CN116581290B - Silicon carbide negative electrode material molten salt thermal battery and preparation and testing methods thereof - Google Patents
Silicon carbide negative electrode material molten salt thermal battery and preparation and testing methods thereof Download PDFInfo
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 116
- 150000003839 salts Chemical class 0.000 title claims abstract description 105
- 238000012360 testing method Methods 0.000 title claims abstract description 65
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000010405 anode material Substances 0.000 claims abstract description 44
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910013618 LiCl—KCl Inorganic materials 0.000 claims description 37
- 238000002484 cyclic voltammetry Methods 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 229910000838 Al alloy Inorganic materials 0.000 claims description 9
- 238000002441 X-ray diffraction Methods 0.000 claims description 9
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 9
- 238000004769 chrono-potentiometry Methods 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 238000011156 evaluation Methods 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 13
- 239000010406 cathode material Substances 0.000 abstract description 11
- 238000007599 discharging Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
- 229910000733 Li alloy Inorganic materials 0.000 abstract description 8
- 239000001989 lithium alloy Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 150000005309 metal halides Chemical class 0.000 abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001768 cations Chemical class 0.000 abstract description 4
- 238000010998 test method Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 230000000007 visual effect Effects 0.000 abstract 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 239000012300 argon atmosphere Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000010963 304 stainless steel Substances 0.000 description 7
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 229910013493 LiCl-LiBr-LiF Inorganic materials 0.000 description 1
- 229910013644 LiCl—LiBr—LiF Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
- G01N23/207—Diffractometry using detectors, e.g. using a probe in a central position and one or more displaceable detectors in circumferential positions
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/378—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC] specially adapted for the type of battery or accumulator
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/30—Deferred-action cells
- H01M6/36—Deferred-action cells containing electrolyte and made operational by physical means, e.g. thermal 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
Abstract
The invention discloses a silicon carbide anode material molten salt thermal battery and a preparation and testing method thereof, and belongs to the technical field of electrodes. The silicon carbide negative electrode material molten salt thermal battery takes silicon carbide as the negative electrode material of the working electrode, and has the advantages of low cost and environmental friendliness. The silicon carbide negative electrode material has no lithium element, so that the problems that the cation proportion in the lithium metal halide electrolyte changes and the solubility of the lithium alloy negative electrode material in the lithium metal halide electrolyte is increased in the discharging process can be reasonably avoided, and the problem that the lithium alloy negative electrode material and the lithium metal halide electrolyte are mutually influenced is solved. The invention also provides a preparation and test method of the molten salt thermal battery, the preparation method has simple process, is convenient for large-scale production and application, has strong pertinence, and provides visual and accurate basis for using silicon carbide as a material for a thermal battery cathode material.
Description
Technical Field
The invention relates to the technical field of electrodes, in particular to a silicon carbide anode material molten salt thermal battery and a preparation and test method thereof.
Background
The thermal battery is a thermal-activated reserve battery which uses the heating system of the battery to heat and melt the non-conductive solid state salt electrolyte into an ionic conductor to enter the working state, and has the specific ratioThe energy is high, the specific power is high, the activation speed is high, the use environment temperature is wide, the storage time is long, the maintenance is not needed, and the like, and the energy is applied to a plurality of advanced high and new technology weapons such as missiles, nuclear weapons, various advanced bombs, artillery, mines and the like. The anode and cathode materials are one of key components of the thermal battery, and influence the electrochemical performance of the thermal battery. The cathode materials studied at present mainly comprise a calcium cathode material, a pure lithium cathode material, a lithium alloy cathode material and the like, wherein the most potential cathode material belongs to the lithium alloy cathode material, and the cathode material is applied to the field of military science at present 2 Batteries have a large market share, such as the negative electrode materials of matched power supply thermal batteries for launching missiles, rockets and shells are all made of lithium silicon alloy powder, and the batteries are more calcium-based (Ca/CaCrO) 4 ，Ca/Fe 2 O 3 ) Magnesium system (Mg/V) 2 O 5 ) The thermal battery has the advantages of high power discharge, high specific energy, compact structure and the like, but the content of active lithium in the lithium-silicon alloy is also greatly reduced, and in the discharge process, a plurality of compounds which reduce the electrode potential and the electrochemical capacity and cause the performance of the thermal battery to be reduced are formed in the alloys.
The invention discloses a LiB electrode material, a preparation method and application thereof, wherein the LiB electrode material is used as a negative electrode, a nano material or a mixture of a framework material and the nano material is used as a raw material to prepare an anti-overflow layer, and the nano material has larger adsorption capacity and capillary action to realize adhesion and blocking on the surface of a LiB alloy, so that overflow of liquid metal lithium in the LiB alloy under high temperature and complex mechanical conditions is inhibited. However, the radius of lithium ions is small, lithium ions still cannot enter the electrolyte in a microcosmic level in a long-term use process, and currently widely applied LiCl-KCl binary electrolyte and LiCl-LiBr-LiF ternary electrolyte have some negative influence on the performance of a lithium alloy negative electrode, the former has continuous entry along with lithium ions in the negative electrode material, so that the proportion of cations in the electrolyte is changed, the melting point of the electrolyte is increased, the resistance is increased, and the reaction is terminated in advance; the latter may cause an increase in solubility of the anode active material therein, resulting in an increase in the self-depletion process caused thereby. It can be seen that the existing anode material cannot meet the higher performance and use requirements of the anode material.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, in a first aspect of the present invention, there is provided a silicon carbide anode material molten salt thermal battery having high electrochemical activity and good stability, the silicon carbide anode material molten salt thermal battery including a working electrode, a counter electrode and an electrolyte in a closed and oxygen-free environment; the working electrode and the counter electrode are respectively connected with a current collector and separated by the electrolyte; the working electrode is made of silicon carbide.
The design idea of the invention is that no lithium element exists in silicon carbide, the silicon carbide is used as a negative electrode material and is used as a working electrode, the problems that the proportion of cations in lithium metal halide electrolyte is changed and the solubility of the negative electrode material in the lithium metal halide electrolyte is increased caused by the negative electrode material of the lithium alloy thermal battery can be avoided, and the silicon carbide is expected to become the negative electrode material for replacing the negative electrode material of the existing thermal battery.
Preferably, the counter electrode is made of graphite or magnesium aluminum alloy.
Preferably, the electrolyte is LiCl-KCl molten salt.
In a second aspect of the invention, a preparation method of a silicon carbide anode material molten salt thermal battery with simple process and convenient preparation is provided, which comprises the following steps:
s1, preparing a working electrode by powdery silicon carbide tabletting, and connecting the working electrode, a counter electrode and a current collector for later use;
s2, in a closed environment and an inert gas atmosphere, placing a working electrode and a counter electrode which are connected with a current collector in an electrolyte and separating the electrolyte to form a two-electrode system, so as to obtain the silicon carbide negative electrode material molten salt thermal battery.
In a third aspect of the invention, a testing method of a silicon carbide anode material molten salt thermal battery is provided, the testing method comprises the steps of assembling the testing silicon carbide anode material molten salt thermal battery and evaluating the silicon carbide anode material used by the testing silicon carbide anode material molten salt thermal battery, the testing silicon carbide anode material molten salt thermal battery comprises a three-electrode system consisting of a working electrode, a counter electrode and a reference electrode, and the evaluating method comprises at least one of cyclic voltammetry, an X-ray diffraction method and a chronopotentiometry.
Because silicon carbide is an innovative attempt as a thermal battery anode material and the property of the silicon carbide is greatly different from that of a lithium-containing anode material, the conventional testing method of the lithium-containing anode material has the defects of poor pertinence and incomplete pertinence. In order to verify the feasibility of using silicon carbide material as the negative electrode material of the thermal battery, the invention assembles and designs the test method proposed for the requirement. And evaluating the electrochemical activity and the structural stability of the silicon carbide negative electrode material by a cyclic voltammetry, an X-ray diffraction method and a chronopotentiometric method to judge whether the silicon carbide reaches the standard of the thermal battery negative electrode material.
Preferably, the method for assembling the silicon carbide anode material molten salt thermal battery for testing comprises the following steps:
the powdered silicon carbide is pressed into a working electrode by tabletting, graphite or magnesium aluminum alloy is used as a counter electrode, and a silver electrode is used as a reference electrode; and respectively connecting the working electrode and the counter electrode with a current collector, then inserting the working electrode, the counter electrode and the reference electrode into an electrolyte under the closed environment and inert gas atmosphere, separating the working electrode, the counter electrode and the reference electrode and packaging the working electrode, the counter electrode and the reference electrode to form a three-electrode system, thereby obtaining the silicon carbide negative electrode material molten salt thermal battery for testing.
Further preferably, the mass of the silicon carbide is 0.5-1.5 g.
Preferably, the cyclic voltammetry and the chronopotentiometry are both performed under an inert gas atmosphere.
Further preferably, when evaluating by cyclic voltammetry, graphite is selected as a counter electrode adopted by the silicon carbide negative electrode material molten salt thermal battery.
Further preferably, the temperature of the test is 400-550 ℃ when evaluated by cyclic voltammetry.
Further preferably, the voltage window for the test comprises at least one of 0.3 to-1.5V, 0 to-2.1V and 0.5 to-2.1V when evaluated by cyclic voltammetry.
Further preferably, the scanning rate of the test is 0.1 to 1mV/s when evaluated by cyclic voltammetry.
Further preferably, the silicon carbide after primary charging and discharging of the silicon carbide anode material molten salt thermal battery is evaluated by adopting an X-ray diffraction method, the diffraction range of the test is 5-90 degrees, and the scanning rate is 3-10 degrees/min.
Further preferably, when the evaluation is performed by adopting a chronopotentiometric method, a counter electrode adopted by the fused salt thermal battery of the silicon carbide anode material is made of magnesium-aluminum alloy.
Further preferably, the temperature of the test is 400-500 ℃ when the evaluation is performed by a chronopotentiometry.
Further preferably, the constant current range of the test is 0.1 to 1A when the evaluation is performed by a chronopotentiometric method.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention provides a silicon carbide negative electrode material molten salt thermal battery, which takes silicon carbide as a negative electrode material of a working electrode and has the advantages of low cost and environmental friendliness. The silicon carbide negative electrode material has no lithium element, so that the problems that the cation proportion in the lithium metal halide electrolyte changes and the solubility of the lithium alloy negative electrode material in the lithium metal halide electrolyte is increased in the discharging process can be reasonably avoided, and the problem that the lithium alloy negative electrode material and the lithium metal halide electrolyte are mutually influenced is solved.
The invention provides a preparation method of a silicon carbide negative electrode material molten salt thermal battery, which adopts a working electrode and a counter electrode which are made of silicon carbide to form a two-electrode system in electrolyte, and has the advantages of simple process, convenient preparation and convenient mass production and application.
The invention provides a testing method of a silicon carbide negative electrode material molten salt thermal battery, which has strong pertinence, tests the performance of the thermal battery under a three-electrode system by a cyclic voltammetry, an X-ray diffraction method and a chronopotentiometry, and provides an intuitive and accurate basis for using silicon carbide as a material for the negative electrode material of the thermal battery.
Drawings
FIG. 1 shows cyclic voltammograms of silicon carbide under different voltage windows for a molten salt thermal battery of silicon carbide negative electrode material for test of example 1, wherein (a) corresponds to the cyclic voltammograms of a blank, (b) corresponds to the cyclic voltammograms of 0 to-2.1V, (c) corresponds to the cyclic voltammograms of 0.3 to-1.5V, and (d) corresponds to the cyclic voltammograms of-1.5 to-2.1V;
FIG. 2 is a cyclic voltammogram of silicon carbide of the silicon carbide anode material molten salt thermal battery for test of example 2 under a voltage window of 0.3 to-1.5V;
FIG. 3 is a cyclic voltammogram of silicon carbide at a voltage window of-0.5 to-2.1V for the silicon carbide negative electrode material molten salt thermal battery for testing of example 3;
FIG. 4 is an X-ray diffraction chart of silicon carbide after one charge and discharge of the molten salt thermal battery of the silicon carbide anode material for test in example 4, wherein plum blossom marks represent diffraction peak positions on a standard PDF- #72-0018 card of silicon carbide;
fig. 5 is a chart showing the time-potential of silicon carbide in the molten salt thermal battery of the silicon carbide anode material for test of example 5.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
In the following examples, liCl-KCl mixed salts contained 45wt.% LiCl and 55wt.% KCl.
Example 1
The testing method of the silicon carbide anode material molten salt thermal battery comprises the following steps:
assembling a silicon carbide anode material molten salt thermal battery for testing:
pressing silicon carbide powder into a pressed sheet with the mass of 0.5g under the pressure of 10MPa, taking the silicon carbide pressed sheet as a working electrode, and binding the pressed sheet on a metal molybdenum wire current collector with the diameter of 1.5mm by using a molybdenum wire with the diameter of 0.3mm for fixing; a graphite rod with the diameter of 10mm is directly used as a counter electrode, and is connected with a 304 stainless steel wire current collector with the diameter of 2 mm; silver electrode is used as reference electrode;
drying 700g of LiCl-KCl mixed salt in a vacuum drying oven at 300 ℃ and 10Pa to remove water, then placing the dried LiCl-KCl mixed salt in an alumina crucible with the diameter of 150mm, and placing the alumina crucible in a reactor;
suspending a working electrode, a counter electrode and a reference electrode above LiCl-KCl mixed salt, sealing the reactor, vacuumizing the reactor, continuously introducing argon into the reactor through an air inlet on the reactor, discharging through an air outlet, and forming an argon atmosphere in the reactor;
heating to 400 ℃ to enable the LiCl-KCl mixed salt to be completely melted to form LiCl-KCl molten salt, inserting a working electrode, a counter electrode and a reference electrode into the LiCl-KCl molten salt to form a three-electrode system, wherein the horizontal interval of the three electrodes is 0.5cm respectively, and completing the assembly of the silicon carbide negative electrode material molten salt thermal battery for testing.
Cyclic voltammetry was evaluated:
and (3) carrying out cyclic voltammetry test on the silicon carbide negative electrode material molten salt thermal battery for test assembled in the embodiment for a preset number of times by using an electrochemical workstation under the voltage windows of 0.3 to 1.5V, 0 to 2.1V and 0.5 to 2.1V in an argon atmosphere, wherein the scanning rate of the test is 1mV/s, and the test uses molybdenum wires without silicon carbide tablets as blank control. FIG. 1 shows cyclic voltammograms of silicon carbide negative electrode materials under different voltage windows, wherein obvious reduction peaks appear at-1.0V and-0.6V and obvious oxidation peaks appear at-0.8V and-0.4V in the first circulation of the silicon carbide negative electrode materials, which shows that the silicon carbide materials have high electrochemical activity and initially meet the conditions of serving as the thermal battery negative electrode materials.
Example 2
The testing method of the silicon carbide anode material molten salt thermal battery comprises the following steps:
assembling a silicon carbide anode material molten salt thermal battery for testing:
pressing silicon carbide powder into a pressed sheet with the mass of 1.0g under the pressure of 10MPa, taking the silicon carbide pressed sheet as a working electrode, and binding the pressed sheet on a metal molybdenum wire current collector with the diameter of 1.5mm by using a molybdenum wire with the diameter of 0.3mm for fixing; a graphite rod with the diameter of 10mm is directly used as a counter electrode, and is connected with a 304 stainless steel wire current collector with the diameter of 2 mm; silver electrode is used as reference electrode;
drying 700g of LiCl-KCl mixed salt in a vacuum drying oven at 300 ℃ and 10Pa to remove water, then placing the dried LiCl-KCl mixed salt in an alumina crucible with the diameter of 150mm, and placing the alumina crucible in a reactor;
suspending a working electrode, a counter electrode and a reference electrode above LiCl-KCl mixed salt, sealing the reactor, vacuumizing the reactor, continuously introducing argon into the reactor through an air inlet on the reactor, discharging through an air outlet, and forming an argon atmosphere in the reactor;
heating to 400 ℃ to enable the LiCl-KCl mixed salt to be completely melted to form LiCl-KCl molten salt, inserting a working electrode, a counter electrode and a reference electrode into the LiCl-KCl molten salt to form a three-electrode system, wherein the horizontal interval of the three electrodes is 0.5cm respectively, and completing the assembly of the silicon carbide negative electrode material molten salt thermal battery for testing.
Cyclic voltammetry was evaluated:
and (3) carrying out cyclic voltammetry test on the silicon carbide anode material fused salt thermal battery for test assembled in the embodiment for a preset number of times by utilizing an electrochemical workstation under a voltage window of 0.3 to-1.5V in an argon atmosphere, wherein the scanning rate of the test is 1mV/s. FIG. 2 shows multi-cycle voltammograms of the silicon carbide negative electrode material at 400 ℃ and a scanning speed of 1mV/s under a voltage window of 0.3 to-1.5V, and the curves show good coincidence, which indicates that the silicon carbide has good cycle performance and meets the condition of being used as the negative electrode material of the thermal battery.
Example 3
The testing method of the silicon carbide anode material molten salt thermal battery comprises the following steps:
assembling a silicon carbide anode material molten salt thermal battery for testing:
pressing silicon carbide powder into a pressed sheet with the mass of 0.5g under the pressure of 10MPa, taking the silicon carbide pressed sheet as a working electrode, and binding the pressed sheet on a metal molybdenum wire current collector with the diameter of 1.5mm by using a molybdenum wire with the diameter of 0.3mm for fixing; a graphite rod with the diameter of 10mm is directly used as a counter electrode, and is connected with a 304 stainless steel wire current collector with the diameter of 2 mm; silver electrode is used as reference electrode;
drying 700g of LiCl-KCl mixed salt in a vacuum drying oven at 300 ℃ and 10Pa to remove water, then placing the dried LiCl-KCl mixed salt in an alumina crucible with the diameter of 150mm, and placing the alumina crucible in a reactor;
suspending a working electrode, a counter electrode and a reference electrode above LiCl-KCl mixed salt, sealing the reactor, vacuumizing the reactor, continuously introducing argon into the reactor through an air inlet on the reactor, discharging through an air outlet, and forming an argon atmosphere in the reactor;
heating to 400 ℃ to enable the LiCl-KCl mixed salt to be completely melted to form LiCl-KCl molten salt, inserting a working electrode, a counter electrode and a reference electrode into the LiCl-KCl molten salt to form a three-electrode system, wherein the horizontal interval of the three electrodes is 0.5cm respectively, and completing the assembly of the silicon carbide negative electrode material molten salt thermal battery for testing.
Cyclic voltammetry was evaluated:
and (3) carrying out cyclic voltammetry test on the silicon carbide anode material fused salt thermal battery for test assembled in the embodiment for a preset number of times by utilizing an electrochemical workstation under a voltage window of minus 0.5 to minus 2.1V in an argon atmosphere, wherein the scanning rate of the test is 0.1mV/s. FIG. 3 shows a multi-cycle voltammogram of a silicon carbide negative electrode material at a temperature of 550 ℃ and a scanning speed of 0.1mV/s under a voltage window of-0.5 to-2.1V, and the curve also shows good coincidence, which indicates that the silicon carbide material has good cycle performance and meets the basic condition of being used as a thermal battery negative electrode material.
Example 4
The testing method of the silicon carbide anode material molten salt thermal battery comprises the following steps:
assembling a silicon carbide anode material molten salt thermal battery for testing:
pressing silicon carbide powder into a pressed sheet with the mass of 0.5g under the pressure of 10MPa, taking the silicon carbide pressed sheet as a working electrode, and binding the pressed sheet on a metal molybdenum wire current collector with the diameter of 1.5mm by using a molybdenum wire with the diameter of 0.3mm for fixing; a graphite rod with the diameter of 10mm is directly used as a counter electrode, and is connected with a 304 stainless steel wire current collector with the diameter of 2 mm; silver electrode is used as reference electrode;
drying 700g of LiCl-KCl mixed salt in a vacuum drying oven at 300 ℃ and 10Pa to remove water, then placing the dried LiCl-KCl mixed salt in an alumina crucible with the diameter of 150mm, and placing the alumina crucible in a reactor;
suspending a working electrode, a counter electrode and a reference electrode above LiCl-KCl mixed salt, sealing the reactor, vacuumizing the reactor, continuously introducing argon into the reactor through an air inlet on the reactor, discharging through an air outlet, and forming an argon atmosphere in the reactor;
heating to 400 ℃ to enable the LiCl-KCl mixed salt to be completely melted to form LiCl-KCl molten salt, inserting a working electrode, a counter electrode and a reference electrode into the LiCl-KCl molten salt to form a three-electrode system, wherein the horizontal interval of the three electrodes is 0.5cm respectively, and completing the assembly of the silicon carbide negative electrode material molten salt thermal battery for testing.
The X-ray diffraction method was evaluated:
the working electrode which is assembled in the embodiment and is cooled after the primary charge-discharge circulation is carried out at the working temperature (400-500 ℃), is taken out and put into deionized water, liCl-KCl molten salt on the surface of the working electrode is removed by cleaning, the working electrode is dried for 12 hours at 80 ℃, then, the silicon carbide is collected for X-ray diffraction test, the silicon carbide is filled into a groove of a sample rack to prepare a test piece with a flat plane, and then the test is carried out at the speed of 5 DEG/min within the range of 5-90 ℃.
As shown in FIG. 4, the diffraction peak of the silicon carbide after one charge and discharge is consistent with the diffraction peak position on the card of the silicon carbide standard PDF- #72-0018, which shows that the composition of the silicon carbide is not changed, and the silicon carbide material has good structural stability in the charge and discharge process, and meets the standard of the thermal battery cathode material.
Example 5
The testing method of the silicon carbide anode material molten salt thermal battery comprises the following steps:
assembling a silicon carbide anode material molten salt thermal battery for testing:
pressing silicon carbide powder into a pressed sheet with the mass of 0.5g under the pressure of 10MPa, taking the silicon carbide pressed sheet as a working electrode, and binding the pressed sheet on a metal molybdenum wire current collector with the diameter of 1.5mm by using a molybdenum wire with the diameter of 0.3mm for fixing; directly taking a magnesium aluminum alloy with the diameter of 10mm as a counter electrode, and connecting the counter electrode with a 304 stainless steel wire current collector with the diameter of 2 mm; silver electrode is used as reference electrode;
drying 700g of LiCl-KCl mixed salt in a vacuum drying oven at 300 ℃ and 10Pa to remove water, then placing the dried LiCl-KCl mixed salt in an alumina crucible with the diameter of 150mm, and placing the alumina crucible in a reactor;
suspending a working electrode, a counter electrode and a reference electrode above LiCl-KCl mixed salt, sealing the reactor, vacuumizing the reactor, continuously introducing argon into the reactor through an air inlet on the reactor, discharging through an air outlet, and forming an argon atmosphere in the reactor;
heating to 400 ℃ to enable the LiCl-KCl mixed salt to be completely melted to form LiCl-KCl molten salt, inserting a working electrode, a counter electrode and a reference electrode into the LiCl-KCl molten salt to form a three-electrode system, wherein the horizontal interval of the three electrodes is 0.5cm respectively, and completing the assembly of the silicon carbide negative electrode material molten salt thermal battery for testing.
Chronopotentiometry evaluation:
and (3) applying constant current of 0.15A at 400 ℃ in an argon atmosphere, and testing the silicon carbide anode material fused salt thermal battery for testing assembled in the embodiment by adopting a chronopotentiometry. The obtained voltage-time curve is shown in fig. 5, and according to the capacity=current time/active substance mass, the silicon carbide material is calculated to have the capacity of 5700C/g, and the requirement of the thermal battery cathode material is also met.
Example 6
The preparation method of the silicon carbide anode material molten salt thermal battery comprises the following steps:
s1, pressing silicon carbide powder into a pressed sheet with the mass of 0.5g under the pressure of 10MPa, taking the silicon carbide pressed sheet as a working electrode, and binding the pressed sheet on a metal molybdenum wire current collector with the diameter of 1.5mm by using a molybdenum wire with the diameter of 0.3mm for fixing; directly taking a magnesium aluminum alloy with the diameter of 10mm as a counter electrode, and connecting the counter electrode with a 304 stainless steel wire current collector with the diameter of 2mm for standby;
s2, placing 700g of LiCl-KCl mixed salt in a vacuum drying oven at 300 ℃ and 10Pa to remove water, placing the dried mixed salt in an alumina crucible with the diameter of 150mm, and placing the alumina crucible in a reactor; suspending a working electrode and a counter electrode above LiCl-KCl mixed salt, sealing the reactor, vacuumizing the reactor, continuously introducing argon into the reactor through an air inlet on the reactor, discharging through an air outlet, and forming an argon atmosphere in the reactor; and heating to 500 ℃ to enable the electrolyte to be completely melted, inserting the working electrode and the counter electrode into molten salt to form a two-electrode system, wherein the horizontal interval between the two electrodes is 0.5cm, and obtaining the silicon carbide negative electrode material molten salt thermal battery.
Example 7
The preparation method of the silicon carbide anode material molten salt thermal battery comprises the following steps:
s1, pressing silicon carbide powder into a pressed sheet with the mass of 1.5g under the pressure of 10MPa, taking the silicon carbide pressed sheet as a working electrode, and binding the pressed sheet on a metal molybdenum wire current collector with the diameter of 1.5mm by using a molybdenum wire with the diameter of 0.3mm for fixing; directly taking a magnesium aluminum alloy with the diameter of 10mm as a counter electrode, and connecting the counter electrode with a 304 stainless steel wire current collector with the diameter of 2mm for standby;
s2, placing 700g of LiCl-KCl mixed salt in a vacuum drying oven at 300 ℃ and 10Pa to remove water, placing the dried mixed salt in an alumina crucible with the diameter of 150mm, and placing the alumina crucible in a reactor; suspending a working electrode and a counter electrode above LiCl-KCl mixed salt, sealing the reactor, vacuumizing the reactor, continuously introducing argon into the reactor through an air inlet on the reactor, discharging through an air outlet, and forming an argon atmosphere in the reactor; and heating to 500 ℃ to enable the electrolyte to be completely melted, inserting the working electrode and the counter electrode into molten salt to form a two-electrode system, wherein the horizontal interval between the two electrodes is 0.5cm, and obtaining the silicon carbide negative electrode material molten salt thermal battery.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (3)
1. A silicon carbide negative electrode material molten salt thermal battery is characterized in that: the silicon carbide negative electrode material molten salt thermal battery comprises a working electrode, a counter electrode and an electrolyte which are in a closed and anaerobic environment; the working electrode and the counter electrode are respectively connected with a current collector and separated by the electrolyte; the working electrode is made of silicon carbide; the counter electrode is made of graphite or magnesium-aluminum alloy; the electrolyte is LiCl-KCl molten salt.
2. A method for preparing a silicon carbide anode material molten salt thermal battery as claimed in claim 1, comprising the steps of:
s1, preparing a working electrode by powdery silicon carbide tabletting, and connecting the working electrode, a counter electrode and a current collector for later use;
s2, in a closed environment and an inert gas atmosphere, placing a working electrode and a counter electrode which are connected with a current collector in an electrolyte and separating the electrolyte to form a two-electrode system, so as to obtain the silicon carbide negative electrode material molten salt thermal battery.
3. A method for testing a molten salt thermal battery of a silicon carbide anode material according to claim 1, comprising assembling the molten salt thermal battery of the silicon carbide anode material for testing and evaluating the silicon carbide anode material used therein, characterized in that: the silicon carbide negative electrode material molten salt thermal battery for testing comprises a three-electrode system consisting of a working electrode, a counter electrode and a reference electrode, and the method adopted by the evaluation comprises at least one of cyclic voltammetry, an X-ray diffraction method and a chronopotentiometry;
the cyclic voltammetry and the chronopotentiometry are tested in an inert gas atmosphere;
when the cyclic voltammetry is adopted for evaluation, graphite is selected as a counter electrode adopted by the silicon carbide anode material molten salt thermal battery; the temperature for testing is 400-550 ℃; the voltage window for testing comprises at least one of 0.3 to-1.5V, 0 to-2.1V and 0.5 to-2.1V; the scanning rate of the test is 0.1-1 mV/s;
the X-ray diffraction method is adopted to evaluate the silicon carbide after the silicon carbide anode material molten salt thermal battery is charged and discharged for one time, and the diffraction range of the test is 5-90 degrees; the scanning speed is 3-10 degrees/min;
when the timing potential method is adopted for evaluation, a counter electrode adopted by the silicon carbide negative electrode material molten salt thermal battery is made of magnesium-aluminum alloy; the temperature for testing is 400-500 ℃; the constant current range of the test is 0.1-1A;
the method for assembling the silicon carbide anode material molten salt thermal battery for testing comprises the following steps of: the powdered silicon carbide is pressed into a working electrode by tabletting, graphite or magnesium aluminum alloy is used as a counter electrode, and a silver electrode is used as a reference electrode; respectively connecting a working electrode and a counter electrode with a current collector, then inserting the working electrode, the counter electrode and a reference electrode into an electrolyte under a closed environment and an inert gas atmosphere, separating the working electrode, the counter electrode and the reference electrode and packaging the working electrode, the reference electrode and the electrolyte to form a three-electrode system, thereby obtaining the silicon carbide negative electrode material molten salt thermal battery for testing; the mass of the silicon carbide is 0.5-1.5 g.
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