CN114122510B - Four-component inorganic molten salt electrolyte for lithium-based liquid metal battery - Google Patents
Four-component inorganic molten salt electrolyte for lithium-based liquid metal battery Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 104
- 150000003839 salts Chemical class 0.000 title claims abstract description 64
- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 42
- 230000008018 melting Effects 0.000 claims abstract description 42
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims abstract description 19
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 16
- 230000001276 controlling effect Effects 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007773 negative electrode material Substances 0.000 abstract description 7
- 239000007774 positive electrode material Substances 0.000 abstract description 7
- 230000007423 decrease Effects 0.000 abstract description 4
- 239000006181 electrochemical material Substances 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004146 energy storage Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229910013360 LiBr—LiI Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000001360 synchronised effect Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- -1 halogen salt Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
-
- 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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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a four-component inorganic molten salt electrolyte for a lithium-based liquid metal battery, which belongs to the technical field of electrochemical materials. The electrolyte comprises the following components in percentage by mass: 7-40% of LiF, 10-40% of LiCl, 10-40% of LiBr and 10-50% of LiI; the melting point of the electrolyte is reduced to 336 ℃ by regulating and controlling the dosage of LiI and other components, and the density is kept to be 2.3g/cm 3 ～2.4g/cm 3 . The electrolyte widens the working temperature range of the liquid metal battery to 336-550 ℃, and reduces the running cost of the battery; overcomes the great increase of density caused by the decrease of the melting point of the electrolyte, ensures the density of the electrolyte to be controlled at 2.2g/cm 3 ～2.4g/cm 3 And between the densities of the positive electrode material and the negative electrode material, a three-layer structure of the liquid metal battery can be spontaneously formed in a molten state.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a four-component inorganic molten salt electrolyte for a lithium-based liquid metal battery.
Background
The large-scale energy storage technology plays an important role in expanding the renewable energy grid-connected scale, improving the power supply reliability of the power system, reducing the peak-valley difference of the power grid, constructing a micro-grid and the like, and is a support technology for constructing a future intelligent power grid and realizing energy interconnection.
Among various existing large-scale energy storage technologies, the electrochemical energy storage technology is one of the main energy storage technologies for new energy grid connection in the future due to the advantages of high energy density, quick response time, low maintenance cost, flexibility, convenience and the like. However, from the perspective of power grid application, the existing various battery energy storage technologies cannot completely meet the market requirements on key indexes such as energy storage price, cycle life and the like.
Liquid Metal Batteries (LMBS) are low-cost and high-efficiency electrochemical energy storage technologies, and have wide development prospects in the field of large-scale energy storage.
Liquid metal batteries are under operating conditions: the electrode material and the electrolyte material are in a liquid state. The working temperature of the liquid metal battery is 300-700 ℃, and the positive electrode material, the negative electrode material and the electrolyte material are mutually immiscible due to different densities and can be automatically divided into three layers, so that the normal working of the liquid metal battery is ensured.
The inorganic salt electrolyte of the liquid metal battery generally meets (1) an appropriate density between the positive and negative electrodes so that the sealed interior can automatically separate into three layers of liquid at operating temperature; (2) No spontaneous reaction with the electrode material, so that the internal consumption of the battery is reduced, and the cycle performance of the battery is enhanced; (3) The solubility of the liquid metal in the molten salt is minimum, so that the loss of electrode materials is reduced, and the service life of the battery is prolonged; (4) The melting temperature is low, the working temperature of the battery is reduced, and the energy efficiency is improved; (5) The high ion conductivity improves the output power of the battery and enhances the performance of the battery.
The physical properties of the inorganic molten salt electrolyte of the liquid metal battery have great influence on the working state and the performance of the battery. According to the law of entropy increase in the law of thermodynamics, there is a tendency for high temperature to low temperature transition when the system tends to disorder. Based on the above, the method expands into binary, ternary, quaternary and other multi-element inorganic molten salt electrolyte systems on the basis of the pure-component inorganic molten salt electrolyte LiF, liCl, liBr, liI. However, it does not mean that the lower the melting point is, the better the physical properties such as density, ionic conductivity, viscosity, etc. of the multi-element inorganic molten salt electrolyte will also affect the performance of the liquid metal cell. Therefore, when constructing an inorganic molten salt electrolyte system for a liquid metal battery, a combination of various physical properties is required.
