CN114824512A - Sodium-based liquid metal battery based on replacement reaction and preparation method thereof - Google Patents
Sodium-based liquid metal battery based on replacement reaction and preparation method thereof Download PDFInfo
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- 239000011734 sodium Substances 0.000 title claims abstract description 142
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 87
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 82
- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 99
- 150000003839 salts Chemical class 0.000 claims abstract description 87
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 38
- 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 36
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000956 alloy Substances 0.000 claims abstract description 27
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 26
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000011780 sodium chloride Substances 0.000 claims abstract description 19
- 150000002739 metals Chemical class 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 17
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 16
- 229910052745 lead Inorganic materials 0.000 claims abstract description 15
- 229910052718 tin Inorganic materials 0.000 claims abstract description 15
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 18
- 238000006073 displacement reaction Methods 0.000 claims description 15
- 238000006467 substitution reaction Methods 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- 229910052714 tellurium Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011160 research Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 238000007599 discharging Methods 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- -1 cation halide Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/399—Cells with molten salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0048—Molten electrolytes used at high temperature
Abstract
The invention discloses a sodium-based liquid metal battery based on a replacement reaction and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a negative electrode, a negative electrode and an initial electrolyte, wherein the negative electrode is a simple substance of metal Na or an alloy of the metal Na and other metals, and the other metals comprise one or more of Li, Ca, Mg, Zn, Pb, Sn and Cd; the initial electrolyte comprises sodium-containing molten salt with a molar ratio not more than 10% and lithium-containing molten salt with a molar ratio not less than 45%, wherein the sodium-containing molten salt comprises one or more of NaCl, NaBr and NaI, and the lithium-containing molten salt comprises one or more of LiF, LiCl, LiBr and LiI; when the battery is at the working temperature, the sodium element in the negative electrode and the lithium-containing molten salt in the initial electrolyte are subjected to a replacement reaction to form a stable electrolyte. Research shows that the replacement of metal sodium and lithium ions can be realized by reducing the sodium ion concentration in the initial electrolyte to a very low value, and the coulomb efficiency and the stability of the battery can be improved by spontaneously increasing the content of the sodium-containing molten salt through the replacement reaction compared with the traditional method.
Description
Technical Field
The invention belongs to the technical field of energy storage batteries, and particularly relates to a sodium-based liquid metal battery based on a displacement reaction and a preparation method thereof.
Background
The energy storage can realize that renewable energy with strong intermittence is merged into the electric wire netting, promotes electric energy quality etc.. As a novel energy storage technical device, the liquid metal battery usually adopts liquid metal/alloy as two poles of the earth to separate through melting inorganic salt, because there are great density difference and incompatibility between the three and have unique full liquid three layer construction, can realize self-healing during the in service, effectively avoided the structure that traditional solid-state electrode appears at the circulation charge-discharge in-process to collapse and dendrite, consequently the battery has overlength life in service. In recent years, numerous liquid metal battery systems have been reported, and among them, lithium-based liquid metal batteries have been receiving much attention due to their excellent electrochemical characteristics. Many practical works based on lithium-based liquid metal batteries have been developed in succession, but the related practical works have been limited because lithium vapor inside the batteries can cause severe corrosion of the ceramic seals. While the scarcity of lithium resources and increasing drain rates have further limited the development of lithium-based liquid metal batteries.
The sodium and the lithium have similar electrochemical properties, and the reserves are richer, so the cost is lower, meanwhile, the sodium is weaker than the lithium in reduction, and the sodium has good compatibility with numerous ceramics, and the problem of corrosion of a battery sealing part can be effectively solved by adopting the sodium as an electrode, so that the battery has longer service life, and is more expected to realize large-scale energy storage application. However, sodium has a high solubility in its molten halide, resulting in severe self-discharge of the battery and very low efficiency.
Disclosure of Invention
In view of the above defects or improvement needs of the prior art, the present invention provides a sodium-based liquid metal battery based on a displacement reaction and a preparation method thereof, which aims to suppress the solubility of the negative electrode inside the sodium-based liquid metal battery in molten salt and improve the battery efficiency.
To achieve the above objects, according to one aspect of the present invention, there is provided a method of manufacturing a sodium-based liquid metal battery,
preparing a negative electrode, wherein the negative electrode is a simple substance of metal Na or an alloy of the metal Na and other metals, and the other metals comprise one or more of Li, Ca, Mg, Zn, Pb, Sn and Cd;
preparing a positive electrode, wherein the positive electrode is any single substance or alloy consisting of any two or more elements of Bi, Sb, Sn, Te and Pb;
preparing an initial electrolyte, wherein the initial electrolyte comprises sodium-containing molten salt with a molar ratio not more than 10% and lithium-containing molten salt with a molar ratio not less than 45%, wherein the sodium-containing molten salt comprises one or more of NaCl, NaBr and NaI, and the lithium-containing molten salt comprises one or more of LiF, LiCl, LiBr and LiI;
and when the battery is at the working temperature, the sodium element in the negative electrode and the lithium-containing molten salt in the initial electrolyte are subjected to a replacement reaction to form a stable electrolyte, wherein the molar ratio of the sodium-containing molten salt of the stable electrolyte is larger than that of the sodium-containing molten salt of the initial electrolyte.
In one embodiment, the alloy negative electrode is any one of:
Na 50～100 ～Li 0～50 ，Na 80～100 ～Ca 0～20 ，Na 80～100 ～Mg 0～20 ，Na 70～100 ～Zn 0～30 ，Na 50～100 ～Pb 50～100 ，Na 50～100 ～Sn 50～100 ，Na 50～100 ～Cd 50～100 wherein the sum of the mole percentages of the elements in the alloy is 100 percent.
In one embodiment, the starting electrolyte further comprises KCl, KI, KBr, CaCl 2 ，CaBr 2 One or more of (a).
In one embodiment, the initial electrolyte is any one of:
(LiCl) 45～65 ～(NaCl) 0～10 ～(KCl) 30～50 ；
(LiBr) 45～65 ～(NaBr) 0～10 ～(KBr) 30～50 ；
(LiBr) 45～65 ～(NaBr) 0～10 ～(KCl) 30～50 ；
(LiI) 45～70 ～(NaI) 0～10 ～(KI) 30～50 ；
(LiCl) 45～65 ～(NaCl) 0～10 ～(CaCl 2 ) 25～45 。
in one embodiment, preparing the initial electrolyte comprises:
drying the salt of each component to remove water in the salt;
uniformly mixing the treated salt in a dry atmosphere;
and preserving the heat of the mixed salt for 2-10 hours at the temperature of 100-250 ℃, then heating the mixed salt to be above the melting point of the molten salt, carrying out melting treatment for 2-10 hours, and cooling the mixed salt to obtain the mixed cation electrolyte.
In accordance with another aspect of the present invention, there is provided a sodium-based liquid metal battery comprising a negative electrode, a positive electrode, and an initial electrolyte,
the negative electrode is a metal Na simple substance or an alloy of metal Na and other metals, and the other metals comprise one or more of Li, Ca, Mg, Zn, Pb, Sn and Cd;
the positive electrode is any one simple substance or an alloy consisting of any two or more elements of Bi, Sb, Sn, Te and Pb;
the initial electrolyte comprises sodium-containing molten salt with a molar ratio not more than 10% and lithium-containing molten salt with a molar ratio not less than 45%, wherein the sodium-containing molten salt comprises one or more of NaCl, NaBr and NaI, and the lithium-containing molten salt comprises one or more of LiF, LiCl, LiBr and LiI.
In one embodiment, the alloy negative electrode is any one of:
Na 50～100 ～Li 0～50 ，Na 80～100 ～Ca 0～20 ，Na 80～100 ～Mg 0～20 ，Na 70～100 ～Zn 0～30 ，Na 50～100 ～Pb 50～100 ，Na 50～100 ～Sn 50～100 ，Na 50～100 ～Cd 50～100 wherein the sum of the mole percentages of the elements in the alloy is 100 percent.
In one embodiment, the initial electrolyteAlso comprises KCl, KI, KBr, CaCl 2 ，CaBr 2 One or more of (a).
In one embodiment, the initial electrolyte is any one of:
(LiCl) 45～65 ～(NaCl) 0～10 ～(KCl) 30～50 ；
(LiBr) 45～65 ～(NaBr) 0～10 ～(KBr) 30～50 ；
(LiBr) 45～65 ～(NaBr) 0～10 ～(KCl) 30～50 ；
(LiI) 45～70 ～(NaI) 0～10 ～(KI) 30～50 ；
(LiCl) 45～65 ～(NaCl) 0～10 ～(CaCl 2 ) 25～45 。
in one embodiment, when the battery is at an operating temperature, the sodium element in the negative electrode and the lithium-containing molten salt in the initial electrolyte undergo a substitution reaction to form a stable electrolyte, wherein the molar ratio of the sodium-containing molten salt of the stable electrolyte is greater than the molar ratio of the sodium-containing molten salt of the initial electrolyte.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
the mixed cation halide is designed as the electrolyte, so that the dissolution of the negative electrode in the sodium-based liquid metal battery in the molten salt can be effectively inhibited, and the working efficiency and the stability of the battery are further improved by combining a special preparation process. In the conventional art, it is common to directly arrange the contents of the components thereof in accordance with the electrolyte required for stable operation of the battery. In the application, the conventional preparation idea is broken through, when the liquid metal battery is prepared, the proportion of the sodium-containing molten salt in the initial electrolyte is greatly reduced, the initial proportion of the sodium-containing molten salt is not enough to maintain normal charging and discharging work of the battery, after the battery is prepared, when the temperature is raised to the working temperature of the battery, the negative electrode and the initial electrolyte are in a molten state to perform a displacement reaction, so that the metal sodium and lithium ions perform the displacement reaction, and the proportion of the sodium ions in the electrolyte is gradually increased and stabilized. In conventional recognition, on one hand, the electrolyte should be prepared in a required proportion directly in order to ensure the coulomb efficiency and stability of the battery; on the other hand, in conventional recognition, sodium has a higher precipitation potential than lithium in an aqueous solution (difference of about 0.3V), and therefore it is generally considered that sodium cannot replace lithium ions with lithium metal alone. However, in the present application, it has been found through research that the substitution of metallic sodium with lithium ions can be achieved by reducing the sodium ion concentration in the initial electrolyte to 10% or less, and the coulombic efficiency and stability of the battery can be improved more than the conventional method by spontaneously increasing the content of the sodium-containing molten salt through the substitution reaction.
Drawings
FIG. 1 is a flow chart illustrating steps in a method of manufacturing a sodium-based liquid metal battery according to one embodiment;
fig. 2 is a schematic structural diagram of a liquid metal battery according to an embodiment;
FIG. 3 is a graph showing the content ratio of each element in the electrolyte before and after the test (before and after the occurrence of the substitution reaction) according to an example;
FIG. 4 is a DSC curve of the electrolyte in examples 1, 2;
FIG. 5 is a graph showing the solubility of metallic Na in the electrolytes used in examples 1 and 2 and the electrolyte used in comparative example 2;
fig. 6 is a charge-discharge curve of a battery assembled by using example 2;
FIG. 7 is a graph of the cycle performance of a battery assembled using example 2;
fig. 8 is a graph showing the cycle performance of the assembled battery using comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and 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. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The preparation method of the sodium-based liquid metal battery comprises the steps of preparing a negative electrode, a positive electrode and an initial electrolyte.
Fig. 1 is a flow chart illustrating steps of a manufacturing method according to an embodiment, the manufacturing method including:
step S100: preparing a negative electrode, wherein the negative electrode is a simple substance of metal Na or an alloy of the metal Na and other metals, and the other metals comprise one or more of Li, Ca, Mg, Zn, Pb, Sn and Cd.
The prepared cathode can be a simple substance of metal Na, or an alloy of the metal Na and other metals, and the other metals can be one or more of Li, Ca, Mg, Zn, Pb, Sn and Cd.
For example, when the negative electrode is a metal alloy, Na may be specifically mentioned 50～100 ～Li 0～50 ，Na 80～100 ～Ca 0～20 ，Na 80～100 ～Mg 0～20 ，Na 70～100 ～Zn 0～30 ，Na 50～100 ～Pb 50～100 ，Na 50～100 ～Sn 50～100 ，Na 50～100 ～Cd 50～100 Any one of the above, wherein the sum of the mole percentages of the elements in the alloy is 100%. The activity of sodium is reduced by alloying other metals with metallic sodium, the dissolution of sodium is inhibited, and the stable operation of the battery is realized.
In one embodiment, the preparation method for preparing the alloy cathode specifically comprises the following steps: weighing two element simple substances forming the alloy in proportion, carrying out eutectic melting at a proper temperature, placing the negative current collector in the molten alloy, soaking for 5-6 hours, and then carrying out vacuum treatment to ensure that the alloy material can be absorbed into the negative current collector.
Step S200: preparing a positive electrode, wherein the positive electrode is any single substance or alloy consisting of any two or more elements of Bi, Sb, Sn, Te and Pb.
The prepared anode can be any single substance or an alloy consisting of any two or more elements of Bi, Sb, Sn, Te and Pb.
Step S300: preparing an initial electrolyte, wherein the initial electrolyte comprises sodium-containing molten salt with a molar ratio not more than 10% and lithium-containing molten salt with a molar ratio not less than 45%, wherein the sodium-containing molten salt comprises one or more of NaCl, NaBr and NaI, and the lithium-containing molten salt comprises one or more of LiF, LiCl, LiBr and LiI.
Wherein the prepared initial electrolyte is a mixed cation molten salt electrolyte which comprises sodium-containing molten salt and lithium-containing molten salt, the initial content of the sodium-containing molten salt is not more than 10%, preferably 4-7%, and the lithium-containing molten salt is not less than 45%. Specifically, the sodium-containing molten salt comprises one or more of NaCl, NaBr and NaI, and the lithium-containing molten salt comprises one or more of LiF, LiCl, LiBr and LiI. In one embodiment, the primary electrolyte may further include K ions, Ca ions, and may also include, for example, KCl, KI, KBr, CaCl 2 ，CaBr 2 One or more of (a).
In one embodiment, the molar ratio of the mixed cationic electrolyte is any one of:
(LiCl) 45～65 ～(NaCl) 0～10 ～(KCl) 30～50 ；
(LiBr) 45～65 ～(NaBr) 0～10 ～(KBr) 30～50 ；
(LiBr) 45～65 ～(NaBr) 0～10 ～(KCl) 30～50 ；
(LiI) 45～70 ～(NaI) 0～10 ～(KI) 30～50 ；
(LiCl) 45～65 ～(NaCl) 0～10 ～(CaCl 2 ) 25～45 。
wherein the sum of the mole percentages of the components in each mixed salt equals 100%.
Specifically, the process for preparing the mixed cation electrolyte comprises the following steps: firstly, drying the salt of each component to remove water in the salt; uniformly mixing the treated salt in a dry atmosphere; and respectively preserving the heat of the mixed salt for 2-10 hours at the temperature of 100-250 ℃, then heating the mixed salt to be above the melting point of the molten salt, carrying out melting treatment for 2-10 hours, and cooling the mixed salt to obtain the mixed cation electrolyte.
The order of battery production is not limited.
Correspondingly, the application also relates to a sodium-based liquid metal battery prepared by the method, when the sodium-based liquid metal battery is in an initial form, the negative electrode of the sodium-based liquid metal battery is a simple substance of metal Na or an alloy of the metal Na and other metals, and the other metals comprise one or more of Li, Ca, Mg, Zn, Pb, Sn and Cd; the anode is any single substance or alloy consisting of any two or more elements of Bi, Sb, Sn, Te and Pb; the initial electrolyte comprises sodium-containing molten salt with the molar ratio not more than 10% and lithium-containing molten salt with the molar ratio not less than 45%, wherein the sodium-containing molten salt comprises one or more of NaCl, NaBr and NaI, and the lithium-containing molten salt comprises one or more of LiF, LiCl, LiBr and LiI. When the battery is at the working temperature, the sodium element in the negative electrode and the lithium-containing molten salt in the initial electrolyte are subjected to a replacement reaction to form a stable electrolyte, wherein the molar ratio of the sodium-containing molten salt of the stable electrolyte is greater than that of the sodium-containing molten salt of the initial electrolyte, and the sodium ion content of the stable electrolyte can meet the charge and discharge requirements of the battery. After a stable electrolyte is formed, the electrolyte composition and content of the subsequent battery are substantially unchanged. The specific embodiments of the components can be introduced with reference to the above descriptions, and are not described herein again.
Fig. 2 is a schematic structural diagram of a liquid metal battery in an embodiment, which includes a negative electrode 1, an electrolyte 2, a positive electrode 3, an insulating ceramic member 4, a battery case 5, and a current collector 6. The battery shell comprises a top cover and a shell body, the top cover and the shell body are both made of metal materials, the battery shell is in direct contact with a positive electrode material and also used as a positive current collector, a round hole is formed in the center of the top cover, a negative current collector is led out from the center and is insulated through non-conductive ceramic, the negative current collector is a metal tooth bar, and a foam metal material and a metal nut are assembled.
In the application, on one hand, the mixed cation halide is formed to be used as the electrolyte, so that the dissolution of the negative electrode in the sodium-based liquid metal battery in the molten salt is effectively inhibited, the battery efficiency is improved, the long-acting stable operation of the battery is realized, and the cost of the battery is reduced. On the other hand, when the battery is prepared, the conventional cognition is broken, the proportion of the sodium-containing molten salt in the initial electrolyte is greatly reduced, after the battery is prepared, when the temperature is raised to the working temperature of the battery, the negative electrode and the initial electrolyte are in a molten state to generate a displacement reaction, so that the metal sodium and lithium ions generate the displacement reaction, and the proportion of sodium ions in the electrolyte is gradually increased and stabilized. Compared with the traditional method, the method has the advantage that the working efficiency and stability of the battery can be improved by spontaneously increasing the content of the sodium-containing molten salt through the replacement reaction.
Although some liquid metal batteries can achieve charging and discharging through a displacement reaction, it is a completely different technical solution to perform charging and discharging through a displacement reaction and to self-regulate and stabilize the electrolyte concentration through a displacement reaction, and the electrolyte concentration of a liquid metal battery that achieves charging and discharging through a displacement reaction is also directly configured, and the displacement reaction is reversible during charging and discharging. The sodium-based liquid metal battery prepared by the method can generate the replacement reaction no matter whether the battery is charged or not as long as the temperature is increased, and once the battery is stable, the replacement reaction is stopped, and the process is irreversible. After the sodium-based liquid metal battery is connected to a circuit, charging and discharging are carried out based on a charge-discharge principle (non-displacement reaction) of an alloying reaction between a negative electrode and a positive electrode.
A comparison of the performance of 16 sodium-based liquid metal batteries manufactured by the method of the present application and 2 batteries to a comparative example is shown below, wherein comparative example 1 is a directly prepared electrolyte and no substitution reaction occurs, and the electrolyte of comparative example 2 contains only sodium ions, as shown in table 1 below:
TABLE 1
As shown in fig. 3, which is a ratio of content of each element in the electrolyte before and after the test (before and after the substitution reaction), it can be found that after the battery operates for a certain period of time, the content of NaCl in the electrolyte increases through the substitution reaction, which is beneficial to the operation of the battery.
For the coulombic efficiency, in examples 1 to 16 using the electrolyte provided by the present invention, the coulombic efficiency of the battery is higher than 90%, which is obviously higher than that of comparative example 2, indicating that the coulombic efficiency of the mixed cation electrolyte is obviously higher than that of the single cation electrolyte in the comparative example. In addition, the coulombic efficiency of examples 1 to 16 using the electrolyte provided by the present invention is also higher than that of comparative example 1 (the electrolyte does not undergo a substitution reaction).
With respect to the operating temperature, the operating temperature of the liquid metal batteries of examples 1 to 16 (with mixed cation electrolyte) using the electrolyte provided by the present invention was also lower than that of comparative example 1. Moreover, as for the electrolytes in the present application, as shown in fig. 4, which is the DSC curve of the electrolytes in examples 1 and 2, it can be found that these electrolytes all have melting points lower than 400 ℃, which lays the foundation for the battery to operate at lower temperature.
With respect to the solubility of sodium in the negative electrode, fig. 5 shows the solubility of metal Na in the electrolytes used in examples 1 and 2 and the electrolyte used in comparative example 2, and it can be found that the solubility of metal Na in the example of the present invention is much lower than that in the electrolyte used in comparative example 2.
For charging and discharging, fig. 6 is a charging and discharging curve of the assembled battery in example 2, and it can be found that the discharging voltage of the battery is 0.6-0.75V and shows a double discharging platform.
With respect to the life and stability of the battery, fig. 7 is a cycle performance diagram of the assembled battery of example 2, and it can be found that the battery can stably operate over 700 cycles with coulomb efficiency of about 97%, and the capacity is slowly increased as the battery operates. Fig. 8 is a graph showing that the electrolyte was directly treated in proportion to the components after the cycle in comparative example 1 for a battery, and the test results showed that the spontaneous regulation was not performed in the stage of the substitution reaction, the battery life was short, and the stability was poor.
In summary, the solubility of the negative electrode metal in the mixed cation molten salt is very low (<1 mol%), which indicates that the design of the mixed cation halide helps to suppress the solubility of the metal Na in the molten salt electrolyte; in addition, the prepared batteries show higher coulombic efficiency (> 90%), meanwhile, the working temperature of the batteries can be reduced to 450 ℃, the batteries can stably run for more than 700 circles, and the coulombic efficiency is maintained at about 97%.
It is to be emphasized again that in conventional wisdom, on one hand, it is considered that in order to ensure the working efficiency and stability of the battery, the electrolyte should be prepared in the required proportion directly; on the other hand, in conventional recognition, sodium has a higher precipitation potential than lithium in an aqueous solution (difference of about 0.3V), and therefore it is generally considered that sodium cannot replace lithium ions with lithium metal simple substance. In the application, the conventional preparation idea is broken through, when the liquid metal battery is prepared, the proportion of the sodium-containing molten salt in the initial electrolyte is greatly reduced, the initial proportion of the sodium-containing molten salt is not enough to maintain normal charging and discharging work of the battery, after the battery is prepared, when the temperature is raised to the working temperature of the battery, the negative electrode and the initial electrolyte are in a molten state to perform a displacement reaction, so that the metal sodium and lithium ions perform the displacement reaction, and the proportion of the sodium ions in the electrolyte is gradually increased and stabilized. Research shows that the replacement of metal sodium and lithium ions can be realized by reducing the sodium ion concentration in the initial electrolyte to a very low value, and the coulomb efficiency and the stability of the battery can be improved by spontaneously increasing the content of the sodium-containing molten salt through the replacement reaction compared with the traditional method.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a sodium-based liquid metal battery based on a replacement reaction is characterized in that,
preparing a negative electrode, wherein the negative electrode is a metal Na simple substance or an alloy of metal Na and other metals, and the other metals comprise one or more of Li, Ca, Mg, Zn, Pb, Sn and Cd;
preparing a positive electrode, wherein the positive electrode is any single substance or alloy consisting of any two or more elements of Bi, Sb, Sn, Te and Pb;
preparing an initial electrolyte, wherein the initial electrolyte comprises sodium-containing molten salt with a molar ratio not more than 10% and lithium-containing molten salt with a molar ratio not less than 45%, wherein the sodium-containing molten salt comprises one or more of NaCl, NaBr and NaI, and the lithium-containing molten salt comprises one or more of LiF, LiCl, LiBr and LiI;
and when the battery is at the working temperature, the sodium element in the negative electrode and the lithium-containing molten salt in the initial electrolyte are subjected to a replacement reaction to form a stable electrolyte, wherein the molar ratio of the sodium-containing molten salt of the stable electrolyte is larger than that of the sodium-containing molten salt of the initial electrolyte.
2. The method of claim 1, wherein the alloy negative electrode is any one of the following:
Na 50～100 ～Li 0～50 ，Na 80～100 ～Ca 0～20 ，Na 80～100 ～Mg 0～20 ，Na 70～100 ～Zn 0～30 ，Na 50～100 ～Pb 50～100 ，Na 50～100 ～Sn 50～100 ，Na 50～100 ～Cd 50～100 wherein the sum of the mole percentages of the elements in the alloy is 100 percent.
3. The method of claim 1, wherein the starting electrolyte further comprises KCl, KI, KBr, CaCl 2 ，CaBr 2 One or more of (a).
4. The method of making a sodium-based liquid metal battery of claim 3, wherein the starting electrolyte is any one of:
(LiCl) 45～65 ～(NaCl) 0～10 ～(KCl) 30～50 ；
(LiBr) 45～65 ～(NaBr) 0～10 ～(KBr) 30～50 ；
(LiBr) 45～65 ～(NaBr) 0～10 ～(KCl) 30～50 ；
(LiI) 45～70 ～(NaI) 0～10 ～(KI) 30～50 ；
(LiCl) 45～65 ～(NaCl) 0～10 ～(CaCl 2 ) 25～45 。
5. the method of making a sodium-based liquid metal battery of claim 1, wherein making the initial electrolyte comprises:
drying the salt of each component to remove water in the salt;
uniformly mixing the treated salt in a dry atmosphere;
and preserving the heat of the mixed salt for 2-10 hours at the temperature of 100-250 ℃, then heating the mixed salt to be above the melting point of the molten salt, carrying out melting treatment for 2-10 hours, and cooling the mixed salt to obtain the mixed cation electrolyte.
6. A sodium-based liquid metal battery based on a displacement reaction comprises a negative electrode, a positive electrode and an initial electrolyte, and is characterized in that,
the negative electrode is a metal Na simple substance or an alloy of the metal Na and other metals, and the other metals comprise one or more of Li, Ca, Mg, Zn, Pb, Sn and Cd;
the anode is any one simple substance or alloy consisting of any two or more elements of Bi, Sb, Sn, Te and Pb;
the initial electrolyte comprises sodium-containing molten salt with a molar ratio not more than 10% and lithium-containing molten salt with a molar ratio not less than 45%, wherein the sodium-containing molten salt comprises one or more of NaCl, NaBr and NaI, and the lithium-containing molten salt comprises one or more of LiF, LiCl, LiBr and LiI.
7. The sodium-based liquid metal battery of claim 6, wherein the alloy negative electrode is any one of:
Na 50～100 ～Li 0～50 ，Na 80～100 ～Ca 0～20 ，Na 80～100 ～Mg 0～20 ，Na 70～100 ～Zn 0～30 ，Na 50～100 ～Pb 50～100 ，Na 50～100 ～Sn 50～100 ，Na 50～100 ～Cd 50～100 wherein the sum of the mole percentages of the elements in the alloy is 100 percent.
8. The sodium-based liquid metal cell of claim 6, wherein the starting electrolyte further comprises KCl, KI, KBr, CaCl 2 ，CaBr 2 One or more of (a).
9. The sodium-based liquid metal battery of claim 8, wherein the initial electrolyte is any one of:
(LiCl) 45～65 ～(NaCl) 0～10 ～(KCl) 30～50 ；
(LiBr) 45～65 ～(NaBr) 0～10 ～(KBr) 30～50 ；
(LiBr) 45～65 ～(NaBr) 0～10 ～(KCl) 30～50 ；
(LiI) 45～70 ～(NaI) 0～10 ～(KI) 30～50 ；
(LiCl) 45～65 ～(NaCl) 0～10 ～(CaCl 2 ) 25～45 。
10. the sodium-based liquid metal battery of claim 6, wherein the sodium element in the negative electrode undergoes a substitution reaction with the lithium-containing molten salt in the initial electrolyte to form a stable electrolyte when the battery is at an operating temperature, wherein a molar ratio of the sodium-containing molten salt of the stable electrolyte is greater than a molar ratio of the sodium-containing molten salt of the initial electrolyte.
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