fig. 5 that the solid electrolyte of the present invention has good electrochemical stability.
Example 4
Mixing a Pt-containing catalyst, a conductive agent acetylene black and a binder polyvinylidene fluoride according to a mass ratio of 7:2:1, coating the mixture on the surface of a current collector carbon paper, punching the mixture into a circular sheet with the diameter of 10mm, and drying the circular sheet in vacuum to obtain the positive plate.
The positive plate, the solid electrolyte sheet of example 2 and the metal zinc negative electrode of example 2 were combined into a sandwich structure, the sandwich was the solid electrolyte sheet, which was then placed into a cell mold housing and pressed to make an all-solid zinc-air cell. Then the assembled battery can be charged with zinc-air battery at 0.1mA/cm2The curve obtained by the test of charging and discharging at constant current is shown in fig. 6.
It can be seen from fig. 6 that the solid electrolyte provided enables stable operation of all-solid zinc-air batteries at room temperature, and the batteries have longer cycle stability and higher energy density.
Example 5
The solid electrolyte consists of 1-methyl-1-ethyl pyrrolidinium bis (trifluoromethyl sulfonyl) imide salt, zinc bis (trifluoromethyl sulfonyl imide) and nano aluminum oxide. Heating 1-methyl-1-ethyl pyrrolidinium bis (trifluoromethylsulfonyl) imide salt at 90 ℃ to melt, adding 20% of bis (trifluoromethylsulfonyl) zinc and 10% of nano alumina into the 1-methyl-1-ethyl pyrrolidinium bis (trifluoromethylsulfonyl) imide salt melt according to mass percent, and cooling to room temperature to obtain the solid electrolyte.
The solid electrolyte obtained is photographed, and the solid system dimension is kept stable at room temperature.
Pressing the electrolyte into a circular sheet with the diameter of 10mm to obtain a solid electrolyte sheet, wherein the positive plate of the embodiment 4 is used as a positive electrode, and the zinc plate of the embodiment 2 is used as a metal negative electrode; and (3) forming a sandwich structure by the solid electrolyte sheet, the positive plate and the metal zinc negative electrode, wherein the interlayer is the solid electrolyte sheet, then placing the solid electrolyte sheet into a shell of a battery die, and pressurizing to obtain the all-solid-state zinc-air battery. The solid electrolyte obtained by detecting the assembled battery has good electrochemical stability and high zinc ion conductivity, so that the all-solid-state zinc-air battery can stably operate at room temperature, and the battery has longer circulation stability.
Claims (7)
1. A solid electrolyte suitable for room temperature all-solid-state zinc-air batteries is characterized in that: the solid electrolyte consists of a plastic crystal micromolecule matrix, anhydrous zinc salt and inert inorganic nano-filler; wherein, the anhydrous zinc salt accounts for 1-20% of the total mass of the solid electrolyte, and the inert inorganic nano filler accounts for 2-10% of the total mass of the solid electrolyte.
2. The solid electrolyte of claim 1, wherein: the plastic crystal micromolecule matrix is butanedinitrile or 1-methyl-1-ethyl pyrrolidinium bis (trifluoromethyl sulfonyl) imide salt; the zinc salt is zinc trifluoromethanesulfonate or bis (trifluoromethanesulfonyl) zinc imide; the inert inorganic nano filler is one or more of nano silicon dioxide, nano titanium dioxide and nano aluminum oxide, and the particle size is 10-50 nm.
3. A method for producing a solid electrolyte according to claim 1, characterized in that: heating the plastic crystal micromolecule matrix at 80-90 ℃ until the plastic crystal micromolecule matrix is molten, then adding anhydrous zinc salt and inert inorganic nano filler into the plastic crystal melt according to the proportion in claim 1, and cooling to room temperature to obtain the waxy solid state electrolyte.
4. Use of the solid-state electrolyte of claim 1, wherein: the solid electrolyte is applied to the preparation of all-solid-state zinc-air batteries.
5. An all-solid-state zinc-air battery is composed of an electrolyte, an air anode, a metal zinc cathode and a battery shell, and is characterized in that: the battery is of a sandwich structure, the interlayer is the solid electrolyte, and the two sides of the battery are respectively provided with a zinc cathode and an air anode.
6. The all-solid-state zinc-air battery of claim 5, wherein: the air anode is prepared by dispersing a Pt-containing catalyst into a mixed solution of a Nafion solution and absolute ethyl alcohol to obtain a dispersion liquid, and then dripping the dispersion liquid on carbon cloth or carbon paper to dry at room temperature; the metal zinc cathode is one or more of a zinc sheet, a zinc foil, a porous zinc net, foamed zinc and zinc powder.
7. Preparation of an all-solid-state zinc-air battery according to claim 5 or 6, characterized in that:
A. pressing the solid electrolyte of claim 1 to obtain a solid electrolyte sheet;
B. obtaining an air cathode for use as recited in claim 6;
C. polishing the metal zinc negative electrode of claim 6; or, mixing and pressing zinc powder and conductive carbon material for standby;
D. and C, forming a sandwich structure by the solid electrolyte sheet obtained in the step A, the positive plate obtained in the step B and the metal zinc negative electrode obtained in the step C, wherein the sandwich layer is the solid electrolyte sheet, then placing the solid electrolyte sheet into a battery mould shell, and pressurizing to obtain the all-solid-state zinc-air battery.
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