CN108400316B - Self-repairing oxide film coated Na-K liquid alloy electrode and preparation method and application thereof - Google Patents
Self-repairing oxide film coated Na-K liquid alloy electrode and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-efficiency self-repairing oxide film coated Na-K liquid alloy electrode, a preparation method thereof and application of the high-efficiency self-repairing oxide film coated Na-K liquid alloy electrode as a negative electrode, wherein K metal and Na metal are respectively heated until being melted under the protection of inert gas, then a conductive carrier is contacted with the metal, the melted metal slowly wets the conductive carrier, and the conductive carrier loaded with the K metal and the Na metal is respectively obtained after cooling to room temperature; the self-repairing oxide film coated Na-K liquid alloy electrode with a stable structure is prepared at room temperature by a physical stacking alloying method. The electrode comprises a conductive carrier, Na-K liquid alloy adsorbed on the carrier and a self-repairing oxide film on the surface. The electrode has the characteristics of high coulombic efficiency, no dendritic crystal growth, stable structure and the like, can be used as a potassium metal cathode and a sodium metal cathode simultaneously, and can obviously improve the energy density and the cycling stability of the whole battery when being matched with positive electrode materials such as sulfur, Prussian blue and the like.
Description
Technical Field
The invention relates to the technical field of alkali metal secondary battery cathode materials, in particular to a self-repairing oxide film coated Na-K liquid alloy electrode, a preparation method thereof and application of the self-repairing oxide film coated Na-K liquid alloy electrode as an alkali metal secondary battery cathode material.
Background
With the popularization of new energy automobiles and mobile electronic devices, the development of batteries with high specific capacity, high safety, long cycle life and low cost is urgently needed. The alkali metal secondary battery as a novel energy storage device has the characteristics of large storage capacity, low preparation cost, wide electrochemical window and the like, and has wide application prospect in the fields of mobile communication, electric automobiles, energy storage and the like. The alkali metal cathode has higher specific capacity compared with carbon materials, metal oxides and the like, but dendrites are easily generated in the use process of the alkali metal cathode, so that the short circuit of the battery is caused, and potential safety hazards are caused. The liquid alloy represented by Na-K alloy can completely inhibit the growth of dendrite, and becomes a new research direction of non-dendrite electrode materials. However, the Na-K liquid alloy has a large surface tension and is difficult to wet on the surface of the current collector, which seriously hinders the commercial application of the Na-K liquid alloy. Therefore, the research on the liquid metal electrode with stable structure at normal temperature has important significance for the application development of the alkali metal secondary battery.
Research shows that the Na-K liquid alloy is a high-performance dendrite-free electrode material with great development potential, and has the characteristics of low toxicity, wide stable temperature (existing in a liquid state at normal temperature even at-12.6 ℃) and the like. In order to obtain a Na-K liquid alloy electrode with stable structure, the following problems (as shown in figure 1) need to be solved: 1) the Na-K liquid alloy is difficult to form, the surface tension of the Na-K alloy is large, the Na-K alloy is difficult to wet on the surface of a current collector, and the Na-K liquid alloy has certain fluidity due to the liquid state and is difficult to form a fixed state; 2) the interface between the Na-K liquid alloy electrode and the electrolyte is unstable, the Na-K liquid alloy is easy to fall off from the surface of the electrode, free liquid metal is formed in the electrolyte, the stable interface between the Na-K liquid alloy electrode and the electrolyte is difficult to maintain, and voltage fluctuation in the battery circulation process is caused.
Research shows that the wettability of Na-K liquid alloy on carbon paper can be improved by high-temperature treatment (>420 ℃), and meanwhile, more Na-K liquid alloy can be captured by the porous structure substrate, so that the problem of the fluidity of the Na-K liquid alloy is solved. However, at room temperature, the surface tension of the Na-K liquid alloy is recovered, so that the exposed Na-K liquid alloy on the surface of the composite electrode falls off, and the problem of interface stability cannot be essentially solved by the Na-K liquid alloy loaded on the simple carbon carrier.
At present, research on the interface between a stable Na-K liquid alloy electrode and electrolyte is not provided at home and abroad, and no solution strategy is provided for the Na-K liquid alloy shuttling problem at home and abroad. Therefore, the construction of a stable electrode and electrolyte interface is a key problem to be continuously solved by the large-scale application of the Na-K liquid alloy cathode.
Disclosure of Invention
Aiming at the problems in the background art, the invention aims to provide a high-efficiency self-repairing oxide film coated Na-K liquid alloy electrode, a preparation method thereof and application of the high-efficiency self-repairing oxide film coated Na-K liquid alloy electrode as a negative electrode material of an alkali metal secondary battery.
A preparation method of a high-efficiency self-repairing oxide film coated Na-K liquid alloy electrode comprises the following steps:
1) under the protection of inert gas, heating the K metal until the K metal is molten, then contacting the conductive carrier with the molten K metal, slowly wetting the conductive carrier by the molten K metal, and cooling after the K metal is completely absorbed to obtain the conductive carrier loaded with the K metal;
under the protection of inert gas, heating the Na metal until the Na metal is molten, then contacting the conductive carrier with the molten Na metal, slowly wetting the conductive carrier by the molten Na metal, and cooling after the Na metal is completely absorbed to obtain the Na metal-loaded conductive carrier;
2) under the protection of inert gas, physically stacking the conductive carrier loaded with the K metal and the conductive carrier loaded with the Na metal, which are prepared in the step 1), so that alloying reaction of the K metal and the Na metal occurs, and an oxide film is generated at the same time, so that a self-repairing oxide film coated Na-K liquid alloy electrode is obtained;
or soaking the K metal-loaded conductive carrier and the Na metal-loaded conductive carrier prepared in the step 1) in electrolyte, stacking, carrying out alloying reaction, and simultaneously generating a self-repairing oxide film to obtain the Na-K liquid alloy electrode coated with the self-repairing oxide film.
In the step 1), the conductive carrier can be conductive carriers of various dimensions, such as films, blocks, powder and the like from the structural angle, and can be polymers, metals, metal oxides, metal organic frameworks, carbon materials and the like from the material angle. Preferably a two-dimensional thin film conductive support of a certain thickness, most preferably a two-dimensional thin film carbon material of a certain thickness and area.
The carbon material can be quantum dots, carbon tubes, multi-walled carbon tubes, carbon fibers, graphene rolls, carbon arrays, vertical graphene, carbon cloth, mesoporous carbon, hollow spheres, multi-layer hollow spheres, nanoflowers, biomass carbon materials and the like. The conductive carrier material can be a composite of a plurality of materials. The carbon material may be hard carbon or soft carbon.
Further preferably, the conductive carrier is carbon cloth.
The thickness of the conductive carrier is 0.1mm to 10mm, more preferably 0.5mm to 5mm, and most preferably 1mm to 2 mm.
The area of the conductive carrier is 0.1cm2～10cm2More preferably 0.2cm2～2cm2Most preferably 0.5cm2～1.5cm2The length and width of the material is not limited, and a square or a circle is preferable.
In the step 1), the K metal is 0.001gcm calculated according to the area of the conductive carrier-2～10gcm-2More preferably 0.01 g/cm-2～5g·cm-2Most preferably 0.05 g.cm-2～0.2g·cm-2The mass of Na metal is calculated according to a certain proportion relative to the mass of K metal.
The Na metal is 0.00028 g-cm calculated according to the area of the conductive carrier-2～2.8g·cm-2More preferably 0.0028 g/cm-2～1.4g·cm-2Most preferably 0.014g cm-2～0.056g·cm-2。
The amount of K and Na is in a certain proportion, and the mass ratio of K metal to Na metal is 70-86: 14 to 30, more preferably 75 to 81: 19 to 25, more preferably 77 to 79: 21 to 23.
The K metal and the Na metal are pure K and pure Na.
The K metal and the Na metal need to be cut to remove surface oxides before use.
In the step 1), heating the K metal to 300-500 ℃, and most preferably to 350-450 ℃;
the Na metal is heated to a temperature of 300 ℃ to 500 ℃, most preferably 350 ℃ to 450 ℃.
In the step 2), the obtained composite electrode can be soaked in electrolyte to obtain a self-repairing oxide film containing new components.
The self-repairing oxidation film is mainly wrapped on the surface of the electrode in a film form.
The solute of the electrolyte is KPF6、KClO4、KTFSI、NaPF6、NaClO4One or more mixed electrolytes such as NaTFSI; the solvent is Ethylene Carbonate (EC), DEC, dimethyl carbonate (DMC), DIGOne or more of LYM, PC, etc., and various additives, such as F-containing additives, etc. More preferably, the solute in the electrolyte is mixed in a molar ratio of 1: KPF of 16And NaPF6And the solute solvent in the electrolyte is prepared from the following components in a volume ratio of 1: 1 solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC), KPF6And NaPF6The concentration in the electrolyte is 0.5mol/L to 3mol/L, and more preferably 1 mol/L.
The new components are KF and NaF with high ionic conductivity.
In the step 2), the Na-K alloy is completely absorbed in the conductive carrier.
The self-repairing oxide film can be automatically repaired after being mechanically damaged.
The mechanical damage is mainly film removal, cracking, crushing due to extrusion, and the like.
In the step 1) and the step 2), the content of nitrogen or oxygen in the inert gas can be adjusted to obtain the self-repairing oxide film with different components.
The inert gas is argon, preferably high-purity argon. The water content is less than 0.1ppm in the inert gas filled environment.
The content of the nitrogen or oxygen is 0.1ppm to 100ppm, more preferably 0.1ppm to 10ppm, and most preferably 0.1ppm to 0.5ppm, wherein the content of the nitrogen and the oxygen are independently adjusted and do not need to be in a fixed ratio.
The Na-K alloy in the obtained Na-K alloy composite electrode is liquid at normal temperature, the surface oxide film is solid, the dendritic crystal growth condition does not exist, and the Na-K alloy composite electrode can be used as a K ion battery negative electrode material and a Na ion battery negative electrode material at the same time.
The self-repairing oxide film coated Na-K liquid alloy electrode comprises a conductive carrier, Na-K liquid alloy deposited on the conductive carrier and a self-repairing oxide film formed on the surface, namely the self-repairing oxide film comprises the conductive carrier, the Na-K liquid alloy adsorbed on the conductive carrier and the self-repairing oxide film on the surface
The self-repairing oxide film coated Na-K liquid alloy electrode is applied as a negative electrode material of an alkali metal secondary battery.
Compared with the prior art, the invention has the following advantages and outstanding effects:
the invention aims to prepare a dendrite-free liquid alloy cathode electrode with a stable structure. The invention has the following two advantages: the invention provides a novel electrode structure, wherein the Na-K alloy composite electrode comprises a conductive substrate, Na-K alloy deposited on a conductive carrier and a self-repairing oxidation film formed on the surface, and the structure can increase the structural stability of the electrode structure, enhance the conductivity and improve the high power performance and the coulombic efficiency; the preparation method is convenient, the conventional preparation method needs to heat the Na-K liquid alloy at high temperature, and has certain danger, and the self-repairing oxide film coated Na-K liquid alloy electrode can be obtained at normal temperature through a simple physical superposition mode. The composite cathode improves the safety performance and the cycle performance of alkali metal, and is beneficial to promoting the development of alkali metal secondary batteries with high energy density and high stability.
The high-efficiency self-repairing oxide film coated Na-K liquid alloy electrode has the characteristics of high coulombic efficiency, no dendritic crystal growth, stable structure and the like, can be used as a potassium metal cathode and a sodium metal cathode simultaneously, and can be matched with positive electrode materials such as sulfur, Prussian blue and the like, so that the energy density and the cycling stability of the whole battery are remarkably improved.
Drawings
FIG. 1 is a diagram of the present invention;
FIG. 2 is a schematic diagram of a carbon cloth loaded Na-K alloy/oxide film composite electrode;
FIG. 3 is an XRD diffraction pattern of the surface of the self-repairing oxide film coated Na-K liquid alloy electrode prepared in example 1;
FIG. 4 is a graph of the self-repairing oxide film coated Na-K liquid alloy electrode prepared in example 1 under different multiplying power after being assembled into a symmetrical electrode.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
Example 1
0.1g K metal and 0.028g Na metal were heated to 450 ℃ and melted in a glove box, and a carbon cloth (thickness: 2mm) having a length and width of 1cm was brought into contact with the two molten metals with tweezers, and after the two molten metals were completely absorbed, the mixture was cooled to 25 ℃. Stacking the carbon cloth loaded with K metal and Na metal respectively, carrying out alloying reaction on the two metals on the surface of the carbon cloth, forming a self-repairing oxide film on the surface, and reacting for a period of time to form a Na-K liquid alloy electrode coated with the self-repairing oxide film.
