CN111564592B - High-specific-power single thermal battery and preparation method thereof - Google Patents

High-specific-power single thermal battery and preparation method thereof Download PDF

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CN111564592B
CN111564592B CN202010436675.6A CN202010436675A CN111564592B CN 111564592 B CN111564592 B CN 111564592B CN 202010436675 A CN202010436675 A CN 202010436675A CN 111564592 B CN111564592 B CN 111564592B
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single battery
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micron film
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CN111564592A (en
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王明灿
冉岭
唐军
张祖逸
潘志鹏
王京亮
赵洪楷
张小洪
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary 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
    • H01M4/06—Electrodes for primary cells
    • H01M4/08—Processes of manufacture
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • 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
    • H01M50/44—Fibrous material
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
    • H01M6/5038—Heating or cooling of cells or batteries

Abstract

The scheme discloses a high-specific-power thermal battery single battery and a preparation method thereof, and belongs to the technical field of thermal batteries 2 O 5 The composite diaphragm, the LiB alloy sheet and the Al-Ni micron film heating sheet are sequentially superposed according to a certain sequence; wherein Cu-CuO-V 2 O 5 The thickness of the film is 0.05 mm-0.3 mm, the thickness of the boron nitride fiber composite diaphragm is 0.1 mm-0.3 mm, the thickness of the LiB alloy sheet is 0.1 mm-0.2 mm, and the Al-Ni micron film is 5-50 layers. The high-specific-power single battery can meet the requirements of single batteries with high specific power and high utilization rate, has the advantages of good electrochemical performance, strong stability, formability, thin thickness, low internal resistance, low high-current density voltage drop, strong adverse environment resistance, high safety and the like, has a proper heating temperature range, and can be well suitable for matching the use environment of the thermal battery.

Description

High-specific-power single thermal battery and preparation method thereof
Technical Field
The invention belongs to the technical field of thermal batteries, and particularly relates to a single thermal battery with high specific power and a preparation method thereof.
Background
The thermal battery is a thermal activation reserve battery which is put into an operating state by heating and melting non-conductive salt electrolyte in a solid state into an ionic conductor by means of a heating system of the thermal battery. The thermal battery has the characteristics of activation at any angle, high activation speed, long storage time, strong capability of bearing environmental mechanical conditions and the like, has wide military application, is also emphasized in the civil field, and has been reported as an emergency power supply of an airplane, a fire alarm power supply and an underground high-temperature mine exploration power supply.
With the continuous development and the updating of military equipment, the requirements on the performance of the thermal battery are higher and higher, and the requirements on output power and high specific property are higher and higher. The thermal battery mainly comprises a substrate, a positive plate, a negative plate, an electrolyte sheet (or a diaphragm sheet), a sheet current collector, a heating system (an electric ignition head or a fire cap, ignition paper and a heating sheet), a heat-insulating gasket, a battery shell and a battery cover with a connecting post, wherein the influence of the single battery of the thermal battery on the specific power of the single battery is the most critical. According to the working principle of the thermal battery, the smaller the voltage drop of the single battery is, the better the output high ratio characteristic is under the high current density of the thermal battery. High specific power thermal battery cells generally need to have the following characteristics: (1) the thickness of the single battery is small; (2) the product has good formability, and can be cut into sheets with the diameter of 10 mm-120 mm; (3) has good conductivity, 1cm for electric cell 2 The internal resistance per unit area is less than 0.05 omega, and the large-current discharge characteristic is good; (4) the voltage platform of the single battery anode material is high, the heat resistance is good, and the decomposition of the anode material is reduced; (5) gas is not generated in the combustion process, large volume change is not generated, and the excessive pressure in the thermal battery is prevented.
Nowadays, the single battery of the thermal battery is composed of a substrate and a composite sheet (positive electrode + separator)Film), negative pole piece, current collector, heating plate. The anode material mainly comprises FeS 2 、NiCl 2 、CoS 2 The composite sheet is formed by pressing a positive electrode and an electrolyte, and the thickness of the composite sheet is more than 0.8 mm; the cathode material is LiB and LiSi; the heating plates are Fe and KClO 4 The mixture is pressed, the thickness of the single battery is larger, usually more than 2mm, the high specific property of the thermal battery is low, and the specific power and the material utilization rate of the battery are reduced.