Iodide-based thermoelectric cell electrolytes were studied in 2006 by Patrick Masset (Patrick Masset; "Iodied-based electrolytes: A promising alternative for thermal batteries"; journal of Power Sources 160 (2006) 688-697). The report mainly researches that the component of the inorganic molten salt electrolyte is 9.6LiF-22LiCl-68.4LiBr with the working temperature of 443 ℃;3.2LiF-13LiCl-83.8LiI with an operating temperature of 341 ℃; the working temperature of 4.9LiF-11.2LiCl-34.9LiBr-49LiI was 360 ℃.
In 2010 FUJIWARA S, INABA M, TASAKA A2010.New molten salt systems for high-temperature molten salt batteries: liF-LiCl-LiBr-based four-component systems journal of Power Sources [ J ],195:7691-7700. Quaternary inorganic molten salt electrolyte systems based on (16-20) LiF- (20-22) LiBr- (57-60) LiI were studied, wherein the fourth component material was: naF, KF, naCl, KCl, naBr, KBr. For example, 20LiF-22LiBr-57LiI-1NaF has a melting point of 440℃and an ionic conductivity of 3.33S/cm at 500 ℃; the melting point of 16LiF-22LiBr-59LiI-3NaF is 435 ℃, and the ionic conductivity at 500 ℃ is 3.30S/cm; the melting point of the 19LiF-22LiBr-58LiI-1KF is 440 ℃, and the ionic conductivity at 500 ℃ is 3.36S/cm; the melting point of 16LiF-21LiBr-60LiI-3KF is 435 ℃, and the ionic conductivity at 500 ℃ is 3.28S/cm.
FUJIWARAS, INABAM, TASAKA A2011.New molten salt systems for high temperature molten salt batteries:Ternary and quaternary molten salt systems based on LiF-LiCl, liF-LiBr, and LiCl-LiBr. Journal of Power Sources [ J ],196:4012-4018. Ternary and quaternary inorganic molten salt electrolyte systems constructed based on binary inorganic molten salt electrolytes LiF-LiCl, liF-LiBr, liCl-LiBr were studied. For example, 2LiF-84LiCl-14KF has a melting point of 450℃and an ionic conductivity of 2.65S/cm at 500 ℃; the melting point of 21LiCl-66LiBr-13KF is 405 ℃, and the ionic conductivity at 500 ℃ is 2.56S/cm; the melting point of 4LiCl-59LiBr-23NaCl-14KCl is 420 ℃, the ionic conductivity at 500 ℃ is 2.73S/cm, etc.
An electrolyte of the type mentioned in 2014 Kangli Wang, kai Jiang et al Lithium-anti-lead liquid metal battery for grid-level energy storage [ J ], NATURE,2014,514,348-350, having a composition of 20LiF-50LiCl-30LiI operating at 450 ℃.
In the publication of Self-sealing Li-Bi liquid metal battery for grid-scale energy storage [ J ]. Journal of Power Sources,2015,275:370-376 by Xiaohui Ning, satyajit Phadke et al, 2015, an electrolyte is mentioned which has a composition of 30LiCl-70LiF and an operating temperature of 550 ℃.
High Performance Liquid Metal Battery with Environmentally Friendly Antimony-Tin Positive Electrode [ J ]. ACS Applied Materials & Interfaces ] published by Haomiao Li et al, 2016, an electrolyte having a composition of 22LiF-31LiCl-47LiBr and a working temperature of 500 ℃.
Correlation of Valence Electron Structures and Thermal and Electric Properties in Li Sb-Based Liquid Metal Batteries [ J ] published by Tong Su, jian Zhang et al in 2020]ACS Applied energy materials an electrolyte of the type mentioned, having a composition of 56LiCl-24LiBr-20LiI, a working temperature of 468℃and a density of 2.07g/cm 3 The solubility was 0.352mol%.