The XRD diffractogram of the surface of the self-repairing oxide film coated Na-K liquid alloy electrode prepared in example 1 is shown in FIG. 3. As shown, the prepared electrode had no characteristic peaks for Na metal and K metal, indicating that the alloy formed was a liquid Na — K alloy. While finding faint KO2And K2The peak of O indicates that the Na-K alloy surface has a solid oxide film and the main component is KO2And K2O。
Example 2
The oxygen content in the glove box was adjusted to 0.2ppm and the nitrogen content to 0.1 ppm. 0.2g K metal and 0.056g Na metal are respectively heated to 400 ℃ in a glove box to be melted, then a carbon cloth (with the thickness of 2mm) with the length and the width of 1cm is respectively contacted with the two molten metals by tweezers, and after the two molten metals are completely absorbed, the mixture is taken out and cooled to the room temperature of 25 ℃. Stacking the carbon cloth loaded with K metal and Na metal respectively, carrying out alloying reaction on the two metals on the surface of the carbon cloth, forming a self-repairing oxide film on the surface, and reacting for a period of time to form a Na-K liquid alloy electrode coated with the self-repairing oxide film.
The XRD diffractogram of the electrode obtained was similar to that of example 1, and moreover a small amount of KN was found3Peak of (2).
Example 3
0.2g K metal and 0.056g Na metal are respectively heated to 400 ℃ in a glove box to be melted, then a carbon cloth (with the thickness of 2mm) with the length and the width of 1cm is respectively contacted with the two molten metals by tweezers, and after the two molten metals are completely absorbed, the mixture is taken out and cooled to the room temperature of 25 ℃. Carbon cloths loaded with K metal and Na metal respectively are immersed in the electrolyte (solute is KPF with the molar ratio of 1: 16And NaPF6(ii) a The organic solvent isThe volume ratio of 1: 1 solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC), KPF6And NaPF6The concentration of the electrolyte is 1mol/L), and the two metals are stacked, the alloying reaction is carried out on the two metals on the surface of the carbon cloth, a self-repairing oxide film with new components is formed on the surface, and after the reaction for a period of time, the Na-K liquid alloy electrode coated by the self-repairing oxide film is formed.
The XRD diffraction pattern of the obtained electrode was similar to that of example 1, and further, a small amount of a peak of KF was found.
Performance testing
The N self-repairing oxide film coated Na-K liquid alloy electrodes prepared in the embodiments 1 to 3 are respectively used as a counter electrode and a working electrode of a button cell, and the electrolyte is 1M KPF6(or 1M NaPF6) In the electrolyte, the current density was 1mA cm-2The circulating electric quantity is 1mAh cm-2And measuring the overpotential of the K (or Na) metal negative electrode in the symmetrical electrode system in an environment of 25 +/-1 ℃.
The performance test results are as follows:
the Na-K alloy composite electrodes of examples 1, 2 and 3 were each at 1mA · cm-2The current density is circulated for 200 times, the overvoltage can be stabilized within 22mV, 19mV and 17mV respectively, the voltage platform is stable without obvious fluctuation, and the potential fluctuation of the Na-K liquid alloy composite electrode without an oxide film is severe. In addition, the coulombic efficiency of 100 electrode cycles can be maintained above 97.9%, 98.5% and 99.2%, respectively. Therefore, the prepared Na-K alloy composite electrode is low in overvoltage, good in circulation stability and high in coulombic efficiency. The graph of the self-repairing oxide film coated Na-K liquid alloy electrode prepared in example 1 under different multiplying powers after being assembled into a symmetrical electrode is shown in FIG. 4.
The self-repairing oxide film provides a stable interface for the Na-K alloy, and the Na-K alloy in a liquid state at normal temperature avoids dendritic crystals, so that the stability of the electrode structure is ensured.
Therefore, the high-efficiency self-repairing oxide film coated Na-K liquid alloy electrode has the characteristics of high coulombic efficiency, obvious inhibition of dendritic crystal growth, stable interface structure and the like, has good guiding significance on metal negative electrode modification of the alkali metal secondary battery, and is beneficial to large-scale application of the alkali metal negative electrode without dendritic crystals.
Claims (10)
1. A preparation method of a self-repairing oxide film coated Na-K liquid alloy electrode is characterized by comprising the following steps:
1) under the protection of inert gas, heating the K metal until the K metal is molten, then contacting the conductive carrier with the molten K metal, slowly wetting the conductive carrier by the molten K metal, and cooling after the K metal is completely absorbed to obtain the conductive carrier loaded with the K metal;
under the protection of inert gas, heating the Na metal until the Na metal is molten, then contacting the conductive carrier with the molten Na metal, slowly wetting the conductive carrier by the molten Na metal, and cooling after the Na metal is completely absorbed to obtain the Na metal-loaded conductive carrier;
2) under the protection of inert gas, adjusting the content of nitrogen or oxygen in the inert gas, physically stacking the conductive carrier loaded with K metal and the conductive carrier loaded with Na metal prepared in the step 1), carrying out alloying reaction on the K metal and the Na metal, and simultaneously generating an oxide film to obtain a self-repairing oxide film coated Na-K liquid alloy electrode;
or, 2) soaking the K metal-loaded conductive carrier and the Na metal-loaded conductive carrier prepared in the step 1) in electrolyte, stacking, carrying out alloying reaction, and simultaneously generating a self-repairing oxide film to obtain the Na-K liquid alloy electrode coated with the self-repairing oxide film.
2. The method according to claim 1, wherein in step 1), the K metal is heated to a temperature of 300 ℃ to 500 ℃;
heating Na metal to 300-500 ℃.
3. The method according to claim 1, wherein in step 1), the conductive carrier is a carbon cloth.
4. The method according to claim 1, wherein in step 1), the thickness of the conductive carrier is 0.5mm to 5 mm;
the area of the conductive carrier is 0.2cm2～2cm2。
5. The method according to claim 1, wherein the K metal in step 1) is 0.01 g-cm calculated on the area of the conductive support-2～5g·cm-2；
The Na metal is 0.0028 g-cm calculated according to the area of the conductive carrier-2～1.4g·cm-2。
6. The preparation method according to claim 1, wherein in the step 1), the mass ratio of the K metal to the Na metal is 70-86: 14 to 30.
7. The preparation method according to claim 1, wherein in the step 2), the solute in the electrolyte is dissolved in a molar ratio of 1: KPF of 16And NaPF6And the solute solvent in the electrolyte is prepared from the following components in a volume ratio of 1: 1 solution of ethylene carbonate and dimethyl carbonate, KPF6And NaPF6The concentration of the electrolyte is 0.5-3 mol/L.
8. The self-repairing oxide film coated Na-K liquid alloy electrode prepared by the preparation method of any one of claims 1 to 7.
9. The self-repairing oxide film coated Na-K liquid alloy electrode of claim 8, comprising a conductive carrier, a Na-K liquid alloy deposited on the conductive carrier, and a self-repairing oxide film formed on the surface.
10. The application of the self-repairing oxide film coated Na-K liquid alloy electrode as a negative electrode material of an alkali metal secondary battery according to claim 8.
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| CN109244441B (en) * | 2018-08-29 | 2020-06-05 | 浙江大学 | non-Newtonian fluid Na-K alloy electrode and preparation method and application thereof |
| CN109273672B (en) * | 2018-08-29 | 2020-12-01 | 浙江大学 | Na-K liquid alloy electrode coated with in-situ SEI film as well as preparation method and application thereof |
| CN109244323B (en) * | 2018-09-17 | 2020-08-18 | 浙江大学 | Preparation method and application of low-cost alkali metal battery diaphragm |
| CN110649227A (en) * | 2019-09-18 | 2020-01-03 | 天津大学 | Three-dimensional composite potassium metal cathode and preparation method and application thereof |
| CN113113593A (en) * | 2021-02-26 | 2021-07-13 | 华北理工大学 | Room temperature solid sodium ion battery based on liquid alloy |
| CN113258035B (en) * | 2021-05-12 | 2022-05-17 | 哈尔滨工业大学 | Dendrite-free alloy cathode with solid-liquid phase conversion mechanism and preparation method thereof |
| CN113745464B (en) * | 2021-07-13 | 2022-09-27 | 南京工业大学 | Preparation and application of liquid sodium-potassium alloy @ flexible hollow carbon paper electrode |
| CN114094042A (en) * | 2021-11-10 | 2022-02-25 | 惠州亿纬锂能股份有限公司 | Liquid metal negative pole piece and preparation method and application thereof |
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