CN114122510A - 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
- Publication number
- CN114122510A CN114122510A CN202111414695.4A CN202111414695A CN114122510A CN 114122510 A CN114122510 A CN 114122510A CN 202111414695 A CN202111414695 A CN 202111414695A CN 114122510 A CN114122510 A CN 114122510A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- molten salt
- liquid metal
- metal battery
- lithium
- 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.)
- Granted
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 107
- 150000003839 salts Chemical class 0.000 title claims abstract description 64
- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 44
- 230000008018 melting Effects 0.000 claims abstract description 44
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims abstract description 36
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 32
- 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 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 abstract description 7
- 239000007774 positive electrode material Substances 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000006181 electrochemical material Substances 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 description 13
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 12
- 238000004146 energy storage Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000001360 synchronised effect Effects 0.000 description 6
- 229910013360 LiBr—LiI Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 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
- 239000000463 material Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000000739 chaotic 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
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 halide salt Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- HOWHQWFXSLOJEF-MGZLOUMQSA-N systemin Chemical compound NCCCC[C@H](N)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CC(O)=O)C(=O)OC(=O)[C@@H]1CCCN1C(=O)[C@H]1N(C(=O)[C@H](CC(O)=O)NC(=O)[C@H](CCCN=C(N)N)NC(=O)[C@H](CCCCN)NC(=O)[C@H](CO)NC(=O)[C@H]2N(CCC2)C(=O)[C@H]2N(CCC2)C(=O)[C@H](CCCCN)NC(=O)[C@H](CO)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](NC(=O)[C@H](C)N)C(C)C)CCC1 HOWHQWFXSLOJEF-MGZLOUMQSA-N 0.000 description 1
- 108010050014 systemin Proteins 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
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
Landscapes
- 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, belonging to the technical field of electrochemical materials. The electrolyte comprises the following components in percentage by mol: 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/cm3～2.4g/cm3. The electrolyte widens the working temperature area of the liquid metal battery to 336-550 ℃, and reduces the operation cost of the battery; overcomes the defect of great density increase caused by the reduction of the melting point of the electrolyte and ensures that the density of the electrolyte is controlled at 2.2g/cm3～2.4g/cm3The three-layer structure of the liquid metal battery can be spontaneously formed in a molten state between the densities of the positive electrode material and the negative electrode material.
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 has important effects on the aspects of expanding the renewable energy grid-connected scale, improving the power supply reliability of a power system, reducing the peak-valley difference of a power grid, constructing a micro-grid and the like, and is a supporting 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 has the advantages of high energy density, quick response time, low maintenance cost, flexibility, convenience and the like, and becomes one of the main energy storage technologies for new energy grid connection in the future. 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 and cycle life.
The Liquid Metal Battery (LMBS) is a low-cost and high-efficiency electrochemical energy storage technology, and shows a wide development prospect in the field of large-scale energy storage.
Liquid metal batteries under operating conditions: the electrode material and the electrolyte material are in liquid states. The working temperature of the liquid metal battery is 300-700 ℃, and the three substances can be automatically divided into three layers due to different densities and mutual non-miscibility of the anode material, the cathode material and the electrolyte material, so that the normal work of the liquid metal battery is ensured.
Liquid metal battery inorganic salt electrolytes typically meet (1) a suitable density between the positive and negative electrodes to enable the sealed interior to automatically separate into three layers of liquid at operating temperatures; (2) the material has no spontaneous reaction with electrode materials, 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) high ionic conductivity, high output power and high performance.
The physical property of the inorganic molten salt electrolyte of the liquid metal battery has 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 as the system tends to be chaotic and disordered. Based on the method, on the basis of pure-component inorganic molten salt electrolytes such as LiF, LiCl, LiBr and LiI, the method is expanded into binary, ternary, quaternary and other multi-element inorganic molten salt electrolyte systems. However, it is not meant that the lower the melting point, the better, the physical properties such as density, ionic conductivity, viscosity, etc. of the multi-element inorganic molten salt electrolyte also affect the performance of the liquid metal battery. Therefore, in constructing an inorganic molten salt electrolyte system for a liquid metal battery, it is necessary to combine various physical properties.
An iodide-based thermal battery electrolyte was studied in Patrick Masset 2006 (Patrick Masset; "Iodic-based electrolytes: A technological alternative for thermal batteries"; Journal of Power resources 160(2006) 688-697). The report mainly investigated the composition of inorganic molten salt electrolyte as 9.6LiF-22LiCl-68.4LiBr working temperature at 443 ℃; the working temperature of 3.2LiF-13LiCl-83.8LiI is 341 ℃; the working temperature of 4.9LiF-11.2LiCl-34.9LiBr-49LiI is 360 ℃.
In 2010 FUJIWARA S, INABAM, TASAKA A2010, New molted en salt systems for high-temperature more than n.LiF-LiCl-LiBr-based quaternary 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 substance was: NaF, KF, NaCl, KCl, NaBr and 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 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 and the like.
In 2011 FUJIWARAS, INABAM, TASAKA A2011, New molten salt systems for high temperature salt systems, Ternary and quaternary mol salt systems based on LiF-LiCl, LiF-LiBr, and LiCl-LiBr journal of Power Source [ J ],196:4012-4018, Ternary and quaternary inorganic molten salt electrolyte systems constructed on the basis of LiF-LiCl, LiF-LiBr and 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 is 2.56S/cm at 500 ℃; 4LiCl-59LiBr-23NaCl-14KCl has a melting point of 420 ℃ and an ionic conductivity of 2.73S/cm at 500 ℃.
An electrolyte provided in Lithium-electrolyte-Lithium metal battery for grid-level energy storage [ J ], NATURE,2014,514,348 and 350 published by Kangli Wang, Kai Jiang et al in 2014 comprises 20LiF-50LiCl-30LiI with a working temperature of 450 ℃.
Self-heating Li-Bi lithium metal battery for grid-scale energy storage [ J ]. Journal of Power Sources,2015,275: 370-.
An electrolyte provided in High Performance Liquid Metal Battery with environmental Positive Electrode [ J ] published by Haomiao Li et al, 2016, and having a composition of 22LiF-31LiCl-47LiBr, and a working temperature of 500 ℃.
Calibration of volume Electron Structures and Thermal and Electric Properties in Li/Sb-Based Liquid metals [ J/Sb-Based Liquid metals ] published by Tong Su, Jian Zhang et al in 2020]An electrolyte mentioned in ACS Applied energy materials, the component is 56LiCl-24LiBr-20LiI, the working temperature is 468 ℃, and the density is 2.07g/cm3The solubility was 0.352 mol%.
Through the comparison of documents, the working temperature of the inorganic molten salt electrolyte containing Li element halide salt series 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 positive electrode and the negative electrode, so that certain viscosity, ionic conductivity and thermal conductivity are ensured, 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 inorganic molten salt electrolyte 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 mol: 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/cm3～2.4g/cm3. The method is suitable for large-scale energy storage liquid metal battery monomers.
The electrolyte comprises the following components in percentage by mol: 7 to 12 percent of LiF, 10 to 40 percent of LiCl, 18 to 28 percent of LiBr and 33 to 50 percent of LiI.
The electrolyte comprises the following components in percentage by mol: 7 to 9 percent of LiF, 30 to 40 percent of LiCl, 18 to 22 percent of LiBr and 33 to 40 percent of LiI.
Aiming at a LiF-LiCl-LiBr-LiI quaternary electrolyte system, because LiI has the largest density and the lowest melting point and has an important effect on adjusting the physical properties of the quaternary electrolyte system, the research on the relative content of LiI has a vital influence on the electrolyte system. As shown in fig. 1 and fig. 2, the melting point of the inorganic molten salt electrolyte is inversely proportional 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 due to increased density are encountered. The density of the electrolyte is closely related to the structure of the liquid metal battery, and the density of the electrolyte is only ensured to be controlled at 2.2g/cm3～2.4g/cm3Within the range, the three-layer structure of the liquid metal battery can be maintained only when the density of the positive electrode material and the negative electrode material is within the range.
The solubility of the cathode 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 more than 0.1S/cm, the viscosity is moderate, the effective working temperature region of the liquid metal battery is expanded to a certain extent, the battery cost is controlled, and the working efficiency of the battery is ensured.
The working temperature region of the electrolyte is 336-550 ℃, the viscosity is 2.1-2.2 mPa.s, the ionic conductivity is more than 0.1S/cm, the thermal conductivity is 0.5-0.6W/mK, and the solubility of the cathode 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 melt heat treatment was performed at 450 ℃.
The application of four-component inorganic molten salt electrolyte in liquid metal battery with metal lithium as negative electrode and metal lithium alloy as positive electrode.
The invention has the beneficial effects that:
1. the invention is one kind ofThe four-component inorganic molten salt electrolyte for the lithium-based liquid metal battery has good comprehensive physical properties, widens the working temperature range of the liquid metal battery to 336-550 ℃, and reduces the operation cost of the battery; overcomes the defect of great density increase caused by the reduction of the melting point of the electrolyte and ensures that the density of the electrolyte is controlled at 2.2g/cm3～2.4g/cm3The three-layer structure of the liquid metal battery can be spontaneously formed between the densities of the positive electrode material and the negative electrode material in a molten state; and the solubility is low, only 0.28% -0.30%, 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, and physical properties such as density, solubility, viscosity, ionic conductivity, thermal conductivity and the like of the electrolyte are calculated.
Drawings
FIG. 1 is a graph showing the relationship between the relative content of LiI and the density and melting point;
FIG. 2 is a graph showing the relationship between density and viscosity, ionic conductivity, and thermal conductivity;
FIG. 3 is a DSC thermogram of 9.1LiF-30LiCl-21.7LiBr-39.2LiI which is a four-component inorganic molten salt electrolyte of example 1 of the present invention;
FIG. 4 is a DSC thermogram of a four-component inorganic molten salt electrolyte, 7.8LiF-40LiCl-18.6LiBr-33.6LiI, of example 2 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
LiF, LiCl, LiBr and LiI in the invention are all analytical pure medicines purchased in chemical markets, the purity is 99.99%, and samples are prepared by proportioning with an electronic balance with the precision of 0.001 g.
After the preparation of the sample, the water is removed at 250 ℃ in an argon atmosphere, and the melt heat treatment is carried out at 450 ℃.
After the heat treatment is finished, a German relaxation-resistant synchronous thermal analyzer STA449F3 is used for melting point test, and Al is selected for the test2O3The temperature rise speed of the crucible is 10K/min.
The density calculation formula when the temperature of the inorganic molten salt electrolyte is T is as follows:
wherein xiIs the mole fraction of the inorganic molten salt electrolyte; rhoiIs the density of the inorganic molten salt electrolyte at temperature T.
The solubility calculation formula of the cathode metal Li in the molten salt electrolyte is as follows:
where ρ is0、V0Is Li+The liquid density, volume of (d); r is0Is Li+A radius; rhoi、ViThe density and volume of the liquid inorganic molten salt electrolyte; r isiIs the ionic radius of the inorganic molten salt electrolyte.
The viscosity of the inorganic molten salt electrolyte is calculated by the formula:
wherein etaiIs the viscosity, x, of the inorganic molten salt electrolyteiIs the mole fraction of the inorganic molten salt electrolyte.
The ion conductivity of the inorganic molten salt electrolyte at the temperature T is calculated by the formula:
wherein
Is the equivalent conductivity of the inorganic molten salt electrolyte, MiIs the formula weight of the electrolyte,
is made withoutDensity of the machine-fused salt electrolyte.
The heat conductivity of the inorganic molten salt electrolyte is calculated by the formula:
wherein λiIs the thermal conductivity, x, of the inorganic molten salt electrolyteiIs the mole fraction of the inorganic molten salt electrolyte.
The physical properties of four pure-component inorganic molten salt electrolytes of LiF, LiCl, LiBr and LiI are shown in Table 1, wherein the melting point of LiF is the highest, and the melting point of LiI is the lowest; in contrast, LiI is the highest density, LiCl is 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 ℃. From Table 1, it can be seen that LiF, LiCl, LiBr and LiI are superior and inferior in properties. The different physical properties of the four components are combined to determine the performance of the multi-component electrolyte system. In general, density is inversely related to viscosity, ionic conductivity and thermal conductivity, that is, when the density is increased, the viscosity, ionic conductivity and thermal conductivity of the electrolyte are reduced, and vice versa.
TABLE 1LiF, LiCl, LiBr, LiI Performance parameters
Aiming at a LiF-LiCl-LiBr-LiI quaternary electrolyte system, because LiI has the largest density and the lowest melting point and has an important effect on adjusting the physical properties of the quaternary electrolyte system, the research on the relative content of LiI has a vital influence on the electrolyte system. As shown in fig. 1, the melting point of the inorganic molten salt electrolyte is inversely proportional 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 encountered. FIG. 2 shows the density and solubility, viscosity, electrical conductivity and thermal conductivity of different-composition LiF-LiCl-LiBr-LiI quaternary electrolyte systemIn the relational graph, abscissa components 1, 2, 3 and 4 respectively represent 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, the content of the LiI is gradually reduced, and the density is in inverse relation with other physical properties. The density of the electrolyte is closely related to the structure of the liquid metal battery, and the density of the electrolyte is only ensured to be controlled at 2.2g/cm3～2.4g/cm3Within the range, the three-layer structure of the liquid metal battery can be maintained only when the density of the positive electrode material and the negative electrode material is within the range, so that the overall performance of the battery is optimized.
Example 1
The invention relates to a four-component inorganic molten salt electrolyte for a lithium-based liquid metal battery, which is characterized in that a sample is prepared according to 9.1LiF-30LiCl-21.7LiBr-39.2LiI, after the sample is prepared, water is removed for 4 hours at 250 ℃ in an argon atmosphere, melting heat treatment is carried out at 450 ℃, after the heat treatment is finished, a melting point of the sample is measured by using a synchronous thermal analyzer STA449F3, and a thermal analysis curve chart shown in the attached figure 3 is obtained, wherein the melting point is 336.1 ℃. The physical properties of the component electrolytes were calculated using the formulas (1) to (5), respectively. At an operating temperature of 500 ℃, the properties were as follows: the density is 2.409g/cm3The 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 characterized in that a sample is prepared according to 7.8LiF-40LiCl-18.6LiBr-33.6LiI, after the sample is prepared, water is removed for 4 hours at 250 ℃ in an argon atmosphere, melting heat treatment is carried out at 450 ℃, after the heat treatment is finished, a melting point of the sample is measured by using a synchronous thermal analyzer STA449F3, and a thermal analysis curve chart shown in the attached figure 4 is obtained, wherein the melting point is 336.5 ℃. The physical properties of the component electrolytes were calculated using the formulas (1) to (5), respectively. At an operating temperature of 500 ℃, the properties were as follows: the density is 2.286g/cm3The 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 drugs LiF, LiCl, LiBr were purchased from the chemical market. Preparing a sample according to 31LiCl-22LiF-47LiBr, removing water at 250 ℃ in an argon atmosphere after the preparation is finished, performing melting heat treatment at 450 ℃, and measuring a melting point by using a synchronous thermal analyzer STA449F3, wherein the melting point is 430 ℃, and the density is 2.120g/cm after calculation at 500 ℃ of working temperature3The 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. Preparing a sample according to 13LiF-31LiBr-56LiI, removing water in an argon atmosphere at 250 ℃ after the preparation is finished, performing melting heat treatment at 450 ℃, and measuring a melting point by using a synchronous thermal analyzer STA449F3, wherein the melting point is 375 ℃, and the density is 2.646g/cm after calculation at a working temperature of 500 DEG C3The 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 drugs LiF, LiCl, LiBr, LiI were purchased from the chemical market. Preparing a sample according to 10.8LiF-26.1LiCl-10LiBr-53.1LiI, removing water at 250 ℃ in an argon atmosphere after the preparation is finished, performing melting heat treatment at 450 ℃, and measuring a melting point by using a synchronous thermal analyzer STA449F3, wherein the melting point is 340 ℃, and the density is 2.51g/cm calculated when the working temperature is 500 DEG C3The 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 above analysis of the examples and comparative examples, it can be seen that:
1. 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 has melting points of 336.1 ℃ and 336.5 ℃ respectively, and is reduced by nearly 100 ℃ compared with the melting point 430 ℃ of the electrolyte component LiCl-LiBr prepared in the comparative example 1; on the basis of the density of the electrolyte of the example 1 and the example 2, the working temperature is 500 ℃, and the density is kept at 2.409g/cm3And 2.286g/cm3Compared with 2.120g/cm of comparative example 13The density of (2) is slightly increased by the addition of LiI, but is deviated by only 0.289g/cm3And is maintained at 2.2g/cm3～2.4g/cm3The three-layer structure of the liquid metal battery can be well maintained within the density range of the positive and negative electrode materials.
In addition, the electrolytes obtained in examples 1 and 2 have a solubility of the negative electrode metal Li in the molten salt electrolyte reduced by 0.1%, and at the same time, the cycle performance of the battery is remarkably improved. Meanwhile, the ionic conductivity shows a great improvement effect.
2. In the embodiment, the melting point of 13LiF-31LiBr-56LiI prepared by the proportion 2 and the matrix electrolyte is reduced by 39 ℃, and the density is reduced by 0.2-0.4 g/cm3Although the solubility of the negative electrode metal Li in the molten salt electrolyte is slightly increased, mainly associated with a decrease in the ratio of LiI, it is improved to a greater extent than the other properties.
3. Compared with the comparative example 3, the composition components of the examples 1 and 2 are LiF-LiCl-LiBr-LiI, the melting point of the examples is reduced by 4 ℃, and the density of the examples is reduced by 0.1-0.2 g/cm3The 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.
In comprehensive comparison, the density of the electrolyte is 2.2g/cm3～2.4g/cm3The density of the positive electrode material and the negative electrode material is between that of the positive electrode material and the negative electrode material, so that a three-layer structure of the liquid metal battery can be maintained; the solubility of the cathode 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 more than 0.1S/cm, the viscosity is moderate, the effective working temperature region of the liquid metal battery is expanded to a certain extent, the battery cost is controlled, and the working efficiency of the battery is ensured.
Claims (6)
1. A four-component inorganic molten salt electrolyte for a lithium-based liquid metal battery, the electrolyte comprising, in terms of mole percent: LiF 7-40%, LiCl 10-40%, LiBr 10-40%, and LiI 10-40%10% -50%; 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/cm3～2.4g/cm3。
2. The four-component inorganic molten salt electrolyte for a lithium-based liquid metal battery of claim 1, wherein the electrolyte comprises, in terms of composition and molar mass percent: 7 to 12 percent of LiF, 10 to 40 percent of LiCl, 18 to 28 percent of LiBr and 33 to 50 percent of LiI.
3. The four-component inorganic molten salt electrolyte for a lithium-based liquid metal battery of claim 2, wherein the electrolyte comprises the following components in percentage by molar mass: 7 to 9 percent of LiF, 30 to 40 percent of LiCl, 18 to 22 percent of LiBr and 33 to 40 percent of LiI.
4. The four-component inorganic molten salt electrolyte for a lithium-based liquid metal battery according to any one of claims 1 to 3, wherein the working temperature range of the electrolyte is 336 to 550 ℃, the viscosity is 2.1 to 2.2 mPa-S, the ionic conductivity is more than 0.1S/cm, the thermal conductivity is 0.5 to 0.6W/mK, and the solubility of the negative electrode metal Li in the electrolyte is 0.28 to 0.30%.
5. A method for preparing four-component inorganic molten salt electrolyte for lithium-based liquid metal battery is characterized in that a sample is fully ground, dewatered for 4 hours at 250 ℃ in argon atmosphere, and subjected to melting heat treatment at 450 ℃.
6. The application of four-component inorganic molten salt electrolyte in liquid metal battery with metal lithium as negative electrode and metal lithium alloy as positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111414695.4A CN114122510B (en) | 2021-11-25 | 2021-11-25 | Four-component inorganic molten salt electrolyte for lithium-based liquid metal battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111414695.4A CN114122510B (en) | 2021-11-25 | 2021-11-25 | Four-component inorganic molten salt electrolyte for lithium-based liquid metal battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114122510A true CN114122510A (en) | 2022-03-01 |
| CN114122510B CN114122510B (en) | 2024-03-19 |
Family
ID=80373239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111414695.4A Active CN114122510B (en) | 2021-11-25 | 2021-11-25 | Four-component inorganic molten salt electrolyte for lithium-based liquid metal battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114122510B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2508712A1 (en) * | 1981-06-26 | 1982-12-31 | Mine Safety Appliances Co | THERMAL BATTERIES |
| GB2101395A (en) * | 1981-06-26 | 1983-01-12 | Mine Safety Appliances Co | Thermal electric cells |
| US20080299447A1 (en) * | 2007-05-25 | 2008-12-04 | Syozo Fujiwara | Molten salt and thermal battery |
| CN102544536A (en) * | 2010-12-24 | 2012-07-04 | 中国电子科技集团公司第十八研究所 | Electrolyte for thermal battery and provided with 4-component inorganic fused salt |
| CN102738481A (en) * | 2012-07-11 | 2012-10-17 | 中国科学院上海微系统与信息技术研究所 | Preparation method of molten salt electrolyte |
| CN103259033A (en) * | 2013-04-16 | 2013-08-21 | 华中科技大学 | Semi-liquid metal electrode energy storage battery |
| CN106532145A (en) * | 2016-12-23 | 2017-03-22 | 东莞威胜储能技术有限公司 | Liquid metal battery |
| KR101739803B1 (en) * | 2017-04-06 | 2017-06-08 | 국방과학연구소 | A thermal batteries using a eutectic salt coated solid-electrolyte and a manufacturing method therefor |
| CN112952211A (en) * | 2021-01-27 | 2021-06-11 | 华中科技大学 | Liquid metal battery and preparation method thereof |
-
2021
- 2021-11-25 CN CN202111414695.4A patent/CN114122510B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2508712A1 (en) * | 1981-06-26 | 1982-12-31 | Mine Safety Appliances Co | THERMAL BATTERIES |
| GB2101395A (en) * | 1981-06-26 | 1983-01-12 | Mine Safety Appliances Co | Thermal electric cells |
| US20080299447A1 (en) * | 2007-05-25 | 2008-12-04 | Syozo Fujiwara | Molten salt and thermal battery |
| CN102544536A (en) * | 2010-12-24 | 2012-07-04 | 中国电子科技集团公司第十八研究所 | Electrolyte for thermal battery and provided with 4-component inorganic fused salt |
| CN102738481A (en) * | 2012-07-11 | 2012-10-17 | 中国科学院上海微系统与信息技术研究所 | Preparation method of molten salt electrolyte |
| CN103259033A (en) * | 2013-04-16 | 2013-08-21 | 华中科技大学 | Semi-liquid metal electrode energy storage battery |
| CN106532145A (en) * | 2016-12-23 | 2017-03-22 | 东莞威胜储能技术有限公司 | Liquid metal battery |
| KR101739803B1 (en) * | 2017-04-06 | 2017-06-08 | 국방과학연구소 | A thermal batteries using a eutectic salt coated solid-electrolyte and a manufacturing method therefor |
| CN112952211A (en) * | 2021-01-27 | 2021-06-11 | 华中科技大学 | Liquid metal battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| SYOZO FUJIWARA等: "New iodide-based molten salt systems for high temperature molten salt batteries", 《JOURNAL OF POWER SOURCES》, pages 1180 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114122510B (en) | 2024-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Heligman et al. | Zn-Sn interdigitated eutectic alloy anodes with high volumetric capacity for lithium-ion batteries | |
| Zhao et al. | High-performance antimony–bismuth–tin positive electrode for liquid metal battery | |
| Fukunaga et al. | Intermediate-temperature ionic liquid NaFSA-KFSA and its application to sodium secondary batteries | |
| Egan et al. | Developments in electrode materials and electrolytes for aluminium–air batteries | |
| Zhou et al. | A sodium liquid metal battery based on the multi-cationic electrolyte for grid energy storage | |
| Wang et al. | Molecular design of a metal–organic framework material rich in fluorine as an interface layer for high-performance solid-state Li metal batteries | |
| Muñoz-Torrero et al. | A critical perspective on rechargeable Al-ion battery technology | |
| CN103259004B (en) | Anode material for liquid-state and semi-liquid-state metal energy-storing batteries | |
| Xia et al. | Room-temperature stable inorganic halide perovskite as potential solid electrolyte for chloride ion batteries | |
| Wang et al. | High area capacity and dendrite-free anode constructed by highly potassiophilic Pd/Cu current collector for low-temperature potassium metal battery | |
| CN106757169A (en) | A kind of hydrogen bearing alloy rare earth intermediate alloy and preparation method thereof | |
| WO2016180057A1 (en) | Rechargeable molten salt battery with aluminum ion and preparation method thereof | |
| Li et al. | In Situ Constructing Coordination Compounds Interphase to Stabilize Zn Metal Anode for High‐Performance Aqueous Zn–SeS2 Batteries | |
| Zhu et al. | Bimetallic Bi–Sn microspheres as high initial coulombic efficiency and long lifespan anodes for sodium-ion batteries | |
| CN112952211A (en) | Liquid metal battery and preparation method thereof | |
| Zheng et al. | Temperature dependence of the electrochemical behavior of LiCoO2 in quaternary ammonium-based ionic liquid electrolyte | |
| CN111916721A (en) | Magnesium-sulfur secondary battery with magnesium-lithium alloy as negative electrode | |
| CN109950640B (en) | Metal graphite medium-temperature energy storage battery and preparation method thereof | |
| Zhou et al. | Low-temperature, high cycling stability, and high Coulombic efficiency liquid metal batteries enabled by lithium halide-potassium halide molten salt electrolytes | |
| Parthasarathy et al. | High temperature sodium-zinc chloride batteries with sodium beta-alumina solid electrolyte | |
| Lu et al. | Aqueous aluminum-zinc hybrid ion batteries with urea-based hydrated eutectic electrolytes | |
| CN114122510A (en) | Four-component inorganic molten salt electrolyte for lithium-based liquid metal battery | |
| Wang et al. | Preparation of Cu6Sn5-encapsulated carbon microsphere anode materials for Li-ion batteries by carbothermal reduction of oxides | |
| CN102569836A (en) | Preparation method of quadruple inorganic molten salt electrolyte | |
| Meng et al. | Discharge performance of Al-0.1 Sn-0.1 In-0.05 Ga alloy for Al–air battery anodes |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |