CN114792847B - Low-temperature liquid metal battery and preparation method thereof - Google Patents
Low-temperature liquid metal battery and preparation method thereof Download PDFInfo
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- CN114792847B CN114792847B CN202210480460.3A CN202210480460A CN114792847B CN 114792847 B CN114792847 B CN 114792847B CN 202210480460 A CN202210480460 A CN 202210480460A CN 114792847 B CN114792847 B CN 114792847B
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- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 56
- 238000002844 melting Methods 0.000 claims abstract description 38
- 230000008018 melting Effects 0.000 claims abstract description 38
- -1 lithium halides Chemical class 0.000 claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 31
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 14
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 52
- 239000011261 inert gas Substances 0.000 claims description 49
- 229910045601 alloy Inorganic materials 0.000 claims description 47
- 239000000956 alloy Substances 0.000 claims description 47
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 31
- 229910052797 bismuth Inorganic materials 0.000 claims description 30
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 29
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 29
- 229910052718 tin Inorganic materials 0.000 claims description 29
- 238000003466 welding Methods 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 22
- 239000006260 foam Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002001 electrolyte material Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 229910001419 rubidium ion Inorganic materials 0.000 abstract description 14
- 229910002804 graphite Inorganic materials 0.000 description 40
- 239000010439 graphite Substances 0.000 description 40
- 239000002245 particle Substances 0.000 description 32
- 238000012360 testing method Methods 0.000 description 26
- 150000003839 salts Chemical class 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 10
- 229910016338 Bi—Sn Inorganic materials 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Inorganic materials [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Inorganic materials [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229910013370 LiBr—RbBr Inorganic materials 0.000 description 1
- 229910017835 Sb—Sn Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000003068 static effect 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
- H01M10/36—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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0048—Molten electrolytes used at high temperature
- H01M2300/0054—Halogenides
Abstract
The invention discloses a low-temperature liquid metal battery and a preparation method thereof, wherein the battery comprises a shell, and a positive electrode, a negative electrode and an electrolyte which are sealed in the shell, wherein the negative electrode comprises metallic lithium; the electrolyte comprises two or more metal halide salts, the metal halide salts comprise lithium halides, and also comprise rubidium halides and/or cesium halides, and the melting point of the electrolyte is not more than 300 ℃. By introducing rubidium ions and cesium ions into the electrolyte of the liquid metal battery, the melting point of the electrolyte is greatly reduced on the premise of not sacrificing the stability of the electrolyte.
Description
Technical Field
The invention belongs to the technical field of energy storage batteries, and particularly relates to a low-temperature liquid metal battery and a preparation method thereof.
Background
The liquid metal battery consists of three layers of mutually-insoluble liquid, has extremely long service life in theory, and is very suitable for large-scale static energy storage of a power grid level. However, in order to meet the melting points of both the electrode and the electrolyte, the liquid metal battery needs to be operated at high temperature. For example, the working temperatures of current competitive liquid metal battery systems such as Li Sb-Pb, li Sb-Sn, li Bi, li Sb, ca-Mg Bi and the like are 480-550 ℃, and higher working temperatures pose great challenges for battery sealing and corrosion resistance and add a great deal of additional heat preservation power consumption. Therefore, developing a liquid metal battery that not only inherits the core advantages of the liquid metal battery (electrode deformation self-healing, electrolyte and active electrode do not have side reactions), but also has lower working temperature has important theoretical and practical significance.
Disclosure of Invention
In view of the above-mentioned drawbacks or improvements of the prior art, the present invention provides a low-temperature liquid metal battery and a method for manufacturing the same, which aims to reduce the operating temperature of the liquid metal battery.
In order to achieve the above object, according to one aspect of the present invention, there is provided a low-temperature liquid metal battery including a case, and a positive electrode, a negative electrode and an electrolyte sealed in the case,
The negative electrode includes lithium metal;
The electrolyte comprises two or more metal halide salts, the metal halide salts comprise lithium halides, and also comprise rubidium halides and/or cesium halides, and the melting point of the electrolyte is not more than 300 ℃.
In one embodiment, the electrolyte is any combination of the following:
LiBr20-60-RbBr80-40；
LiBr20-60-CsCl80-40；
LiBr40-80-CsBr60-20；
LiI45-85-CsI55-15；
LiCl20-80-KCl0-30-CsCl0-40；
LiCl40-80-KCl10-30-RbCl0-20-CsCl0-40；
LiBr40-80-KBr10-30-CsBr0-40；
LiI40-80-KI0-30-CsI0-40；
LiBr5-20-LiI40-80-KI10-30-CsI10-40；
LiCl1-10-LiBr0-20-LiI30-70-KI0-30-CsI0-40；
Wherein the mole percentages of the components in the electrolyte add up to 100%.
