CN111354954A - Novel fluorine ion thermal battery and preparation method thereof - Google Patents

Novel fluorine ion thermal battery and preparation method thereof Download PDF

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CN111354954A
CN111354954A CN202010207655.1A CN202010207655A CN111354954A CN 111354954 A CN111354954 A CN 111354954A CN 202010207655 A CN202010207655 A CN 202010207655A CN 111354954 A CN111354954 A CN 111354954A
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electrolyte
thermal battery
plate
novel
diaphragm
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唐军
占志强
贾怀杰
赵文莉
谢天舒
赵贵平
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Guizhou Meiling Power Supply Co Ltd
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Guizhou Meiling Power Supply Co Ltd
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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
    • 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
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • 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
    • H01M6/005—Devices for making primary cells
    • 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
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/182—Cells with non-aqueous electrolyte with solid electrolyte with halogenide as solid electrolyte
    • H01M6/183—Cells with non-aqueous electrolyte with solid electrolyte with halogenide as solid electrolyte with fluoride as solid electrolyte
    • 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
    • H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature

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Abstract

The invention discloses a novel fluoride ion thermal battery, which consists of a substrate (1), a positive plate (2), a diaphragm plate (3), a negative plate (4), a current collecting plate (5) and a heating plate (6), wherein the diaphragm plate (3) is a ternary perfluorinated diaphragm plate and is formed by mixing and sintering electrolyte and asbestos fiber modified by magnesium oxide, and the positive plate (2) is made of fluoride, conductive material and electrolyte. The novel fluorine ion thermal battery has good chemical stability, and no capacity loss exists in the high-temperature working process; the specific energy is high, and the specific energy of the thermal battery can be improved; the discharge capacity of fluorine ions can be improved, and the negative electrode can be made of other metals except lithium alloy, so that the cost of the thermal battery is reduced; the open-circuit voltage of the single thermal battery is more than 2.8V, and the space height of the battery can be reduced.

Description

Novel fluorine ion thermal battery and preparation method thereof
Technical Field
The invention belongs to the technical field of thermal battery production and processing, and particularly relates to a novel fluorine ion thermal battery and a preparation method thereof.
Background
The thermal battery is a molten salt electrolyte storage battery, the electrolyte is non-conductive solid at normal temperature, and when the thermal battery is used, a fire cap is impacted or an electric ignition head is ignited to ignite a firework heat source in the thermal battery unit, so that the electrolyte is molten, and the thermal battery is activated, and therefore required current and voltage are provided for electric equipment. The electrolyte for the existing thermal battery is generally a mixture of binary E (LiCl and KCL) or ternary full lithium (LiCl, LiBr and LiF), conductive ions in the electrolyte are lithium ions, and FeS is adopted as a positive electrode material2Or CoS2. The reaction of the two electrodes occurs at different positions, electrons do work when passing through an external circuit to generate electric energy, and the inside of the battery is conducted by lithium ions to conduct electricity. There is a dynamic equilibrium on the electrodes such that once the external circuit is switched on, the excess electrons on the Li-Si alloy electrode flow to the iron disulfide electrode where the iron disulfide is reduced. The chemical reaction at the electrode will continue as long as the circuit is completed, or until the active species is depleted. With Li (Si)/FeS2The battery system is an example, and the chemical reactions are as follows:
electrode reaction:
and (3) positive electrode: FeS2+4e-→Fe+2S2-；
Negative electrode: 4 Li-4 e-→4Li+；
The total reaction of the battery: FeS2+4Li→2Li2S+Fe。
Li-Si/FeS2The operating principle of the battery system is shown in fig. 1.
However, the conventional thermal battery positive electrodeThe actual capacity of the material is only 150 mAh/g. Along with the development of a large number of high, fine and sharp novel weapon systems in China, the requirements on the power and the specific energy of a matched thermal battery are higher and higher. For example, aiming at the problem that the underwater weapon requires high output power and specific energy of a power supply, no obvious advantages exist in the technical aspect of the existing thermal battery, and the research and development of an electrochemical system, particularly the research and development aspect of a high monomer voltage system, needs to be enhanced. Metal fluorides generally have high-capacity characteristics, e.g. BiF3、CuF2、FeF3And CoF3The theoretical capacities of the materials respectively reach 302mAh/g, 528mAh/g, 712mAh/g and 694 mAh/g; the potential plateau of the corresponding metal lithium of the fluorine ion thermal battery is more than 2.5V, but the current Li-Si/FeS2The effective voltage platform of the system is about 1.8V; the selection range of the negative electrode material of the fluorine ion thermal battery is wide, and the negative electrode material can be a negative electrode of other metal alloys besides lithium-silicon alloy, such as metal alloy of Na and Mg. Therefore, the fluorine ion thermal battery is a novel thermal battery with a wide prospect, the energy density of the fluorine ion thermal battery is far higher than that of a lithium ion battery, and the environmental impact generated in the process of obtaining raw materials of the fluorine ion thermal battery is far less than the environmental impact caused by extracting lithium and cobalt.
At present, no fluoride is reported to be used for the anode material, but in the actual test process, the capacity of the fluoride anode material has no advantage, and the anode material is required to be a lithium alloy, so that the production cost of the thermal battery is increased.
Disclosure of Invention
The invention provides a novel fluoride ion thermal battery and a preparation method thereof for solving the technical problems. The novel fluorine ion thermal battery has good chemical thermal stability, and no capacity loss exists in the high-temperature working process; the specific energy is high, and the specific energy of the thermal battery can be improved; the discharge capacity of fluorine ions can be improved, and the negative electrode can be made of other metals except lithium alloy, so that the cost of the thermal battery is reduced; the single open-circuit voltage of the thermal battery is more than 2.8V, so that the space height of the battery can be saved; the used positive plate has fluorine ion conduction and electronic conduction at the same time at high temperature; the diaphragm is a ternary perfluorinated diaphragm, and has fluorine ion conductivity at high temperature; the negative plate is made of lithium-silicon alloy powder and a perfluorinated electrolyte, other metal powder except lithium alloy can be selected, a fluorine ion conductive agent is added into the negative alloy powder, positive fluorine ions are directionally transferred to the negative electrode through the diaphragm, and the fluorine ions can completely react with a negative electrode material, so that the utilization rate of the negative electrode material is improved, the efficiency is improved, and the cost of raw materials is reduced.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the utility model provides a novel fluorine ion thermal battery, novel fluorine ion thermal battery comprises substrate, positive plate, diaphragm, negative pole piece, current collector, heating plate, the diaphragm is the perfluor diaphragm of ternary, is formed by the asbestos fibre mixed sintering that electrolyte and magnesium oxide are modified, the positive plate is made by fluoride, conducting material, electrolyte.
Further, the electrolyte is a high-conductivity ternary perfluorinated electrolyte, namely LiF-NaF-KF.
Further, the fluoride is BiF3And CoF3The complex of (1).
Further, the mass percent of the fluoride is more than 99%, and the fluoride is dehydrated in an argon atmosphere at 220 ℃ before use, and then is subjected to a molar ratio BiF3:CoF31:1 mixing, simultaneously adding 1 percent of lithium-silicon alloy powder and 5 percent of superfine light magnesium oxide, and finally keeping the mixture in an argon atmosphere at 450 ℃ for 2 hours
Further, the negative plate is made of lithium-silicon alloy powder and electrolyte, and the electrolyte is high-conductivity ternary perfluorinated electrolyte, namely LiF-NaF-KF.
Further, the preparation method of the novel fluoride ion thermal battery comprises the following steps:
① preparation of Positive electrode plate
Firstly, drying an electrolyte in vacuum, then mixing the electrolyte with fluoride and a conductive material according to a certain proportion, performing ball milling, sintering, crushing and sieving, performing ball milling again, sealing with wax after drying, and storing in a dryer to obtain the positive plate for later use;
② preparation of diaphragm sheet
Respectively dehydrating and drying LiF, NaF and KF, then weighing, uniformly mixing the materials according to the mass ratio of 30-11-59, calcining the mixture at a high temperature of 500 ℃ in an ammonia atmosphere, quickly cooling, crushing, sieving and drying the mixture to obtain eutectic powder, adding 30% of superfine light magnesium oxide subjected to high-temperature treatment, uniformly mixing the eutectic powder, performing high-temperature treatment, quickly cooling, crushing, sieving and drying the mixture to obtain a diaphragm sheet;
③ preparation of negative plate
Uniformly mixing the lithium-silicon alloy powder and the electrolyte, and then sieving and drying to prepare a negative plate;
④ preparation of heating sheet
Uniformly mixing the superfine iron powder and the dried potassium perchlorate to prepare a heating sheet;
⑤ preparation of Current collector sheet
Punching a stainless steel foil into a circular sheet, and drying the circular sheet for later use after surface decontamination and deoiling treatment;
⑥ preparation of novel fluorinion thermal battery
Assemble substrate, positive plate, diaphragm, negative pole piece, current collector, heating plate according to the thermal battery equipment mode, obtain according to substrate, compound piece (positive plate + diaphragm), negative pole piece, current collector, heating plate stack together in proper order novel fluoride ion thermal battery.
Further, in step ①, the mass ratio of the electrolyte, the fluoride, and the conductive material is 8-10: 38-41: 1.
Further, in step ②, the electrolyte mass ratio LiF-NaF-KF is 30-11-59, and 70% electrolyte is mixed with 30% ultra-fine light magnesium oxide.
Further, in step ④, the mass ratio of the ultrafine iron powder to the potassium perchlorate is 4.5-6: 1.
In the present application:
for the practical application of a fluorine ion thermal battery, the electrolyte with fluorine ion conductivity at 500 ℃ is prepared by mixing and sintering the electrolyte and asbestos fiber modified by magnesium oxide, the conductivity in the electrolyte is conductive by internal conduction of fluorine ions, the traditional thermal battery is conductive by lithium ion migration, the novel fluorine ion thermal battery electrolyte is a fluorine-containing solid electrolyte due to different principles of the novel fluorine ion thermal battery, LiF-NaF-KF mixed electrolyte is selected according to a certain proportion through experiments, a diaphragm material (EB) is formed by mixing and sintering electrolyte (E) and adsorbent (B) according to a certain proportion, the electrolyte adopted by the invention is high-conductivity ternary perfluorinated electrolyte LiF-NaF-KF, and the technological processes of mixing, ball milling, sintering, crushing, dehydrating, drying and the like are carried out according to the proportion of different electrolytes, sealing in a wide-mouth bottle, and sealing in a dryer for later use.
The adopted anode material is a Bi-CoFx fluoride composite anode material, wherein the raw material BiF3And CoF3The mass percentage of the anode material is more than 99 percent, and BiF3And CoF3Fluoride materials need to be treated by certain processes before being used as electrode materials and applied to batteries. The raw materials are fully dried, then electronic conductive additives such as graphite, carbon nano tubes and the like are added, then the raw materials are mixed according to a certain proportion, and the mixture is obtained through the processes of drying, sintering, crushing and ball milling, and is sealed in a dryer for standby. The additive of the conventional thermal battery contains an ionic conductive agent and an electronic conductive agent, and the novel fluorine ion thermal battery only needs to be added with the electronic conductive agent.
The conventional thermal battery is conductive to lithium ions, the negative electrode is made of lithium silicon material, the lithium ions can move freely at high temperature, and a fluorine ion conductive agent is not required to be added; in the novel fluorine ion thermal battery, a negative electrode material is a lithium-silicon alloy, the negative electrode can be made conductive only by adding a fluorine ion conductive agent electrolyte, so that fluorine ions can fully react with the negative electrode material, the fluorine ion conductive internal resistance is reduced, and LiSi alloy powder and a perfluorinated ion electrolyte are mixed and then directly used;
novel Li-Si/BiF3Schematic diagram of the working principle of the thermal battery (fig. 2), the dynamic equilibrium exists on the electrode, once the external circuit is switched on, the surplus electrons on the Li-Si alloy electrode flow to BiF3Electrode in BiF3BiF on the electrode3Is reduced, and BiF in the thermal battery3The fluorine ions on the electrode move to the Li-Si alloy electrode through the molten electrolyteThe negative electrode lithium reacts. The chemical reaction at the electrode will continue as long as the circuit is completed, or until the active species is depleted. The chemical equation is as follows:
electrode reaction
And (3) positive electrode: BiF3+e-→Bi+F-
Negative electrode: li-e-+F-→LiF
The total reaction of the battery: BiF3+Li→LiF+BiF2
The principle of the conventional thermal battery is that negative lithium ions flow to a positive electrode through a lithium ion conductive electrolyte, and the lithium ions obtained at the positive electrode react; and new types of fluoride ion thermal batteries (e.g., Li-Si/BiF)3Thermal battery) is a reaction in which fluorine ions are supplied from the positive electrode to the negative electrode through the fluorine ion conductive agent and the fluorine ions are obtained from the negative electrode.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
(1) the material used by the positive plate of the thermal battery is metal fluoride, the decomposition temperature of the metal fluoride is higher than that of the traditional positive material (700 ℃), the chemical thermal stability is good, and no capacity loss exists in the high-temperature working process.
(2) The novel positive electrode material of the fluorine ion thermal battery has high specific energy and has higher specific energy than a conventional thermal battery system.
(3) The utility model discloses the novel fluorine ion thermal battery monomer open circuit voltage is greater than 2.8V, and relative LiB-CoS2 thermal battery can reduce the battery height 20%.
(4) The development and application of the new material can realize a new system, further improve the efficiency and reduce the cost of raw materials.
(5) The utility model provides a novel fluorinion thermal battery can improve fluorinion discharge capacity, and other metals except lithium alloy can be chooseed for use to the negative pole, reduces the thermal battery cost.
(6) The positive plate used in the application has fluorine ion conduction and electronic conduction at the same time at high temperature; the diaphragm is a ternary perfluorinated diaphragm, and has fluorine ion conductivity at high temperature; the negative plate is made of lithium-silicon alloy powder and a perfluorinated electrolyte, other metal powder except lithium alloy can be selected, a fluorine ion conductive agent is added into the negative alloy powder, positive fluorine ions are directionally transferred to the negative electrode through the diaphragm, the fluorine ions can completely react with a negative electrode material, and the utilization rate of the negative electrode material is improved.
The Buddha's material the present application has the characteristics that our solution is only applied to thermal batteries, and the performance of the thermal batteries produced is changed only because the Buddha itself has the performance, and the creativity is not enough, so the patent application cn201410328708.x discloses: the insoluble compatible electrolyte is fluoride (LiF, NaF) with high stability and oxidation resistance, so the application of the fluoride on a thermal battery is disclosed in the literature, and the inventive concept of the invention is not inventive
The creativity of the application is insufficient, and a teacher in Tang province is asked to supplement some technical features and relevant experimental data for proving so as to improve the creativity of the application, if the technical features and the relevant experimental data cannot be provided, the later-stage response process is difficult to obtain authorization, and the teacher is asked to know and thank you for cooperation.
Drawings
In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the drawings needed in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only some examples of the present invention, and for a person skilled in the art, without inventive step, other drawings can be obtained according to these drawings:
fig. 1 is a schematic structural diagram of a novel fluoride ion single cell of the present application;
FIG. 2 is a diagram of the novel Li-Si/BiF of the present application3The working principle of the thermal battery is shown schematically;
FIG. 3 is a flow chart of a process for preparing a positive plate according to the present application;
FIG. 4 is a flow chart of a process for preparing a negative plate according to the present application;
FIG. 5 is a flow chart of a process for making a membrane sheet according to the present application.
In the drawings: 1-a substrate; 2, positive plate; 3-a membrane sheet; 4-negative pole piece; 5-a current collector; 6-heating plate.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
The utility model provides a novel fluorine ion thermal battery, novel fluorine ion thermal battery comprises substrate 1, positive plate 2, diaphragm 3, negative pole piece 4, current collector 5, heating plate 6, diaphragm 3 is the perfluorinated diaphragm of ternary, is formed by the asbestos fibre hybrid sintering of electrolyte and magnesium oxide modification, positive plate 2 is made by fluoride, conducting material, electrolyte.
Further, the electrolyte is a high-conductivity ternary perfluorinated electrolyte, namely LiF-NaF-KF; the fluoride is Bi-Co-FxA complex; the analytical grade fluoride starting material was dehydrated in an argon atmosphere at 220 ℃ and then subjected to a molar ratio of BiF3:CoF31:1, mixing, simultaneously adding 1 percent of lithium-silicon alloy powder and 5 percent of superfine light magnesium oxide, and finally keeping the mixture in an argon atmosphere at 450 ℃ for 2 hours; the negative plate 4 is made of lithium-silicon alloy powder and electrolyte, and the electrolyte is high-conductivity ternary perfluorinated electrolyte, namely LiF-NaF-KF.
A preparation method of a novel fluoride ion thermal battery comprises the following steps:
① preparation of Positive electrode plate
Firstly, drying an electrolyte in vacuum, then mixing the electrolyte with fluoride and a conductive material according to a certain proportion, performing ball milling, sintering, crushing and sieving, performing ball milling again, sealing with wax after drying, and storing in a dryer to obtain the positive plate for later use; the mass ratio of the electrolyte to the fluoride to the conductive material is 8:38: 1;
② preparation of diaphragm sheet
Respectively dehydrating and drying LiF, NaF and KF, then weighing, uniformly mixing the materials according to the mass ratio of 30-11-59, calcining the mixture at a high temperature of 500 ℃ in an ammonia atmosphere, quickly cooling, crushing, sieving and drying the mixture to obtain eutectic powder, adding 30% of superfine light magnesium oxide subjected to high-temperature treatment, uniformly mixing the eutectic powder and the superfine light magnesium oxide, performing high-temperature treatment, quickly cooling, crushing, sieving and drying the mixture to obtain the diaphragm.
③ preparation of negative plate
Uniformly mixing the lithium-silicon alloy powder and the electrolyte, and then sieving and drying to prepare a negative plate;
④ preparation of heating sheet
Uniformly mixing the superfine iron powder and the dried potassium perchlorate to prepare a heating sheet; the mass ratio of the superfine iron powder to the potassium perchlorate is 4.5: 1;
⑤ preparation of Current collector sheet
Punching a stainless steel foil into a circular sheet, and drying the circular sheet for later use after surface decontamination and deoiling treatment;
⑥ preparation of novel fluorinion thermal battery
And assembling the substrate, the positive plate, the diaphragm plate, the negative plate, the current collecting plate and the heating plate according to a thermal battery assembly mode to obtain the novel fluorine ion thermal battery.
Example 2
The utility model provides a novel fluorine ion thermal battery, novel fluorine ion thermal battery comprises substrate 1, positive plate 2, diaphragm 3, negative pole piece 4, current collector 5, heating plate 6, diaphragm 3 is the perfluorinated diaphragm of ternary, is formed by the asbestos fibre hybrid sintering of electrolyte and magnesium oxide modification, positive plate 2 is made by fluoride, conducting material, electrolyte.
Further, the electrolyte is a high-conductivity ternary perfluorinated electrolyte, namely LiF-NaF-KF; the fluoride is Bi-CoFXA complex; the mass percent of the fluoride is more than 99 percent, analyzing the raw material of the fluoride, removing water in an argon atmosphere at 220 ℃, and then performing molar ratio BiF3:CoF31:1, mixing, simultaneously adding 1 percent of lithium-silicon alloy powder and 5 percent of superfine light magnesium oxide, and finally keeping the mixture in an argon atmosphere at 450 ℃ for 2 hours; the negative plate 4 is made of lithium-silicon alloy powder and electrolyte, and the electrolyte is high-conductivity ternary perfluorinated electrolyte, namely LiF-NaF-KF.
A preparation method of a novel fluoride ion thermal battery comprises the following steps:
① preparation of Positive electrode plate
Firstly, drying an electrolyte in vacuum, then mixing the electrolyte with fluoride and a conductive material according to a certain proportion, performing ball milling, sintering, crushing and sieving, performing ball milling again, sealing with wax after drying, and storing in a dryer to obtain the positive plate for later use; the mass ratio of the electrolyte to the fluoride to the conductive material is 10:41: 1;
② preparation of diaphragm sheet
Respectively dehydrating and drying LiF, NaF and KF, then weighing, uniformly mixing the materials according to the mass ratio of 30-11-59, calcining the mixture at a high temperature of 500 ℃ in an ammonia atmosphere, quickly cooling, crushing, sieving and drying the mixture to obtain eutectic powder, adding 30% of superfine light magnesium oxide subjected to high-temperature treatment, uniformly mixing the eutectic powder, performing high-temperature treatment, quickly cooling, crushing, sieving and drying the mixture to obtain a diaphragm sheet;
③ preparation of negative plate
Uniformly mixing the lithium-silicon alloy powder and the electrolyte, and then sieving and drying to prepare a negative plate;
④ preparation of heating sheet
Uniformly mixing the superfine iron powder and the dried potassium perchlorate to prepare a heating sheet; the mass ratio of the superfine iron powder to the potassium perchlorate is 6: 1;
⑤ preparation of Current collector sheet
Punching a stainless steel foil into a circular sheet, and drying the circular sheet for later use after surface decontamination and deoiling treatment;
⑥ preparation of novel fluorinion thermal battery
Assemble substrate, positive plate, diaphragm, negative pole piece, current collector, heating plate according to the thermal battery equipment mode, stack together in proper order according to substrate, compound piece (positive plate + diaphragm), negative pole piece, current collector, heating plate, obtain novel fluorine ion thermal battery.
Example 3
The utility model provides a novel fluorine ion thermal battery, novel fluorine ion thermal battery comprises substrate 1, positive plate 2, diaphragm 3, negative pole piece 4, current collector 5, heating plate 6, diaphragm 3 is the perfluorinated diaphragm of ternary, is formed by the asbestos fibre hybrid sintering of electrolyte and magnesium oxide modification, positive plate 2 is made by fluoride, conducting material, electrolyte.
Further, the electrolyte is a high-conductivity ternary perfluorinated electrolyte, namely LiF-NaF-KF; the fluoride is CuF2、FeF3And CoF3(ii) a The fluoride is an analytical grade raw material, water is removed in an argon atmosphere at 220 ℃, and then molar ratio BiF is carried out3:CoF31:1, mixing, simultaneously adding 1 percent of lithium-silicon alloy powder and 5 percent of superfine light magnesium oxide, and finally keeping the mixture in an argon atmosphere at 450 ℃ for 2 hours; the negative plate 4 is made of lithium-silicon alloy powder and electrolyte, and the electrolyte is high-conductivity ternary perfluorinated electrolyte, namely LiF-NaF-KF.
A preparation method of a novel fluoride ion thermal battery comprises the following steps:
① preparation of Positive electrode plate
Firstly, drying an electrolyte in vacuum, then mixing the electrolyte with fluoride and a conductive material according to a certain proportion, performing ball milling, sintering, crushing and sieving, performing ball milling again, sealing with wax after drying, and storing in a dryer to obtain the positive plate for later use; the mass ratio of the electrolyte to the fluoride to the conductive material is 8.5:39: 1;
② preparation of diaphragm sheet
Respectively dehydrating and drying LiF, NaF and KF, then weighing, uniformly mixing the materials according to the mass ratio of 30-11-59, calcining the mixture at a high temperature of 500 ℃ in an ammonia atmosphere, quickly cooling, crushing, sieving and drying the mixture to obtain eutectic powder, adding 30% of superfine light magnesium oxide subjected to high-temperature treatment, uniformly mixing the eutectic powder, performing high-temperature treatment, quickly cooling, crushing, sieving and drying the mixture to obtain a diaphragm sheet;
③ preparation of negative plate
Uniformly mixing the lithium-silicon alloy powder and the electrolyte, and then sieving and drying to prepare a negative plate;
④ preparation of heating sheet
Uniformly mixing the superfine iron powder and the dried potassium perchlorate to prepare a heating sheet; the mass ratio of the superfine iron powder to the potassium perchlorate is 5.0: 1;
⑤ preparation of Current collector sheet
Punching a stainless steel foil into a circular sheet, and drying the circular sheet for later use after surface decontamination and deoiling treatment;
⑥ preparation of novel fluorinion thermal battery
Assemble substrate, positive plate, diaphragm, negative pole piece, current collector, heating plate according to the thermal battery equipment mode, stack together in proper order according to substrate, compound piece (positive plate + diaphragm), negative pole piece, current collector, heating plate, obtain novel fluorine ion thermal battery.
Example 4
The utility model provides a novel fluorine ion thermal battery, novel fluorine ion thermal battery comprises substrate 1, positive plate 2, diaphragm 3, negative pole piece 4, current collector 5, heating plate 6, diaphragm 3 is the perfluorinated diaphragm of ternary, is formed by the asbestos fibre hybrid sintering of electrolyte and magnesium oxide modification, positive plate 2 is made by fluoride, conducting material, electrolyte.
Further, the electrolyte is a high-conductivity ternary perfluorinated electrolyte, namely LiF-NaF-KF; the fluoride is BiF3、CuF2、FeF3(ii) a The fluoride is an analytical grade raw material, water is removed in an argon atmosphere at 220 ℃, and then molar ratio BiF is carried out3:CoF31:1, mixing, simultaneously adding 1 percent of lithium-silicon alloy powder and 5 percent of superfine light magnesium oxide, and finally keeping the mixture in an argon atmosphere at 450 ℃ for 2 hours; the negative plate 4 is made of lithium-silicon alloy powder and electrolyte, and the electrolyte is high-conductivity ternary perfluorinated electrolyte, namely LiF-NaF-KF.
A preparation method of a novel fluoride ion thermal battery comprises the following steps:
① preparation of Positive electrode plate
Firstly, drying an electrolyte in vacuum, then mixing the electrolyte with fluoride and a conductive material according to a certain proportion, performing ball milling, sintering, crushing and sieving, performing ball milling again, sealing with wax after drying, and storing in a dryer to obtain the positive plate for later use; the mass ratio of the electrolyte to the fluoride to the conductive material is 9.5:40: 1;
② preparation of diaphragm sheet
Respectively dehydrating and drying LiF, NaF and KF, then weighing, uniformly mixing the materials according to the mass ratio of 30-11-59, calcining the mixture at a high temperature of 500 ℃ in an ammonia atmosphere, quickly cooling, crushing, sieving and drying the mixture to obtain eutectic powder, adding 30% of superfine light magnesium oxide subjected to high-temperature treatment, uniformly mixing the eutectic powder, performing high-temperature treatment, quickly cooling, crushing, sieving and drying the mixture to obtain a diaphragm sheet;
③ preparation of negative plate
Uniformly mixing the lithium-silicon alloy powder and the electrolyte, and then sieving and drying to prepare a negative plate;
④ preparation of heating sheet
Uniformly mixing the superfine iron powder and the dried potassium perchlorate to prepare a heating sheet; the mass ratio of the superfine iron powder to the potassium perchlorate is 5.5: 1;
⑤ preparation of Current collector sheet
Punching a stainless steel foil into a circular sheet, and drying the circular sheet for later use after surface decontamination and deoiling treatment;
⑥ preparation of novel fluorinion thermal battery
Assemble substrate, positive plate, diaphragm, negative pole piece, current collector, heating plate according to the thermal battery equipment mode, stack together in proper order according to substrate, compound piece (positive plate + diaphragm), negative pole piece, current collector, heating plate, obtain novel fluorine ion thermal battery.
Example 5
The utility model provides a novel fluorine ion thermal battery, novel fluorine ion thermal battery comprises substrate 1, positive plate 2, diaphragm 3, negative pole piece 4, current collector 5, heating plate 6, diaphragm 3 is the perfluorinated diaphragm of ternary, is formed by the asbestos fibre hybrid sintering of electrolyte and magnesium oxide modification, positive plate 2 is made by fluoride, conducting material, electrolyte.
Further, the electrolyte is a high-conductivity ternary perfluorinated electrolyte, namely LiF-NaF-KF; the fluoride is Bi-Co-FXA complex; the fluoride is an analytical grade raw material, water is removed in an argon atmosphere at 220 ℃, and then molar ratio BiF is carried out3:CoF31:1 mixing while mixingAdding 1 percent of lithium-silicon alloy powder and 5 percent of superfine light magnesium oxide, and finally keeping the mixture for 2 hours at 450 ℃ in an argon atmosphere; the negative plate 4 is made of lithium-silicon alloy powder and electrolyte, and the electrolyte is high-conductivity ternary perfluorinated electrolyte, namely LiF-NaF-KF.
A preparation method of a novel fluoride ion thermal battery comprises the following steps:
① preparation of Positive electrode plate
Firstly, drying an electrolyte in vacuum, then mixing the electrolyte with fluoride and a conductive material according to a certain proportion, performing ball milling, sintering, crushing and sieving, performing ball milling again, sealing with wax after drying, and storing in a dryer to obtain the positive plate for later use; the mass ratio of the electrolyte to the fluoride to the conductive material is 9:40: 1;
② preparation of diaphragm sheet
Respectively dehydrating and drying LiF, NaF and KF, then weighing, uniformly mixing the materials according to the mass ratio of 30-11-59, calcining the mixture at a high temperature of 500 ℃ in an ammonia atmosphere, quickly cooling, crushing, sieving and drying the mixture to obtain eutectic powder, adding 30% of superfine light magnesium oxide subjected to high-temperature treatment, uniformly mixing the eutectic powder, performing high-temperature treatment, quickly cooling, crushing, sieving and drying the mixture to obtain a diaphragm sheet;
③ preparation of negative plate
Uniformly mixing the lithium-silicon alloy powder and the electrolyte, and then sieving and drying to prepare a negative plate;
④ preparation of heating sheet
Uniformly mixing the superfine iron powder and the dried potassium perchlorate to prepare a heating sheet; the mass ratio of the superfine iron powder to the potassium perchlorate is 5.3: 1;
⑤ preparation of Current collector sheet
Punching a stainless steel foil into a circular sheet, and drying the circular sheet for later use after surface decontamination and deoiling treatment;
⑥ preparation of novel fluorinion thermal battery
Assemble substrate, positive plate, diaphragm, negative pole piece, current collector, heating plate according to the thermal battery equipment mode, stack together in proper order according to substrate, compound piece (positive plate + diaphragm), negative pole piece, current collector, heating plate, obtain novel fluorine ion thermal battery.
Comparative example 1
A method for preparing a thermal battery, comprising the steps of:
(1) uniformly mixing the components in a mass ratio of 30-11-59, calcining at a high temperature of 500 ℃ in an ammonia atmosphere, mixing and sintering, adding 30% of superfine light magnesium oxide to test the conductivity of fluorine ions in a molten state, and testing internal resistance calculation after preparing the mixture into a fluorine ion battery;
(2) mixing LiF-NaF-KF and asbestos fiber modified by magnesium oxide in different proportions, sintering, assembling into a battery, and testing the performance of the battery;
(3) mixing LiF-NaF-KF and the asbestos fiber modified by magnesium oxide according to a certain proportion, and sintering at different temperatures;
(4) adding a fluorine ion conductive agent and a non-fluorine ion conductive agent into the negative electrode alloy powder, respectively filling the negative electrode alloy powder into a battery for discharging, and performing performance comparison;
(5) the positive fluoride is subjected to temperature rise treatment at different high temperatures, and then is loaded into a battery for performance comparison.
To further illustrate that the present invention can achieve the technical effects, the following experiments were performed:
the thermal batteries prepared by the methods of examples 1-5 and comparative example 1 are applied to production, and the results show that the open circuit voltage of the thermal battery monomer prepared by the method of comparative example 1 is higher than or equal to 2.8V, the chemical stability is poor, the capacity loss exists in the working process, and the production cost is high.
The novel fluoride ion thermal battery prepared in the embodiment 1-5 of the application has no problems, and the single open circuit voltage of the novel fluoride ion thermal battery is higher than 2.8V, so that the space height of the battery can be reduced; the chemical stability is good, and no capacity loss exists in the high-temperature working process; the specific energy is high, and the specific energy of the thermal battery can be improved; the fluorine ion discharge capacity can be improved, and other metals except lithium alloy can be selected as the negative electrode, so that the cost of the thermal battery is reduced.
In summary, the material used by the positive plate of the thermal battery is the metal fluoride, the decomposition temperature of the metal fluoride is higher than that of the traditional positive material (700 ℃), the chemical thermal stability is good, and no capacity loss exists in the high-temperature working process; the specific energy is high, and the specific energy of the thermal battery can be improved; the discharge capacity of fluorine ions can be improved, and the negative electrode can be made of other metals except lithium alloy, so that the cost of the thermal battery is reduced; the open-circuit voltage of the novel fluorine ion thermal battery monomer is more than 2.8V, so that the space height of the battery can be saved; the development and application of new materials can realize a new system, further improve the efficiency and reduce the cost of raw materials. The positive plate used in the application has fluorine ion conduction and electronic conduction at the same time at high temperature; the diaphragm is a ternary perfluorinated diaphragm, and has fluorine ion conductivity at high temperature; the negative plate is made of lithium-silicon alloy powder and a perfluorinated electrolyte, other metal powder except lithium alloy can be selected, a fluorine ion conductive agent is added into the negative alloy powder, positive fluorine ions are directionally transferred to the negative electrode through the diaphragm, the fluorine ions can completely react with a negative electrode material, and the utilization rate of the negative electrode material is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (9)

1. A novel fluorine ion thermal battery is characterized in that: the novel fluoride ion thermal battery is composed of a substrate (1), a positive plate (2), a diaphragm (3), a negative plate (4), a current collecting plate (5) and a heating plate (6), wherein the diaphragm (3) is a ternary perfluorinated diaphragm and is formed by mixing and sintering asbestos fibers modified by electrolyte and magnesium oxide, and the positive plate (2) is made of fluoride, conductive materials and electrolyte.
2. The novel fluoride ion thermal battery of claim 1, wherein: the electrolyte is a high-conductivity ternary perfluorinated electrolyte, namely LiF-NaF-KF.
3. The novel fluoride ion thermal battery of claim 1, wherein: the fluoride is Bi-Co-FXAnd (c) a complex.
4. The novel fluoride ion thermal battery of claim 1, wherein: the fluoride is an analytical grade raw material, water is removed in an argon atmosphere at 220 ℃, and then molar ratio BiF is carried out3:CoF31:1 mixing, simultaneously adding 1 percent of lithium-silicon alloy powder and 5 percent of superfine light magnesium oxide, and finally keeping the mixture in an argon atmosphere at 450 ℃ for 2 hours.
5. The novel fluoride ion thermal battery of claim 1, wherein: the negative plate (4) is made of lithium-silicon alloy powder and electrolyte, and the electrolyte is high-conductivity ternary perfluorinated electrolyte, namely LiF-NaF-KF.
6. A preparation method of a novel fluoride ion thermal battery is characterized by comprising the following steps:
① preparation of Positive electrode plate
Firstly, drying an electrolyte in vacuum, then mixing the electrolyte with fluoride and a conductive material according to a certain proportion, performing ball milling, sintering, crushing and sieving, performing ball milling again, sealing with wax after drying, and storing in a dryer to obtain the positive plate for later use;
② preparation of diaphragm sheet
Respectively dehydrating and drying LiF, NaF and KF, then weighing, uniformly mixing the materials according to the mass ratio of 30-11-59, calcining the mixture at a high temperature of 500 ℃ in an ammonia atmosphere, quickly cooling, crushing, sieving and drying the mixture to obtain eutectic powder, adding 30% of superfine light magnesium oxide subjected to high-temperature treatment, uniformly mixing the eutectic powder, performing high-temperature treatment, quickly cooling, crushing, sieving and drying the mixture to obtain a diaphragm sheet;
③ preparation of negative plate
Uniformly mixing the lithium-silicon alloy powder and the electrolyte, and then sieving and drying to prepare a negative plate;
④ preparation of heating sheet
Uniformly mixing the superfine iron powder and the dried potassium perchlorate to prepare a heating sheet;
⑤ preparation of Current collector sheet
Punching a stainless steel foil into a circular sheet, and drying the circular sheet for later use after surface decontamination and deoiling treatment;
⑥ preparation of novel fluorinion thermal battery
Assemble substrate, positive plate, diaphragm, negative pole piece, current collector, heating plate according to the thermal battery equipment mode, stack together in proper order according to substrate, compound piece (positive plate + diaphragm), negative pole piece, current collector, heating plate, obtain novel fluorine ion thermal battery.
7. The method of claim 6, wherein in step ①, the positive electrode material is Bi-Co-FXThe composite, 1 percent of lithium-silicon alloy powder and 5 percent of superfine light magnesium oxide are finally kept for 2 hours at 450 ℃ in argon atmosphere.
8. The method of claim 6, wherein in step ②, the electrolyte is mixed according to mass ratio LiF-NaF-KF 30-11-59, and then 30% by mass of ultra-fine light magnesium oxide is added.
9. The method for preparing a novel fluoride ion thermal battery according to claim 6, wherein in step ④, the mass ratio of the ultrafine iron powder to the potassium perchlorate is 4.5-6: 1.
CN202010207655.1A 2020-03-23 2020-03-23 Novel fluorine ion thermal battery and preparation method thereof Pending CN111354954A (en)

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Application publication date: 20200630