Disclosure of Invention
The invention provides a single battery of a high-specific-power thermal battery and a preparation method thereof to solve the technical problems.
The single battery of the high-specific power thermal battery comprises sequentially superposed Cu-CuO-V 2 O 5 The anode material, the boron nitride fiber composite diaphragm, the LiB alloy sheet and the Al-Ni micron film heating sheet.
Further, the Cu-CuO-V 2 O 5 The thickness of the anode material is 0.05 mm-0.2 mm; the thickness of the boron nitride fiber composite diaphragm is 0.1 mm-0.3 mm; the thickness of the LiB alloy sheet is 0.1 mm-0.3 mm; the number of layers of the Al-Ni micron film heating sheet contained in the single battery of the high-specific power thermal battery is 5-50.
Further, the Cu-CuO-V 2 O 5 The mass of the positive electrode material is 3-8 times of that of the LiB alloy sheet.
Further, the Al-Ni micron film heating sheet accounts for 70-90% of the weight of the single battery.
Further, the Cu-CuO-V 2 O 5 Mass of CuO substance in positive electrode material and V 2 O 5 The mass ratio of the substances is 3: 1-1: 2.2.
The preparation method of the single battery of the high specific power thermal battery comprises the following steps:
1) cleaning and de-oxidation of materials: preparing a LiB alloy sheet, a foam copper, an aluminum foil and a nickel foil, respectively putting the foam copper, the aluminum foil and the nickel foil into 0.1-0.3 mol/L hydrochloric acid for cleaning and ensuring the complete frameworks of the foam copper, the aluminum foil and the nickel foil, and drying after cleaning;
2) preparation of Cu-CuO-V 2 O 5 A positive electrode material: reacting NH 4 VO 3 Putting into water with the temperature of 50-80 ℃ to prepare NH 4 VO 3 A saturated solution; then adding the foam copper prepared in the step 1), heating to 60-90 ℃, and keeping for 5-120 min; taking out the foamy copper, putting the foamy copper into a baking oven with the temperature of 60-100 ℃ for calcining for 30 min-48 h, then transferring the foamy copper into a tubular furnace with the temperature of 600-650 ℃ for calcining for 2 h-24 h, and finally pressing the foamy copper into tablets under the pressure of 10-30 MPa;
3) preparing a boron nitride fiber composite diaphragm: the cutting area is 18cm 2 ～80cm 2 The boron nitride fiber cloth is soaked in a high-conductivity low-melting point electrolyte in a molten state at the temperature of 300-400 ℃ for 20-300 s, taken out and put into a vacuum drying oven at the temperature of 80-175 ℃, and the vacuum drying time is more than 30 min;
4) Preparing an Al-Ni micron film heating sheet: pressing the aluminum foil and the nickel foil prepared in the step 1) into a sheet to obtain an Al-Ni micron film heating sheet;
5) the Cu-CuO-V prepared by the steps 2 O 5 The high-specific power thermal battery single battery is formed by sequentially overlapping a positive electrode material, a boron nitride fiber composite diaphragm, a LiB alloy sheet and a plurality of Al-Ni micron film heating sheets; the superposition mode of the plurality of Al-Ni micron film heating sheets is that an aluminum foil faces downwards and a nickel foil faces upwards.
Furthermore, the thickness of the foam copper raw material is 0.1 mm-2 mm, the aperture is 0.1 mm-0.5 mm, and the porosity is more than 80%.
Further, the thickness of aluminium foil is 1um ~ 2um, and the thickness of nickel foil is 1um ~ 2 um.
Further, the high-conductivity low-melting-point electrolyte is any one of LiF-LiCl-LiBr-LiI, LiBr-RbBr, LiBr-CsCl, LiI-KI, LiBr-CsBr, LiCl-KCl-CsCl, LiCl-KCl-RbCl-CsCl, LiBr-KBr-CsBr, LiBr-LiI-KI-CsI and LiCl-LiBr-LiI-KI-CsI.
The beneficial technical effects of the invention are as follows:
1. the single battery with high specific power prepared by the method can exert the advantages of respective raw materials, can meet the requirements of the single battery with high specific power and high utilization rate, has the advantages of good electrochemical performance, strong stability, formability, thin thickness, low internal resistance, small large current density voltage drop, strong capability of resisting severe environment, high safety and the like, has a proper heating temperature range, and can be well suitable for matching the use environment of the thermal battery.
The thickness of the single battery of the high-specific-power thermal battery can be within 0.5mm at the thinnest, which is 1/4 of the thickness of the conventional single battery, and the occupied space volume is obviously reduced; the single battery of the high specific power thermal battery has better conductivity, and the single battery of the high specific power thermal battery is 1cm 2 Internal resistance per unit area of less than 0.05 omega, good discharge characteristic at high current, and current density of 4A/cm 2 The voltage drop of the lower single battery is less than 0.3V, and the large-current discharge characteristic is good; the heating sheet is composed of an Al-Ni micron film, so that thermal shock is small, and the safety of the battery is high; the utilization rate of the anode and cathode materials is high, and the high specific property of the battery is improved.
2. The preparation method has the advantages of simple preparation process, strong operability, low equipment cost and contribution to large-scale production. Compared with the traditional single battery, the single battery of the high-specific-power thermal battery has no pressing of various powder materials, the battery assembly process is simple, and the later-stage realization automation degree is high; compared with the conventional single battery, the single battery prepared by high specific power heat has the specific power improved by more than 50 percent, and the utilization rate of positive and negative electrode materials reaches 80 percent.
Drawings
Fig. 1 is a no-load graph of a unit cell in which a conventional unit cell and a high specific power unit cell according to the present invention are assembled to have the same volume;
FIG. 2 shows the area of the electrode sheet is 18.08cm 2 The conventional single battery and the high-specific-power single battery have single voltage drop under different pulse currents.
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.
The LiB alloy sheets in the following examples were all purchased directly.
Example 1: the preparation method of the single battery of the high specific power thermal battery comprises the following steps:
1) cleaning and de-oxidation of materials: preparing foam copper, aluminum foil and nickel foil, respectively putting the foam copper, the aluminum foil and the nickel foil into 0.1mol/L hydrochloric acid for cleaning for 2min, and putting the cleaned foam copper, aluminum foil and nickel foil into a vacuum drying oven for drying; the area of the foamy copper is 18.08cm 2 The thickness of the round sheet is 1mm, the aperture is 0.3mm, and the porosity is 85%;
2) preparation of Cu-CuO-V 2 O 5 A positive electrode material: reacting NH 4 VO 3 Putting into water of 50 ℃ to prepare NH 4 VO 3 A saturated solution; then adding the foam copper prepared in the step 1), heating to 90 ℃, and keeping for 120 min; taking out the foamy copper, putting the foamy copper into a 60 ℃ oven for calcining for 8h, transferring the foamy copper into a 600 ℃ tube furnace for calcining for 4h, and finally pressing the foamy copper to the thickness of 0.18mm under the pressure of 10 MPa;
3) Preparing a boron nitride fiber composite diaphragm: the cutting area is 18.08cm 2 Soaking a boron nitride fiber cloth wafer with the thickness of 0.2mm in LiF-LiCl-LiBr-LiI electrolyte in a molten state at the temperature of 300 ℃ for 60s, taking out and putting into a vacuum drying oven at the temperature of 80 ℃, wherein the vacuum drying time is 35 min;
4) preparing 30 layers of Al-Ni micron film heating sheets: stacking the aluminum foil and the nickel foil prepared in the step 1) at intervals, and then punching the aluminum foil and the nickel foil into a shape with the area of 18.46cm 2 The Al-Ni micron film heating sheet is obtained from the round sheet, and the surfaces of the aluminum foil and the nickel foil have no oxide layers; and 30 Al-Ni micron film heating sheets are superposed together in a way that an aluminum foil faces downwards and a nickel foil faces upwards;
5) the Cu-CuO-V prepared by the steps 2 O 5 Sequentially overlapping a positive electrode material, a boron nitride fiber composite diaphragm, a LiB alloy sheet with the thickness of 0.2mm and a superposed Al-Ni micron film heating sheet to form the single battery of the high-specific-power thermal battery provided by the invention, wherein the thickness of the single battery of the high-specific-power thermal battery is 0.41 mm;
in which Cu-CuO-V is used 2 O 5 The mass of the positive electrode material is 6 times of that of the LiB alloy sheet; the Al-Ni micron film heating plate accounts for 75 percent of the weight of the single battery.
Example 2: the preparation method of the single battery of the high specific power thermal battery comprises the following steps:
1) Cleaning and de-oxidation of materials: preparing foam copper, aluminum foil and nickel foil, respectively putting the foam copper, the aluminum foil and the nickel foil into 0.3mol/L hydrochloric acid for cleaning for 1min, and putting the cleaned foam copper, aluminum foil and nickel foil into a vacuum drying oven for drying; the area of the copper foam is 18.08cm 2 The thickness of the wafer is 2mm, the aperture is 0.5mm, and the porosity is 90 percent;
2) preparation of Cu-CuO-V 2 O 5 A positive electrode material: reacting NH 4 VO 3 Putting into water of 70 ℃ to prepare NH 4 VO 3 A saturated solution; then adding the foam copper prepared in the step 1), heating to 90 ℃, and keeping for 60 min; taking out the foam copper, putting the foam copper into a baking oven at 100 ℃ for calcining for 18h, then transferring the foam copper into a tubular furnace at 600 ℃ for calcining for 4h, and finally pressing the foam copper to be 0.2mm in thickness under the pressure of 30 MPa;
3) preparing a boron nitride fiber composite diaphragm: the cutting area is 18.08cm 2 Soaking a boron nitride fiber cloth wafer with the thickness of 0.2mm in LiCl-KCl-RbCl-CsCl electrolyte in a molten state at the temperature of 400 ℃ for 40s, taking out and putting into a vacuum drying oven at the temperature of 110 ℃, wherein the vacuum drying time is 40 min;
4) preparing 50 layers of Al-Ni micron film heating plates: the procedure is the same as in example 1 except that the number of Al-Ni micron film heating sheets is 50;
5) the Cu-CuO-V prepared by the steps 2 O 5 Sequentially overlapping a positive electrode material, a boron nitride fiber composite diaphragm, a LiB alloy sheet with the thickness of 0.3mm and an overlapped Al-Ni micron film heating sheet to form the single battery of the high-specific-power thermal battery provided by the invention, wherein the thickness of the single battery of the high-specific-power thermal battery is 0.52 mm; in which Cu-CuO-V is used 2 O 5 The mass of the positive electrode material is 8 times of that of the LiB alloy sheet; the Al-Ni micron film heating plate accounts for 70 percent of the weight of the single battery.
Example 3: the preparation method of the single battery of the high specific power thermal battery comprises the following steps:
1) cleaning and de-oxidation of materials: preparing foam copper, aluminum foil and nickel foil, respectively washing in 0.1mol/L hydrochloric acid for 2minCleaning, and drying in a vacuum drying oven; the area of the copper foam is 18.08cm 2 The thickness of the wafer is 0.5mm, the aperture is 0.1mm, and the porosity is 82%;
2) preparation of Cu-CuO-V 2 O 5 A positive electrode material: reacting NH 4 VO 3 Putting into water of 60 ℃ to prepare NH 4 VO 3 A saturated solution; then adding the foam copper prepared in the step 1), heating to 90 ℃, and keeping for 120 min; taking out the foamy copper, putting the foamy copper into a baking oven at 100 ℃ for calcining for 2h, transferring the foamy copper into a tubular furnace at 600 ℃ for calcining for 2h, and finally pressing the foamy copper to be 0.15mm in thickness under the pressure of 10 MPa;
3) preparing a boron nitride fiber composite diaphragm: the cutting area is 18.08cm 2 Soaking a boron nitride fiber cloth wafer with the thickness of 0.3mm in LiBr-RbBr electrolyte in a molten state at the temperature of 320 ℃ for 20s, taking out and putting into a vacuum drying oven with the temperature of 80 ℃, wherein the vacuum drying time is 50 min;
4) preparing 40 layers of Al-Ni micron film heating sheets: the procedure is the same as example 1 except that the number of Al-Ni micron film heating sheets is 40;
5) The Cu-CuO-V prepared by the steps 2 O 5 Sequentially overlapping a positive electrode material, a boron nitride fiber composite diaphragm, a LiB alloy sheet with the thickness of 0.2mm and an overlapped Al-Ni micron film heating sheet to form the single battery of the high-specific-power thermal battery provided by the invention, wherein the thickness of the single battery of the high-specific-power thermal battery is 0.36 mm; in which Cu-CuO-V is used 2 O 5 The mass of the positive electrode material is 3 times of that of the LiB alloy sheet; the Al-Ni micron film heating plate accounts for 80 percent of the weight of the single battery.
Example 4: the preparation method of the single battery of the high specific power thermal battery comprises the following steps:
1) cleaning and de-oxidation of materials: preparing foam copper, aluminum foil and nickel foil, respectively putting the foam copper, the aluminum foil and the nickel foil into 0.3mol/L hydrochloric acid for cleaning for 1min, and putting the cleaned foam copper, aluminum foil and nickel foil into a vacuum drying oven for drying; the area of the copper foam is 18.08cm 2 The thickness of the wafer is 0.2mm, the pore diameter is 0.4mm, and the porosity is 95 percent;
2) preparation of Cu-CuO-V 2 O 5 A positive electrode material: reacting NH 4 VO 3 Putting into water of 80 ℃ to prepare NH 4 VO 3 A saturated solution; then adding the foam copper prepared in the step 1), heating to 90 ℃, and keeping for 5 min; taking out the foam copper, putting the foam copper into a baking oven at 100 ℃ for calcining for 30min, then transferring the foam copper into a tubular furnace at 600 ℃ for calcining for 2h, and finally pressing the foam copper to be 0.08mm in thickness under the pressure of 10 MPa;
3) Preparing a boron nitride fiber composite diaphragm: the cutting area is 18.08cm 2 Soaking a boron nitride fiber cloth wafer with the thickness of 0.2mm in LiI-KI electrolyte in a molten state at the temperature of 400 ℃ for 20s, taking out and putting into a vacuum drying oven at the temperature of 80 ℃, wherein the vacuum drying time is 50 min;
4) preparing 10 layers of Al-Ni micron film heating sheets: the procedure is the same as example 1 except that the number of Al-Ni micron film heating sheets is 10;
5) the Cu-CuO-V prepared by the steps 2 O 5 Sequentially overlapping a positive electrode material, a boron nitride fiber composite diaphragm, a LiB alloy sheet with the thickness of 0.1mm and an overlapped Al-Ni micron film heating sheet to form the single battery of the high-specific-power thermal battery provided by the invention, wherein the thickness of the single battery of the high-specific-power thermal battery is 0.30 mm; in which Cu-CuO-V is used 2 O 5 The mass of the positive electrode material is 5 times of that of the LiB alloy sheet; the Al-Ni micron film heating plate accounts for 90 percent of the weight of the single battery.
Example 5: the preparation method of the single battery of the high specific power thermal battery comprises the following steps:
1) cleaning and de-oxidation of materials: preparing foam copper, aluminum foil and nickel foil, respectively putting the foam copper, the aluminum foil and the nickel foil into 0.3mol/L hydrochloric acid for cleaning for 1min, and putting the cleaned foam copper, aluminum foil and nickel foil into a vacuum drying oven for drying; the area of the copper foam is 18.08cm 2 The thickness of the wafer is 0.1mm, the aperture is 0.3mm, and the porosity is 90 percent;
2) preparation of Cu-CuO-V 2 O 5 A positive electrode material: reacting NH 4 VO 3 Putting into water of 50 ℃ to prepare NH 4 VO 3 A saturated solution; then adding the foam copper prepared in the step 1), heating to 90 ℃, and keeping for 5 min; taking out the foam copper, putting the foam copper into an oven at 80 ℃ for calcining for 30min, transferring the foam copper into a tubular furnace at 600 ℃ for calcining for 2h, and finally, calcining under the pressure of 10MPaPressing under strong force until the thickness is 0.06 mm;
3) preparing a boron nitride fiber composite diaphragm: the cutting area is 18.08cm 2 Soaking a boron nitride fiber cloth wafer with the thickness of 0.1mm in LiCl-KCl-CsCl electrolyte in a molten state at the temperature of 400 ℃ for 20s, taking out and putting into a vacuum drying oven at the temperature of 80 ℃, wherein the vacuum drying time is 55 min; wherein the electrolyte is;
4) preparing 5 layers of Al-Ni micron film heating sheets: the procedure is the same as example 1 except that the number of Al-Ni micron film heating sheets is 5;
5) the Cu-CuO-V prepared by the steps 2 O 5 The high-specific power thermal battery single battery provided by the invention is formed by sequentially overlapping a positive electrode material, a boron nitride fiber composite diaphragm, a LiB alloy sheet with the thickness of 0.1mm and an overlapped Al-Ni micron film heating sheet, and the thickness of the obtained high-specific power thermal battery single battery is 0.28 mm; in which Cu-CuO-V is used 2 O 5 The mass of the positive electrode material is 3 times of that of the LiB alloy sheet; the Al-Ni micron film heating plate accounts for 85 percent of the weight of the single battery.
Test example 1: the preparation method of the single battery of the high specific power thermal battery comprises the following steps:
1) cleaning and de-oxidation of materials: preparing foam copper, aluminum foil and nickel foil, respectively putting the foam copper, the aluminum foil and the nickel foil into 0.3mol/L hydrochloric acid for cleaning for 1min, and putting the cleaned foam copper, aluminum foil and nickel foil into a vacuum drying oven for drying; the area of the copper foam is 18.08cm 2 The thickness of the wafer is 0.1mm, the aperture is 0.1mm, and the porosity is 95 percent;
2) preparation of Cu-CuO-V 2 O 5 A positive electrode material: reacting NH 4 VO 3 Putting into water of 80 ℃ to prepare NH 4 VO 3 A saturated solution; then adding the foam copper prepared in the step 1), heating to 90 ℃, and keeping for 5 min; taking out the foam copper, putting the foam copper into a baking oven at 100 ℃ for calcining for 30min, then transferring the foam copper into a tubular furnace at 600 ℃ for calcining for 10h, and finally pressing the foam copper under the pressure of 10MPa until the thickness is 0.08 mm;
3) preparing a boron nitride fiber composite diaphragm: the cutting area is 18.08cm 2 A boron nitride fiber cloth wafer with the thickness of 0.2mm is dipped in LiCl-LiBr-LiI-containing material in a melting state at the temperature of 350 DEG CKeeping the KI-CsI electrolyte for 20s, taking out and putting into a vacuum drying oven with the temperature of 80 ℃, wherein the vacuum drying time is 45 min; wherein the electrolyte is;
4) Preparing 10 layers of Al-Ni micron film heating sheets: the procedure is the same as example 1 except that the number of Al-Ni micron film heating sheets is 10;
5) the Cu-CuO-V prepared by the steps 2 O 5 The high-specific-power single battery is formed by sequentially overlapping a positive electrode material, a boron nitride fiber composite diaphragm, a LiB alloy sheet with the thickness of 0.1mm and an overlapped Al-Ni micron film heating sheet, wherein the thickness of the single battery is 0.32 mm; in which Cu-CuO-V is used 2 O 5 The mass of the positive electrode material is 8 times of that of the LiB alloy sheet; the Al-Ni micron film heating plate accounts for 80 percent of the weight of the single battery.
For the prepared single battery of the high specific power thermal battery, the selected materials are as follows: Cu-CuO-V with thickness of 0.2mm 2 O 5 Positive electrode material, wherein CuO: v 2 O 5 The mass ratio of the substances is 1: 1; the boron nitride fiber composite diaphragm with the thickness of 0.2 mm; LiB alloy sheet with thickness of 0.1mm, 10 layers of Al-Ni micron films, and the area of each selected material is 18.08cm 2 The size of the cylinder body is phi 60mm x 50mm, the cylinder body is assembled into a high specific power thermal battery single battery to carry out no-load test and electrical performance test, and is compared with a conventional single battery with the same volume, 40 high specific power single batteries can be arranged in the cylinder body with the size of phi 60mm x 50mm, the conventional single battery can only be provided with 16 single batteries, the no-load test result is shown in figure 1, and the voltage discharge platform is high and the output power is high in figure 1; fig. 2 shows that the discharge performance of the single battery of the high specific power thermal battery is compared with that of the conventional single battery, two single batteries discharge under the same high-current pulse current density, and compared with the conventional single battery, the single battery of the high specific power thermal battery has smaller single voltage drop.
In addition, the method also prepares a high-specific power single battery anode material of the thermal battery, and excessive NH 4 VO 3 Putting into water of 80 ℃ to prepare NH 4 VO 3 A saturated solution of (a); then adding foam copper with the thickness of 1mm, raising the temperature to 90 ℃,keeping for 5 min; and (3) taking out the foam copper, putting the foam copper into a high-temperature oven at 100 ℃ for high-temperature calcination for 1h, 2h, 3h and 4h, and measuring the open-circuit voltage of the material. The open circuit voltages of the prepared 4 pieces of positive electrode materials are 3.25V, 3.20V, 3.16V and 3.15V respectively.

Claims (7)

1. A preparation method of a single battery of a high-specific-power thermal battery is characterized by comprising the following steps: the single battery comprises sequentially superposed Cu-CuO-V 2 O 5 A positive electrode material, a boron nitride fiber composite diaphragm, a LiB alloy sheet, an Al-Ni micron film heating sheet, Cu-CuO-V 2 O 5 The thickness of the anode material is 0.05 mm-0.2 mm; the thickness of the boron nitride fiber composite diaphragm is 0.1 mm-0.3 mm; the thickness of the LiB alloy sheet is 0.1 mm-0.3 mm; the number of layers of the Al-Ni micron film heating sheet contained in the single battery of the high-specific-power thermal battery is 5-50, and the preparation method comprises the following steps:
1) cleaning and de-oxidation of materials: preparing a LiB alloy sheet, a foam copper, an aluminum foil and a nickel foil, respectively putting the foam copper, the aluminum foil and the nickel foil into 0.1-0.3 mol/L hydrochloric acid for cleaning and ensuring the complete frameworks of the foam copper, the aluminum foil and the nickel foil, and drying after cleaning;
2) Preparation of Cu-CuO-V 2 O 5 A positive electrode material: reacting NH 4 VO 3 Putting into water with the temperature of 50-80 ℃ to prepare NH 4 VO 3 A saturated solution; then adding the foam copper prepared in the step 1), heating to 60-90 ℃, and keeping for 5-120 min; taking out the foamy copper, putting the foamy copper into a baking oven with the temperature of 60-100 ℃ for calcining for 30 min-48 h, then transferring the foamy copper into a tubular furnace with the temperature of 600-650 ℃ for calcining for 2 h-24 h, and finally pressing the foamy copper into tablets under the pressure of 10-30 MPa;
3) preparing a boron nitride fiber composite diaphragm: the cutting area is 18cm 2 ~80cm 2 The boron nitride fiber cloth is soaked in a high-conductivity low-melting point electrolyte in a molten state at the temperature of 300-400 ℃ for 20-300 s, taken out and put into a vacuum drying oven at the temperature of 80-175 ℃, and the vacuum drying time is more than 30 min;
4) preparing an Al-Ni micron film heating sheet: pressing the aluminum foil and the nickel foil prepared in the step 1) into sheets to obtain Al-Ni micron film heating sheets;
5) the Cu-CuO-V prepared by the steps 2 O 5 The high-specific-power single battery is formed by sequentially overlapping a positive electrode material, a boron nitride fiber composite diaphragm, a LiB alloy sheet and a plurality of Al-Ni micron film heating sheets; the superposition mode of the plurality of Al-Ni micron film heating sheets is that an aluminum foil faces downwards and a nickel foil faces upwards.
2. The method of claim 1, wherein the method comprises the steps of: the Cu-CuO-V 2 O 5 The mass of the positive electrode material is 3-8 times of that of the LiB alloy sheet.
3. The method of claim 1, wherein the method comprises the steps of: the Al-Ni micron film heating sheet accounts for 70-90% of the weight of the single battery.
4. The method of claim 1, wherein the method comprises the steps of: the Cu-CuO-V 2 O 5 Mass of CuO substance in positive electrode material and V 2 O 5 The mass ratio of the substances is 3: 1-1: 2.2.
5. The method of claim 1, wherein the method comprises the steps of: the thickness of the foam copper raw material is 0.1 mm-2 mm, the aperture is 0.1 mm-0.5 mm, and the porosity is more than 80%.
6. The method of manufacturing a high specific power thermal battery cell according to claim 1 or 5, characterized in that: the thickness of aluminium foil is 1um ~ 2um, and the thickness of nickel foil is 1um ~ 2 um.
7. The method of claim 6, wherein the method comprises the steps of: the high-conductivity low-melting-point electrolyte is any one of LiF-LiCl-LiBr-LiI, LiBr-RbBr, LiBr-CsCl, LiI-KI, LiBr-CsBr, LiCl-KCl-CsCl, LiCl-KCl-RbCl-CsCl, LiBr-KBr-CsBr, LiBr-LiI-KI-CsI and LiCl-LiBr-LiI-KI-CsI.
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