CN114497827B - Manufacturing method of solid-state potassium air battery - Google Patents
Manufacturing method of solid-state potassium air battery Download PDFInfo
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- CN114497827B CN114497827B CN202111663643.0A CN202111663643A CN114497827B CN 114497827 B CN114497827 B CN 114497827B CN 202111663643 A CN202111663643 A CN 202111663643A CN 114497827 B CN114497827 B CN 114497827B
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 33
- 239000011591 potassium Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 239000004744 fabric Substances 0.000 claims abstract description 25
- 238000007873 sieving Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000003825 pressing Methods 0.000 claims abstract description 19
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000006260 foam Substances 0.000 claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000004806 packaging method and process Methods 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 11
- RQPCXPDUSNVHSU-UHFFFAOYSA-N [O].[K] Chemical compound [O].[K] RQPCXPDUSNVHSU-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000010790 dilution Methods 0.000 abstract description 8
- 239000012895 dilution Substances 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 230000037427 ion transport Effects 0.000 description 5
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910006715 Li—O Inorganic materials 0.000 description 1
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal cation Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001149 cognitive effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a new typeA method for manufacturing a solid-state potassium air battery relates to the technical field of battery manufacturing, and comprises the following steps: step 1: hydrothermally synthesizing K 2 Fe 4 O 7 Ball milling and drying the single crystal; step 2: preparing PVA aqueous solution at K 2 Fe 4 O 7 Adding medium PVA into the powder, adding water for dilution, and heating to completely dry; step 3: k containing PVA 2 Fe 4 O 7 Sieving, and cold pressing to obtain tablets; step 4: pressing the solid electrolyte sheet and the hydrophilic carbon cloth together, and then placing the solid electrolyte sheet and the hydrophilic carbon cloth in a constant temperature and humidity box for balancing; step 5: and stacking metal potassium, a GF/D diaphragm of the double-layer electrolyte containing trace potassium ions, a solid electrolyte sheet after balancing humidity, hydrophilic carbon cloth and foam nickel, and packaging the stacked metal potassium, the double-layer electrolyte sheet between the anode and the cathode shells. The invention provides a method for increasing K 2 Fe 4 O 7 The intrinsic potassium ion conductivity, the grain boundary conductivity and the method for improving the interfacial ion transmission of the battery are simple and convenient to operate.
Description
Technical Field
The invention relates to the technical field of battery manufacturing, in particular to a manufacturing method of a solid-state potassium air battery.
Background
In all known battery systems, lithium oxygen (Li-O 2 ) Batteries have become a long-felt successor to lithium ion batteries because of the highest theoretical energy density. However, their practical use is limited by low energy efficiency, slow kinetics and the presence of oxygen reduction and precipitation reaction (ORR/OER) catalysts.
The potassium metal is a thermodynamically stable superoxide (KO) 2 ) The lightest alkali metal cation of the product. This results in potassium oxygen (K-O) 2 ) The battery can pass O 2 /KO 2 Is operated by a simple single electron redox process. This system provides a solution to the persistent kinetic challenge of ORR/OER in air cells without the use of any electrocatalyst. However, the system is very immature in the field of metal-air batteries, unstable decomposition of electrolyte and irreversible corrosion to a negative electrode are main bottlenecks for limiting the improvement of the battery performance, and in addition, dangerous accidents such as combustion, explosion and the like caused by short circuit and liquid leakage can be avoided by assembling the solid-state battery. Thus, there is an urgent need forThe potassium ion solid electrolyte can be used for the battery system to solve the problems caused by liquid electrolyte. Unfortunately, there has been no report to date on solid state potassium air batteries due to the scarcity of room temperature potassium ion conductors currently available.
K 2 Fe 4 O 7 Is one of the potassium ion solid electrolytes at present. The material has a three-dimensional pore canal structure and is a potential electrolyte material. But current development is in the cognitive immature stage. The material cannot be sintered and compacted at present, so that the grain boundary resistance is overlarge, and the ion transport state in the bulk phase resistance is incompletely known. Developing such solid-state electrolytes and applying them to new solid-state battery systems is a current challenge.
Existing K 2 Fe 4 O 7 The solid-state battery is simply stacked for each part to be manufactured into a button battery, and when the button battery is applied to an ion battery, interface contact is not tight, and ion transportation between electrolyte and an anode interface is difficult. The capacity of the battery is low and has certain limitations.
