CN110911690B - Liquid metal battery positive current collector with carbide coating - Google Patents
Liquid metal battery positive current collector with carbide coating Download PDFInfo
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Abstract
The invention discloses a liquid metal battery anode current collector with a metal carbide coating with a concave-convex surface microstructure, which is characterized in that a layer of metal carbide coating with a special surface morphology is additionally arranged on a conductive substrate, so that the stability of contact with liquid metal, the corrosion resistance and the wear resistance of the liquid metal are effectively improved on the basis of ensuring good conductivity of the current collector; the related preparation method is simple, has low cost and has wide industrialized application prospect.
Description
Technical Field
The invention belongs to the technical field of liquid metal batteries, and particularly relates to a liquid metal battery anode current collector with a concave-convex surface microstructure carbide coating.
Background
In recent years, in order to meet the requirement of large-scale energy storage of a power grid, sodoway et al propose a concept of a liquid metal energy storage battery, wherein the battery uses active metals such as Li, na and the like as a negative electrode material, uses high-potential liquid metals such as Bi, sb and the like as a positive electrode material, uses molten salt as electrolyte, and self-assembles into a battery with a three-layer structure comprising a negative electrode, electrolyte and a positive electrode under the action of gravity. The battery has the advantages of higher power density, high energy density, low energy storage cost, long service life and the like, and has wide application prospect in the field of medium-small distributed energy storage.
Because the working temperature of the liquid metal battery is high (300-700 ℃), and meanwhile, the battery current collector is soaked in high-temperature liquid metal for a long time, so that the current collector material selection faces a great challenge: firstly, metal elements in a current collector react with liquid metal at high temperature, so that the current collector is severely corroded, and substances in a battery can be possibly leaked; secondly, the consumption of the positive electrode liquid metal can cause remarkable attenuation of the battery capacity, so that the battery is difficult to meet the design performance requirement of the battery; in addition, the selective consumption of the corrosion reaction causes a change in the proportion of liquid metal, which causes a change in the cell voltage. Aiming at the technical problems, the corrosion problem of the current collector can be effectively solved by adding the graphite lining in the current collector.
However, the use of graphite liners has the following drawbacks: 1) The introduction of the graphite lining can easily enable the liquid metal positive electrode to bulge under the action of surface tension, so that the battery is easy to be short-circuited; 2) In the charging and discharging process and the battery using and transporting process, the liquid surface of the liquid electrode is easy to fluctuate due to the processes, and in the long-term use process, the graphite lining is easy to be worn by the intense fluctuation of the liquid metal at high temperature, so that the graphite lining is lost; 3) The preparation requirement and the preparation cost related to the spectrum pure graphite lining are high, the process popularization and the application are not facilitated, and the weight of the whole battery is increased due to the added spectrum pure graphite between the stainless steel shell and the liquid metal, so that the energy density of the battery is reduced.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the liquid metal battery anode current collector with the concave-convex surface appearance carbide coating, and the stability of the obtained metal liquid battery is effectively improved on the basis of ensuring the good conductivity of the current collector by additionally arranging a layer of carbide coating with special surface appearance on a conductive substrate; the preparation method is simple, has low cost and is suitable for popularization and application.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a positive electrode current collector of a liquid metal battery with a metal carbide coating with a concave-convex surface microstructure comprises a conductive substrate and the metal carbide coating arranged on the surface of the conductive substrate, wherein the metal carbide coating has the concave-convex surface microstructure formed by stacking metal carbide particles.
In the above scheme, the concave-convex surface microstructure is a three-dimensional network structure or a corrugated structure formed by stacking metal carbide particles.
In the scheme, the size of the metal carbide particles is 50 nm-10 mu m.
In the scheme, the contact angle between the metal carbide coating and the liquid metal in the liquid metal battery is 1-20 o 。
In the above scheme, the metal carbide coating comprises WC and W 2 C、MoC、Mo 2 C、Cr 3 C 2 A composite coating formed by mixing one or more of the above materials.
In the above scheme, the conductive substrate is graphite, low carbon steel or stainless steel.
