CN114388756B - A high-performance thermal battery composite positive electrode material and preparation method thereof - Google Patents
A high-performance thermal battery composite positive electrode material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 107
- 239000003792 electrolyte Substances 0.000 claims abstract description 65
- 150000003839 salts Chemical class 0.000 claims abstract description 65
- 238000000498 ball milling Methods 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 19
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims description 27
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 27
- 230000000996 additive effect Effects 0.000 claims description 25
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 24
- 239000000395 magnesium oxide Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229910013618 LiCl—KCl Inorganic materials 0.000 claims description 2
- 239000011149 active material Substances 0.000 abstract description 3
- 238000002955 isolation Methods 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000010405 anode material Substances 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229910000521 B alloy Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical class [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000339 iron disulfide Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- -1 al 2O3 Chemical compound 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
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- 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
- H01M4/582—Halogenides
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- 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
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- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a high-performance thermal battery composite positive electrode material and a preparation method thereof, wherein the high-performance thermal battery composite positive electrode material is obtained by mixing and ball milling nickel chloride and composite molten salt electrolyte powder, the mass fraction of the nickel chloride is 60-90%, and the mass fraction of the composite molten salt electrolyte powder is 10-40%. The positive electrode material obtained by mixing and ball milling nickel chloride and composite molten salt electrolyte powder maintains a higher proportion of active materials, and has excellent high-current discharge performance and stable voltage platform.
Description
Technical Field
The invention belongs to the technical field of electrodes composed of or comprising active materials, and particularly relates to a high-performance thermal battery composite positive electrode material and a preparation method thereof.
Background
The thermal battery has wide application fields due to various advantages of the thermal battery, such as quick activation, long storage time, large output current, adaptation to harsh environments and the like. With the rapid development of industrialization, the conventional thermal battery (such as Li/FeS 2) is difficult to meet the performance requirement of upgrading electronic information equipment, so that the conventional thermal battery system needs to be further developed and a new thermal battery system needs to be explored, so that the performance of the thermal battery is improved.
Currently, more mature positive electrode materials include sulfide systems based on iron disulfide and oxide systems based on vanadium oxide (LVO), but due to some defects of the materials themselves, they are limited in application, such as problems of high resistivity, easy decomposition, etc. of iron disulfide limit the applicable temperature range, and the problem of matching oxide materials with electrolytes is also a big obstacle to application. Compared with the traditional positive electrode material, the chloride positive electrode material has the characteristics of higher theoretical voltage, suitability for large-current discharge, high decomposition temperature and the like, is the research focus in the field of the current thermal battery positive electrode material, but the further development and application of the chloride positive electrode material are limited by the high resistivity of the chloride positive electrode material such as nickel chloride and the phenomenon of easy leaching leakage with electrolyte. The common method for improving the leakage defect of the positive electrode is to add additives such as MgO, al 2O3、SiO2 and the like into the positive electrode, and inhibit leakage by utilizing the bonding property of additive powder, but the method often leads to the reduction of the content of active substances in the positive electrode due to the introduction of excessive insulating binders, thereby increasing the internal resistance of the battery and reducing the overall discharge property of the battery.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a high-performance thermal battery composite positive electrode material taking nickel chloride as an active substance and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
The high-performance thermal battery composite positive electrode material is obtained by mixing and ball milling nickel chloride and composite molten salt electrolyte powder, wherein the mass fraction of the nickel chloride is 60-90%, and the mass fraction of the composite molten salt electrolyte powder is 10-40%.
According to the scheme, the preparation method of the nickel chloride comprises the steps of placing NiCl 2·6H2 O in a vacuum drying oven, drying at 200 ℃ for 2-4 hours, cooling, taking out, grinding, transferring into a tube furnace, heating to 250-350 ℃ from room temperature at a heating rate of 10 ℃ per minute, preserving heat for 2-4 hours, heating to 500-700 ℃ and preserving heat for 4-6 hours to obtain pure-phase NiCl 2 powder. The NiCl 2 material prepared according to the scheme is loose, has a microstructure in a sheet shape of 20-40 mu m, and has a thickness of about 2 mu m. The loose sheet structure is favorable for uniformly mixing the anode materials, and has a certain promotion effect on improving the discharge performance of the battery.
According to the scheme, the composite molten salt electrolyte powder is obtained by mixing and ball milling the molten salt electrolyte powder and the additive for 1-2 hours, wherein the mass fraction of the molten salt electrolyte powder is 30-70%, and the mass fraction of the additive is 30-70%. Preferably, the mass ratio of the molten salt electrolyte powder to the additive is 1:1.
According to the scheme, the molten salt electrolyte powder is one of LiCl-KCl molten salt powder, liCl-LiF-LiBr molten salt powder and LiF-LiBr-KBr molten salt powder, and LiCl-LiF-LiBr molten salt powder is preferable. And (3) placing raw material powder for preparing the molten salt electrolyte powder into a ball milling tank for ball milling under an argon atmosphere, then carrying out premelting treatment on the ball-milled mixed powder to obtain molten salt, crushing the molten salt, and carrying out ball milling for 2-3 hours at a rotating speed of 300-400 rpm to obtain the molten salt electrolyte powder.
According to the scheme, the premelting treatment process conditions are that premelting is carried out under the protection of argon atmosphere, the premelting temperature is 100-150 ℃ higher than the eutectic temperature of the raw material powder, the premelting time is 4-6 h, and finally the raw material powder is cooled to room temperature along with a furnace.
According to the scheme, the additive is mixed powder obtained by mixing and ball milling magnesium oxide and titanium nitride, wherein the mass fraction of the magnesium oxide is 0-90%, and the mass fraction of the titanium nitride is 10-100%. Preferably, the mass ratio of magnesium oxide to titanium nitride is one of 0:10, 3:7, 5:5, 7:3. The magnesium oxide and the titanium nitride are used as additives of the positive electrode material, the excellent adsorption performance of the magnesium oxide and the titanium nitride can prevent the nickel chloride material from melting and leaching leakage in the operation process of the thermal battery, and meanwhile, the electric conductivity of the positive electrode material is improved by the electric conductivity of the titanium nitride material, the internal resistance of the battery is reduced, and the discharge performance of the battery is improved.
The invention also provides a preparation method of the high-performance thermal battery composite positive electrode material, which comprises the following specific steps:
1) Weighing nickel chloride and composite molten salt electrolyte powder according to a proportion for standby;
2) And (3) mixing and ball milling the nickel chloride and the composite molten salt electrolyte powder weighed in the step (1) to obtain the high-performance thermal battery composite positive electrode material.
According to the scheme, the ball milling process conditions in the step 2) are that the ball milling rotating speed is 200-350 rpm, and the ball milling time is 1-2 hours.
The invention also comprises application of the high-performance thermal battery composite positive electrode material serving as the positive electrode material in the field of thermal batteries.
On the basis of containing molten salt electrolyte powder in the thermal battery anode material, the composite additive obtained by adding NiCl 2, magnesium oxide and titanium nitride into the molten salt electrolyte powder and mixing and ball milling the molten salt electrolyte powder integrates the adsorption effect of the magnesium oxide on the electrolyte and the excellent conductivity of the titanium nitride, avoids the defect of increasing the internal resistance due to adding an insulating additive (such as magnesium oxide), improves the discharge specific capacity and voltage platform of the battery on the premise of not changing the content of active substances in the anode, and provides a new solution for solving the problems of leaching leakage in the discharge process of the NiCl 2 anode and high resistivity of the NiCl 2 material.
The invention has the beneficial effects that 1, the positive electrode material obtained by mixing and ball milling nickel chloride and composite molten salt electrolyte powder maintains higher active material proportion, and has excellent high-current discharge performance and stable voltage platform. 2. The preparation method has simple process and low cost.