Through literature comparison, the working temperature of the inorganic fused salt electrolyte containing the halogen salt series of the Li element is 341-550 ℃. In addition, the working temperature of the inorganic molten salt electrolyte is lower than the decomposition temperature of the electrode material, and the liquid density is between the anode and the cathode, so that certain viscosity, ionic conductivity and thermal conductivity are ensured, and therefore, when the inorganic molten salt electrolyte for the liquid metal battery is screened, the relationship among the physical properties needs to be comprehensively considered, and the relationship cannot only depend on the melting point.
Disclosure of Invention
In order to solve the problems, the invention provides a four-component inorganic molten salt electrolyte for a lithium-based liquid metal battery, which comprises the following components in percentage by mass: 7-40% of LiF, 10-40% of LiCl, 10-40% of LiBr and 10-50% of LiI; the melting point of the electrolyte is reduced to 336 ℃ by regulating and controlling the dosage of LiI and other components, and the density is kept to be 2.3g/cm 3 ～2.4g/cm 3 . The method is suitable for large-scale energy storage liquid metal battery monomers.
The electrolyte comprises the following components in percentage by mass: 7% -12% of LiF, 10% -40% of LiCl, 18% -28% of LiBr and 33% -50% of LiI.
The electrolyte comprises the following components in percentage by mass: 7% -9% of LiF, 30% -40% of LiCl, 18% -22% of LiBr and 33% -40% of LiI.
For LiF-LiCl-LiBr-LiI quaternary electrolyte system, because LiI has the greatest density and lowest melting point, the research on the relative content of LiI has a crucial effect on the electrolyte system because the research has an important role in adjusting the physical properties of the quaternary electrolyte system. As shown in fig. 1 and 2, the melting point of the inorganic molten salt electrolyte is the same as the phase of LiIInversely proportional to the content, i.e. if the lowest temperature of the working temperature zone of the electrolyte is lowered, a series of problems with increased density are faced. The density of the electrolyte is closely related to the structure of the liquid metal battery, and only the density of the electrolyte is controlled to be 2.2g/cm 3 ～2.4g/cm 3 In the range, the three-layer structure of the liquid metal battery can be maintained only between the densities of the positive electrode material and the negative electrode material.
The solubility of the negative metal Li in the molten salt electrolyte is only 0.28-0.30%, so that the loss of electrode materials is reduced; the ionic conductivity is larger than 0.1S/cm, the viscosity is moderate, the effective working temperature area of the liquid metal battery is expanded to a certain extent, the battery cost is controlled, and the battery working efficiency is ensured.
The working temperature area of the electrolyte is 336-550 ℃, the viscosity is 2.1 mPas-2.2 mPas, the ionic conductivity is more than 0.1S/cm, the thermal conductivity is 0.5W/mK-0.6W/mK, and the solubility of the negative electrode metal Li in the electrolyte is 0.28-0.30%.
After the sample was sufficiently ground, water was removed at 250℃for 4 hours under an argon atmosphere, and a heat treatment of melting was performed at 450 ℃.
The application of the four-component inorganic molten salt electrolyte in the liquid metal battery with the metal lithium as a negative electrode and the metal lithium alloy as a positive electrode.
The invention has the beneficial effects that:
1. the four-component inorganic molten salt electrolyte for the lithium-based liquid metal battery has good comprehensive physical properties, expands the working temperature range of the liquid metal battery to 336-550 ℃, and reduces the battery operation cost; overcomes the great increase of density caused by the decrease of the melting point of the electrolyte, ensures the density of the electrolyte to be controlled at 2.2g/cm 3 ～2.4g/cm 3 Between the densities of the positive electrode material and the negative electrode material, a three-layer structure of the liquid metal battery can be spontaneously formed in a molten state; and the solubility is low and is only 0.28-0.30%, so that the loss of electrode materials is reduced, the cost of the battery is controlled, and the working stability of the battery is improved.
2. The invention relates to a four-component inorganic molten salt electrolyte for a lithium-based liquid metal battery, which is used for calculating physical properties such as density, solubility, viscosity, ionic conductivity, thermal conductivity and the like.
Drawings
FIG. 1 shows the relative content of LiI as a function of density and melting point;
FIG. 2 is a schematic diagram of density versus viscosity, ionic conductivity, and thermal conductivity;
FIG. 3 is a DSC thermogram of the four-component inorganic molten salt electrolyte 9.1LiF-30LiCl-21.7LiBr-39.2LiI of example 1 of the present invention;
FIG. 4 is a DSC thermogram of a four-component inorganic molten salt electrolyte of example 2, 7.8LiF-40LiCl-18.6LiBr-33.6LiI of the present invention.