In the above scheme, the thickness of the metal carbide coating is 0.001-1000 μm.
In the scheme, the binding force of the metal carbide coating to the conductive substrate is 1-150N.
In the above scheme, the positive electrode liquid metal suitable for the positive electrode current collector is one of Te, sn-Te, sb, pb-Sb, sn-Sb, bi and Pb-Bi.
In the scheme, the using temperature range of the liquid metal battery anode current collector is 100-750 ℃.
In the scheme, the contact resistance of the positive current collector of the liquid metal battery is 0.001-500m Ω cm 2 。
The preparation method of the liquid metal battery anode current collector with the concave-convex surface microstructure metal carbide coating comprises the following steps:
1) Preparing a molten electrolyte; mixing a carbon source, metal salt corresponding to metal carbide and supporting electrolyte, and heating and melting under a protective atmosphere to obtain molten electrolyte;
2) And (3) taking graphite or stainless steel as a cathode, taking metal corresponding to the metal carbide as an anode, applying voltage or current to electrolyze, taking out the cathode, and washing to obtain the liquid metal battery anode current collector with the metal carbide coating with the concave-convex surface microstructure.
In the above scheme, the supporting electrolyte is one or more of molten fluoride salt, chloride salt and carbonate; the carbon source is carbonate; the metal salt corresponding to the metal carbide is one or more of molybdate, tungstate and chromate.
In the above scheme, the molten electrolyte is a molten electrolyte containing carbonate and one or more of molybdate, tungstate and chromate; preferably, it is: naF-KF-Na 2 CO 3 -Li 2 MoO 4 、NCl-KCl-Li 2 CO 3 - Na 2 WO 4 、Na 2 CO 3 -K 2 CO 3 -Li 2 MoO 4 、NaF-KF-LiF-Li 2 CO 3 -K 2 CrO 4 。
In the scheme, the electrolysis temperature is 500-1000 ℃ and the electrolysis time is 0.1-8 h.
In the scheme, the molten salt electrolysis mode is a potentiostatic electrolysis method or a galvanostatic electrolysis method or a potentiostatic electrolysis method.
In the scheme, the voltage adopted by the constant-cell-pressure electrolysis of the molten salt electrolysis is 0.1-4.0V; the constant current electrolysis adopts the current density of 0.1-500 mA cm -2 。
The invention adopts the principle that:
1) According to the invention, the carbide coating is additionally arranged on the surface of the conductive substrate, the surface of the conductive substrate is provided with a concave-convex surface structure formed by mutually connected carbide particles, the surface roughness is increased, the wettability of a current collector relative to liquid metal is improved to a certain extent, meanwhile, the liquid metal on the surface of the current collector can be divided into a plurality of parts, so that the liquid metal stays in different areas, the fractal limit effect is realized on the liquid metal, and the wettability is further improved; in addition, the liquid metal liquid level fixed on different areas of the surface of the carbide coating is stable, the liquid level is prevented from shaking due to charge and discharge or battery transportation, the abrasion to the current collector is less, the abrasion resistance and the corrosion resistance are effectively improved, and the stability and the safety performance of the obtained current collector are further ensured.
2) In the invention, a one-step molten salt electrolysis process is adopted, carbonate ions and metal cations are reduced simultaneously to generate carbon atoms and metal atoms under the condition of current or voltage applied at the initial stage of molten salt electrolysis, a plurality of single metal carbide crystal nuclei are generated on the surface of a conductive substrate, and along with the extension of electrolysis time, the plurality of crystal nuclei generated by the reaction continuously grow, so that a concave-convex surface micro-nano structure formed by interconnecting and stacking the metal carbides is formed.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention provides a liquid metal battery anode current collector with a carbide coating with a concave-convex surface microstructure for the first time, which effectively improves the conductivity and the liquid metal abrasion resistance of the current collector, and the special concave-convex surface microstructure of the carbide coating surface can effectively improve the wettability and the working stability between the liquid metal battery anode current collector and metal, and effectively avoid the problems of short circuit and the like of the battery in the use process.
2) The liquid metal battery anode current collector only needs to adopt a one-step molten salt electrolysis process, and the preparation method is simple, low in cost and wide in industrial application prospect.
Drawings
FIG. 1 shows the microstructure of the surface coating according to example 1 of the present invention.
FIG. 2 shows the microstructure of the surface coating according to example 2 of the present invention.
FIG. 3 shows the microstructure of the surface coating according to example 4 of the present invention.
FIG. 4 shows the microstructure of the surface coating obtained in comparative example 2.
Fig. 5 is a cross-sectional view of 304 stainless steel obtained by collecting charge and discharge cycles after a charge and discharge cycle test of the positive electrode current collector obtained in comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The preparation method of the liquid metal battery anode current collector with the concave-convex surface microstructure carbide coating comprises the following steps:
1) By NaF-KF-Na 2 CO 3 -Li 2 MoO 4 Melting electrolyte: 500g of NaF-KF in a molar ratio of 2:3 are weighed and 15g of Na are added 2 CO 3 And 25g Li 2 MoO 4 Mixing, placing in alumina crucible, placing in a 300 deg.C drying oven for 48 hr to remove water, taking out, and placing in high temperature resistorHeating to 780 ℃ at a speed of 3 ℃/min under the protection of argon atmosphere, and preserving heat for 2 hours to obtain a molten electrolyte;
2) Using SS304 as cathode, molybdenum sheet as anode, under the condition of molten electrolyte, using 2.5V tank pressure to make electrolysis for 3 hr, after the electrolysis is completed, extracting electrode until it is cooled, then washing with water so as to obtain the invented liquid metal cell positive electrode current collector (SS 304/Mo 2 C）。
In the positive electrode current collector of the liquid metal battery of the embodiment, the obtained Mo 2 The thickness of the C coating is about 80 mu m, and the surface of the C coating is provided with Mo which has uniform particle size and is connected with each other 2 C a concave-convex surface structure (three-dimensional network structure) formed by particles (average particle diameter is 3 μm) dividing the liquid metal on the surface of the current collector into a plurality of parts (the coating surface structure is shown in fig. 1); the bonding force between the surface coating and the SS304 substrate was about 60N.
SS304/Mo obtained in this example 2 C current collector for use in 500 ℃ liquid metal battery using liquid metal Sn-Sb as positive electrode material, the contact resistance between the current collector and liquid metal being 130mΩ cm 2 Contact angle with liquid Sn-Sb of 5 o (contact resistance of conventional graphite-lined Current collector with Sn-Sb is 122mΩ cm) 2 Contact angle of 55 o ) The method comprises the steps of carrying out a first treatment on the surface of the Then at 300mA cm -2 The current density of the battery is 400 times in charge and discharge cycles, the short circuit phenomenon does not occur in the battery, and the thickness of the positive current collector is about 400nm due to friction loss of liquid metal.
Example 2
The preparation method of the liquid metal battery anode current collector with the concave-convex surface microstructure carbide coating comprises the following steps:
1) NaCl-KCl-Li is adopted 2 CO 3 -Na 2 WO 4 Melting electrolyte: 500g of NaCl-KCl with the molar ratio of 1:1 is weighed and 15g of Li is added 2 CO 3 And 25g Na 2 WO 4 Mixing, placing in an alumina crucible, placing in a 200 ℃ drying oven for 24 hours to remove water, taking out, placing in a high-temperature resistance furnace, heating to 850 ℃ at a speed of 4 ℃/min under the protection of argon atmosphere, and preserving heat for 2 hours to obtain molten electrolyte;
2) Using SS430 as cathode, tungsten sheet as anode, under the condition of molten electrolyte, using 2.0V tank pressure to make electrolysis for 2 hr, after the electrolysis is completed, raising electrode until it is cooled, then washing with water so as to obtain the invented liquid metal battery anode current collector (SS 430/W) with spherical raised microstructure tungsten carbide coating layer 2 C) The surface coating structure is shown in fig. 2.
In the positive current collector of the liquid metal battery of the embodiment, the obtained W 2 The thickness of the C coating is about 30 mu m, and the surface of the C coating has W with uniform particle size and interconnection 2 C particles (average particle diameter 300 nm) forming a concave-convex surface structure (corrugated structure) capable of dividing the liquid metal on the surface of the current collector into a plurality of portions; the bonding force between the surface coating and the SS430 substrate was about 70N.
SS430/W obtained in this example 2 C current collector for 500 ℃ liquid metal battery using Pb-Bi as positive electrode material, with contact resistance between current collector and metal of 121mΩ cm 2 Contact angle with liquid Pb-Bi of 8 o (contact resistance of conventional graphite-lined Current collector with Pb-Bi was 125mΩ cm) 2 Contact angle of 48 o ) Then at 250mA cm -2 The current density of the battery is 500 times in charge-discharge cycle, the short circuit phenomenon does not occur in the battery, and the thickness of the positive current collector is about 260nm due to friction loss of liquid metal.
Example 3
The preparation method of the liquid metal battery anode current collector with the concave-convex surface microstructure carbide coating comprises the following steps:
1) By NaF-KF-LiF-Li 2 CO 3 -K 2 CrO 4 Melting electrolyte: 500g of NaF-KF-LiF with the mass ratio of 30:60:10 is weighed, and 15g of Li is added 2 CO 3 And 25g K 2 CrO 4 Mixing, placing in an alumina crucible, placing in a 250 ℃ drying oven for 24 hours to remove water, taking out, placing in a high temperature resistance furnace, heating to 950 ℃ at a speed of 4 ℃/min under the protection of argon atmosphere, and preserving heat for 2 hours to obtain molten electrolyte;
2) SS430 as cathode, cr plate as anode, under the condition of molten electrolyte, 150mA cm -2 After the electrolysis is finished, the electrode is taken out until the electrode is cooled, and then the electrode is washed by water to obtain the liquid metal battery anode current collector (SS 430/Cr 3 C 2 ）。
In the positive electrode current collector of the liquid metal battery of the embodiment, the obtained Cr 3 C 2 The thickness of the coating is about 20 mu m, and the surface of the coating has Cr with uniform particle size and interconnection 3 C 2 The particles (average particle size 500 nm) form a concave-convex surface structure, and the bonding force between the surface coating and the SS430 substrate is about 65N.
SS430/Cr obtained in this example 3 C 2 The current collector is used in a 500 ℃ liquid metal battery taking liquid metal Pb-Bi as a positive electrode material, and the contact resistance between the current collector and the metal is 105mΩ cm 2 Contact angle with liquid Pb-Bi of 6 o (contact resistance of conventional graphite-lined Current collector with Pb-Bi was 125mΩ cm) 2 Contact angle of 48 o ) The method comprises the steps of carrying out a first treatment on the surface of the Then at 250mA cm -2 The current density of the battery is 300 times in charge-discharge cycle, the short circuit phenomenon does not occur in the battery, and the thickness of the positive current collector is about 220nm due to friction loss of liquid metal.
Example 4
The preparation method of the liquid metal battery anode current collector with the concave-convex surface microstructure carbide coating comprises the following steps:
1) By NaF-KF-LiF-Li 2 CO 3 -K 2 CrO 4 - Na 2 MoO 4 Melting electrolyte: 500g of NaF-KF-LiF with the mass ratio of 30:60:10 is weighed, and 15g of Li is added 2 CO 3 、25g K 2 CrO 4 And 25g Na 2 MoO 4 Mixing, placing in an alumina crucible, placing in a 200 ℃ drying oven for 48 hours to remove water, taking out, placing in a high-temperature resistance furnace, heating to 950 ℃ at a speed of 4 ℃/min under the protection of argon atmosphere, and preserving heat for 2 hours to obtain molten electrolyte;
2) Under the condition of melting electrolyte, SS316L is taken as a cathode, cr slices are taken as an anode, and 200mA cm is taken as a cathode -2 Is electrolyzed for 5h, and after the electrolysis is finished, the electrode is taken outCooling, washing with water to obtain the final product (SS 316L/Cr) 3 C 2 -Mo 2 C）。
In the positive electrode current collector of the liquid metal battery of the embodiment, the obtained Cr 3 C 2 -Mo 2 The thickness of the C coating is about 45 mu m, and the surface of the C coating has Cr with uniform particle size and interconnection 3 C 2 And Mo (Mo) 2 The C particles (average particle size 750 nm) form a concave-convex surface structure, the surface microstructure is shown in fig. 3, and the bonding force between the surface coating and the SS430 substrate is about 55N.
SS430/Cr obtained in this example 3 C 2 -Mo 2 C current collector for use in 500 ℃ liquid metal battery with Sn-Sb as positive electrode material, the contact resistance between the current collector and metal being 113mΩ cm 2 Contact angle with liquid Pb-Bi of 4.5 o (contact resistance of conventional graphite-lined Current collector with Pb-Bi was 122mΩ cm 2 Contact angle of 55 o ) The method comprises the steps of carrying out a first treatment on the surface of the Then at 350mA cm -2 The current density of the battery is 200 times in charge-discharge cycle, the short circuit phenomenon does not occur in the battery, and the thickness of the positive current collector is about 195nm due to friction loss of liquid metal.
Example 5
The preparation method of the liquid metal battery anode current collector with the concave-convex surface microstructure carbide coating comprises the following steps:
1) Adopts Na 2 CO 3 -K 2 CO 3 -Li 2 CO 3 -K 2 CrO 4 Melting electrolyte: na was weighed in a molar ratio of 55.5:44.5 2 CO 3 -K 2 CO 3 500g in total, and 15g Li is added 2 CO 3 And 25g K 2 CrO 4 Mixing, placing in an alumina crucible, placing in a drying oven at 200 ℃ for 48 hours to remove water, taking out, placing in a high-temperature resistance furnace, heating to 900 ℃ at a speed of 4 ℃/min under the protection of argon atmosphere, and preserving heat for 2 hours to obtain molten electrolyte;
2) Under the condition of melting electrolyte, SS316L is taken as a cathode, cr slices are taken as an anode, and 200mA cm is taken as a cathode -2 Is electrolyzed for 5 hours, and Cr is deposited in SS316L after the electrolysis is finished 3 C 2 Layer, add 25g Li 2 MoO 4 And the Cr piece anode was replaced with a Mo piece anode, likewise 200mA cm -2 Is electrolyzed for 5h by current density, and Mo is deposited 2 And C layer, extracting the electrode until cooling, and washing to obtain the liquid metal battery anode current collector with the chromium carbide and molybdenum carbide double-layer coating with the spherical convex microstructure, (SS 316L/Cr) 3 C 2 /Mo 2 C）。
In the positive electrode current collector of the liquid metal battery of the embodiment, the obtained Cr 3 C 2 /Mo 2 The thickness of the C coating is about 60 μm, wherein Cr 3 The thickness of the C2 coating is 28 mu m, mo 2 The thickness of the C coating is about 32 mu m, and the surface of the C coating has Mo which has uniform particle size and is connected with each other 2 Concave-convex surface structure formed by C particles (average particle diameter is 2.1 μm), surface Mo 2 The bonding force between the C coating and the SS316L substrate was about 58N.
SS316L/Cr obtained in this example 3 C 2 /Mo 2 C current collector for use in 500 ℃ liquid metal battery using liquid metal Sn-Sb as positive electrode material, the contact resistance between the current collector and metal being 119mΩ cm 2 Contact angle with liquid Sn-Sb of 4 o (contact resistance of conventional graphite-lined Current collector with Sn-Sb is 122mΩ cm) 2 Contact angle of 55 o ) The method comprises the steps of carrying out a first treatment on the surface of the Then at 350mA cm -2 The current density of the battery is 200 times in charge-discharge cycle, the short circuit phenomenon does not occur in the battery, and the thickness of the positive current collector is about 195nm due to friction loss of liquid metal.
Example 6
The preparation method of the liquid metal battery anode current collector with the concave-convex surface microstructure metal carbide coating comprises the following steps:
1) NaCl-CaCl is adopted 2 -CaCO 3 -Na 2 WO 4 Melting electrolyte: the NaCl-CaCl with the molar ratio of 47.9:52.1 is weighed 2 500g in total, and 15g CaCO was added 3 And 25g Na 2 WO 4 Mixing, placing in an alumina crucible, placing in a 300 deg.C drying oven for 48 hr to remove water, taking out, and placingHeating the high-temperature resistance furnace to 850 ℃ at a speed of 4 ℃/min under the protection of argon atmosphere, and preserving heat for 2 hours to obtain a molten electrolyte;
2) Using SS304 as cathode, tungsten plate as anode, under the condition of molten electrolyte, using 2.2V tank pressure to make electrolysis for 4 hr, after the electrolysis is completed, raising electrode until it is cooled, then washing with water so as to obtain the invented liquid metal battery anode current collector (SS 304/W) with tungsten carbide coating layer of spherical raised microstructure 2 C）。
In the positive current collector of the liquid metal battery of the embodiment, the obtained W 2 The thickness of the C coating is about 35 mu m, and the surface of the C coating has W with uniform particle size and interconnection 2 The C particles (average particle diameter is 450 nm) form a concave-convex surface structure, and the binding force between the surface coating and the SS304 substrate is about 63N.
SS304/W obtained in this example 2 C current collector for use in 500 ℃ liquid metal battery using Pb-Bi as positive electrode material, the contact resistance between the current collector and metal being 95mΩ cm 2 Contact angle with liquid Pb-Bi of 8 o (contact resistance of conventional graphite-lined Current collector with Pb-Bi was 122mΩ cm 2 Contact angle of 55 o ) The method comprises the steps of carrying out a first treatment on the surface of the Then at 250mA cm -2 The current density of the battery is 500 times in charge-discharge cycle, the short circuit phenomenon does not occur in the battery, and the thickness of the positive current collector is about 210nm due to friction loss of liquid metal.
Comparative example 1
The positive electrode current collector was directly made of 316 stainless steel with a graphite layer (thickness: 40 μm) plated on the surface, and was used in the liquid metal battery using liquid metal Sn-Sb as a positive electrode material described in example 5, and the obtained battery capacity was 100Ah, and the positive electrode interface area was 100cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The resulting battery was measured at 100mA/cm 2 The current density of the battery is circularly operated during charging and discharging, the phenomenon that the voltage drops too fast during discharging occurs when the battery runs to 13 circles, and the battery is short-circuited when the battery runs to 25 circles, so that the battery cannot continue to run.
Comparative example 2
The preparation method of the nickel-coating-modified liquid metal battery anode current collector comprises the following steps of:
1) NaCl-KCl-NiCl is adopted 2 Molten salt electrolyte: 500g of NaCl-KCl salt in a molar ratio of 1:1 are weighed and 20g of NiCl is added 2 Mixing, placing in an alumina crucible, placing in a drying oven at 300 ℃ for 48h to remove water, taking out, placing in a high-temperature resistance furnace, heating to 750 ℃ at a speed of 4 ℃/min under the protection of argon atmosphere, and preserving heat for 2h;
2) And (3) taking SS304 as a cathode, taking a nickel sheet as an anode, carrying out electrolysis for 4 hours under the cell pressure of 2.2V, after the electrolysis is finished, lifting the electrode until cooling, and washing with water to obtain the liquid metal battery anode current collector (SS 304/Ni) with the nickel coating.
The surface morphology of the positive electrode current collector of the liquid metal battery of this embodiment is shown in fig. 4, and the thickness of the obtained Ni coating is about 40 μm, and the bonding force between the surface coating and the SS304 substrate is about 53N.
The SS304/Ni current collector obtained in the example is used in a 500 ℃ liquid metal battery taking liquid metal Sn-Sb as a positive electrode material, and the contact angle between the current collector and the liquid metal is tested to be 5 o The contact resistance with the liquid metal is 100m Ω cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Then at 250mA cm -2 The current density of the battery is charged and discharged 500 times, the short circuit phenomenon does not occur in the battery, but the surface coating of the positive electrode current collector is completely lost due to friction loss and corrosion of liquid metal, and the 304 stainless steel substrate is further severely corroded and lost; the cross-sectional view of the obtained 304 stainless steel is shown in fig. 5, and it can be seen that the thickness of the stainless steel is greatly reduced, and a cracking phenomenon occurs.
The above examples are presented for clarity of illustration only and are not limiting of the embodiments. Other variations and modifications of the above description will be apparent to those of ordinary skill in the art, and it is not necessary or exhaustive of all embodiments, and thus all obvious variations or modifications that come within the scope of the invention are desired to be protected.
Claims (8)
1. The positive electrode current collector of the liquid metal battery with the metal carbide coating comprises a conductive substrate and the metal carbide coating arranged on the surface of the conductive substrate, wherein the metal carbide coating is provided with a concave-convex surface microstructure formed by stacking metal carbide particles, and the concave-convex surface microstructure is a three-dimensional net structure or a corrugated structure formed by stacking metal carbide particles, so that the liquid metal on the surface of the current collector is divided into a plurality of parts;
the size of the metal carbide particles is 50 nm-10 mu m;
the preparation method comprises the following steps:
1) Preparing a molten electrolyte, mixing a carbon source, metal salt corresponding to the prepared metal carbide and a supporting electrolyte, and heating and melting under a protective atmosphere to obtain the molten electrolyte;
2) Taking graphite or stainless steel as a cathode, taking metal corresponding to metal carbide as an anode, applying voltage or current to electrolyze, taking out the cathode, and washing to obtain the liquid metal battery anode current collector with the metal carbide coating with the concave-convex surface microstructure;
the electrolysis temperature is 850-950 ℃ and the electrolysis time is 2-4 h.
2. The positive electrode current collector of a liquid metal cell as claimed in claim 1, wherein the contact angle between the metal carbide coating and the liquid metal in the liquid metal cell is 1-20 °.
3. The liquid metal battery positive current collector of claim 1, wherein the metal carbide coating comprises WC, W 2 C、MoC、Mo 2 C、Cr 3 C 2 A composite coating formed by mixing one or more of the above materials.
4. The positive electrode current collector of a liquid metal battery according to claim 1, wherein the metal carbide coating is a single-layer coating or a composite coating composed of multiple layers of different carbide coatings.
5. The liquid metal battery positive electrode current collector of claim 1, wherein the metal carbide coating has a thickness of 0.001-1000 μm; the binding force of the coating is 1-150N.
6. The positive current collector of a liquid metal battery according to claim 1, wherein the contact resistance of the positive current collector of the liquid metal battery is 0.001-500mΩ cm2.
7. The method for preparing the positive electrode current collector of the liquid metal battery as claimed in any one of claims 1 to 6, comprising the following steps:
1) Preparing a molten electrolyte, mixing a carbon source, metal salt corresponding to the prepared metal carbide and a supporting electrolyte, and heating and melting under a protective atmosphere to obtain the molten electrolyte;
2) And (3) taking graphite or stainless steel as a cathode, taking metal corresponding to the metal carbide as an anode, applying voltage or current to carry out electrolysis, taking out the cathode, and washing to obtain the liquid metal battery anode current collector with the metal carbide coating with the concave-convex surface microstructure.
8. The method according to claim 7, wherein the supporting electrolyte is one or more of molten fluoride salt, chloride salt, and carbonate salt; the carbon source is carbonate; the metal salt corresponding to the metal carbide is one or more of molybdate, tungstate and chromate.
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| US3933521A (en) * | 1975-02-13 | 1976-01-20 | The United States Of America As Represented By The United States Energy Research And Development Administration | Anode for a secondary, high-temperature electrochemical cell |
| CN105648465A (en) * | 2016-01-13 | 2016-06-08 | 江西理工大学 | Method for preparing tungsten carbide through molten salt electrolysis |
| CN106654072A (en) * | 2016-10-27 | 2017-05-10 | 中国西电电气股份有限公司 | High-temperature fusant battery apparatus and preparation process thereof |
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