CN110890549B - Array type positive current collector for liquid metal battery - Google Patents

Array type positive current collector for liquid metal battery Download PDF

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CN110890549B
CN110890549B CN201911244018.5A CN201911244018A CN110890549B CN 110890549 B CN110890549 B CN 110890549B CN 201911244018 A CN201911244018 A CN 201911244018A CN 110890549 B CN110890549 B CN 110890549B
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battery
liquid metal
current collector
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CN110890549A (en
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汪的华
李闻淼
杜开发
刘威
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Wuhan University WHU
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/669—Steels
    • 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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Abstract

The invention discloses an array type positive current collector for a liquid metal battery, wherein a columnar array pointing to the direction of a negative electrode is arranged at the bottom of a positive current collector shell, so that the distribution uniformity of a positive electrode interface of the liquid metal battery is effectively improved, the internal stress of an interface alloy layer is reduced, more attachment points are provided for the alloy layer, and the short circuit risk in the operation process of a large-size battery is effectively eliminated; meanwhile, the mass transfer process of the battery in the charging and discharging process can be effectively ensured, and the safe, stable and efficient operation of the battery is promoted.

Description

Array type positive current collector for liquid metal battery
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to an array type positive current collector for a liquid metal battery.
Background
The liquid metal battery is a high-temperature secondary battery for distributed power grid energy storage proposed in 2009 by the teaching of Sadoway of Massachusetts university. The energy storage system has the advantages of ultra-long cycle life, excellent rate capability, high coulombic efficiency, high energy efficiency and the like, is widely concerned by the scientific research community in recent years, and is expected to become a new generation of high-efficiency distributed power grid energy storage technology.
However, the battery cell faces certain technical challenges in the engineering amplification process, and the reason why the battery cell is difficult to amplify is mainly as follows:
1) The uneven distribution and growth of the solid alloy layer at the interface of the battery anode, in order to avoid the corrosion of anode metal to the conventional metal current collector, graphite is generally added into the anode current collector in the liquid metal battery to be used as a lining, however, the introduction of the graphite lining easily makes the liquid metal be in an upward convex arch shape under the action of interface tension; meanwhile, the liquid metal negative electrode is mainly bound in the foam nickel-iron current collector in the middle of the battery, the liquid metal negative electrode is not distributed on the peripheral edge, the middle of the positive electrode interface is closest to the negative electrode, and the edge is far away from the negative electrode, so that when the battery runs, the current is distributed in a form of large middle and small periphery, and the solid phase alloy layer is preferentially generated and grows in the middle to generate a dendritic-like alloy layer, so that the running of the battery is unstable; when the uneven growth of the interface is serious, the dendritic crystal-like alloy can pierce through the electrolyte layer to contact with the negative electrode, so that the battery is short-circuited; particularly, when the battery is enlarged, the nonuniformity of the interface current distribution is aggravated by a larger-area positive electrode interface, so that the growth rate difference of different areas of the positive electrode interface is larger, and the short circuit risk of the battery is aggravated;
2) The alloy layer at the interface of the battery anode generates cracks or fractures under the action of internal stress; during the discharge process of the battery, a solid phase alloy layer is formed at the interface of the positive electrode, and along with the continuous thickening and growth of the solid phase alloy layer, larger stress is generated inside the solid phase alloy layer, so that the alloy layer is cracked or cracked; along with the increase of the size of the battery, the internal pressure of the interface solid phase alloy layer is increased, and the fracture phenomenon is more serious; under the condition of lacking of attachments, the cracked alloy layer is easy to partially or completely separate from the positive electrode interface under the action of internal disturbance of the battery and is in contact with the negative electrode current collector, so that the coulomb efficiency of the battery is reduced, even the battery is short-circuited, and the battery is unstable in operation; particularly, in a liquid metal battery system containing metal Sb in the anode, the density of a solid phase alloy layer is low, and the alloy cracked at the interface can move along with the liquid level due to slight fluctuation of the liquid level, so that the battery is easily short-circuited.
Aiming at the technical problems, in order to ensure the larger capacity of the battery, increasing the size of the battery is a necessary way for enlarging the engineering monomer of the liquid metal battery; however, larger cell sizes exacerbate the uneven distribution of the interface and increase the internal stress of the alloy layer, further increasing the cell short circuit risk.
Disclosure of Invention
The invention mainly aims to solve the problems of instability and the like in the amplification process of the anode interface of the existing liquid metal battery, and provides an array type anode current collector.
In order to achieve the purpose, the invention adopts the technical scheme that:
an array type positive electrode current collector for a liquid metal battery comprises a conductive shell and a columnar array arranged on the bottom surface of the shell, wherein the columnar array points to the direction of a negative electrode.
In the above scheme, the columnar array is perpendicular to the bottom surface of the shell.
In the scheme, the area of the positive electrode interface adopted by the liquid metal battery is 50-2000cm 2 。
In the above scheme, the repeating units in the columnar array are cylindrical or prismatic.
In the above scheme, the conductive shell is a graphite shell, a stainless steel shell or a low carbon steel shell.
In the scheme, the columnar array is made of one of graphite, stainless steel, low-carbon steel, metal W and metal Mo.
In the scheme, the surface of the conductive shell and/or the surface of the columnar array is/are additionally provided with the corrosion-resistant protective layer, and the protective layer material can be selected from metal W, metal Mo, metal WC and metal W 2 C、MoC、Mo 2 C、Cr 3 C 2 、TiB 2 One kind of (1).
In the scheme, the height of the columnar array exceeds the liquid level of the liquid metal of the anode by 0.1-50mm and is lower than the lower liquid level of the liquid metal of the cathode.
In the above scheme, the equivalent diameter of the repeating unit in the columnar array is 1-50mm.
In the above scheme, the number of the repeating units in the columnar array is 1-200.
In the above scheme, the arrangement mode of the columnar arrays is one or more of concentric circle arrangement, triangular arrangement and quadrilateral arrangement.
In the above scheme, the liquid metal of the positive electrode suitable for the array type positive electrode current collector is an alloy composed of one or more of Te, bi, sb, pb, and Sn.
In the scheme, the molten salt electrolyte applicable to the array type positive current collector is LiF, liCl, liBr, naCl, naF, naBr or MgF 2 、MgCl 2 、MgBr 2 、GaF 2 、GaCl 2 、GaBr 2 Electrolyte of any one or more of KF, KCl and KBr.
In the scheme, the working temperature range applicable to the array type positive current collector is 100-800 ℃.
The principle of the invention is as follows:
the invention provides an array type anode current collector for the first time, wherein a convex anode liquid metal interface formed under the condition of a large-area anode interface is divided into a plurality of areas with smaller areas and lower convex degrees by introducing columnar units arranged in an array manner, so that the integral uniformity of the large-area anode interface is improved, the internal stress of an alloy layer (particularly the volume expansion stress brought by dispersible solid matters during generation) is reduced, and meanwhile, the attachment points of the solid alloy layer can be increased, so that the short-circuit risk of a large-size liquid metal battery is effectively eliminated; in addition, the introduced columnar unit is beneficial to ensuring the mass transfer process in the charge-discharge process and the overall energy density of the battery, and further promotes the safe, stable and efficient operation of the battery.
Compared with the prior art, the invention has the beneficial effects that:
1) The array type positive electrode current collector provided by the invention can effectively improve the distribution uniformity of the positive electrode interface of the liquid metal battery, reduce the internal stress of the interface alloy layer and provide more attachment sites for the alloy layer, thereby eliminating the short circuit risk in the operation process of a large-size battery.
2) The array type anode current collector provided by the invention adopts a columnar array structure, improves the interface uniformity, is favorable for ensuring the mass transfer process and the energy density of the battery in the anode liquid metal, and ensures the safe and efficient operation of the battery.
3) The columnar array materials of the array type positive electrode current collector provided by the invention are all substances with better conductivity, so that the conductivity of a positive electrode can be effectively improved, the internal resistance of a battery is reduced, and the energy efficiency of the battery is improved.
Drawings
Fig. 1 is a schematic structural diagram of an array-type positive electrode current collector obtained in embodiment 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The array type positive current collector for the liquid metal battery comprises a graphite conductive shell and a columnar array arranged on the bottom surface of the conductive shell, wherein the columnar array consists of 8 graphite columnar repeating units with vertical bottom surfaces upward, the array is arranged in a triangular mode, and each columnar repeating unit is 1.5mm in diameter and 55mm high.
The current collector is used for positive electrode Sn 6 Sb 4 In a Li-Sn-Sb liquid metal battery with alloy and electrolyte of LiF-LiCl-LiBr ternary mixed salt and the operation temperature of 500 ℃, the design capacity of the battery is 300Ah, and the interface area of the anode is 300cm 2 The graphite columnar array is 9mm higher than the liquid level of the liquid metal of the anode and lower than the lower liquid level of the liquid metal of the cathode, and a raised anode liquid metal interface is divided into a plurality of areas with smaller areas and lower raised degrees.
The obtained liquid metal battery is charged at 200mA/cm 2 The current density is circularly charged and discharged for 200 circles, the battery runs stably, the short circuit phenomenon does not occur, the coulomb efficiency of the battery after 200 circles is 93%, and the capacity retention rate is more than 94%.
Comparative example 1
Graphite was directly used as a positive electrode current collector, and the positive electrode current collector was used as Sn for the positive electrode described in example 1 6 Sb 4 In a Li-Sn-Sb liquid metal battery with alloy and electrolyte of LiF-LiCl-LiBr ternary mixed salt and the operation temperature of 500 ℃, the design capacity of the battery is 300Ah, and the interface area of the anode is 300cm 2 。
The obtained liquid metal battery is heated at 200mA/cm 2 The current density is charged and discharged circularly, the voltage is reduced too fast when the battery runs for 3 circles, and the battery is short-circuited when the battery runs for 9 circles, so that the charging and discharging can not be continued.
Example 2
An array type positive current collector for a liquid metal battery comprises a 304 steel conductive shell and a columnar array arranged on the bottom surface of the conductive shell, wherein the columnar array consists of 15 304 steel columnar repeating units with vertical bottom surfaces upward, the array is arranged in concentric circles, and each columnar repeating unit is 1.6mm in diameter and 55mm high.
The current collector is used for positive electrode Sn 6 Sb 4 In the Li-Sn-Sb liquid metal battery with the alloy and electrolyte being LiF-LiCl-LiBr ternary mixed salt and the operation temperature being 500 ℃, the design capacity of the battery is 300Ah, and the interface area of the anode is 300cm 2 The 304 steel columnar array is 8mm higher than the liquid level of the anode liquid metal and lower than the lower liquid level of the cathode liquid metal, and divides the raised anode liquid metal interface into a plurality of areas with smaller area and lower raised degree.
The obtained liquid metal battery was charged at 150mA/cm 2 The current density is circularly charged and discharged for 200 circles, the battery runs stably without short circuit, the coulombic efficiency of the battery after 200 circles is 82%, the capacity retention rate is about 67%, and the main reason for poor coulombic efficiency and capacity retention rate is that a 304 steel material current collector is easily corroded by the liquid-state anode alloy.
Comparative example 2
304 steel was directly used as a positive electrode current collector, and the positive electrode current collector was used as Sn in example 2 6 Sb 4 In a Li-Sn-Sb liquid metal battery with alloy and electrolyte of LiF-LiCl-LiBr ternary mixed salt and the operation temperature of 500 ℃, the design capacity of the battery is 300Ah, and the interface area of the anode is 300cm 2 。
The obtained liquid metal battery is heated at 150mA/cm 2 The current density is charged and discharged circularly, and the short circuit phenomenon occurs when the battery runs for 7 circles, so that the charging and discharging can not be continued.
Example 3
An array type positive current collector for a liquid metal battery comprises a 316 steel conductive shell and a columnar array arranged on the bottom surface of the conductive shell, wherein the columnar array consists of 10 316 steel columnar repeating units with vertical bottom surfaces upward, the array is arranged in concentric circles, and each columnar repeating unit is 1.2mm in diameter and 53mm in height.
Applying the current collector to the anode as Sn 6 Sb 4 Alloy and electrolyte are LiF-L5363A Li-Sn-Sb liquid metal battery with a ternary mixed salt of iCl-LiBr and an operating temperature of 500 ℃ has a design capacity of 300Ah and a positive electrode interface area of 300cm 2 And the 316 steel columnar array is 5mm higher than the liquid level of the anode liquid metal and lower than the lower liquid level of the cathode liquid metal, and divides the raised anode liquid metal interface into a plurality of areas with smaller area and lower raised degree.
The obtained liquid metal battery is charged at 300mA/cm 2 The current density is circularly charged and discharged for 200 circles, the battery runs stably without short circuit, the coulombic efficiency of the battery after 200 circles is 75%, the capacity retention rate is about 65%, and the main reason for poor coulombic efficiency and capacity retention rate is that 316 steel material current collectors are easily corroded by liquid anode alloy.
Comparative example 3
316 steel was used as the positive electrode current collector, and the positive electrode current collector was used as Sn in example 3 6 Sb 4 In a Li-Sn-Sb liquid metal battery with alloy and electrolyte of LiF-LiCl-LiBr ternary mixed salt and the operation temperature of 500 ℃, the design capacity of the battery is 300Ah, and the interface area of the anode is 300cm 2 。
The obtained liquid metal battery is charged at 300mA/cm 2 The current density is charged and discharged circularly, and the short circuit phenomenon occurs when the battery runs for 6 circles, so that the charging and discharging can not be continued.
Example 4
An array type positive current collector for a liquid metal battery comprises a 304 steel conductive shell and a columnar array arranged on the bottom surface of the conductive shell; the surfaces of the conductive shell and the columnar array are respectively coated with a metal Mo protective layer with the thickness of 30 mu m, the columnar array is composed of 15 304 steel columnar repeating units vertical to the bottom surface of the conductive shell and upward, the array is arranged in concentric circles, and each columnar repeating unit is 1.1mm in diameter and 59mm in height.
The current collector is used for positive electrode Sn 6 Sb 4 In the Li-Sn-Sb liquid metal battery with the alloy and electrolyte being LiF-LiCl-LiBr ternary mixed salt and the operation temperature being 500 ℃, the design capacity of the battery is 350Ah, and the interface area of the anode is 350cm 2 304 steel columnar array over-headThe liquid level of the liquid metal with the maximum liquid state is 9mm and is lower than the lower liquid level of the liquid metal with the negative electrode, and the raised liquid metal interface with the positive electrode is divided into a plurality of areas with smaller areas and lower raised degrees.
The obtained liquid metal battery is charged at 200mA/cm 2 The current density is circularly charged and discharged for 300 circles, the battery runs stably without short circuit, the coulomb efficiency of the battery after 300 circles is 98%, and the capacity retention rate is about 95%.
Comparative example 4
The positive electrode current collector made of 304 steel coated with a protective layer of Mo (30 μm) was used as Sn for the positive electrode described in example 4 6 Sb 4 In a Li-Sn-Sb liquid metal battery with alloy and electrolyte of LiF-LiCl-LiBr ternary mixed salt and the operation temperature of 500 ℃, the design capacity of the battery is 350Ah, and the area of the positive electrode interface is 350cm 2 。
The obtained liquid metal battery is charged at 300mA/cm 2 The current density is charged and discharged circularly, and the short circuit phenomenon occurs when the battery runs for 18 circles, so that the charging and discharging can not be continued.
Example 5
An array type positive current collecting body for a liquid metal battery comprises a 316 steel conductive shell and a columnar array arranged on the bottom surface of the conductive shell; wherein, the surfaces of the conductive shell and the columnar array are respectively coated with metal TiB with the thickness of 27 mu m 2 And the protective layer is characterized in that the columnar array consists of 18 316 steel columnar repeating units which are vertical to the bottom surface of the conductive shell and face upwards, the array is arranged in concentric circles, and each columnar repeating unit is 1.1mm in diameter and 59mm in height.
The current collector is used for positive electrode Sn 6 Sb 4 In a Li-Sn-Sb liquid metal battery with alloy and electrolyte of LiF-LiCl-LiBr ternary mixed salt and the operation temperature of 500 ℃, the design capacity of the battery is 400Ah, and the interface area of a positive electrode is 400cm 2 And the 316 steel columnar array is 9mm higher than the liquid level of the anode liquid metal and lower than the lower liquid level of the cathode liquid metal, and divides the raised anode liquid metal interface into a plurality of areas with smaller area and lower raised degree.
The resulting liquid metal cell was charged at 300mA/cm 2 The current density is circularly charged and discharged for 300 circles, the battery runs stably without short circuit, the coulomb efficiency of the battery after 300 circles is 97%, and the capacity retention rate is about 94%.
Comparative example 5
Directly coating TiB 2 316 steel coated with a (27 μm) protective layer was used as a positive electrode current collector for Sn as the positive electrode described in example 5 6 Sb 4 In a Li-Sn-Sb liquid metal battery with alloy and electrolyte of LiF-LiCl-LiBr ternary mixed salt and the operation temperature of 500 ℃, the design capacity of the battery is 400Ah, and the interface area of a positive electrode is 400cm 2 。
The obtained liquid metal battery is charged at 300mA/cm 2 The current density is charged and discharged circularly, and the short circuit phenomenon occurs when the battery runs for 21 circles, so that the charging and discharging can not be continued.
Example 6
An array type positive current collector for a liquid metal battery comprises a graphite conductive shell and a columnar array arranged on the bottom surface of the conductive shell, wherein the columnar array consists of 15 graphite hexagonal prism-shaped repeating units with vertical bottom surfaces upward, the array is arranged in concentric circles, and the side length of each hexagonal prism-shaped repeating unit hexagon is 1mm, and the height of each hexagonal prism-shaped repeating unit is 55mm.
The current collector is used in a Li-Bi liquid metal battery with a positive electrode of Bi metal, an electrolyte of LiF-LiCl-LiBr ternary mixed salt and an operating temperature of 500 ℃, the design capacity of the battery is 300Ah, and the interface area of the positive electrode is 300cm 2 The graphite columnar array is 7mm higher than the liquid level of the liquid metal of the anode and lower than the lower liquid level of the liquid metal of the cathode, and a raised anode liquid metal interface is divided into a plurality of areas with smaller area and lower raised degree.
The obtained liquid metal battery is charged at 200mA/cm 2 The current density is circularly charged and discharged for 250 circles, the battery runs stably, the short circuit phenomenon does not occur, the coulomb efficiency of the battery after 200 circles is 95%, and the capacity retention rate is more than 96%.
Comparative example 6
Graphite was directly used as a positive electrode current collector, and the positive electrode current collector was used in example 6 in which the positive electrode was made of metal Bi,In the Li-Bi liquid metal battery with LiF-LiCl-LiBr ternary mixed salt as electrolyte and 500 ℃ of operating temperature, the design capacity of the battery is 300Ah, and the area of the positive electrode interface is 300cm 2 。
The obtained liquid metal battery is charged at 200mA/cm 2 The current density is charged and discharged circularly, the voltage is reduced too fast when the battery runs for 4 circles, and the battery is short-circuited when the battery runs for 11 circles, so that the charging and discharging can not be continued.
Example 7
An array type positive electrode current collector for a liquid metal battery comprises a 304 steel conductive shell and a columnar array arranged on the bottom surface of the conductive shell, wherein the columnar array is composed of 9 304 steel columnar repeating units with vertical bottom surfaces upward, the array is arranged in a circular shape, and each columnar repeating unit is 1.6mm in diameter and 55mm in height.
The current collector is used in a Li-Bi liquid metal battery with a positive electrode of metal Bi, electrolyte of LiF-LiCl-LiBr ternary mixed salt and an operating temperature of 500 ℃, the design capacity of the battery is 300Ah, and the area of the positive electrode interface is 300cm 2 The 304 steel columnar array is 6mm higher than the liquid level of the anode liquid metal and lower than the lower liquid level of the cathode liquid metal, and divides the raised anode liquid metal interface into a plurality of areas with smaller area and lower raised degree.
The obtained liquid metal battery is charged at 300mA/cm 2 The current density is circularly charged and discharged for 200 circles, the battery runs stably without a short circuit phenomenon, the coulombic efficiency of the battery after 200 circles is 78%, the capacity retention rate is about 64%, and the main reason that the coulombic efficiency and the capacity retention rate are poor is that a 304 steel current collector is easily corroded by liquid metal Bi.
Comparative example 7
304 steel was directly used as the positive electrode current collector, which was used in the Li-Bi liquid metal battery of example 7, in which the positive electrode was made of Bi metal, the electrolyte was LiF-LiCl-LiBr ternary mixed salt, and the operating temperature was 500 ℃, the battery design capacity was 300Ah, and the positive electrode interfacial area was 300cm 2 。
The obtained liquid metal battery is charged at 300mA/cm 2 Current density cycling charge and discharge, battery operationThe short circuit phenomenon occurs in charging in 2 circles, and charging and discharging cannot be continued.
Example 8
An array type positive electrode current collector for a liquid metal battery comprises a 304 steel conductive shell and a columnar array arranged on the bottom surface of the conductive shell; the surfaces of the conductive shell and the columnar array are respectively coated with a metal W protective layer with the thickness of 40 mu m, wherein the columnar array is composed of 15 304 steel columnar repeating units vertical to the bottom surface of the conductive shell and upward, the array is arranged in concentric circles, and each columnar repeating unit is 1.1mm in diameter and 59mm in height.
The current collector is used in a Li-Bi liquid metal battery with a positive electrode of metal Bi, electrolyte of LiF-LiCl-LiBr ternary mixed salt and an operating temperature of 500 ℃, the design capacity of the battery is 350Ah, and the area of a positive electrode interface is 350cm 2 The 304 steel columnar array is 7mm higher than the liquid level of the anode liquid metal and lower than the lower liquid level of the cathode liquid metal, and divides the raised anode liquid metal interface into a plurality of areas with smaller area and lower raised degree.
The obtained liquid metal battery is charged at 200mA/cm 2 The current density is circularly charged and discharged for 300 circles, the battery runs stably without short circuit, the coulomb efficiency of the battery after 300 circles is 97%, and the capacity retention rate is about 96%.
Comparative example 8
The 304 steel coated with a metal W (30 μm) protective layer was directly used as a positive electrode current collector, and the positive electrode current collector was used in a Li-Bi liquid metal battery in which the positive electrode described in example 8 was a metal Bi, the electrolyte was LiF-LiCl-LiBr ternary mixed salt, and the operating temperature was 500 ℃, the battery design capacity was 350Ah, and the positive electrode interface area was 350cm 2 。
The obtained liquid metal battery is charged at 300mA/cm 2 The current density is charged and discharged circularly, and the short circuit phenomenon occurs when the battery runs for 12 circles, so that the charging and discharging can not be continued.
The above embodiments are only examples for clearly illustrating the present invention and are not intended to limit the present invention. Other variants and modifications will be apparent to those skilled in the art in light of the foregoing description, which are not necessarily exhaustive of all embodiments and are therefore intended to be within the scope of the invention.

Claims (8)

1. An array type positive current collector for a liquid metal battery comprises a conductive shell and a columnar array arranged on the bottom surface of the shell, wherein the columnar array points to the negative direction;
the interface area of the positive electrode adopted by the liquid metal battery is 50-2000cm 2 ；
The number of the repeating units in the columnar array is 1-200.
2. The arrayed positive electrode current collector of claim 1, wherein the repeating units in the columnar array are cylindrical or prismatic.
3. The array positive electrode current collector of claim 1, wherein the conductive casing is a graphite casing, a stainless steel casing or a low carbon steel casing.
4. The array positive electrode current collector of claim 1, wherein the columnar array is made of one of graphite, stainless steel, low carbon steel, metal W and metal Mo.
5. The array type positive electrode current collector of claim 1, wherein a corrosion-resistant protective layer is additionally arranged on the surface of the conductive shell and/or the surface of the columnar array.
6. The array positive electrode current collector of claim 1, wherein the height of the columnar arrays is 0.1-50mm above the liquid metal level of the positive electrode and below the liquid metal level of the negative electrode.
7. The arrayed positive electrode current collector of claim 1, wherein the equivalent diameter of the repeating units in the columnar array is 1-50mm.
8. The array type positive electrode current collector of claim 1, wherein the columnar arrays are arranged in one or more combinations of concentric circle arrangement, triangular arrangement and quadrilateral arrangement.
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CN108470902A (en) * 2018-03-23 2018-08-31 西北工业大学 A kind of semi-liquid metal dynamic lithium battery suitable for deep-sea pressure resistance
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US4440837A (en) * 1982-09-27 1984-04-03 The United States Of America As Represented By The United States Department Of Energy Positive electrode current collector for liquid metal cells
CN206727162U (en) * 2017-01-20 2017-12-08 江南山 A kind of multitube sodium-sulphur battery
CN108470902A (en) * 2018-03-23 2018-08-31 西北工业大学 A kind of semi-liquid metal dynamic lithium battery suitable for deep-sea pressure resistance
CN109841910A (en) * 2019-02-28 2019-06-04 西安西电电气研究院有限责任公司 A kind of liquid metal cell

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