Detailed Description
The invention is described in further detail below with reference to the attached drawings and specific examples:
LiF, liCl, liBr, liI in the invention is an analytically pure medicine purchased in the chemical market, the purity is 99.99%, and an electronic balance with the precision of 0.001g is used for proportioning and preparing a sample.
After the sample preparation was completed, water was removed at 250℃under an argon atmosphere, and a heat treatment was performed at 450 ℃.
After the heat treatment is finished, a German relaxation-resistant synchronous thermal analyzer STA449F3 is used for carrying out a melting point test, and Al is selected as a test 2 O 3 The temperature of the crucible is raised by 10K/min.
The density calculation formula at the inorganic molten salt electrolyte temperature of T:
wherein x is i Is the mole fraction of the inorganic molten salt electrolyte; ρ i Is the density of the inorganic molten salt electrolyte at temperature T.
The solubility of the negative electrode metal Li in the molten salt electrolyte is calculated as:
wherein ρ is 0 、V 0 Is Li + Is a liquid density, volume; r is (r) 0 Is Li + Radius; ρ i 、V i The density and the volume of the electrolyte are liquid inorganic molten salt; r is (r) i Is the ionic radius of the inorganic molten salt electrolyte.
The viscosity calculation formula of the inorganic molten salt electrolyte is as follows:
wherein eta i Viscosity, x of inorganic molten salt electrolyte i Is the mole fraction of the inorganic molten salt electrolyte.
The ionic conductivity calculation formula of the inorganic molten salt electrolyte at the temperature T is as follows:
wherein the method comprises the steps ofIs the equivalent conductivity of inorganic fused salt electrolyte, M i Is of the formula weight of the electrolyte->Is the density of the inorganic molten salt electrolyte.
The thermal conductivity of the inorganic molten salt electrolyte is calculated according to the formula:
wherein lambda is i Is the thermal conductivity of inorganic fused salt electrolyte, x i Is the mole fraction of the inorganic molten salt electrolyte.
LiF, liCl, liBr, liI the physical properties of the four pure component inorganic molten salt electrolytes are shown in table 1, with the highest melting point of lif and the lowest melting point of LiI; in contrast, liI has the highest density, liCl has the lowest density, followed by LiF. The invention relates to a four-component inorganic molten salt electrolyte for a lithium-based liquid metal battery, which is constructed on the basis of 13LiF-31LiBr-56LiI, and the melting point of the system is 375 ℃. It can be seen from table 1 that LiF, liCl, liBr, liI each has a merit in terms of performance. The combination of the different physical properties of the four components determines the performance of the polyelectrolyte system. In combination, there is a negative correlation of density with viscosity, ionic conductivity, thermal conductivity, i.e., as density increases, viscosity, ionic conductivity, thermal conductivity of the electrolyte decreases, and vice versa.
TABLE 1LiF LiCl, liBr, liI Performance parameters
For LiF-LiCl-LiBr-LiI quaternary electrolyte system, because LiI has the greatest density and lowest melting point, the research on the relative content of LiI has a crucial effect on the electrolyte system because the research has an important role in adjusting the physical properties of the quaternary electrolyte system. As shown in fig. 1, the melting point of an inorganic molten salt electrolyte is inversely related to the relative content of LiI, i.e., if the lowest temperature of the working temperature region of the electrolyte is lowered, a series of problems with increased density are faced. FIG. 2 shows the relationship between the density and the solubility, the viscosity, the electrical conductivity and the thermal conductivity of LiF-LiCl-LiBr-LiI quaternary electrolyte systems with different components, and the abscissa components 1, 2, 3 and 4 respectively show that the contents of 11.7LiF-10LiCl-27.9LiBr-50.4LiI, 10.4LiF-20LiCl-24.8LiBr-44.8LiI, 9.1LiF-30LiCl-21.7LiBr-39.2LiI and 7.8LiF-40LiCl-18.6LiBr-33.6LiI are gradually reduced, and the density and other physical properties have inverse proportion. The density of the electrolyte is closely related to the structure of the liquid metal battery, and only the density of the electrolyte is controlled to be 2.2g/cm 3 ～2.4g/cm 3 In the range, the three-layer structure of the liquid metal battery can be maintained between the densities of the positive electrode material and the negative electrode material, so that the overall performance of the battery is optimized.