Disclosure of Invention
The invention aims to provide a manufacturing method of a solid-state potassium air battery, which aims to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for manufacturing a solid-state potassium air battery, which changes a crystal structure by introducing water so as to improve ion conductivity, and prepares the solid-state potassium air battery into a solid-state potassium-oxygen battery, comprises the following specific operation steps: step 1: hydrothermally synthesizing K 2 Fe 4 O 7 Ball milling and drying the single crystal; step 2: preparing a PVA aqueous solution with the concentration of 1% or 5%, adding the prepared PVA into K2Fe4O7 powder, adding water for dilution, stirring, and heating to completely dry; step 3: the obtained PVA-containing K 2 Fe 4 O 7 Sieving and granulating, dividing into equal parts, and cold pressing to obtain solid electrolyte sheets; step 4: slightly pressing the solid electrolyte sheet and the hydrophilic carbon cloth, placing the solid electrolyte sheet and the hydrophilic carbon cloth in a closed constant temperature and humidity box to balance different humidity, and keeping the process for more than 12 hours to obtain the solid electrolyte sheet and the hydrophilic carbon after balancing the humidityCloth; step 5: and stacking the metal potassium, the double-layer GF/D diaphragm containing the micro potassium ion electrolyte, the solid electrolyte sheet after balancing the humidity, the hydrophilic carbon cloth and the foam nickel, and packaging the stacked metal potassium, the double-layer GF/D diaphragm containing the micro potassium ion electrolyte and the foam nickel between positive and negative electrode shells to obtain the solid potassium air battery, wherein the positive electrode is one electrode containing holes.
Based on the technical scheme, the invention also provides the following optional technical schemes:
in one alternative: the PVA amount required to be added into the aqueous solution in the step 2 is K 2 Fe 4 O 7 1 to 5 percent of the weight.
In one alternative: the stirring in the step 2 is carried out under the condition that the rotating speed is 100-300 r/min.
In one alternative: and (3) sieving and granulating in the step (3) to obtain a sieving mesh number of 30-100.
In one alternative: in the step 4, the temperature of the solid electrolyte sheet and the hydrophilic carbon cloth is 20-30 ℃ and the humidity is 50-80% when the constant temperature and constant humidity box is balanced.
In one alternative: the concentration of the double-layer electrolyte containing trace potassium ions is 0.5-1mol/L, and the volume is 80-150 mu L.
Compared with the prior art, the invention has the following beneficial effects:
1. on the basis of the original process of pressing the potassium ion into a tablet to manufacture a battery, the water is introduced, the original crystal structure is changed after the water is introduced, potassium ions in the structure are rapidly moved by the introduced protons to change the original conduction mode, the intrinsic potassium ion conductivity is greatly improved, and the original potassium ion conductivity is changed from 10 -10 s cm -1 About 10 is lifted to -3 ～10 -5 s cm -1 The simple potassium ion diffusion coefficient is greatly improved from 10 -15 m 2 s -1 Lifting to 10 -9 m 2 s -1 The order of magnitude is such that it meets the application requirements; the potassium ion precipitate fills the grain boundary, so that the conductivity of the grain boundary is greatly improved;
2. in the solid-state battery assembling process, the positive electrode becomes hydrophilic carbon cloth and is pressed together with the solid electrolyte containing water, and the interface is connected by a small amount of potassium ion aqueous solution, so that the ion transportation at the three-phase interface is smooth.
Drawings
Fig. 1 is a graph showing the water absorption characteristics of the solid electrolyte prepared in the present invention.
Fig. 2 shows the structural changes before and after water absorption of the solid electrolyte prepared in the present invention.
Fig. 3 is a diagram showing the intrinsic ion transport state change of the present invention.
Fig. 4 is an ion diffusion coefficient of a solid electrolyte prepared in the present invention. In the figure, D is the diffusion coefficient, T is the temperature, ea is the ion transport activation energy.
FIG. 5 shows K in the present invention 2 Fe 4 O 7 The overall conductivity changes before and after the introduction of water.
FIG. 6 shows the change in conduction mode of ions at grain boundaries in the present invention.
FIG. 7 is a graph showing that the potassium-oxygen solid-state battery of the present invention was at 0.05mA cm -2 Is cycled at a current density of (c).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and examples; the examples set forth herein are intended to be illustrative of the invention and are not intended to limit the scope of the invention. Any obvious modifications or alterations to the invention, as would be apparent, are made without departing from the spirit and scope of the present invention.
Example 1
The manufacturing method of the solid-state potassium air battery comprises the following steps:
step 1: 0.2. 0.2g K to hydro-thermal Synthesis 2 Fe 4 O 7 Ball milling and drying the single crystal;
step 2: 5% PVA in water was prepared at 0.2. 0.2g K 2 Fe 4 O 7 Adding 0.04g of PVA solution prepared in the step 2 into the powder, adding a certain amount of water for dilution, stirring, and heating to completely dry;
step 3: the obtained PVA-containing K 2 Fe 4 O 7 Sieving, cold pressing and tabletting；
Step 4: slightly pressing the solid electrolyte sheet and the hydrophilic carbon cloth, and then placing the solid electrolyte sheet and the hydrophilic carbon cloth in a closed constant temperature and humidity box to balance different humidity, wherein the temperature is set to 25 ℃, the humidity is set to 50%, and the process lasts for 12 hours;
step 5: stacking and packaging metallic potassium, a GF/D diaphragm which is soaked with 100 mu L of 1.0M KPF6-DEGEME electrolyte, the component subjected to the step 4 humidity balancing and foam nickel between a positive shell and a negative shell to obtain a solid-state potassium air battery; wherein the positive electrode is a positive electrode with holes;
the stirring in the step 2 is carried out under the condition of the rotating speed of 300 r/min.
The number of the sieving meshes for sieving and granulating in the step 3 is 50.
The cell specification is 2025.
Example 2
The manufacturing method of the solid-state potassium air battery comprises the following steps:
step 1: 0.2. 0.2g K to hydro-thermal Synthesis 2 Fe 4 O 7 Ball milling and drying the single crystal;
step 2: 1% PVA in water was prepared at 0.15. 0.15g K 2 Fe 4 O 7 Adding 0.06g of PVA solution prepared in the step 2 into the powder, adding a certain amount of water for dilution, stirring, and heating to completely dry;
step 3: the obtained PVA-containing K 2 Fe 4 O 7 Sieving, and cold pressing to obtain tablets;
step 4: slightly pressing the solid electrolyte sheet and the hydrophilic carbon cloth, and then placing the solid electrolyte sheet and the hydrophilic carbon cloth in a closed constant temperature and humidity box to balance different humidity, wherein the temperature is set to 20 ℃, the humidity is set to 60%, and the process lasts for 12 hours;
step 5: the metallic potassium, the GF/D membrane soaked with 150 mu L of 0.8M KPF6-DEGEME electrolyte, the component after the equilibrium humidity in the step 4 and the foam nickel are stacked and packaged between the positive and negative electrode shells. Wherein the positive electrode is a hole-containing positive electrode.
The stirring in the step 2 is carried out under the condition of the rotating speed of 100 r/min.
The number of the sieving meshes for sieving and granulating in the step 3 is 60.
The cell specification is 2025.
Example 3
The manufacturing method of the solid-state potassium air battery comprises the following steps:
step 1: 0.25 to g K to hydro-thermal Synthesis 2 Fe 4 O 7 Ball milling and drying the single crystal;
step 2: 5% PVA in water was prepared at 0.25. 0.25g K 2 Fe 4 O 7 Adding 0.1g of PVA solution prepared in the step 2 into the powder, adding a certain amount of water for dilution, stirring, and heating to completely dry;
step 3: the obtained PVA-containing K 2 Fe 4 O 7 Sieving, and cold pressing to obtain tablets;
step 4: slightly pressing the solid electrolyte sheet and the hydrophilic carbon cloth, and then placing the solid electrolyte sheet and the hydrophilic carbon cloth in a closed constant temperature and humidity box to balance different humidity, wherein the temperature is set to 28 ℃, the humidity is set to 70%, and the process lasts for 12 hours;
step 5: stacking and packaging metallic potassium, a GF/D diaphragm which is soaked with 120 mu L of 1.0M KPF6-DEGEME electrolyte, the component subjected to the step 4 humidity balancing and foam nickel between a positive shell and a negative shell; thus, the solid-state potassium air battery is obtained, wherein the positive electrode is a hole-containing positive electrode.
The stirring in the step 2 is carried out under the condition of the rotating speed of 250 r/min.
The number of the sieving mesh of the sieving granulation in the step 3 is 70.
The cell specification is 2025.
Example 4
The manufacturing method of the solid-state potassium air battery comprises the following steps:
step 1: 0.3. 0.3g K to be hydrothermally synthesized 2 Fe 4 O 7 Ball milling and drying the single crystal;
step 2: 5% PVA in water was prepared at 0.3. 0.3g K 2 Fe 4 O 7 Adding 0.18g of PVA solution prepared in the step 2 into the powder, adding a certain amount of water for dilution, stirring, and heating to completely dry;
step 3: the obtained PVA-containing K 2 Fe 4 O 7 Sieving, and cold pressing to obtain tablets;
step 4: slightly pressing the solid electrolyte sheet and the hydrophilic carbon cloth, and then placing the solid electrolyte sheet and the hydrophilic carbon cloth in a closed constant temperature and humidity box to balance different humidity, wherein the temperature is set to 30 ℃, the humidity is set to 80%, and the process lasts for 12 hours;
step 5: stacking and packaging metallic potassium, a GF/D diaphragm which is soaked with 150 mu L of 1.0M KPF6-DEGEME electrolyte, the component subjected to the step 4 humidity balancing and foam nickel between positive and negative electrode shells to obtain a solid-state potassium air battery; wherein the positive electrode is a hole-containing positive electrode.
The cell specification is 2025.
The stirring in the step 2 is carried out under the condition of 150r/min of rotating speed.
The number of the sieving meshes for sieving and granulating in the step 3 is 80.
Example 5
The manufacturing method of the solid-state potassium air battery comprises the following steps:
step 1: 0.18. 0.18g K to hydro-thermal Synthesis 2 Fe 4 O 7 Ball milling and drying the single crystal;
step 2: 5% PVA in water was prepared at 0.18. 0.18g K 2 Fe 4 O 7 Adding 0.18g of PVA solution prepared in the step 2 into the powder, adding a certain amount of water for dilution, stirring, and heating to completely dry;
step 3: the obtained PVA-containing K 2 Fe 4 O 7 Sieving, and cold pressing to obtain tablets;
step 4: slightly pressing the solid electrolyte sheet and the hydrophilic carbon cloth, then placing the solid electrolyte sheet and the hydrophilic carbon cloth in a closed constant temperature and humidity box to balance different humidity, setting the temperature to 23 ℃, setting the humidity to 65%, and continuing the process for 12 hours;
step 5: stacking and packaging metallic potassium, a GF/D diaphragm which is soaked with 80 mu L of 1.0M KPF6-DEGEME electrolyte, the component subjected to the step 4 humidity balancing and foam nickel between a positive shell and a negative shell to obtain a solid-state potassium air battery; wherein the positive electrode is a hole-containing positive electrode.
The stirring in the step 2 is carried out under the condition of the rotating speed of 120 r/min.
The number of the sieving meshes for sieving and granulating in the step 3 is 50.
The cell specification is 2025.
Example 6
The manufacturing method of the solid-state potassium air battery comprises the following steps:
step 1: 0.15 to g K to hydro-thermal Synthesis 2 Fe 4 O 7 Ball milling and drying the single crystal;
step 2: 5% PVA aqueous solution was prepared at 0.15. 0.15g K 2 Fe 4 O 7 Adding 0.09g of PVA solution prepared in the step 2 into the powder, adding a certain amount of water for dilution, stirring, and heating to completely dry;
step 3: the obtained PVA-containing K 2 Fe 4 O 7 Sieving, and cold pressing to obtain tablets;
step 4: slightly pressing the solid electrolyte sheet and the hydrophilic carbon cloth, then placing the solid electrolyte sheet and the hydrophilic carbon cloth in a closed constant temperature and humidity box to balance different humidity, setting the temperature to 24 ℃, setting the humidity to 75%, and continuing the process for 12 hours;
step 5: stacking and packaging metallic potassium, a GF/D diaphragm which is soaked with 90 mu L of 1.0M KPF6-DEGEME electrolyte, the component subjected to the step 4 humidity balancing and foam nickel between a positive shell and a negative shell to obtain a solid-state potassium air battery; wherein the positive electrode is a hole-containing positive electrode.
The stirring in the step 2 is carried out under the condition of 180r/min of rotating speed.
The number of the sieving meshes for sieving and granulating in the step 3 is 80.
The cell specification is 2025.
Water absorbency is shown in FIG. 1
Structural modifications with reference to figure 2,
intrinsic ion transport State Change see FIG. 3
The intrinsic ion diffusion coefficient is significantly improved as shown in fig. 4, where D is the diffusion coefficient, T is the temperature, and Ea is the ion transport activation energy.
K 2 Fe 4 O 7 The overall resistance (including grain boundary resistance) is significantly reduced after the introduction of water, which changes the ion in the crystalIon transport mode at boundary
The total conductivity change before and after introduction of water is shown in FIG. 5
The change in conduction mode of ions at grain boundaries is shown in FIG. 6
The potassium-oxygen solid-state battery has better performance, and the performance is 0.05mA cm -2 The overpotential is only 0.1V at current density cycling, see fig. 7.
The foregoing is merely specific embodiments of the disclosure, but the protection scope of the disclosure is not limited thereto, and any person skilled in the art can easily think about changes or substitutions within the technical scope of the disclosure, and it is intended to cover the scope of the disclosure. Therefore, the protection scope of the present disclosure shall be subject to the protection scope of the claims.
Claims (5)
1. A method for manufacturing a solid-state potassium-air battery is characterized in that the method changes a crystal structure by introducing water so as to improve ion conductivity, and the method is used for manufacturing the solid-state potassium-oxygen battery, and comprises the following specific operation steps:
step 1: hydrothermally synthesizing K 2 Fe 4 O 7 Ball milling and drying the single crystal;
step 2: preparing PVA aqueous solution with concentration of 1% or 5%, and mixing with K 2 Fe 4 O 7 Adding PVA into the powder, diluting with water, stirring, and heating to completely dry;
step 3: the obtained PVA-containing K 2 Fe 4 O 7 Sieving and granulating, dividing into equal parts, and cold pressing to obtain solid electrolyte sheets;
step 4: slightly pressing the solid electrolyte sheet and the hydrophilic carbon cloth, and then placing the solid electrolyte sheet and the hydrophilic carbon cloth in a closed constant temperature and humidity box to balance different humidity, wherein the process lasts for more than 12 hours to obtain the solid electrolyte sheet and the hydrophilic carbon cloth after balancing the humidity;
step 5: stacking metal potassium, a double-layer GF/D diaphragm containing trace potassium ion electrolyte, a solid electrolyte sheet with balanced humidity, hydrophilic carbon cloth and foam nickel, and packaging the stacked metal potassium, the double-layer GF/D diaphragm containing trace potassium ion electrolyte and the foam nickel between positive and negative electrode shells to obtain the solid potassium air battery, wherein the positive electrode is one electrode containing holes;
the PVA amount required to be added into the aqueous solution in the step 2 is K 2 Fe 4 O 7 1% -5% of the amount.
2. The method for manufacturing a solid-state potassium-air battery according to claim 1, wherein the stirring in the step 2 is performed at a rotation speed of 100-300 r/min.
3. The method for manufacturing a solid-state potassium-air battery according to claim 1, wherein the number of the sieving meshes for sieving and granulating in the step 3 is 30-100.
4. The method according to claim 1, wherein the solid electrolyte sheet and the hydrophilic carbon cloth in the step 4 have a temperature of 20 to 30 ℃ and a humidity of 50 to 80% when they are balanced in a constant temperature and humidity chamber.
5. The method for manufacturing a solid-state potassium-air battery according to claim 4, wherein the concentration of the electrolyte containing a trace amount of potassium ions in the double layer is 0.5-1mol/L, and the volume is 80-150. Mu.L.
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| JP6845507B2 (en) * | 2015-12-07 | 2021-03-17 | 国立研究開発法人産業技術総合研究所 | Positive electrode active material for potassium ion secondary battery and its manufacturing method |
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| Title |
|---|
| K_2FeO_4-Zn碱性固态电解质电池电化学性能研究;王永龙;吴玉菊;薄晋科;叶世海;吴锋;宋德瑛;;化学学报(17);全文 * |
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