Drawings
FIG. 1 is a graph showing the discharge curves of a thermal battery and a comparative sample assembled when the additive in the positive electrode material of example 1 of the present invention is titanium nitride at 500℃and 0.2A/cm 2;
FIG. 2 is an SEM image of the composite positive electrode material prepared in example 1;
FIG. 3 is an SEM and EDS image of a cell stack after discharge at 500℃and 0.1A/cm 2 of the assembled battery of example 1;
FIG. 4 is a graph showing the discharge curve at 500℃and 0.1A/cm 2 for a thermal battery assembled with magnesium oxide to titanium nitride=3:7 in the positive electrode material additive of example 2;
FIG. 5 is a graph showing the discharge curve at 500℃and 0.3A/cm 2 for a thermal battery assembled with magnesium oxide to titanium nitride=5:5 in the positive electrode material additive of example 3;
fig. 6 is a discharge curve of a thermal battery assembled at 500 ℃ under conditions of 0.1A/cm 2 when magnesium oxide to titanium nitride=5:5 and nickel chloride to composite molten salt electrolyte powder=7:3 in the positive electrode material additive of example 4.
Detailed Description
The present invention will be described in further detail below with reference to the accompanying drawings, so that those skilled in the art can better understand the technical scheme of the present invention.
The raw material reagents used in the embodiment of the invention are all analytically pure, wherein the particle size of the titanium nitride powder used is 3-10 mu m. The ball milling process conditions of the embodiment of the invention are not illustrated, but are 300rpm for 1 hour.
Example 1
A preparation method of the high-performance thermal battery composite positive electrode material comprises the following steps:
1) Placing LiCl powder, liF powder and LiBr powder in a ball milling tank according to the mass ratio of 22:9.6:68.4 under argon atmosphere, performing pre-melting treatment on the ball-milled mixed powder to obtain LiCl-LiF-LiBr molten salt, crushing the molten salt, performing ball milling for 2 hours at the rotating speed of 300-400 rpm to obtain molten salt electrolyte powder, and finally weighing the molten salt electrolyte powder and additive titanium nitride powder according to the mass ratio of 1:1, and performing ball milling and mixing for 1 hour to obtain composite molten salt electrolyte powder;
2) Placing NiCl 2·6H2 O in a vacuum drying oven, drying for 4 hours at 200 ℃, naturally cooling, grinding uniformly, transferring into a tube furnace, heating to 300 ℃ from room temperature at a heating rate of 10 ℃ per minute, preserving heat for 2 hours, and heating to 600 ℃ and preserving heat for 4 hours to obtain pure-phase NiCl 2 powder;
3) And (3) weighing the composite molten salt electrolyte powder prepared in the step (1) and the NiCl 2 powder prepared in the step (2) according to the mass ratio of NiCl 2 powder to composite molten salt electrolyte powder=8:2, performing ball milling and mixing, and performing ball milling for 1h at 300rpm to obtain the composite anode material.
The composite positive electrode powder (0.2 g) obtained in the example was tiled in a stainless steel tabletting mold with an inner diameter of 17.5mm under an argon atmosphere, then 0.3g of electrolyte isolation powder (LiCl-LiF-LiBr-MgO) was tiled thereon, tabletting was performed with a pressure of 5MPa for 1min, and demoulding was performed to obtain a positive electrode/electrolyte isolation composite sheet. And further selecting a lithium boron alloy sheet as a negative electrode material, and assembling with the positive electrode/electrolyte isolation composite sheet to obtain the thermal battery monomer.
Under the condition that the temperature of an external heat source is 500 ℃ in an argon environment, the discharge current density of the thermal battery is 0.2A/cm 2, the discharge curve test result is shown as a solid line in the graph in the figure 1 when the cut-off voltage is 0.3V, the specific discharge capacity can reach 373.75mAh/g, the discharge voltage platform is stable, the maximum voltage in the discharge process can reach 2.38V, and the corresponding maximum specific power is 7.15kW/Kg.
The additive titanium nitride powder in the embodiment is changed into magnesia powder with the same quality, the composite anode material is prepared by the same method as the embodiment, and then assembled into a thermal battery monomer to serve as a comparison sample of the embodiment, and a discharge curve is tested under the same condition, wherein a test result is shown as a dotted line in fig. 1, a discharge voltage platform is stable, the maximum voltage in the discharge process reaches 2.26V, and the corresponding maximum specific power is 6.79kW/Kg. Compared with the composite positive electrode material of the embodiment, the composite positive electrode material has a slightly higher specific capacity, but has lower working voltage and lower specific power.
Fig. 2 is an SEM picture of the composite cathode material prepared in this example, in which molten salt electrolyte and irregularly shaped titanium nitride powder are uniformly distributed around flaky nickel chloride.
Fig. 3 is an SEM and EDS diagram of a single cell stack after discharge at 500 ℃ and 0.1A/cm 2 of the thermal battery prepared in this example, and it can be seen from the figure that delamination of the positive electrode, the electrolyte layer and the negative electrode in the stack after high-temperature discharge is obvious, no obvious leakage phenomenon is found, and the EDS element distribution diagram shows that titanium nitride as a positive electrode additive well maintains the form of the positive electrode in the discharge process, and no diffusion or leakage phenomenon of the positive electrode material to the electrolyte layer occurs.
Example 2
A preparation method of the high-performance thermal battery composite positive electrode material comprises the following steps:
1) Fully ball-milling and mixing dried magnesium oxide and titanium nitride according to the mass ratio of 3:7 to obtain additive powder, placing LiCl powder, liF powder and LiBr powder according to the mass ratio of 22:9.6:68.4 in a ball-milling tank for ball-milling under the argon atmosphere, then pre-melting the well-milled mixed powder to obtain LiCl-LiF-LiBr molten salt, crushing the molten salt, ball-milling for 2 hours at the rotating speed of 300-400 rpm to obtain molten salt electrolyte powder, and finally weighing the molten salt electrolyte powder and the additive powder according to the mass ratio of 1:1 for ball-milling and mixing for 1 hour to obtain composite molten salt electrolyte powder;
2) Placing NiCl 2·6H2 O in a vacuum drying oven, drying for 4 hours at 200 ℃, naturally cooling, grinding uniformly, transferring into a tube furnace, heating to 300 ℃ from room temperature at a heating rate of 10 ℃ per minute, preserving heat for 2 hours, and then heating to 600 ℃ and preserving heat for 4 hours to obtain pure-phase NiCl 2 powder;
3) And (3) weighing the composite molten salt electrolyte powder prepared in the step (1) and the NiCl 2 powder prepared in the step (2) according to the mass ratio of the NiCl 2 powder to the composite molten salt electrolyte powder=8:2, and then performing ball milling and mixing to obtain the composite anode material.
The composite positive electrode powder (0.2 g) obtained in the example was tiled in a stainless steel tabletting mold with an inner diameter of 17.5mm under an argon atmosphere, then 0.3g of electrolyte isolation powder (LiCl-LiF-LiBr-MgO) was tiled thereon, tabletting was performed with a pressure of 5MPa for 1min, and demoulding was performed to obtain a positive electrode/electrolyte isolation composite sheet. And further selecting a lithium boron alloy sheet as a negative electrode material, and assembling with the positive electrode/electrolyte isolation composite sheet to obtain the thermal battery monomer.
Under the condition that the temperature of an external heat source is 500 ℃ in an argon environment, the discharge current density of the thermal battery is 0.1A/cm 2, the discharge curve test result is shown as a solid line in FIG. 4 when the cut-off voltage is 0.3V, the specific discharge capacity can reach 285.63mAh/g, the discharge voltage platform is stable, the maximum voltage in the discharge process can reach 2.47V, and the corresponding maximum specific power is 3.71kW/Kg.
The additive titanium nitride powder in this example was replaced with magnesium oxide powder of the same quality, the composite positive electrode material was prepared by the same method as in this example, and then assembled into a thermal battery monomer as a comparative sample in this example, and the discharge curve was tested under the same conditions, and the test result was shown by the broken line in fig. 4, and the discharge voltage plateau was stable, the maximum voltage reached 2.44V in the discharge process, and the corresponding maximum specific power was 3.66kW/Kg. Compared with the composite positive electrode material of the embodiment, the composite positive electrode material has a slightly higher specific capacity, but has lower working voltage and lower specific power.
Example 3
A preparation method of the high-performance thermal battery composite positive electrode material comprises the following steps:
1) Fully ball-milling and mixing dried magnesium oxide and titanium nitride according to the mass ratio of 5:5 to obtain additive powder, placing LiCl powder, liF powder and LiBr powder in a ball-milling tank according to the mass ratio of 22:9.6:68.4 under argon atmosphere, then pre-melting the ball-milled mixed powder to obtain LiCl-LiF-LiBr molten salt, crushing the molten salt, ball-milling for 2 hours at the rotating speed of 300-400 rpm to obtain molten salt electrolyte powder, finally weighing the molten salt electrolyte powder and the additive powder according to the mass ratio of 1:1, and ball-milling and mixing for 1 hour to obtain composite molten salt electrolyte powder;
2) Placing NiCl 2·6H2 O in a vacuum drying oven, drying for 4 hours at 200 ℃, naturally cooling, grinding uniformly, transferring into a tube furnace, heating to 300 ℃ from room temperature at a heating rate of 10 ℃ per minute, preserving heat for 2 hours, and then heating to 600 ℃ and preserving heat for 4 hours to obtain pure-phase NiCl 2 powder;
3) And (3) weighing the composite molten salt electrolyte powder prepared in the step (1) and the NiCl 2 powder prepared in the step (2) according to the mass ratio of NiCl 2 powder to composite molten salt electrolyte powder=8:2, and then performing ball milling and mixing to obtain the composite anode material.
The composite positive electrode powder (0.2 g) obtained in the example was tiled in a stainless steel tabletting mold with an inner diameter of 17.5mm under an argon atmosphere, then 0.3g of electrolyte isolation powder (LiCl-LiF-LiBr-MgO) was tiled thereon, tabletting was performed with a pressure of 5MPa for 1min, and demoulding was performed to obtain a positive electrode/electrolyte isolation composite sheet. And further selecting a lithium boron alloy sheet as a negative electrode material, and assembling with the positive electrode/electrolyte isolation composite sheet to obtain the thermal battery monomer.
Under the condition that the temperature of an external heat source is 500 ℃ in an argon environment, the discharge current density of the thermal battery is 0.3A/cm 2, the discharge curve test result is shown as a solid line in FIG. 5 when the cut-off voltage is 0.3V, the specific discharge capacity can reach 385mAh/g, the discharge voltage platform is stable, the maximum voltage in the discharge process can reach 2.25V, and the corresponding maximum specific power is 10.14kW/Kg.
The additive titanium nitride powder in the embodiment is changed into magnesia powder with the same quality, the composite anode material is prepared by the same method as the embodiment, and then assembled into a thermal battery monomer to serve as a comparison sample of the embodiment, and a discharge curve is tested under the same condition, wherein a test result is shown as a dotted line in fig. 5, a discharge voltage platform is stable, the maximum voltage in the discharge process reaches 2.19V, and the corresponding maximum specific power is 9.88kW/Kg. Compared with the composite positive electrode material of the embodiment, the composite positive electrode material has smaller specific power.
Example 4
A preparation method of the high-performance thermal battery composite positive electrode material comprises the following steps:
1) Fully ball-milling and mixing dried magnesium oxide and titanium nitride according to the mass ratio of 5:5 to obtain additive powder, placing LiCl powder, liF powder and LiBr powder in a ball-milling tank according to the mass ratio of 22:9.6:68.4 under the argon atmosphere for ball-milling, then pre-melting the well-milled mixed powder to obtain LiCl-LiF-LiBr molten salt, crushing the molten salt, ball-milling for 2 hours at the rotating speed of 300-400 rpm to obtain molten salt electrolyte powder, and finally weighing the molten salt electrolyte powder and the additive powder according to the mass ratio of 1:1 for ball-milling and mixing for 1 hour to obtain composite molten salt electrolyte powder;
2) Placing NiCl 2·6H2 O in a vacuum drying oven, drying for 4 hours at 200 ℃, naturally cooling, grinding uniformly, transferring into a tube furnace, heating to 300 ℃ from room temperature at a heating rate of 10 ℃ per minute, preserving heat for 2 hours, and then heating to 600 ℃ and preserving heat for 4 hours to obtain pure-phase NiCl 2 powder;
3) And (3) weighing the composite molten salt electrolyte powder prepared in the step (1) and the NiCl 2 powder prepared in the step (2) according to the mass ratio of NiCl 2 powder to composite molten salt electrolyte powder=7:3, and then performing ball milling and mixing to obtain the composite anode material.
The composite positive electrode powder (0.2 g) obtained in the example was tiled in a stainless steel tabletting mold with an inner diameter of 17.5mm under an argon atmosphere, then 0.3g of electrolyte isolation powder (LiCl-LiF-LiBr-MgO) was tiled thereon, tabletting was performed with a pressure of 5MPa for 1min, and demoulding was performed to obtain a positive electrode/electrolyte isolation composite sheet. And further selecting a lithium boron alloy sheet as a negative electrode material, and assembling with the positive electrode/electrolyte isolation composite sheet to obtain the thermal battery monomer.
Under the conditions of argon environment and external heat source temperature of 500 ℃, the measured discharge current density of the thermal battery is 0.1A/cm 2, the test result is shown in figure 6 when the cut-off voltage is 0.3V, the specific discharge capacity can reach 275.71mAh/g, the discharge voltage platform is stable, the maximum voltage in the discharge process can reach 2.48V, and the corresponding maximum specific power is 4.26kW/Kg.
Claims (5)
1. The high-performance thermal battery composite positive electrode material is characterized by being prepared by mixing and ball milling nickel chloride and composite molten salt electrolyte powder, wherein the mass fraction of the nickel chloride is 60-90%, and the mass fraction of the composite molten salt electrolyte powder is 10-40%;
The composite molten salt electrolyte powder is obtained by mixing and ball milling molten salt electrolyte powder and an additive for 1-2 hours, and the mass ratio of the molten salt electrolyte powder to the additive is 1:1;
The molten salt electrolyte powder is one of LiCl-KCl molten salt powder, liCl-LiF-LiBr molten salt powder and LiF-LiBr-KBr molten salt powder;
The additive is mixed powder obtained by mixing and ball milling magnesium oxide and titanium nitride, wherein the mass ratio of the magnesium oxide to the titanium nitride is one of 0:10, 3:7, 5:5 and 7:3.
2. The high-performance thermal battery composite positive electrode material according to claim 1 is characterized in that the preparation method of the nickel chloride is that NiCl 2·6H2 O is placed in a vacuum drying oven, dried at 200 ℃ for 2-4 hours, cooled, taken out and ground, then transferred into a tube furnace, heated to 250-350 ℃ from room temperature at a heating rate of 10 ℃ per minute, kept for 2-4 hours, then heated to 500-700 ℃ and kept for 4-6 hours, and pure-phase NiCl 2 powder is obtained.
3. A method for preparing the high-performance thermal battery composite positive electrode material as claimed in claim 1 or 2, which is characterized by comprising the following specific steps:
1) Weighing nickel chloride and composite molten salt electrolyte powder according to a proportion for standby;
2) And (3) mixing and ball milling the nickel chloride and the composite molten salt electrolyte powder weighed in the step (1) to obtain the high-performance thermal battery composite positive electrode material.
4. The preparation method of the high-performance thermal battery composite positive electrode material according to claim 3, wherein the ball milling process condition in the step 2) is that the ball milling rotating speed is 200-350 rpm, and the ball milling time is 1-2 h.
5. Use of the high-performance thermal battery composite positive electrode material according to claim 1 or 2 as a positive electrode material in the field of thermal batteries.
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| CN109167080A (en) * | 2018-09-12 | 2019-01-08 | 哈尔滨工业大学（威海） | A kind of high voltage lithium thermal cell |
| CN112234162A (en) * | 2020-10-19 | 2021-01-15 | 沈阳理工大学 | A kind of thermal battery nickel dichloride cathode film material and preparation method |
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| CN110120495B (en) * | 2019-04-12 | 2022-02-11 | 贵州梅岭电源有限公司 | Composite positive electrode material capable of reducing self-discharge degree, and preparation method and application thereof |
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