Example 1
The invention relates to a four-component for a lithium-based liquid metal batteryThe inorganic molten salt electrolyte is used for preparing a sample according to 9.1LiF-30LiCl-21.7LiBr-39.2LiI, after the sample preparation is completed, the water is removed at 250 ℃ for 4 hours in an argon atmosphere, and the melting point of the sample is measured by using a synchronous thermal analyzer STA449F3 after the heat treatment is completed, so that a thermal analysis graph of the graph in FIG. 3 is obtained, wherein the melting point is 336.1 ℃. The physical properties of the constituent electrolytes were calculated using the formulas (1) to (5), respectively. At a working temperature of 500 ℃, the performance is as follows: density of 2.409g/cm 3 The solubility of the negative electrode metal Li in the molten salt electrolyte was 0.282%, the viscosity was 2.191 mPas, the ionic conductivity was 3.225S/cm, and the thermal conductivity was 0.591W/mK.
Example 2
The invention relates to a four-component inorganic molten salt electrolyte for a lithium-based liquid metal battery, which is used for preparing a sample according to 7.8LiF-40LiCl-18.6LiBr-33.6LiI, dehydrating for 4 hours in an argon atmosphere at 250 ℃ after the sample preparation is finished, carrying out melt heat treatment at 450 ℃, and measuring the melting point of the sample by using a synchronous thermal analyzer STA449F3 after the heat treatment is finished to obtain a thermal analysis graph of the graph in fig. 4, wherein the melting point is 336.5 ℃. The physical properties of the constituent electrolytes were calculated using the formulas (1) to (5), respectively. At a working temperature of 500 ℃, the performance is as follows: the density is 2.286g/cm 3 The solubility of the negative electrode metal Li in the molten salt electrolyte was 0.307%, the viscosity was 2.178 mPas, the ionic conductivity was 2.82S/cm, and the thermal conductivity was 0.601W/mK.
Comparative example 1
Analytically pure drug LiF, liCl, liBr is purchased from the chemical market. Sample preparation was performed according to 31LiCl-22LiF-47LiBr, after the preparation was completed, water was removed at 250℃under an argon atmosphere, after the melting heat treatment was performed at 450℃the melting point was measured using a simultaneous thermal analyzer STA449F3, the melting point was 430℃and, by calculation, the density was 2.120g/cm at 500℃working temperature 3 The solubility of the negative electrode metal Li in the molten salt electrolyte is 0.4167%, and the ionic conductivity is more than 0.1S/cm.
Comparative example 2
Analytically pure drugs LiF, liBr, liI were purchased from the chemical market. Sample preparation is carried out according to 13LiF-31LiBr-56LiI, and after the preparation is finished, the sample is subjected to argon atmosphere at 250 DEG CDewatering, performing melting heat treatment at 450deg.C, measuring melting point with synchronous thermal analyzer STA449F3, wherein the melting point is 375 deg.C, and the density is 2.646g/cm at 500deg.C 3 The solubility of the negative electrode metal Li in the molten salt electrolyte is 0.2343%, and the ionic conductivity is more than 0.1S/cm.
Comparative example 3
Analytically pure drug LiF, liCl, liBr, liI is purchased from the chemical market. Sample preparation was performed according to 10.8LiF-26.1LiCl-10LiBr-53.1LiI, after the preparation was completed, water was removed at 250℃under argon atmosphere, melting point was measured at 340℃using a simultaneous thermal analyzer STA449F3 after the melting heat treatment at 450℃and density was 2.51g/cm at 500℃as calculated 3 The solubility of the negative electrode metal Li in the molten salt electrolyte was 0.258%, the viscosity was 2.168 mPas, the ionic conductivity was 2.56S/cm, and the thermal conductivity was 0.59W/mK.
Comparative analysis
From the analysis of the above examples and comparative examples, it can be seen that:
1. the melting points of the electrolyte LiF-LiCl-LiBr-LiI for the four-component inorganic molten salt liquid metal battery prepared in the embodiment 1 and the embodiment 2 are 336.1 ℃ and 336.5 ℃ respectively, and the melting point of the electrolyte component LiCl-LiF-LiBr prepared in the comparative example 1 is reduced by nearly 100 ℃ compared with the melting point of the electrolyte component LiCl-LiBr prepared in the comparative example 1; the electrolytes of example 1 and example 2 on this basis maintained a density of 2.409g/cm at an operating temperature of 500 °c 3 And 2.286g/cm 3 2.120g/cm compared to comparative example 1 3 Although the density is slightly increased by the addition of LiI, the density is only deviated by 0.289g/cm 3 And is kept at 2.2g/cm 3 ～2.4g/cm 3 The three-layer structure of the liquid metal battery can be well maintained within the density range of the positive electrode material and the negative electrode material.
Also, the electrolytes obtained in examples 1 and 2 reduced the solubility of the negative electrode metal Li in the molten salt electrolyte by 0.1%, while achieving a significant improvement in the cycle performance of the battery. At the same time, the ion conductivity exhibits a great improvement effect.
2. Examples and matrix electrolyte comparative example 2The melting point of 13LiF-31LiBr-56LiI is reduced by 39 ℃ and the density is reduced by 0.2-0.4 g/cm 3 Although the solubility of the negative electrode metal Li in the molten salt electrolyte is slightly increased, mainly in relation to the decrease in the ratio of LiI, there is a large increase in all the properties as compared with other properties.
3. Examples 1 and 2 each had LiF-LiCl-LiBr-LiI as a constituent compared with comparative example 3, and the melting point was reduced by 4℃and the density was reduced by 0.1 to 0.2g/cm as compared with comparative example 3 The ionic conductivity is increased by 0.3 to 0.7S/cm. The ionic conductivity is greatly improved, and the performance of the battery can be improved.
The electrolyte density was at 2.2g/cm by comparison 3 ～2.4g/cm 3 The three-layer structure of the liquid metal battery can be maintained between the densities of the positive electrode material and the negative electrode material; the solubility of the negative metal Li in the molten salt electrolyte is moderate and is only 0.28-0.30%, so that the loss of electrode materials is reduced; the ionic conductivity is larger than 0.1S/cm, the viscosity is moderate, the effective working temperature area of the liquid metal battery is expanded to a certain extent, the battery cost is controlled, and the battery working efficiency is ensured.
Claims (5)
1. A four-component inorganic molten salt electrolyte for a lithium-based liquid metal battery, characterized in that the electrolyte comprises the following components in percentage by mass: 7-12% of LiF, 10-40% of LiCl, 18-28% of LiBr and 33-50% of LiI; the melting point of the electrolyte is reduced to 336 ℃ by regulating and controlling the dosage of LiI and other components, and the density is kept to be 2.3g/cm 3 ～2.4g/cm 3 。
2. The four-component inorganic molten salt electrolyte for a lithium-based liquid metal battery according to claim 1, wherein the electrolyte comprises the following components in percentage by mass: 7% -9% of LiF, 30% -40% of LiCl, 18% -22% of LiBr and 33% -40% of LiI.
3. The four-component inorganic molten salt electrolyte for a lithium-based liquid metal battery according to any one of claims 1 or 2, wherein the working temperature zone of the electrolyte is 336-550 ℃, the viscosity is 2.1 mPa-S-2.2 mPa-S, the ionic conductivity is greater than 0.1S/cm, the thermal conductivity is 0.5W/mK-0.6W/mK, and the solubility of the negative metal Li in the electrolyte is 0.28-0.30%.
4. A method for producing the four-component inorganic molten salt electrolyte for a lithium-based liquid metal battery according to claim 1 or 2, characterized in that the sample is sufficiently ground, dehydrated for 4 hours at 250 ℃ in an argon atmosphere, and subjected to a fusion heat treatment at 450 ℃.
5. Use of a four-component inorganic molten salt electrolyte according to claim 1 or 2 in a liquid metal battery with metallic lithium as negative electrode and metallic lithium alloy as positive electrode.
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