CN110911691A - Positive current collector for improving stability of liquid metal battery - Google Patents
Positive current collector for improving stability of liquid metal battery Download PDFInfo
- Publication number
- CN110911691A CN110911691A CN201911242528.9A CN201911242528A CN110911691A CN 110911691 A CN110911691 A CN 110911691A CN 201911242528 A CN201911242528 A CN 201911242528A CN 110911691 A CN110911691 A CN 110911691A
- Authority
- CN
- China
- Prior art keywords
- liquid metal
- current collector
- battery
- positive electrode
- tib
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. 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
- H01M4/661—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
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
-
- 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
- H01M4/664—Ceramic materials
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Ceramic Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a positive current collector for improving the stability of a liquid metal battery, which is characterized in that TiB is arranged on the surface of a conductive substrate2The coating effectively reduces the surface interfacial tension of the liquid metal of the anode, enables the liquid metal/molten salt interface of the anode to be spread in a plane, and reduces or even eliminates the phenomenon of uneven interface, thereby effectively promoting the safe and stable operation of the liquid metal battery and eliminating the short circuit risk caused by the wettability of the anode metal and the current collector; in addition, TiB is used2The coating can also effectively reduce the IR drop of the liquid metal battery, improve the output voltage value of the battery, further improve the energy efficiency of the liquid metal battery, and provide a brand new thought for the research and application of the high-performance and high-stability liquid metal battery.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a positive current collector for improving the stability of a liquid metal battery.
Background
The liquid metal battery is a three-layer battery structure which takes two liquid metals (alloys) with larger electronegativity difference as electrode materials and molten inorganic salt as electrolyte (the working temperature is 200-700 ℃), and self-assembles into a positive liquid metal with an upper layer as a negative liquid metal, an intermediate layer as an electrolyte and a lower layer as a negative liquid metal by utilizing the density difference and the immiscible property between the positive liquid metal and the negative liquid metal and the electrolyte. The liquid metal battery has a series of advantages of good rate performance, ultra-long cycle service life, high coulombic efficiency, high energy efficiency and the like due to the characteristics of the all-liquid battery and high working temperature, so that the liquid metal battery has wide application prospect in the field of distributed power grid energy storage, and is expected to become an efficient distributed power grid energy storage technology.
However, the metal activity of the anode of the liquid metal battery is high, and the anode is easy to generate alloying reaction with a conventional metal current collector; this phenomenon not only causes corrosion of the positive current collector and reduces the service life of the battery, but also consumes the positive metal, resulting in a decrease in the battery capacity. In order to solve the above technical problems, the current solution is to add a graphite lining in the positive current collector to prevent the positive metal from directly contacting the metal current collector. However, the introduction of the graphite lining tends to cause the interface between the positive electrode liquid metal and the molten salt to be in an upwardly convex "arch" shape under the action of interfacial tension. The nonuniformity of the interface shape of the positive electrode causes the nonuniform distribution of the interface current density, the bulge of the metal interface of the positive electrode is closest to the metal of the negative electrode, the current density at the bulge is the largest when the metal interface of the positive electrode is discharged, the solid alloy layer is preferentially generated at the bulge, the solid alloy layer at the bulge accumulates a little bit along with the continuous charging and discharging, so the operation of the battery is unstable, and when the alloy layer at the bulge accumulates to a certain height, the alloy layer can be contacted with the negative electrode, so the short. Particularly, in the amplification process of the single battery, the area of the positive electrode interface is increased, the unevenness and instability of the interface are more prominent, and the short-circuit risk of the battery is greater. Limited by the above technical problems, the Li-Sb-Sn liquid metal battery cell is enlarged to 100Ah (the positive electrode interface area is 100 cm)2) The problem of serious unstable operation occurs in time, and the short circuit phenomenon occurs after continuous cyclic charge and discharge; in addition, the molten salt can permeate downwards along the interface of the liquid metal and the graphite, so that the contact area of the anode metal and the graphite is reduced, and the conductivity of the system is further reduced.
Disclosure of Invention
The main object of the present invention is to provide a positive current collector for liquid metal battery, which is obtained by adding TiB to a conductive substrate2The coating solves the problems that the existing liquid metal battery is easy to be short-circuited in operation, difficult to be amplified by a single battery and the like, and is a research on high-performance liquid metal batteriesProvides a new idea.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a positive current collector for improving the stability of a liquid metal battery comprises a conductive substrate and TiB disposed on the surface of the conductive substrate2And (4) coating.
In the above scheme, the conductive substrate may be a metal substrate or a graphite substrate, wherein the metal substrate may be a low-carbon steel substrate or a stainless steel substrate.
Preferably, the conductive substrate and TiB2The carbon intermediate layer is arranged between the coatings, so that the conductive shell is further protected from being corroded by liquid metal, and the corrosion resistance of the obtained current collector is improved.
In the above scheme, the carbon intermediate layer is composed of one or more of graphite, carbon fiber and graphene.
In the scheme, the thickness of the carbon intermediate layer is 0.01-100 mu m.
In the above scheme, the TiB2The binding force of the coating (the binding force of the coating relative to the conductive substrate or the carbon intermediate layer) is 0.5-200N.
In the above scheme, the surface resistivity (i.e., TiB) of the positive current collector2Resistivity of coating) of 10-10-10-4Ω/m2。
In the above scheme, the liquid metal of the positive electrode suitable for the positive electrode current collector is composed of one or more of Te, Bi, Sb, Pb, and Sn.
In the above scheme, the molten salt electrolyte suitable for the positive current collector is LiF, LiCl, LiBr, NaCl, NaF, NaBr, MgF2、MgCl2、MgBr2、GaF2、GaCl2、GaBr2And any one or more of KF, KCl and KBr.
In the above scheme, the working temperature of the liquid metal battery is 100-800 ℃.
Preferably, the liquid metal battery is suitable for the anode interface area of 100-250cm2The conditions of (1).
Compared with the prior art, the invention has the beneficial effects that:
1) the invention firstly proposes to utilize TiB with good wettability with liquid metal2The coating effectively reduces the surface interfacial tension of the liquid metal of the anode, enables the liquid metal/molten salt interface of the anode to be spread in a plane, and reduces or even eliminates the phenomenon of uneven interface, thereby effectively promoting the safe and stable operation of the liquid metal battery and eliminating the short circuit risk caused by the wettability of the anode metal and the current collector; furthermore, TiB2The liquid metal battery has excellent conductivity, the wettability of the positive metal and the current collector is improved, the IR drop of the liquid metal battery can be effectively reduced, the output voltage value of the battery is improved, the energy efficiency of the battery is further improved, and a brand new thought is provided for the research and application of the high-performance and high-stability liquid metal battery.
2)TiB2The lithium ion battery has stable property and high temperature resistance, does not react with liquid metal, can effectively avoid the corrosion problem between the anode liquid metal and the current collector, and ensures the stable operation of the battery.
3) The invention is applied to conductive substrates and TiB2A carbon intermediate layer is additionally arranged between the coatings to effectively prevent TiB2When the local micro-area of the coating is cracked or falls off, the liquid metal anode corrodes the conductive substrate, and gain effects are generated on platform voltage, coulomb efficiency and the like, so that the high-efficiency and ultra-long-life stable operation of the battery can be further ensured.
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
A positive electrode current collector for improving the wettability of liquid metal battery is prepared from 304 steel as substrate through CVD depositing a layer of TiB on the surface of 304 steel2Coating to obtain the component of 304 steel/TiB2The wetting positive current collector of (1), TiB in the current collector2The coating thickness is 20um, the bonding force with the 304 steel shell is 154N, and the surface resistivity is 2.5 x 10-10Ω/m2。
The positive electrode current collector obtained in the embodiment is used as Sb for the positive electrode4Sn6Alloy and electrolyte are LiF-LiCl-LiBr ternary mixed salt, and the operating temperature is 500 ℃ in the Li-Sb-Sn liquid metal battery; the capacity of the obtained battery is 100Ah, and the interfacial area of the positive electrode is 100cm2(ii) a The obtained cell was charged at 100mA/cm2The voltage of a battery discharging platform is 0.8V when the current density is in circulating charging and discharging operation, the battery operates stably after 200 circles of circulating charging and discharging, the short circuit phenomenon does not occur, wherein the voltage of the battery discharging platform after 200 circles of circulating charging and discharging is 0.74V, the coulombic efficiency is 94%, and the capacity retention rate is 90%.
Comparative example 1
The 304 steel shell was directly used as the positive electrode current collector and applied to the positive electrode of Sb in example 16Sn4In the Li-Sb-Sn liquid metal battery with alloy and electrolyte of LiF-LiCl-LiBr ternary mixed salt and the operation temperature of 500 ℃, the capacity of the obtained battery is 100Ah, and the interface area of the positive electrode is 100cm2It was added at 100mA/cm2The discharge platform is 0.63V after the current density charge-discharge cycle runs for 100 circles, the coulombic efficiency is only 70%, the capacity retention rate is 71%, and the shell is seriously corroded.
Example 2
A positive electrode current collector for improving the wettability of liquid metal battery is prepared from 316 steel as substrate through CVD depositing a layer of TiB on the surface of 304 steel2Coating to obtain 316 steel/TiB2The wetting positive current collector of (1), TiB in the current collector2The coating thickness is 25 μm, the bonding force with the 316 steel shell is 154N, and the surface resistivity is 2.5 x 10-9Ω/m2。
The positive electrode current collector obtained in the embodiment is used as Sb for the positive electrode4Sn6Alloy and electrolyte are LiF-LiCl-LiBr ternary mixed salt, and the operating temperature is 500 ℃ in the Li-Sb-Sn liquid metal battery; the capacity of the obtained battery is 100Ah, and the interfacial area of the positive electrode is 100cm2(ii) a The obtained cell was charged at 100mA/cm2The voltage of a battery discharge platform is 0.8V, the battery operates stably after 200 cycles of cyclic charge and discharge without short circuit, wherein 200 cycles of the battery discharge platform is charged and discharged circularlyThe discharge platform of the battery after the ring is 0.76V, the coulombic efficiency is 93%, and the capacity retention rate is 91%.
Comparative example 2
316 steel shell is directly used as the positive electrode current collector, and the positive electrode current collector is applied to Sb as the positive electrode in example 26Sn4In the Li-Sb-Sn liquid metal battery with alloy and electrolyte of LiF-LiCl-LiBr ternary mixed salt and the operation temperature of 500 ℃, the capacity of the obtained battery is 100Ah, and the interface area of the positive electrode is 100cm2It was added at 100mA/cm2The discharge platform is 0.65V after the current density charge-discharge cycle runs for 100 circles, the coulombic efficiency is only 73 percent, the capacity retention rate is 70 percent, and the shell is seriously corroded.
Example 3
A positive electrode current collector for improving the wettability of liquid metal battery is prepared from 304 stainless steel with graphite layer plated on its surface, the thickness of graphite layer is 30 microns, and a layer of TiB is deposited on the surface of graphite layer by CVD technique2Coating to obtain the coating with the composition of 304 steel/graphite/TiB2The wetting positive current collector of (1), TiB in the current collector2The coating thickness is 15um, the bonding force with the graphite layer is 137N, and the surface resistivity is 6.8 x 10-10Ω/m2。
The positive electrode current collector obtained in the embodiment is used as Sb for the positive electrode5Sn5Alloy and electrolyte are LiF-LiCl-LiBr ternary mixed salt, and the operating temperature is 500 ℃ in the Li-Sb-Sn liquid metal battery; the capacity of the obtained battery is 100Ah, and the interfacial area of the positive electrode is 100cm2(ii) a The obtained cell was charged at 100mA/cm2After the current density is circularly charged and discharged for 200 circles, the short circuit phenomenon does not occur, wherein the discharge platform of the battery is 0.8V, the coulombic efficiency reaches more than 97 percent, and the capacity retention rate is more than 95 percent.
Comparative example 3
304 stainless steel with a graphite layer plated on the surface is directly used as a positive electrode current collector, and the positive electrode current collector is used as Sb of the positive electrode in example 35Sn5In the Li-Sb-Sn liquid metal battery with alloy and electrolyte of LiF-LiCl-LiBr ternary mixed salt and the operation temperature of 500 ℃, the capacity of the obtained battery is 100Ah, and the interface area of the positive electrode is 100cm2(ii) a The obtained electricity is usedThe pool rate is 100mA/cm2When the battery runs to 34 circles, the phenomenon that the voltage drops too fast during discharging occurs, and when the battery runs to 41 circles, the battery is in short circuit and cannot continue to run.
Example 4
A positive current collector for improving the wettability of liquid metal battery is prepared from 316 stainless steel with graphite layer plated on its surface, 40 microns thick graphite layer and a layer of TiB deposited on the surface of graphite layer by CVD method2Coating to obtain 316 steel/graphite/TiB2The wetting positive current collector of (1), TiB in the current collector2The coating thickness is 15um, the bonding force with the graphite layer is 137N, and the surface resistivity is 6.8 x 10-10Ω/m2。
The positive electrode current collector obtained in the embodiment is used as Sb for the positive electrode5Sn5Alloy and electrolyte are LiF-LiCl-LiBr ternary mixed salt, and the operating temperature is 500 ℃ in the Li-Sb-Sn liquid metal battery; the capacity of the obtained battery is 100Ah, and the interfacial area of the positive electrode is 100cm2(ii) a The obtained cell was charged at 100mA/cm2After the current density is circularly charged and discharged for 200 circles, the short circuit phenomenon does not occur, wherein the discharge platform of the battery is 0.81V, the coulombic efficiency reaches more than 97 percent, and the capacity retention rate is more than 95 percent.
Comparative example 4
316 stainless steel directly plated with a graphite layer was used as a positive electrode current collector for the positive electrode Sb described in example 45Sn5In the Li-Sb-Sn liquid metal battery with alloy and electrolyte of LiF-LiCl-LiBr ternary mixed salt and the operation temperature of 500 ℃, the capacity of the obtained battery is 100Ah, and the interface area of the positive electrode is 100cm2(ii) a The obtained cell was charged at 100mA/cm2The current density of the battery is charged and discharged in a circulating mode, the voltage is reduced too fast 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.
Example 5
A positive electrode current collector for improving the wettability of liquid metal battery is prepared from 304 steel as substrate through CVD depositing a layer of TiB on the surface of 304 steel2Coating to obtain a compositionIs 304 steel/TiB2The wetting positive current collector of (1), TiB in the current collector2The coating thickness is 20um, the bonding force with the 304 steel shell is 154N, and the surface resistivity is 2.5 x 10-10Ω/m2。
The positive current collector obtained in the embodiment is used for a Li-Bi liquid metal battery with a positive electrode being metal Bi, an electrolyte being LiF-LiCl-LiBr ternary mixed salt and an operating temperature being 500 ℃; the capacity of the obtained battery is 100Ah, and the interfacial area of the positive electrode is 150cm2(ii) a The resulting cell was charged at 150mA/cm2The battery operates stably after 200 cycles of current density cyclic charge and discharge, and the short circuit phenomenon does not occur, wherein the discharge platform of the battery after 200 cycles is 0.61V, the coulombic efficiency is 93%, and the capacity retention rate is 89%.
Comparative example 5
The 304 steel shell was directly used as a positive current collector and applied to the Li-Bi liquid metal battery of example 5, 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 capacity of the battery was 100Ah, and the interface area of the positive electrode was 100cm2It was added at 100mA/cm2After the current density charging and discharging cycle runs for 100 circles, the discharging platform is 0.42V, the coulombic efficiency is only 88%, the capacity retention rate is 73%, and the shell is seriously corroded.
Example 6
A positive electrode current collector for improving the wettability of liquid metal battery is prepared from 316 steel as substrate through CVD depositing a layer of TiB on the surface of 304 steel2Coating to obtain 316 steel/TiB2The wetting positive current collector of (1), TiB in the current collector2The coating thickness is 30um, the bonding force with the 304 steel shell is 127N, and the surface resistivity is 1.4 x 10-9Ω/m2。
The positive current collector obtained in the embodiment is used for a Li-Bi liquid metal battery with a positive electrode being metal Bi, an electrolyte being LiF-LiCl-LiBr ternary mixed salt and an operating temperature being 500 ℃; the capacity of the obtained battery is 100Ah, and the interfacial area of the positive electrode is 150cm2(ii) a The resulting cell was charged at 150mA/cm2After the current density is circularly charged and discharged for 200 circles, the battery runs stably without short circuit, wherein 200 circlesThe discharge plateau of the post-battery is 0.60V, the coulombic efficiency is 92%, and the capacity retention rate is 93%.
Comparative example 6
The 304 steel shell was directly used as the positive current collector and applied to the Li-Bi liquid metal battery of example 6, 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 capacity was 150Ah, and the interface area of the positive electrode was 150cm2It was measured at 150mA/cm2The discharge platform is 0.45V after the current density charge-discharge cycle runs for 31 circles, the coulombic efficiency is only 67%, the capacity retention rate is 90%, and the shell is seriously corroded.
Example 7
A positive electrode current collector for improving the wettability of liquid metal battery is prepared from 304 stainless steel with graphite layer plated on its surface, 40 microns thick, and a layer of TiB deposited on the surface of graphite layer by CVD method2Coating to obtain the coating with the composition of 304 steel/graphite/TiB2The wetting positive current collector of (1), TiB in the current collector2The coating thickness is 20um, the bonding force with the graphite layer is 110N, and the surface resistivity is 4.7 x 10-10Ω/m2。
The positive current collector obtained in the embodiment is used for a Li-Bi liquid metal battery with a positive electrode being metal Bi, an electrolyte being LiF-LiCl-LiBr ternary mixed salt and an operating temperature being 500 ℃; the capacity of the obtained battery is 100Ah, and the interfacial area of the positive electrode is 100cm2(ii) a The obtained cell was charged at 100mA/cm2After the current density is circularly charged and discharged for 200 circles, the short circuit phenomenon does not occur, wherein the discharge platform of the battery is 0.65V, the coulombic efficiency reaches more than 98%, and the capacity retention rate is more than 95%.
Comparative example 7
304 stainless steel with a graphite layer plated on the surface is directly used as a positive electrode current collector, the positive electrode current collector is used in a Li-Bi liquid metal battery with the positive electrode metal Bi, the electrolyte of the Li-Bi liquid metal battery is LiF-LiCl-LiBr ternary mixed salt and the operating temperature of the Li-Bi liquid metal battery is 500 ℃ in example 7, the capacity of the battery is 100Ah, and the area of a positive electrode interface is 100cm2(ii) a The obtained cell was charged at 100mA/cm2The current density of the battery is charged and discharged circularly, and the battery is discharged when the battery runs for 67 circlesWhen the current discharge is over-fast, the battery is short-circuited when the current discharge is operated to 75 circles, and the battery cannot continue to operate.
Example 8
A positive current collector for improving the wettability of liquid metal battery is prepared from 316 stainless steel with graphite layer plated on its surface, 27 microns thick graphite layer and a layer of TiB deposited on the surface of graphite layer by CVD method2Coating to obtain 316 steel/graphite/TiB2The wetting positive current collector of (1), TiB in the current collector2The coating thickness is 30um, the bonding force with the graphite layer is 151N, and the surface resistivity is 5.3 x 10-9Ω/m2。
The positive current collector obtained in the embodiment is used for a Li-Bi liquid metal battery with a positive electrode being metal Bi, an electrolyte being LiF-LiCl-LiBr ternary mixed salt and an operating temperature being 500 ℃; the capacity of the obtained battery is 150Ah, and the area of the positive electrode interface is 152cm2(ii) a The obtained cell was charged at 100mA/cm2After the current density is circularly charged and discharged for 200 circles, the short circuit phenomenon does not occur, wherein the discharge platform of the battery is 0.63V, the coulombic efficiency reaches more than 98%, and the capacity retention rate is more than 95%.
Comparative example 8
316 stainless steel with a graphite layer plated on the surface is directly used as a positive electrode current collector, the positive electrode current collector is used in a Li-Bi liquid metal battery with the positive electrode as described in example 8, the positive electrode is made of metal Bi, electrolyte is LiF-LiCl-LiBr ternary mixed salt, and the operating temperature is 500 ℃, the battery capacity is 150Ah, and the positive electrode interface area is 152cm2(ii) a The obtained cell was charged at 100mA/cm2The current density of the battery is charged and discharged in a circulating mode, the voltage is reduced too fast when the battery runs to 72 circles, and the battery is short-circuited when the battery runs to 81 circles, so that the battery cannot continue to run.
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessary or exhaustive for all embodiments, and are therefore within the scope of the invention.
Claims (10)
1. A positive current collector for improving the stability of a liquid metal battery, comprising a conductive substrate and TiB disposed on the surface thereof2And (4) coating.
2. The positive current collector of claim 1, wherein the conductive substrate is selected from a graphite, low carbon steel, or stainless steel substrate.
3. The positive electrode current collector of claim 1, wherein the TiB2The thickness of the coating is 0.01-100 μm.
4. The positive current collector of claim 1, wherein the conductive substrate and the TiB are bonded together2And a carbon intermediate layer is arranged between the coatings.
5. The positive electrode current collector according to claim 4, wherein the carbon intermediate layer is composed of one or more of graphite, carbon fiber, and graphene.
6. The positive electrode current collector as claimed in claim 4, wherein the thickness of the carbon intermediate layer is 0.01 to 100 μm.
7. The positive electrode current collector of claim 1, wherein the TiB2The binding force of the coating is 0.5-200N.
8. The positive electrode current collector according to claim 1, wherein the surface resistivity thereof is 10-10Ω/m2-10-4Ω/m2。
9. The positive electrode current collector of claim 1, wherein the positive electrode liquid metal in the liquid metal battery consists of one or more of Te, Bi, Sb, Pb, Sn.
10. The positive electrode current collector as claimed in claim 1, wherein the operating temperature of the liquid metal battery is 100-800 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911242528.9A CN110911691A (en) | 2019-12-06 | 2019-12-06 | Positive current collector for improving stability of liquid metal battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911242528.9A CN110911691A (en) | 2019-12-06 | 2019-12-06 | Positive current collector for improving stability of liquid metal battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110911691A true CN110911691A (en) | 2020-03-24 |
Family
ID=69823039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911242528.9A Pending CN110911691A (en) | 2019-12-06 | 2019-12-06 | Positive current collector for improving stability of liquid metal battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110911691A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113193179A (en) * | 2021-03-29 | 2021-07-30 | 西安交通大学 | Liquid metal battery and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US5227045A (en) * | 1989-01-09 | 1993-07-13 | Townsend Douglas W | Supersaturation coating of cathode substrate |
| JP2001250542A (en) * | 2000-03-07 | 2001-09-14 | Sumitomo Metal Ind Ltd | Powder material suitable to negative electrode for lithium secondary battery |
| US20150004455A1 (en) * | 2013-02-12 | 2015-01-01 | Ambri Inc. | Electrochemical energy storage devices |
| US20160254512A1 (en) * | 2015-02-27 | 2016-09-01 | Massachusetts Institute Of Technology | Electrochemical Cell with Bipolar Faradaic Membrane |
| US20170018811A1 (en) * | 2013-10-16 | 2017-01-19 | Ambri Inc. | Seals for high temperature reactive material devices |
| CN107221677A (en) * | 2017-07-05 | 2017-09-29 | 北京科技大学 | A kind of liquid metal cell of high-energy-density |
| CN207368145U (en) * | 2017-07-20 | 2018-05-15 | 东莞威胜储能技术有限公司 | A kind of liquid metal cell |
| CN108682864A (en) * | 2017-12-29 | 2018-10-19 | 上海其鸿新材料科技有限公司 | A kind of lithium battery collector and preparation method thereof |
| US10461311B1 (en) * | 2018-05-17 | 2019-10-29 | Vissers Battery Corporation | Devices, systems, and methods for molten fluid electrode apparatus management |
-
2019
- 2019-12-06 CN CN201911242528.9A patent/CN110911691A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US5227045A (en) * | 1989-01-09 | 1993-07-13 | Townsend Douglas W | Supersaturation coating of cathode substrate |
| JP2001250542A (en) * | 2000-03-07 | 2001-09-14 | Sumitomo Metal Ind Ltd | Powder material suitable to negative electrode for lithium secondary battery |
| US20150004455A1 (en) * | 2013-02-12 | 2015-01-01 | Ambri Inc. | Electrochemical energy storage devices |
| US20170018811A1 (en) * | 2013-10-16 | 2017-01-19 | Ambri Inc. | Seals for high temperature reactive material devices |
| US20160254512A1 (en) * | 2015-02-27 | 2016-09-01 | Massachusetts Institute Of Technology | Electrochemical Cell with Bipolar Faradaic Membrane |
| CN107221677A (en) * | 2017-07-05 | 2017-09-29 | 北京科技大学 | A kind of liquid metal cell of high-energy-density |
| CN207368145U (en) * | 2017-07-20 | 2018-05-15 | 东莞威胜储能技术有限公司 | A kind of liquid metal cell |
| CN108682864A (en) * | 2017-12-29 | 2018-10-19 | 上海其鸿新材料科技有限公司 | A kind of lithium battery collector and preparation method thereof |
| US10461311B1 (en) * | 2018-05-17 | 2019-10-29 | Vissers Battery Corporation | Devices, systems, and methods for molten fluid electrode apparatus management |
Non-Patent Citations (1)
| Title |
|---|
| 戴达煌等: "《功能薄膜及沉积制备技术》", 31 January 2013, 冶金工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113193179A (en) * | 2021-03-29 | 2021-07-30 | 西安交通大学 | Liquid metal battery and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | An artificial polyacrylonitrile coating layer confining zinc dendrite growth for highly reversible aqueous zinc‐based batteries | |
| Bi et al. | Anode material options toward 500 Wh kg− 1 lithium–sulfur batteries | |
| CN108232114B (en) | Composite cathode, preparation and application thereof in preparation of lithium ion battery | |
| US10480090B2 (en) | Electrolytic copper foil, current collector comprising the same, electrode comprising the same, secondary battery comprising the same, and method for manufacturing the same | |
| WO2018103563A1 (en) | Lithium metal negative electrode utilized in lithium battery | |
| Shi et al. | Constructing an elastic solid electrolyte interphase on graphite: a novel strategy suppressing lithium inventory loss in lithium-ion batteries | |
| CN103477477A (en) | Negative electrode active material for a lithium secondary battery, and method for preparing same | |
| KR101272879B1 (en) | Grid for lead-acid battery with electroconductive polymer coating | |
| US20200083556A1 (en) | Battery, battery pack, and uninterruptible power supply | |
| WO2019000700A1 (en) | Pulse charging method for lithium metal battery | |
| US10388964B2 (en) | Graphene-based coating on lead grid for lead-acid batteries | |
| CN110600677A (en) | Lithium metal negative electrode, preparation method thereof and lithium metal, lithium sulfur and lithium air battery | |
| CN110911692B (en) | Corrosion-resistant liquid metal battery positive electrode current collector | |
| CN102660697A (en) | Lead-acid battery grid alloy for power | |
| CN110911691A (en) | Positive current collector for improving stability of liquid metal battery | |
| Xu et al. | Overcoming Challenges: Extending Cycle Life of Aqueous Zinc‐Ion Batteries at High Zinc Utilization through a Synergistic Strategy | |
| Martha et al. | A low-cost lead-acid battery with high specific-energy | |
| CN117587474A (en) | Zinc alloy negative electrode and preparation method and application thereof | |
| CN108390076A (en) | A kind of lead flow battery | |
| CN116314690A (en) | Preparation method of zinc ion battery anode material with three-dimensional structure | |
| CN103259024A (en) | Composite negative plate of cerium and zinc redox flow cell and preparation method of plate | |
| CN110890549B (en) | Array type positive current collector for liquid metal battery | |
| CN102340042B (en) | A kind of solar-energy photo-voltaic cell | |
| CN114744158A (en) | Method for applying organic/inorganic composite coating to surface modification of lithium metal electrode | |
| CN114784383A (en) | Free solvent molecule-free electrolyte system and manufacturing method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |