CN114388756A - High-performance thermal battery composite positive electrode material and preparation method thereof - Google Patents
High-performance thermal battery composite positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN114388756A CN114388756A CN202111607595.3A CN202111607595A CN114388756A CN 114388756 A CN114388756 A CN 114388756A CN 202111607595 A CN202111607595 A CN 202111607595A CN 114388756 A CN114388756 A CN 114388756A
- Authority
- CN
- China
- Prior art keywords
- powder
- molten salt
- positive electrode
- composite
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 110
- 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 47
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 32
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims description 28
- 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 26
- 239000000395 magnesium oxide Substances 0.000 claims description 24
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 22
- 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
- 238000000034 method Methods 0.000 claims description 16
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 15
- 239000010406 cathode material Substances 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- 239000011812 mixed powder Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 229910013618 LiCl—KCl Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000011149 active material Substances 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 description 15
- 238000002955 isolation Methods 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910000521 B alloy Inorganic materials 0.000 description 8
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000007773 negative electrode 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
- 239000013068 control sample Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000339 iron disulfide Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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
- 239000000853 adhesive Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
Images
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
- H01M4/582—Halogenides
-
- 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- 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, 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 positive electrode material obtained by mixing and ball-milling the nickel chloride and the composite molten salt electrolyte powder maintains higher active material proportion, has excellent heavy current discharge performance and stable voltage platform.
Description
Technical Field
The invention belongs to the technical field of electrodes made 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 various advantages such as rapid activation, long storage time, large output current, adaptability to harsh environment and the like, and has wide application fieldAnd 4. preparing the compound. With the rapid development of industrialization, the traditional thermal battery (such as Li/FeS)2) It is difficult to meet the performance requirements of electronic information equipment upgrading, so that the existing thermal battery system needs to be further developed and a new thermal battery system needs to be explored, thereby improving the performance of the thermal battery.
At present, the more mature cathode materials comprise a sulfide system mainly comprising iron disulfide and an oxide system mainly comprising vanadium oxide (LVO), but the application of the cathode materials is limited due to some defects of the materials, such as high resistivity, easy decomposition and the like of iron disulfide limit the applicable temperature range, and the matching problem of the oxide materials and the electrolyte is also a great obstacle of the application. Compared with the traditional anode material, the chloride anode material has the characteristics of higher theoretical voltage, suitability for large-current discharge, high decomposition temperature and the like, and is the key point of research in the field of the anode material of the thermal battery at present, but the high resistivity and the phenomenon of easy occurrence of melt leaching leakage with electrolyte of the chloride anode material such as nickel chloride limit further development and application of the chloride anode material. The common method for improving the leakage defect of the anode is to add MgO and Al into the anode2O3、SiO2And the additives utilize the adhesive property of the additive powder to inhibit leakage, but the mode often causes the content of active substances in the positive electrode to be reduced due to the introduction of excessive insulating adhesive, increases the internal resistance of the battery and reduces the overall discharge performance of the battery.
Disclosure of Invention
The invention aims to solve the technical problem of 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 following steps: mixing NiCl2·6H2Placing O in a vacuum drying oven, drying for 2-4 h at 200 ℃, cooling, taking out, grinding, transferring to a tubular furnace, heating to 250-350 ℃ from room temperature at a heating rate of 10 ℃/min, preserving heat for 2-4 h, then heating to 500-700 ℃, preserving heat for 4-6 h, and obtaining pure-phase NiCl2And (3) powder. NiCl prepared according to the scheme2The material is loose, the microstructure is 20-40 mu m sheet-shaped, and the thickness is about 2 mu m. The loose sheet structure is beneficial to uniform mixing of 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 an 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 preferred. Under the argon atmosphere, placing raw material powder for preparing molten salt electrolyte powder into a ball milling tank for ball milling, then performing pre-melting treatment on the ball-milled mixed powder to obtain molten salt, crushing the molten salt, and performing ball milling at the rotating speed of 300-400 rpm for 2-3 hours to obtain the molten salt electrolyte powder.
According to the scheme, the premelting treatment process conditions are as follows: and pre-melting under the protection of argon atmosphere, wherein the pre-melting temperature is 100-150 ℃ higher than the eutectic temperature of the raw material powder, the pre-melting time is 4-6 h, and finally, cooling to room temperature along with the 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 the magnesium oxide to the titanium nitride is 0: 10, 3: 7, 5: 5 or 7: 3. The magnesium oxide and the titanium nitride are used as additives of the anode material, the nickel chloride material can be prevented from being leached and leaked in the operation process of the thermal battery due to the excellent adsorption performance of the magnesium oxide and the titanium nitride, and meanwhile, the electronic conductivity of the anode material is improved due to the 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 anode material, which comprises the following specific steps:
1) weighing nickel chloride and composite molten salt electrolyte powder according to a proportion for later use;
2) mixing and ball-milling the nickel chloride weighed in the step 1) and the composite molten salt electrolyte powder 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 as follows: the ball milling speed is 200-350 rpm, and the ball milling time is 1-2 h.
The invention also discloses the application of the high-performance thermal battery composite anode material as an anode material in the field of thermal batteries.
The invention adds NiCl into the molten salt electrolyte powder on the basis of containing the molten salt electrolyte powder in the positive electrode material of the thermal battery2The composite additive is obtained by mixing and ball milling with magnesium oxide and titanium nitride, integrates the adsorption effect of magnesium oxide on electrolyte and the excellent conductive performance of titanium nitride, avoids the defect of increasing internal resistance due to the addition of 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 positive electrode, and aims to solve the problem of NiCl2The melting and leaching leakage and NiCl occur in the discharging process of the anode2The problem of high resistivity of the material provides a new solution.
The invention has the beneficial effects that: 1. the positive electrode material obtained by mixing and ball-milling the nickel chloride and the composite molten salt electrolyte powder maintains higher active material proportion, has excellent heavy current discharge performance and stable voltage platform. 2. The preparation method has simple process and low cost.
Drawings
FIG. 1 is a schematic view of a thermal battery assembled when an additive is titanium nitride in a positive electrode material according to example 1 of the present invention and a comparative sample at 500 ℃ and 0.2A/cm2Discharge curve under the condition;
fig. 2 is an SEM image of the composite cathode material prepared in example 1;
FIG. 3 shows the assembled thermal battery of example 1 at 500 ℃ and 0.1A/cm2SEM and EDS picture of monomer galvanic pile after discharging under the condition;
FIG. 4 shows a thermal battery assembled at 500 ℃ and 0.1A/cm with a 3: 7 ratio of MgO to TiN as an additive to the positive electrode material of example 22Discharge curve under the condition;
FIG. 5 shows a thermal battery assembled at 500 ℃ and 0.3A/cm with 5: 5 MgO/TiN as an additive to the positive electrode material of example 32Discharge curve under the condition;
FIG. 6 shows the assembled thermal battery at 500 ℃ and 0.1A/cm of the positive electrode material additive of example 4, in which the ratio of magnesium oxide to titanium nitride is 5: 5 and the ratio of nickel chloride to the composite molten salt electrolyte powder is 7: 32Discharge curve under the conditions.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention is further described in detail below with reference to the accompanying drawings.
The raw material reagents used in the embodiment of the invention are all analytically pure, wherein the particle size of the titanium nitride powder is 3-10 μm. In the case that the ball milling process conditions are not specified, the ball milling is carried out for 1h at 300 rpm.
Example 1
A high-performance thermal battery composite positive electrode material is prepared by the following steps:
1) placing LiCl powder, LiF powder and LiBr powder in a ball milling tank for ball milling according to the mass ratio of 22: 9.6: 68.4 under the argon atmosphere, then 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, 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) mixing NiCl2·6H2Placing O in a vacuum drying oven, vacuum drying at 200 deg.C for 4h, naturally cooling, grinding, transferring to a tube furnace, heating at room temperature at a rate of 10 deg.C/minThe temperature is increased to 300 ℃ and the temperature is kept for 2h, then the temperature is increased to 600 ℃ and the temperature is kept for 4h, and the pure-phase NiCl is obtained2Powder;
3) mixing the composite molten salt electrolyte powder prepared in the step 1) and the NiCl prepared in the step 2)2Powder NiCl according to mass ratio2And weighing the powder and the composite molten salt electrolyte powder according to the proportion of 8: 2, then performing ball milling and mixing, and performing ball milling for 1h at 300rpm to obtain the composite anode material.
In argon atmosphere, the composite anode powder (0.2g) obtained in the embodiment is spread in a stainless steel pressing die with the inner diameter of 17.5mm, then 0.3g of electrolyte isolation powder (LiCl-LiF-LiBr-MgO) is spread on the composite anode powder, pressing is carried out by adopting the pressure of 5MPa, the pressure is maintained for 1min, and the anode/electrolyte isolation composite sheet is obtained after demoulding. And further selecting a lithium boron alloy sheet as a negative electrode material, and assembling the lithium boron alloy sheet and 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 deg.C, the discharge current density of the thermal battery is measured to be 0.2A/cm2The test result of the discharge curve when the cut-off voltage is 0.3V is shown by the solid line in figure 1, the specific discharge capacity can reach 373.75mAh/g, the discharge voltage platform is stable, the maximum voltage can reach 2.38V in the discharge process, and the corresponding maximum specific power is 7.15 kW/Kg.
The titanium nitride powder as the additive in this example was replaced with magnesium oxide powder of the same mass, the composite positive electrode material was prepared by the same method as in this example and assembled into a thermal battery cell as a control sample in this example, and the discharge curve was tested under the same conditions, with the test results shown by the dotted line in fig. 1, the discharge voltage plateau was stable, the maximum voltage reached 2.26V during discharge, and the corresponding maximum specific power was 6.79 kW/Kg. Compared with the composite cathode material of the embodiment, the composite cathode material has slightly higher specific capacity, but has lower working voltage and smaller specific power.
Fig. 2 is an SEM picture of the composite cathode material prepared in this example, and it can be seen that molten salt electrolyte and titanium nitride powder with irregular shape are uniformly distributed around the nickel chloride sheet.
Figure 3 is the bookThe thermal battery prepared in example was operated at 500 ℃ and 0.1A/cm2Under the condition, the SEM and EDS images of the monomer electric pile after discharge show that the positive electrode, the electrolyte layer and the negative electrode of the electric pile after high-temperature discharge are obviously layered, no obvious leakage phenomenon is found, and the EDS element distribution diagram shows that titanium nitride as a positive electrode additive well keeps the form of the positive electrode in the discharge process, and the phenomenon that a positive electrode material diffuses or leaks to the electrolyte layer is not generated.
Example 2
A high-performance thermal battery composite positive electrode material is prepared by the following steps:
1) fully ball-milling and mixing the 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 in a ball-milling tank according to the mass ratio of 22: 9.6: 68.4 in an argon atmosphere for ball milling, then performing pre-melting treatment on the ball-milled mixed powder to obtain LiCl-LiF-LiBr molten salt, crushing the molten salt, ball-milling at the rotating speed of 300-400 rpm for 2 hours 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) mixing NiCl2·6H2Placing O in a vacuum drying oven, vacuum drying at 200 deg.C for 4h, naturally cooling, grinding, transferring into a tube furnace, heating to 300 deg.C at a heating rate of 10 deg.C/min from room temperature, maintaining for 2h, heating to 600 deg.C, and maintaining for 4h to obtain pure-phase NiCl2Powder;
3) mixing the composite molten salt electrolyte powder prepared in the step 1) and the NiCl prepared in the step 2)2The powder is NiCl2Weighing the powder and the composite molten salt electrolyte powder in a mass ratio of 8: 2, and then performing ball milling and mixing to obtain the composite anode material.
In argon atmosphere, the composite anode powder (0.2g) obtained in the embodiment is spread in a stainless steel pressing die with the inner diameter of 17.5mm, then 0.3g of electrolyte isolation powder (LiCl-LiF-LiBr-MgO) is spread on the composite anode powder, pressing is carried out by adopting the pressure of 5MPa, the pressure is maintained for 1min, and the anode/electrolyte isolation composite sheet is obtained after demoulding. And further selecting a lithium boron alloy sheet as a negative electrode material, and assembling the lithium boron alloy sheet and 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 deg.C, the discharge current density of the thermal battery is measured to be 0.1A/cm2The test result of the discharge curve with the cut-off voltage of 0.3V is shown by the solid line in figure 4, 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 3.71 kW/Kg.
The titanium nitride powder as the additive in this example was replaced with magnesium oxide powder of the same mass, the composite positive electrode material was prepared by the same method as in this example and assembled into a thermal battery cell as a control sample in this example, and the discharge curve was tested under the same conditions, with the test results shown by the dotted line in fig. 4, the discharge voltage plateau was stable, the maximum voltage reached 2.44V during discharge, and the corresponding maximum specific power was 3.66 kW/Kg. Compared with the composite cathode material of the embodiment, the composite cathode material has slightly higher specific capacity, but has lower working voltage and smaller specific power.
Example 3
A high-performance thermal battery composite positive electrode material is prepared by the following steps:
1) fully ball-milling and mixing the dried magnesium oxide and the dried 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 for ball milling according to the mass ratio of 22: 9.6: 68.4 under the argon atmosphere, then performing pre-melting treatment on the ball-milled mixed powder to obtain LiCl-LiF-LiBr molten salt, crushing the molten salt, performing ball milling at the rotating speed of 300-400 rpm for 2 hours to obtain molten salt electrolyte powder, finally weighing the molten salt electrolyte powder and additive 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) mixing NiCl2·6H2Placing O in a vacuum drying oven, vacuum drying at 200 deg.C for 4h, naturally cooling, grinding, transferring into a tube furnace, heating to 300 deg.C at a heating rate of 10 deg.C/min from room temperature, maintaining for 2h, heating to 600 deg.C, and maintaining for 4h to obtain pure-phase NiCl2Powder;
3) mixing the composite molten salt electrolyte powder prepared in the step 1) and the NiCl prepared in the step 2)2Powder NiCl according to mass ratio2And weighing the powder and the composite molten salt electrolyte powder in a ratio of 8: 2, and then performing ball milling and mixing to obtain the composite anode material.
In argon atmosphere, the composite anode powder (0.2g) obtained in the embodiment is spread in a stainless steel pressing die with the inner diameter of 17.5mm, then 0.3g of electrolyte isolation powder (LiCl-LiF-LiBr-MgO) is spread on the composite anode powder, pressing is carried out by adopting the pressure of 5MPa, the pressure is maintained for 1min, and the anode/electrolyte isolation composite sheet is obtained after demoulding. And further selecting a lithium boron alloy sheet as a negative electrode material, and assembling the lithium boron alloy sheet and 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 deg.C, the discharge current density of the thermal battery is measured to be 0.3A/cm2The test result of the discharge curve with the cut-off voltage of 0.3V is shown by the solid line in figure 5, 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 10.14 kW/Kg.
The titanium nitride powder as the additive in this example was replaced with magnesium oxide powder of the same mass, the composite positive electrode material was prepared by the same method as in this example and assembled into a thermal battery cell as a control sample in this example, and the discharge curve was tested under the same conditions, with the test results shown by the dotted line in fig. 5, the discharge voltage plateau was stable, the maximum voltage reached 2.19V during discharge, and the corresponding maximum specific power was 9.88 kW/Kg. Compared with the composite cathode material of the embodiment, the composite cathode material has smaller specific power.
Example 4
A high-performance thermal battery composite positive electrode material is prepared by the following steps:
1) fully ball-milling and mixing the 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 for ball milling according to the mass ratio of 22: 9.6: 68.4 in an argon atmosphere, then performing pre-melting treatment on the ball-milled mixed powder to obtain LiCl-LiF-LiBr molten salt, crushing the molten salt, ball-milling at the rotating speed of 300-400 rpm for 2 hours 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) mixing NiCl2·6H2Placing O in a vacuum drying oven, vacuum drying at 200 deg.C for 4h, naturally cooling, grinding, transferring into a tube furnace, heating to 300 deg.C at a heating rate of 10 deg.C/min from room temperature, maintaining for 2h, heating to 600 deg.C, and maintaining for 4h to obtain pure-phase NiCl2Powder;
3) mixing the composite molten salt electrolyte powder prepared in the step 1) and the NiCl prepared in the step 2)2Powder NiCl according to mass ratio2Weighing the powder and the composite molten salt electrolyte powder according to the proportion of 7: 3, and then carrying out ball milling and mixing to obtain the composite anode material.
In argon atmosphere, the composite anode powder (0.2g) obtained in the embodiment is spread in a stainless steel pressing die with the inner diameter of 17.5mm, then 0.3g of electrolyte isolation powder (LiCl-LiF-LiBr-MgO) is spread on the composite anode powder, pressing is carried out by adopting the pressure of 5MPa, the pressure is maintained for 1min, and the anode/electrolyte isolation composite sheet is obtained after demoulding. And further selecting a lithium boron alloy sheet as a negative electrode material, and assembling the lithium boron alloy sheet and 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 deg.C, the discharge current density of the thermal battery is measured to be 0.1A/cm2The test result when the cut-off voltage is 0.3V is shown in figure 6, the discharge specific 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 4.26 kW/Kg.
Claims (9)
1. The high-performance thermal battery composite positive electrode material is characterized by being 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%.
2. The composite positive electrode material for the high-performance thermal battery according to claim 1, wherein the preparation method of the nickel chloride comprises the following steps: mixing NiCl2·6H2Placing O in a vacuum drying oven, drying for 2-4 h at 200 ℃, cooling, taking out, grinding, transferring to a tubular furnace, heating to 250-350 ℃ from room temperature at a heating rate of 10 ℃/min, preserving heat for 2-4 h, then heating to 500-700 ℃, preserving heat for 4-6 h, and obtaining pure-phase NiCl2And (3) powder.
3. The composite positive electrode material of the high-performance thermal battery as claimed in claim 1, wherein the composite molten salt electrolyte powder is obtained by mixing and ball milling the molten salt electrolyte powder and an additive for 1-2 h, wherein the mass fraction of the molten salt electrolyte powder is 30-70%, and the mass fraction of the additive is 30-70%.
4. The composite positive electrode material for the high-performance thermal battery of claim 3, wherein the mass ratio of the molten salt electrolyte powder to the additive is 1: 1.
5. The composite positive electrode material for the high-performance thermal battery according to claim 3, wherein 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.
6. The composite positive electrode material for the high-performance thermal battery as claimed in claim 3, wherein the additive is a 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%.
7. The preparation method of the high-performance thermal battery composite positive electrode material as claimed in any one of claims 1 to 6 is characterized by comprising the following specific steps:
1) weighing nickel chloride and composite molten salt electrolyte powder according to a proportion for later use;
2) mixing and ball-milling the nickel chloride weighed in the step 1) and the composite molten salt electrolyte powder to obtain the high-performance thermal battery composite positive electrode material.
8. The preparation method of the high-performance thermal battery composite cathode material according to claim 7, wherein the ball milling process conditions in the step 2) are as follows: the ball milling speed is 200-350 rpm, and the ball milling time is 1-2 h.
9. The application of the high-performance thermal battery composite positive electrode material as claimed in any one of claims 1 to 6 as a positive electrode material in the field of thermal batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111607595.3A CN114388756A (en) | 2021-12-27 | 2021-12-27 | High-performance thermal battery composite positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111607595.3A CN114388756A (en) | 2021-12-27 | 2021-12-27 | High-performance thermal battery composite positive electrode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114388756A true CN114388756A (en) | 2022-04-22 |
Family
ID=81198279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111607595.3A Pending CN114388756A (en) | 2021-12-27 | 2021-12-27 | High-performance thermal battery composite positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114388756A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311902A (en) * | 1999-06-10 | 2001-09-05 | 三菱电机株式会社 | Cell |
| CN107644985A (en) * | 2017-08-21 | 2018-01-30 | 上海空间电源研究所 | A kind of thermal cell NiCl2GICs composite positive poles and preparation method thereof |
| 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 |
| CN110120495A (en) * | 2019-04-12 | 2019-08-13 | 贵州梅岭电源有限公司 | A kind of composite positive pole and preparation method and application reducing self discharge degree |
| CN112234162A (en) * | 2020-10-19 | 2021-01-15 | 沈阳理工大学 | Thermal battery nickel dichloride positive electrode film material and preparation method thereof |
| CN112563489A (en) * | 2020-12-16 | 2021-03-26 | 北方特种能源集团有限公司西安庆华公司 | Preparation method of nickel chloride anode for novel thermal battery |
-
2021
- 2021-12-27 CN CN202111607595.3A patent/CN114388756A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311902A (en) * | 1999-06-10 | 2001-09-05 | 三菱电机株式会社 | Cell |
| CN107644985A (en) * | 2017-08-21 | 2018-01-30 | 上海空间电源研究所 | A kind of thermal cell NiCl2GICs composite positive poles and preparation method thereof |
| 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 |
| CN110120495A (en) * | 2019-04-12 | 2019-08-13 | 贵州梅岭电源有限公司 | A kind of composite positive pole and preparation method and application reducing self discharge degree |
| CN112234162A (en) * | 2020-10-19 | 2021-01-15 | 沈阳理工大学 | Thermal battery nickel dichloride positive electrode film material and preparation method thereof |
| CN112563489A (en) * | 2020-12-16 | 2021-03-26 | 北方特种能源集团有限公司西安庆华公司 | Preparation method of nickel chloride anode for novel thermal battery |
Non-Patent Citations (1)
| Title |
|---|
| WENJUN LIU等: "Variable-temperature preparation and performance of NiCl2 as a cathode material for thermal batteries", 《SCIENCE CHINA MATERIALS》, 24 January 2017 (2017-01-24) * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109768330B (en) | Preparation method of solid electrolyte lithium ion battery and battery | |
| CN108899486B (en) | Sulfur electrolyte-coated positive electrode active material and preparation method thereof, and all-solid-state lithium sulfur battery and preparation method thereof | |
| CN111162309B (en) | Solid electrolyte-anode composite material and preparation and application methods thereof | |
| CN106784833A (en) | Silicon-carbon cathode material and preparation method thereof | |
| CN112750984A (en) | Preparation method and use method of intermediate buffer film of pre-lithiation lithium ion battery silicon-based negative electrode | |
| CN104659412A (en) | Lithium-carbon-boron oxide solid electrolyte material containing plane triangle group and battery | |
| CN105576221A (en) | Lithium ion battery negative active material precursor, lithium ion battery negative active material and preparation method thereof | |
| CN116613292A (en) | Negative electrode material and preparation method thereof, negative electrode and preparation method thereof, and sodium ion battery | |
| Jin et al. | Bonding lithium metal with garnet electrolyte by interfacial lithiophobicity/lithiophilicity transition mechanism over 380 C | |
| CN112103466B (en) | Positive plate for heat activated battery and preparation method thereof | |
| Liu et al. | Advanced Sn/C composite anodes for lithium ion batteries | |
| CN113097562A (en) | Lithium borohydride-garnet type oxide composite solid electrolyte material and preparation method and application thereof | |
| CN109088057B (en) | Method for preparing lithium battery cathode additive by calcining organic tin compound | |
| CN108717973B (en) | In-situ double-layer coated silicon-carbon negative electrode material and preparation method thereof | |
| CN110723721A (en) | Method for preparing silicon-carbon negative electrode material of lithium battery, negative electrode material and lithium battery | |
| CN114388756A (en) | High-performance thermal battery composite positive electrode material and preparation method thereof | |
| CN115588741A (en) | Composite solid electrolyte material for solid anode and preparation method and application thereof | |
| CN107742698A (en) | A kind of preparation method and applications of embedded Si-C composite material | |
| CN111342051A (en) | Silica modified negative electrode composite material, preparation method and battery | |
| CN114530635A (en) | Method for treating garnet type solid electrolyte and anode interface by ionic liquid | |
| CN109962232B (en) | Positive electrode active material, preparation method, positive electrode and battery | |
| CN111786015A (en) | Novel composite anode and manufacturing method of all-solid-state lithium battery | |
| CN110877903A (en) | High-gram-capacity lithium ion battery silicon-carbon negative electrode material, preparation method thereof and lithium battery | |
| CN116053481B (en) | Graphite composite material, battery cathode using same and battery | |
| CN109888153B (en) | Low-melting-point metal modified composite diaphragm for lithium-sulfur battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |