CN113224313A - Metal organic phosphine frame glass modified metal negative current collector and preparation method thereof - Google Patents
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Abstract
The invention discloses an alkali metal negative current collector modified by a metal organic phosphine frame glass coating and a preparation method thereof, belonging to the technical field of lithium and sodium metal secondary batteries. According to the invention, the metal organic phosphine frame material is coated on the surface of the current collector, and the frame material is melted on the surface of the current collector through simple heating treatment, so that a uniform, continuous and compact metal organic phosphine frame glass coating is formed on the surface of the current collector. The metal organic phosphine framework glass coating inherits the porous structure of the precursor and has the characteristic of isotropy, and can induce alkali metal ions to be uniformly electroplated, so that the growth of dendritic crystals is inhibited. In addition, the metal organic phosphine frame glass coating is used as a protective layer, so that the direct contact between the electrode and the electrolyte can be prevented, and the excessive consumption of the electrolyte is avoided.
Description
Technical Field
The invention relates to the technical field of lithium and sodium metal secondary batteries, in particular to a metal negative current collector modified by a metal organic phosphine frame glass material coating and a preparation method thereof.
Background
With the development of portable electronic devices and electric vehicles, rechargeable batteries with high energy density are urgently required, and alkali metal batteries have received wide attention. Lithium metal cathodes and sodium metal cathodes have higher theoretical capacities, low redox potentials, making them the most ideal cathode materials for next generation energy storage systems. However, both lithium and sodium metal negative electrodes have very high reactivity and are easily reacted with an electrolyte to generate an unstable Solid Electrolyte (SEI) layer. The fragile SEI layer can cause uneven electroplating/stripping of lithium and sodium metals to form metal dendrites, the generation of the dendrites can cause the problems of low coulombic efficiency, dead lithium, dead sodium, capacity attenuation and the like, and the fragile SEI layer can also puncture a diaphragm to cause short circuit of a battery, thereby generating potential safety hazards. Dendrite growth has been the biggest challenge facing lithium and sodium metal negative electrodes, greatly impeding the commercial development of metal secondary batteries.
The current method for solving dendritic crystal growth mainly comprises the following steps: electrolyte optimization, solid electrolyte, artificial SEI layer, current collector and interface engineering and the like. The current collector and interface engineering is a method for directly modifying or modifying the surface of the existing commercial copper or aluminum current collector by using coatings of lithium and sodium-philic organic molecules, metal particles, inorganic ceramics and the like, so as to improve the surface affinity of the current collector. The method has the advantages of simplicity, effectiveness and easy commercial application. The modified current collector is suitable for uniform electroplating/stripping of lithium and sodium, realizes a stable alkali metal cathode structure, can control the electroplating amount of the lithium and sodium metal, and plays a role in saving lithium and sodium metal resources to a certain extent. However, it is a technical difficulty how to design a continuous modified coating on the surface of the current collector, which is easy to induce uniform electroplating of alkali metal ions.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a current collector modified by a metal organic phosphine frame glass coating and a preparation method thereof. The metal organic phosphine frame glass coating enhances the affinity of the current collector to lithium and sodium, inhibits the growth of lithium and sodium metal dendrites, and improves the coulombic efficiency and the cycle life. The preparation method specifically comprises the following steps:
the method comprises the following steps: weighing the organic phosphine ligand and the metal salt according to the molar ratio of 1: 0.1-1: 5, dissolving the organic phosphine ligand and the metal salt in a solvent, mixing the two solutions at room temperature for coordination reaction, filtering or centrifuging after reacting for 0-48 hours, washing unreacted raw materials by using the solvent, and drying to obtain the metal organic phosphine framework material.
Step two: and (3) uniformly coating the metal organic phosphine frame material obtained in the step one on the surface of a current collector, then heating the coated current collector to 100-600 ℃ in an inert atmosphere, preserving heat for 0-5 hours, and naturally cooling to room temperature to obtain the metal organic phosphine frame glass modified current collector.
The further preferable scheme of the invention is as follows:
in the first step, the selected metal salt is one of cobalt salt, copper salt, iron salt, nickel salt, cadmium salt, tin salt, vanadium salt, molybdenum salt, bismuth salt, zinc salt, silver salt, chromium salt, manganese salt, palladium salt and platinum salt.
In the first step, the organic phosphine ligand is selected from 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1,3, 5-triaza-7-phosphaadamantane, tri (p-tolyl) phosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, diphenyl-2-pyridylphosphine, tricyclohexylphosphine, tris (pentafluorophenyl) phosphine, diphenylphosphine, (S) - (-) -2,2' -bis (diphenylphosphino) -1,1' -binaphthyl, 2-di-t-butylphosphine-2 ' - (N, N-dimethylamino) biphenyl, 2' -bis (diphenylphosphino) -1,1' -binaphthyl, 2-diphenylphosphine-6-methylpyridine, One of tris (4-methoxyphenyl) phosphine, phenyldichlorophosphine, 1, 3-bis (dicyclohexylphosphine) propane, tris (2-furyl) phosphine, and tris (1-naphthyl) phosphine.
In the first step, the selected solvent is one of acetone, ethanol, deionized water, methanol, ethylene glycol, dichloromethane, carbon tetrachloride and ammonia water.
In the second step, the selected current collector is a copper current collector or an aluminum current collector.
In the second step, the selected inert atmosphere is nitrogen or argon.
The method for modifying the current collector is applied to a battery system taking lithium metal or sodium metal as a negative electrode, and comprises the following steps: lithium metal batteries, sodium metal batteries, lithium sulfur batteries, sodium sulfur batteries, lithium air batteries, sodium air battery systems.
The invention has the advantages that (1) the metal organic phosphine frame material is used as a precursor, and is melted on the surface of the current collector through simple heating treatment and is changed into a glass state from a crystalline state, so that a uniform, continuous and compact metal organic phosphine frame glass coating is formed on the surface of the current collector. (2) The metal organic phosphine frame glass coating inherits the porous structure of the precursor, has isotropic glass state, can enhance the strength of an SEI film and induce alkali metal ions to be uniformly electroplated, so that the metal organic phosphine frame glass material is used as a protective layer to modify a copper current collector for a lithium metal cathode and a sodium metal cathode, can effectively improve the problems of dendrites and the like, can prevent the direct contact of an electrode and electrolyte to avoid the excessive consumption of the electrolyte, thereby improving the coulombic efficiency, and is easy to realize commercial application. (3) The metal organic phosphine frame glass material has the advantages of multiple used raw materials, low price, simple preparation process, direct coating on the surface of a current collector, and easy realization of large-scale production, and can form a uniform coating by melting.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of the melting change of a 1, 2-bis (diphenylphosphino) ethane/cobalt chloride framework material.
FIG. 2 is an X-ray diffraction pattern of 1, 2-bis (diphenylphosphino) ethane/cobalt chloride framework material and the resultant glass coating after melting.
FIG. 3 is SEM photographs of a copper current collector before and after melting of a 1, 2-bis (diphenylphosphino) ethane/cobalt chloride framework material to form a glass-modified copper current collector.
Fig. 4 is an SEM photograph of sodium metal plating on the surface of the copper current collector before and after modification.
FIG. 5 is a diagram showing the cycle efficiency of a battery assembled from a copper current collector modified with a metal organic phosphine frame glass coating and an unmodified copper current collector, wherein (a) is a current density of 1.0mA cm-2The surface current capacity is 1.0mA h cm-2Coulombic efficiency of the cell in (b) is a current density of 1.0mA cm-2The surface current capacity is 2.0mA h cm-2Coulombic efficiency of the cell in (c) is a current density of 2.0mA cm-2The surface current capacity is 2.0mA h cm-2Time symmetric battery charge and discharge curves.
Detailed Description
The invention is described in detail below with reference to the following figures and examples:
example 1
1) 5.0g of 1, 2-bis (diphenylphosphino) ethane was dissolved in 500mL of acetone, and 3.0g of cobalt chloride hexahydrate (CoCl)2·6H2O) is dissolved in 150mL of acetone, then a metal salt solution is added into an organic phosphine solution for coordination reaction, after 24 hours of reaction, the obtained coordination framework material is subjected to suction filtration and separation, and is washed three times by using acetone. And (3) placing the obtained product in a vacuum drying oven, and heating and drying at the temperature of 80 ℃ to obtain the metal organic phosphine framework material.
2) And (3) uniformly coating the sample obtained in the step on the surface of a copper current collector, heating to 300 ℃ at a heating rate of 1.0 ℃/min under the protection of nitrogen, and preserving heat for 2 h. And finally, naturally cooling to room temperature to obtain the copper current collector modified by the metal organic phosphine frame glass coating.
As shown in the figure 1 of a scanning electron microscope, the 1, 2-bis (diphenylphosphino) ethane/cobalt chloride framework material is melted through heat treatment and gradually melted from a micron-sized cuboid structure to form a glass coating. The transition of the sample from the crystalline state to the glassy material of amorphous structure can be seen as shown in the X-ray diffraction diagram of figure 2. As shown in the scanning electron micrograph of figure 3, the metal organic phosphine frame glass coating is uniformly coated on the surface of the copper current collector.
The copper current collector modified with the metal organic phosphine frame glass coating prepared in example 1 and the copper current collector without modification were used as sodium metal negative current collectors respectively for sodium electroplating behavior test. As shown in fig. 4, SEM images show that sodium metal is uniformly, smoothly and densely plated on the surface of the copper current collector modified by the metal organic phosphine frame glass coating, and no dendrite growth occurs, while sodium metal is not uniformly plated on the copper current collector without modification, and a large number of dendrites are formed. And assembling the copper current collector modified by the metal organic phosphine frame glass coating and the unmodified copper current collector into a battery for electrochemical test.As shown in FIG. 5, at a current density of 1.0mA cm-2The surface current capacity is 1.0mA h cm-2And a current density of 1.0mA cm-2The surface current capacity is 2.0mA h cm-2Under the condition, the modified copper current collector half-cell can stably circulate for more than 700 times, and the coulomb efficiency is kept at 99.8%. The modified electrode is assembled into a symmetrical battery with the current density of 2.0mA cm-2The surface current capacity is 2.0mA h cm-2Can be stably circulated for 3000 hours under the condition.
Example 2
The operation method is the same as that of the embodiment 1, except that the obtained copper current collector modified by the metal organic phosphorus frame glass coating is used for a lithium metal negative electrode current collector, so that the growth of lithium dendrite can be effectively inhibited.
Example 3
The operation method is the same as that of the embodiment 1, except that the sample is uniformly coated on the surface of the aluminum current collector, and the obtained aluminum current collector modified by the metal organic phosphine framework glass coating can effectively inhibit the growth of dendrites when used for lithium and sodium metal negative current collectors.
Example 4
1) 10.0g of 1,3, 5-triaza-7-phosphaadamantane was dissolved in 500ml of absolute ethanol, and 5.00g of copper nitrate trihydrate (Cu (NO)3)2·3H2O) is dissolved in 300ml of absolute ethyl alcohol, then a metal salt solution is added into an organic phosphine solution for coordination reaction, and after the reaction is carried out for 0.5 hour, the obtained coordination framework material is subjected to suction filtration and separation and is washed by the absolute ethyl alcohol. And heating and drying the obtained product in a vacuum drying oven at the temperature of 80 ℃ to prepare the 1,3, 5-triaza-7-phospha adamantane/copper nitrate framework material.
2) And then placing the sample on the surface of a copper current collector, heating to 150 ℃ at the heating rate of 2.0 ℃/min under the protection of nitrogen, and naturally cooling to room temperature to obtain the copper current collector modified by the 1,3, 5-triaza-7-phospha adamantane/copper nitrate frame glass coating.
Example 5
1) 10.0g of 1,3, 5-triaza-7-phosphaadamantane was dissolved in 500ml of absolute ethanol, and 3.4g of cobalt chloride hexahydrate (CoCl)2·6H2O) is dissolved in 250ml of absolute ethyl alcohol, then the metal salt solution is dripped into the organic phosphine solution for coordination reaction, after the reaction is carried out for 1 hour, the obtained coordination framework material is filtered and separated, and is washed by the absolute ethyl alcohol. And heating and drying the obtained product in a vacuum drying oven at the temperature of 80 ℃ to prepare the 1,3, 5-triaza-7-phospha adamantane/cobalt chloride framework material.
2) And then placing the sample on the surface of a copper current collector, heating to 200 ℃ at the heating rate of 1.0 ℃/min under the protection of nitrogen, and naturally cooling to room temperature to obtain the copper current collector modified by the 1,3, 5-triaza-7-phospha adamantane/cobalt chloride frame glass coating.
Example 6
1) 10.0g of 1, 3-bis (diphenylphosphino) propane was dissolved in 500mL of methanol, and 3.0g of iron chloride tetrahydrate (FeCl)2·4H2O) is dissolved in 200mL of methanol, then the metal salt solution is dripped into the organic phosphine solution for coordination reaction, and after the reaction is carried out for 0.5 hour, the obtained coordination framework material is filtered and separated, and is washed by methanol. And (3) drying the obtained product in an oven at the temperature of 80 ℃. Preparing the 1, 3-bis (diphenylphosphino) propane/ferrous chloride framework material.
2) And then placing the sample on the surface of a copper current collector, heating to 500 ℃ at the heating rate of 2.0 ℃/min in the nitrogen atmosphere, and naturally cooling to room temperature to obtain the copper current collector modified by the 1, 3-bis (diphenylphosphine) propane/ferrous chloride frame glass coating.
Example 7
1) 10.0g of 1, 3-bis (diphenylphosphino) propane was dissolved in 500mL of methanol, and 3.2g of nickel chloride hexahydrate (NiCl)2·6H2O) is dissolved in 200mL of methanol and is completely dissolved under the stirring speed of 400r/min, then the metal salt solution is dripped into the organic phosphine solution for coordination reaction, the obtained coordination framework material is filtered and separated after 24 hours of reaction, and the methanol is used for washing. And (3) drying the obtained product in an oven at the temperature of 60 ℃. Preparing the 1, 3-bis (diphenylphosphino) propane/nickel chloride framework material.
2) And then placing the sample on the surface of a copper current collector, heating to 450 ℃ at the heating rate of 0.5 ℃/min in the nitrogen atmosphere, and naturally cooling to room temperature to obtain the copper current collector modified by the 1, 3-bis (diphenylphosphine) propane/nickel chloride frame glass coating.
Example 8
1) 10.0g of diphenyl-2-pyridylphosphine were dissolved in 300mL of deionized water, and 3.5g of zinc chloride (ZnCl)2) Dissolving in 150mL deionized water, completely dissolving at the stirring speed of 300r/min, then slowly dropwise adding a metal salt solution into an organic phosphine solution for coordination reaction, carrying out suction filtration and separation on the obtained coordination framework material after reacting for 36 hours, and washing with deionized water. And (3) drying the obtained product in an oven at the temperature of 60 ℃ to prepare the diphenyl-2-pyridylphosphine/zinc chloride framework material.
2) And then placing the sample on the surface of a copper current collector, heating to 350 ℃ at the heating rate of 0.5 ℃/min in the nitrogen atmosphere, and naturally cooling to room temperature to obtain the copper current collector modified by the diphenyl-2-pyridylphosphine/zinc chloride frame glass coating.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A preparation method of a metal negative current collector modified by metal organic phosphine framework glass is characterized by comprising the following steps:
the method comprises the following steps: weighing an organic phosphine ligand and a metal salt according to a molar ratio of 1: 0.1-1: 5, dissolving the organic phosphine ligand and the metal salt in a solvent, mixing the two solutions at room temperature to perform a coordination reaction, filtering or centrifuging after the reaction is performed for 0-48 hours, washing unreacted raw materials by using the solvent, and drying to obtain a metal organic phosphine framework material;
step two: and (3) uniformly coating the metal organic phosphine frame material obtained in the step one on the surface of a current collector, then heating the coated current collector to 100-600 ℃ in an inert atmosphere, preserving heat for 0-5 hours, and naturally cooling to room temperature to obtain the current collector modified by the metal organic phosphine frame glass coating.
2. The method for preparing a metal negative electrode current collector modified by metal organic phosphine framework glass as defined in claim 1, wherein the method comprises the following steps: in the first step, the metal salt is one of cobalt salt, copper salt, iron salt, nickel salt, cadmium salt, tin salt, vanadium salt, molybdenum salt, bismuth salt, zinc salt, silver salt, chromium salt, manganese salt, palladium salt and platinum salt.
3. The method for preparing a metal negative electrode current collector modified by metal organic phosphine framework glass as defined in claim 1, wherein the method comprises the following steps: in the first step, the organic phosphine ligand is 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1,3, 5-triaza-7-phosphaadamantane, tri (p-tolyl) phosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, diphenyl-2-pyridylphosphine, tricyclohexylphosphine, tris (pentafluorophenyl) phosphine, diphenylphosphine, (S) - (-) -2,2' -bis (diphenylphosphino) -1,1' -binaphthyl, 2-di-t-butylphosphine-2 ' - (N, N-dimethylamino) biphenyl, 2' -bis (diphenylphosphino) -1,1' -binaphthyl, 2-diphenylphosphine-6-methylpyridine, One of tris (4-methoxyphenyl) phosphine, phenyldichlorophosphine, 1, 3-bis (dicyclohexylphosphine) propane, tris (2-furyl) phosphine, and tris (1-naphthyl) phosphine.
4. The method for preparing a metal negative electrode current collector modified by metal organic phosphine framework glass as defined in claim 1, wherein the method comprises the following steps: in the first step, the solvent is one of acetone, ethanol, deionized water, methanol, ethylene glycol, dichloromethane, carbon tetrachloride and ammonia water.
5. The method for preparing a metal negative electrode current collector modified by metal organic phosphine framework glass as defined in claim 1, wherein the method comprises the following steps: in the second step, the current collectors are copper current collectors and aluminum current collectors.
6. The method for preparing a metal negative electrode current collector modified by metal organic phosphine framework glass as defined in claim 1, wherein the method comprises the following steps: in the second step, the inert atmosphere is nitrogen or argon.
7. A metal negative current collector decorated by metal organic phosphine frame glass is characterized in that: a metallic negative electrode current collector obtained by the production method according to any one of claims 1 to 6.
8. The metal organic phosphine framework glass modified metal negative electrode current collector of claim 7 is applied to lithium metal batteries, sodium metal batteries, lithium sulfur batteries, sodium sulfur batteries, lithium air batteries and sodium air battery systems.
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| CN114975892A (en) * | 2022-05-15 | 2022-08-30 | 北京化工大学 | Preparation method of self-supporting liquid alloy electrode |
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| CN114975892A (en) * | 2022-05-15 | 2022-08-30 | 北京化工大学 | Preparation method of self-supporting liquid alloy electrode |
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