In one embodiment, the positive electrode is an alloy of two metals of antimony, bismuth, tin, and lead.
In one embodiment, the positive electrode is any one of the following:
bi 10-90-Sn90-10 alloy;
Bi 10-90-Pb90-10 alloy;
sn 10-90-Pb90-10 alloy;
Sb 5-50-Pb95-50 alloy;
wherein the mole percentages of the components in each positive electrode alloy add up to 100%.
In one embodiment, the battery further comprises a negative electrode current collector, wherein the negative electrode current collector is foam iron nickel or foam carbon.
According to another aspect of the present invention, there is provided a method for manufacturing a low-temperature liquid metal battery, comprising:
under the protection of inert gas, placing a positive electrode material into a crucible, heating, melting, naturally cooling to form a positive electrode, and placing the crucible into a matched stainless steel shell;
under the protection of inert gas, heating, melting and pouring electrolyte materials into the crucible to form electrolyte; the electrolyte comprises two or more metal halide salts, wherein the metal halide salts comprise lithium halides and also comprise rubidium halides and/or cesium halides, and the melting point of the electrolyte is not more than 300 ℃;
Under the protection of inert gas, absorbing liquid metal lithium by using a negative electrode current collector, assembling the negative electrode current collector absorbed with the metal lithium and a top cover on a shell, and then naturally cooling;
and welding the shell and the top cover to obtain the assembled low-temperature liquid metal battery.
In one embodiment, the positive electrode is an alloy formed from two metals of antimony, bismuth, tin, lead;
Placing the positive electrode material in a crucible for heating and melting, comprising:
each metal making up the alloy is placed in a crucible and heated to melt each metal into an alloy.
In one embodiment, the alloy is any one of the following:
bi 10-90-Sn90-10 alloy;
Bi 10-90-Pb90-10 alloy;
sn 10-90-Pb90-10 alloy;
Sb 5-50-Pb95-50 alloy;
wherein the mole percentages of the components in each alloy add up to 100%.
In one embodiment, the electrolyte is any combination of the following:
LiBr20-60-RbBr80-40；
LiBr20-60-CsCl80-40；
LiBr40-80-CsBr60-20；
LiI45-85-CsI55-15；
LiCl20-80-KCl0-30-CsCl0-40；
LiCl40-80-KCl10-30-RbCl0-20-CsCl0-40；
LiBr40-80-KBr10-30-CsBr0-40；
LiI40-80-KI0-30-CsI0-40；
LiBr5-20-LiI40-80-KI10-30-CsI10-40；
LiCl1-10-LiBr0-20-LiI30-70-KI0-30-CsI0-40；
Wherein the mole percentages of the components of each combination add up to 100%.
In one embodiment, the negative electrode current collector is foam iron nickel or foam carbon.
In general, the above technical solutions conceived by the present invention, compared with the prior art, enable the following beneficial effects to be obtained:
The invention provides a multi-element mixed cation electrolyte which is formed by adding rubidium ions/cesium ions into the electrolyte. Researchers generally believe that the addition of rubidium ions and cesium ions can cause unstable battery operation, because metallic lithium can replace rubidium ions and cesium ions in the electrolyte under normal conditions to form rubidium vapor and cesium vapor runaway. In other words, it is generally considered by researchers that when metallic lithium is used as the negative electrode, an electrolyte in which cations are lithium ions only is stable, and an electrolyte containing rubidium ions and cesium ions is unstable due to the presence of substitution reaction. The research and development team combines theoretical analysis and experiments to prove that the substitution reaction can only occur under the constant pressure condition, and the liquid metal battery works under the strictly sealed condition, which belongs to the constant volume condition, and the degree of occurrence of the substitution reaction is very little, so that the multi-element cationic electrolyte containing potassium ions, rubidium ions and cesium ions is stable. Therefore, the invention breaks the conventional thinking, adds rubidium ions/cesium ions into the electrolyte, the electrolyte is kept stable, and experiments show that the addition of rubidium ions/cesium ions into the electrolyte forms a multi-element mixed cation electrolyte, and the melting point of the electrolyte can be reduced to below 300 ℃, thereby greatly reducing the working temperature of the battery.
Drawings
FIG. 1 is a schematic diagram of a liquid metal battery according to an embodiment;
Fig. 2 is an exploded potential diagram of rubidium, cesium and lithium ions of an embodiment;
FIG. 3 is a graph of the melting point test of an example LiCl-LiBr-LiI-KI-CsI electrolyte prior to battery operation;
FIG. 4 is a graph of the melting point test of an example LiCl-LiBr-LiI-KI-CsI electrolyte after battery operation;
fig. 5 is a charge-discharge graph at 290 degrees for the battery of example 4;
Fig. 6 is a graph of the cycling performance of the battery of example 4 at 290 degrees;
Fig. 7 is a discharge graph of the battery of example 8 at 220 degrees.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Fig. 1 is a schematic structural diagram of a liquid metal battery in an embodiment, which includes a case 3, and a negative electrode 4, an electrolyte 5, and a positive electrode 6 enclosed in the case 4. Wherein the negative electrode 4 comprises metallic lithium, the electrolyte 5 comprises two or more metal halide salts, the metal halide salts comprise lithium halides, and further comprise rubidium halides and/or cesium halides, and the melting point of the electrolyte is not more than 300 ℃. Wherein, the metal lithium in the negative electrode is adsorbed on the negative electrode current collector and led out through the negative electrode lead 1, and the negative electrode lead 1 is electrically isolated from the shell 3 through the insulator 2.
As shown in fig. 2, which shows the decomposition potential diagrams of rubidium ions, cesium ions and lithium ions, the rubidium ions and cesium ions do not participate in the electrochemical reaction due to lower reduction potential and do not affect the charge-discharge process of the battery. In one embodiment, the battery has a charge-discharge rate of 0.05 to 0.5C.
In conventional operation, since rubidium ions and cesium ions in the metallic lithium energy electrolyte are replaced, here exemplified by iodide, the following replacement reaction is generally considered to occur:
Li+RbI＝LiI+Rb
Li+CsI＝LiI+Cs
Therefore, in the conventional thinking, researchers generally consider that when metallic lithium is used for the negative electrode, the electrolyte is not capable of adding rubidium ions/cesium ions.
The research and development team has found that the essential reason that the reactions can occur is that the vapor pressure of metal rubidium and cesium is far higher than that of metal lithium, the displaced trace amount of rubidium/cesium is volatilized continuously in vapor form, and the balance of the chemical reaction is forced to move rightwards, so that the displacement reaction can only occur under the constant pressure condition. The liquid metal battery works under a tightly sealed condition (constant volume condition), the displaced rubidium/cesium vapor cannot volatilize, and the chemical reaction balance cannot shift right. Thus, the multi-cation electrolyte containing rubidium ions and cesium ions is stable. The melting point of the LiCl-LiBr-LiI-KI-CsI electrolyte before the operation of the battery was measured as in fig. 3, the melting point of the battery after several months of operation was measured as in fig. 4, and the melting points of the battery before and after the operation were found to be uniform, meaning that the electrolyte properties were stable, and it can also be seen from fig. 3 and 4 that the battery operating temperature was lowered to about 220 ℃.
In a specific embodiment, the molten salt electrolyte has the formula:
LiBr 20-60-RbBr80-40 (minimum melting point of 271 ℃ C. For this system);
LiBr 20-60-CsCl80-40 (minimum melting point of 262 ℃ C. For this system);
LiBr 40-80-CsBr60-20 (minimum melting point of this system is 259 ℃);
LiI 45-85-CsI55-15 (the lowest melting point of the system is 217 ℃);
LiCl 20-80-KCl0-30-CsCl0-40 (the lowest melting point of this electrolyte is 265 ℃);
LiCl 40-80-KCl10-30-RbCl0-20-CsCl0-40 (the lowest melting point of the system is 258 ℃);
LiBr 40-80-KBr10-30-CsBr0-40 (minimum melting point of the system is 236 ℃);
LiI 40-80-KI0-30-CsI0-40 (the lowest melting point of the system is 205 ℃);
LiBr 5-20-LiI40-80-KI10-30-CsI10-40 (minimum melting point of this system is 189 ℃);
LiCl 1-10-LiBr0-20-LiI30-70-KI0-30-CsI0-40 (the lowest melting point of the system is 184 ℃).
In one embodiment, the anode is an alloy of any two metals from bismuth, tin, and lead. Specifically, any one of the following can be selected:
bi 10-90-Sn90-10 alloy (the lowest melting point of the alloy is 141 ℃);
bi 10-90-Pb90-10 alloy (the lowest melting point of the alloy is 125 ℃);
Sn 10-90-Pb90-10 alloy (the lowest melting point of the alloy is 182 ℃);
Sb 5-50-Pb95-50 alloy (the lowest melting point of this alloy is 252 ℃).
Correspondingly, the application also relates to a preparation method of the low-temperature liquid metal battery, which comprises the following steps:
under the protection of inert gas, placing a positive electrode material into a crucible, heating, melting, naturally cooling to form a positive electrode, and placing the crucible into a matched stainless steel shell;
under the protection of inert gas, heating, melting and pouring electrolyte materials into the crucible to form electrolyte; the electrolyte comprises two or more metal halide salts, wherein the metal halide salts comprise lithium halides and also comprise rubidium halides and/or cesium halides, and the melting point of the electrolyte is not more than 300 ℃;
Under the protection of inert gas, absorbing liquid metal lithium by using a negative electrode current collector, assembling the negative electrode current collector absorbed with the metal lithium and a top cover on a shell, and then naturally cooling;
and welding the shell and the top cover to obtain the assembled low-temperature liquid metal battery.
The materials of the positive electrode, the negative electrode and the electrolyte are selected by referring to the above description, and will not be described herein.
The present invention will be described in further detail with reference to specific examples.
Example 1
A Li Bi-Sn liquid metal battery working at 280 ℃ comprises the following steps:
(1) Under the protection of inert gas, weighing 13g of bismuth particles and 11g of tin particles, and placing the bismuth particles and the tin particles in a graphite crucible (with the inner diameter of 56 mm);
(2) Heating the graphite crucible to 300 ℃ on a heating plate under the protection of inert gas, and preserving heat for 1 hour to enable the metal bismuth and the metal tin to be melted to form alloy; then naturally cooling to room temperature, and then placing the graphite crucible in a stainless steel shell matched with the graphite crucible in size;
(3) Under the protection of inert gas, adopting foam carbon to absorb 1.3g of liquid metal lithium as a negative electrode;
(4) Under the protection of inert gas, 60g of dry LiBr-RbBr (molar ratio: 42-58) mixed salt is heated and melted, and poured into the graphite crucible;
(5) Under the protection of inert gas, assembling a negative electrode current collector (carbon foam) adsorbed with metal and a top cover on a shell added with molten salt (not solidified), and then naturally cooling to room temperature;
(6) Welding the shell and the top cover by using laser welding or argon arc welding and the like to obtain an assembled battery;
(7) And placing the battery in a test furnace, heating to the working temperature and maintaining the constant temperature, and connecting a battery test system to perform battery test.
Example 2
A Li Bi-Sn liquid metal battery working at 270 ℃ comprises the following steps:
(1) Under the protection of inert gas, weighing 13g of bismuth particles and 11g of tin particles, and placing the bismuth particles and the tin particles in a graphite crucible (with the inner diameter of 56 mm);
(2) Heating the graphite crucible to 300 ℃ on a heating plate under the protection of inert gas, and preserving heat for 1 hour to enable the metal bismuth and the metal tin to be melted to form alloy; then naturally cooling to room temperature, and then placing the graphite crucible in a stainless steel shell matched with the graphite crucible in size;
(3) Under the protection of inert gas, adopting foam carbon to absorb 1.3g of liquid metal lithium as a negative electrode;
(4) Under the protection of inert gas, 60g of dry LiBr-CsCl (molar ratio: 42-58) mixed salt is heated and melted, and poured into the graphite crucible;
(5) Under the protection of inert gas, assembling a negative electrode current collector (carbon foam) adsorbed with metal and a top cover on a shell added with molten salt (not solidified), and then naturally cooling to room temperature;
(6) Welding the shell and the top cover by using laser welding or argon arc welding and the like to obtain an assembled battery; (7) And placing the battery in a test furnace, heating to the working temperature and maintaining the constant temperature, and connecting a battery test system to perform battery test.
Example 3
A Li Bi-Sn liquid metal battery working at 265 ℃ comprises the following steps:
(1) Under the protection of inert gas, weighing 13g of bismuth particles and 11g of tin particles, and placing the bismuth particles and the tin particles in a graphite crucible (with the inner diameter of 56 mm);
(2) Heating the graphite crucible to 300 ℃ on a heating plate under the protection of inert gas, and preserving heat for 1 hour to enable the metal bismuth and the metal tin to be melted to form alloy; then naturally cooling to room temperature, and then placing the graphite crucible in a stainless steel shell matched with the graphite crucible in size;
(3) Under the protection of inert gas, adopting foam carbon to absorb 1.3g of liquid metal lithium as a negative electrode;
(4) Under the protection of inert gas, 60g of dry LiBr-CsBr (molar ratio: 59-41) mixed salt is heated and melted, and poured into the graphite crucible;
(5) Under the protection of inert gas, assembling a negative electrode current collector (carbon foam) adsorbed with metal and a top cover on a shell added with molten salt (not solidified), and then naturally cooling to room temperature;
(6) Welding the shell and the top cover by using laser welding or argon arc welding and the like to obtain an assembled battery; (7) And placing the battery in a test furnace, heating to the working temperature and maintaining the constant temperature, and connecting a battery test system to perform battery test.
Example 4
A Li Bi-Sn liquid metal battery working at 290 ℃ comprises the following steps:
(1) Under the protection of inert gas, weighing 13g of bismuth particles and 11g of tin particles, and placing the bismuth particles and the tin particles in a graphite crucible (with the inner diameter of 56 mm);
(2) Heating the graphite crucible to 300 ℃ on a heating plate under the protection of inert gas, and preserving heat for 1 hour to enable the metal bismuth and the metal tin to be melted to form alloy; then naturally cooling to room temperature, and then placing the graphite crucible in a stainless steel shell matched with the graphite crucible in size;
(3) Under the protection of inert gas, adopting foam carbon to absorb 1.3g of liquid metal lithium as a negative electrode;
(4) Under the protection of inert gas, 60g of dry LiCl-KCl-CsCl (molar ratio: 72.5-13.3-14.2) mixed salt is heated and melted, and poured into the graphite crucible;
(5) Under the protection of inert gas, assembling a negative electrode current collector (carbon foam) adsorbed with metal and a top cover on a shell added with molten salt (not solidified), and then naturally cooling to room temperature;
(6) Welding the shell and the top cover by using laser welding or argon arc welding and the like to obtain an assembled battery; (7) The battery is placed in a test furnace, heated to the working temperature and maintained at a constant temperature, and a battery test system is connected to perform battery test, wherein the battery is charged and discharged at 290 ℃ as shown in fig. 5, and the battery is cycled at 290 ℃ as shown in fig. 6, which shows that the charging and discharging process is stable and the cycle period is longer.
Example 5
A Li Bi-Sn liquid metal battery working at 245 ℃ comprises the following steps:
(1) Under the protection of inert gas, weighing 13g of bismuth particles and 11g of tin particles, and placing the bismuth particles and the tin particles in a graphite crucible (with the inner diameter of 56 mm);
(2) Heating the graphite crucible to 300 ℃ on a heating plate under the protection of inert gas, and preserving heat for 1 hour to enable the metal bismuth and the metal tin to be melted to form alloy; then naturally cooling to room temperature, and then placing the graphite crucible in a stainless steel shell matched with the graphite crucible in size;
(3) Under the protection of inert gas, adopting foam carbon to absorb 1.3g of liquid metal lithium as a negative electrode;
(4) Under the protection of inert gas, 60g of dry LiBr-KBr-CsBr (molar ratio: 56.1-18.1-25.3) mixed salt is heated and melted, and poured into the graphite crucible;
(5) Under the protection of inert gas, assembling a negative electrode current collector (carbon foam) adsorbed with metal and a top cover on a shell added with molten salt (not solidified), and then naturally cooling to room temperature;
(6) Welding the shell and the top cover by using laser welding or argon arc welding and the like to obtain an assembled battery; (7) And placing the battery in a test furnace, heating to the working temperature and maintaining the constant temperature, and connecting a battery test system to perform battery test.
Example 6
A Li Bi-Sn liquid metal battery working at 210 ℃ comprises the following steps:
(1) Under the protection of inert gas, weighing 13g of bismuth particles and 11g of tin particles, and placing the bismuth particles and the tin particles in a graphite crucible (with the inner diameter of 56 mm);
(2) Heating the graphite crucible to 300 ℃ on a heating plate under the protection of inert gas, and preserving heat for 1 hour to enable the metal bismuth and the metal tin to be melted to form alloy; then naturally cooling to room temperature, and then placing the graphite crucible in a stainless steel shell matched with the graphite crucible in size;
(3) Under the protection of inert gas, adopting foam carbon to absorb 1.3g of liquid metal lithium as a negative electrode;
(4) Under the protection of inert gas, 60g of dry LiI-KI-CsI (molar ratio: 56.1-18.1-25.3) mixed salt is heated and melted, and poured into the graphite crucible;
(5) Under the protection of inert gas, assembling a negative electrode current collector (carbon foam) adsorbed with metal and a top cover on a shell added with molten salt (not solidified), and then naturally cooling to room temperature;
(6) Welding the shell and the top cover by using laser welding or argon arc welding and the like to obtain an assembled battery;
(7) And placing the battery in a test furnace, heating to the working temperature and maintaining the constant temperature, and connecting a battery test system to perform battery test.
Example 7
A Li Bi-Sn liquid metal battery operating at 200 ℃, characterized by the following steps:
(1) Under the protection of inert gas, weighing 13g of bismuth particles and 11g of tin particles, and placing the bismuth particles and the tin particles in a graphite crucible (with the inner diameter of 56 mm);
(2) Heating the graphite crucible to 300 ℃ on a heating plate under the protection of inert gas, and preserving heat for 1 hour to enable the metal bismuth and the metal tin to be melted to form alloy; then naturally cooling to room temperature, and then placing the graphite crucible in a stainless steel shell matched with the graphite crucible in size;
(3) Under the protection of inert gas, adopting foam carbon to absorb 1.3g of liquid metal lithium as a negative electrode;
(4) Under the protection of inert gas, 60g of dry LiBr-LiI-KI-CsI (molar ratio: 9.6-54.3-16.2-19.9) mixed salt is heated and melted, and poured into the graphite crucible;
(5) Under the protection of inert gas, assembling a negative electrode current collector (carbon foam) adsorbed with metal and a top cover on a shell added with molten salt (not solidified), and then naturally cooling to room temperature;
(6) Welding the shell and the top cover by using laser welding or argon arc welding and the like to obtain an assembled battery;
(7) And placing the battery in a test furnace, heating to the working temperature and maintaining the constant temperature, and connecting a battery test system to perform battery test.
Example 8
A Li Bi-Sn liquid metal battery operating at 220 ℃ which is operated by the steps of:
(1) Under the protection of inert gas, weighing 13g of bismuth particles and 11g of tin particles, and placing the bismuth particles and the tin particles in a graphite crucible (with the inner diameter of 56 mm);
(2) Heating the graphite crucible to 300 ℃ on a heating plate under the protection of inert gas, and preserving heat for 1 hour to enable the metal bismuth and the metal tin to be melted to form alloy; then naturally cooling to room temperature, and then placing the graphite crucible in a stainless steel shell matched with the graphite crucible in size;
(3) Under the protection of inert gas, adopting foam carbon to absorb 1.3g of liquid metal lithium as a negative electrode;
(4) Under the protection of inert gas, 60g of dry LiCl-LiBr-LiI-KI-CsI (molar ratio: 3.5-9.2-52.4-15.7-19.2) mixed salt is heated and melted, and poured into the graphite crucible;
(5) Under the protection of inert gas, assembling a negative electrode current collector (carbon foam) adsorbed with metal and a top cover on a shell added with molten salt (not solidified), and then naturally cooling to room temperature;
(6) Welding the shell and the top cover by using laser welding or argon arc welding and the like to obtain an assembled battery;
(7) And placing the battery in a test furnace, heating to the working temperature and maintaining the constant temperature, and connecting a battery test system to perform battery test. The discharge curve of the cell at 220 degrees is shown in fig. 7.
In conclusion, rubidium ions/cesium ions are introduced into the electrolyte of the liquid metal battery, and the melting point of the electrolyte is greatly reduced on the premise of not sacrificing the stability of the electrolyte, so that the liquid metal battery can work at a lower temperature of 190-290 ℃. The lower working temperature not only greatly reduces the power consumption of the thermal management system, but also brings a plurality of benefits for the insulation, corrosion resistance and the like of the battery.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A low-temperature liquid metal battery capable of circularly charging and discharging comprises a shell, and a positive electrode, a negative electrode and an electrolyte which are sealed in the shell, and is characterized in that,
The negative electrode includes lithium metal;
the electrolyte comprises two or more metal halide salts, wherein the metal halide salts comprise lithium halides and also comprise rubidium halides and/or cesium halides, and the melting point of the electrolyte is not more than 300 ℃;
the electrolyte is any combination of the following:
LiBr20-60-RbBr80-40；
LiBr20-60-CsCl80-40；
LiBr40-80-CsBr60-20；
LiI45-85-CsI55-15；
LiCl20-80-KCl0-30-CsCl0-40；
LiCl40-80-KCl10-30-RbCl0-20-CsCl0-40；
LiBr40-80-KBr10-30-CsBr0-40；
LiI40-80-KI0-30-CsI0-40；
LiBr5-20-LiI40-80-KI10-30-CsI10-40；
LiCl1-10-LiBr0-20-LiI30-70-KI0-30-CsI0-40；
Wherein the mole percentages of the components in the electrolyte add up to 100%.
2. The low temperature liquid metal battery of claim 1, wherein the positive electrode is an alloy of two metals of antimony, bismuth, tin, and lead.
3. The low temperature liquid metal battery of claim 2, wherein the positive electrode is any one of:
bi 10-90-Sn90-10 alloy;
Bi 10-90-Pb90-10 alloy;
sn 10-90-Pb90-10 alloy;
Sb 5-50-Pb95-50 alloy;
wherein the mole percentages of the components in each positive electrode alloy add up to 100%.
4. The low temperature liquid metal battery of claim 1, further comprising a negative current collector that is a foam iron nickel or foam carbon.
5. The preparation method of the low-temperature liquid metal battery capable of being circularly charged and discharged is characterized by comprising the following steps of:
under the protection of inert gas, placing a positive electrode material into a crucible, heating, melting, naturally cooling to form a positive electrode, and placing the crucible into a matched stainless steel shell;
under the protection of inert gas, heating, melting and pouring electrolyte materials into the crucible to form electrolyte; the electrolyte comprises two or more metal halide salts, wherein the metal halide salts comprise lithium halides and also comprise rubidium halides and/or cesium halides, and the melting point of the electrolyte is not more than 300 ℃;
Under the protection of inert gas, absorbing liquid metal lithium by using a negative electrode current collector, assembling the negative electrode current collector absorbed with the metal lithium and a top cover on a shell, and then naturally cooling;
Welding the shell and the top cover to obtain an assembled low-temperature liquid metal battery;
Wherein the electrolyte is any combination of the following:
LiBr20-60-RbBr80-40；
LiBr20-60-CsCl80-40；
LiBr40-80-CsBr60-20；
LiI45-85-CsI55-15；
LiCl20-80-KCl0-30-CsCl0-40；
LiCl40-80-KCl10-30-RbCl0-20-CsCl0-40；
LiBr40-80-KBr10-30-CsBr0-40；
LiI40-80-KI0-30-CsI0-40；
LiBr5-20-LiI40-80-KI10-30-CsI10-40；
LiCl1-10-LiBr0-20-LiI30-70-KI0-30-CsI0-40；
Wherein the mole percentages of the components of each combination add up to 100%.
6. The method of manufacturing a low temperature liquid metal battery according to claim 5, wherein the positive electrode is an alloy formed of two metals of antimony, bismuth, tin, and lead;
Placing the positive electrode material in a crucible for heating and melting, comprising:
each metal making up the alloy is placed in a crucible and heated to melt each metal into an alloy.
7. The method of manufacturing a low temperature liquid metal battery according to claim 6, wherein the alloy is any one of the following:
bi 10-90-Sn90-10 alloy;
Bi 10-90-Pb90-10 alloy;
sn 10-90-Pb90-10 alloy;
Sb 5-50-Pb95-50 alloy;
wherein the mole percentages of the components in each alloy add up to 100%.
8. As in claim 5
The preparation method of the low-temperature liquid metal battery is characterized in that the negative electrode current collector is foam iron nickel or foam carbon.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4145806A (en) * | 1977-08-17 | 1979-03-27 | Rockwell International Corporation | Method of assembling an electrochemical cell |
| JP2009009933A (en) * | 2007-05-25 | 2009-01-15 | Panasonic Corp | Molten salt and thermal battery |
| JP2010015890A (en) * | 2008-07-04 | 2010-01-21 | Panasonic Corp | Molten salt and thermal battery |
| CN102437345A (en) * | 2011-12-19 | 2012-05-02 | 梅岭化工厂 | Thermal battery electrolyte with low melting point and high electric conductivity and preparation method thereof |
| CN102544535A (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 5-component inorganic fused salt |
| CN102569836A (en) * | 2010-12-24 | 2012-07-11 | 中国电子科技集团公司第十八研究所 | Preparation method of quadruple inorganic molten salt electrolyte |
| JP2014103032A (en) * | 2012-11-21 | 2014-06-05 | Sony Corp | Active material for secondary battery, electrode for secondary battery, secondary battery, battery pack, electric vehicle, power storage system, electric power tool, and electronic apparatus |
| JP2016018679A (en) * | 2014-07-08 | 2016-02-01 | 三菱瓦斯化学株式会社 | Electrode layer for all-solid battery and all-solid battery |
| US9786955B1 (en) * | 2013-03-13 | 2017-10-10 | Massachusetts Institute Of Technology | Assembly methods for liquid metal battery with bimetallic electrode |
| CN108370060A (en) * | 2015-12-15 | 2018-08-03 | 新罗纳米技术有限公司 | solid electrolyte for safe metal and metal ion battery |
| CN110148779A (en) * | 2019-06-04 | 2019-08-20 | 北京航空航天大学 | Application, low temperature liquid molten salt lithium battery and preparation method of the LiI-KI eutectic salts in low temperature liquid molten salt lithium battery |
| CN110620271A (en) * | 2019-08-07 | 2019-12-27 | 全球能源互联网研究院有限公司 | Low-temperature liquid and semi-liquid metal battery |
| CN113809409A (en) * | 2021-08-16 | 2021-12-17 | 北京科技大学 | Low-melting-point molten salt electrolyte of liquid or semi-liquid metal battery, preparation and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2961634B1 (en) * | 2010-06-17 | 2013-02-15 | Centre Nat Rech Scient | PROCESS FOR THE PRODUCTION OF A LITHIUM OR SODIUM BATTERY |
-
2022
- 2022-05-05 CN CN202210480460.3A patent/CN114792847B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4145806A (en) * | 1977-08-17 | 1979-03-27 | Rockwell International Corporation | Method of assembling an electrochemical cell |
| JP2009009933A (en) * | 2007-05-25 | 2009-01-15 | Panasonic Corp | Molten salt and thermal battery |
| JP2010015890A (en) * | 2008-07-04 | 2010-01-21 | Panasonic Corp | Molten salt and thermal battery |
| CN102544535A (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 5-component inorganic fused salt |
| CN102569836A (en) * | 2010-12-24 | 2012-07-11 | 中国电子科技集团公司第十八研究所 | Preparation method of quadruple inorganic molten salt electrolyte |
| CN102437345A (en) * | 2011-12-19 | 2012-05-02 | 梅岭化工厂 | Thermal battery electrolyte with low melting point and high electric conductivity and preparation method thereof |
| JP2014103032A (en) * | 2012-11-21 | 2014-06-05 | Sony Corp | Active material for secondary battery, electrode for secondary battery, secondary battery, battery pack, electric vehicle, power storage system, electric power tool, and electronic apparatus |
| US9786955B1 (en) * | 2013-03-13 | 2017-10-10 | Massachusetts Institute Of Technology | Assembly methods for liquid metal battery with bimetallic electrode |
| JP2016018679A (en) * | 2014-07-08 | 2016-02-01 | 三菱瓦斯化学株式会社 | Electrode layer for all-solid battery and all-solid battery |
| CN108370060A (en) * | 2015-12-15 | 2018-08-03 | 新罗纳米技术有限公司 | solid electrolyte for safe metal and metal ion battery |
| CN110148779A (en) * | 2019-06-04 | 2019-08-20 | 北京航空航天大学 | Application, low temperature liquid molten salt lithium battery and preparation method of the LiI-KI eutectic salts in low temperature liquid molten salt lithium battery |
| CN110620271A (en) * | 2019-08-07 | 2019-12-27 | 全球能源互联网研究院有限公司 | Low-temperature liquid and semi-liquid metal battery |
| CN113809409A (en) * | 2021-08-16 | 2021-12-17 | 北京科技大学 | Low-melting-point molten salt electrolyte of liquid or semi-liquid metal battery, preparation and application |
Non-Patent Citations (1)
| Title |
|---|
| 基于熔盐电解质的电动势法测定合金体系活度的研究;孔令鑫;徐俊杰;;民营科技(第06期);66-67 * |
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