CN113270578B - High specific energy composite electrode plate for thermal battery and preparation method thereof - Google Patents

High specific energy composite electrode plate for thermal battery and preparation method thereof Download PDF

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CN113270578B
CN113270578B CN202110534397.2A CN202110534397A CN113270578B CN 113270578 B CN113270578 B CN 113270578B CN 202110534397 A CN202110534397 A CN 202110534397A CN 113270578 B CN113270578 B CN 113270578B
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composite electrode
electrolyte
thermal battery
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CN113270578A (en
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唐军
冉岭
王毅
唐立成
赵文莉
潘志鹏
王京亮
赵洪楷
李云伟
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Guizhou Meiling Power Supply Co Ltd
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    • 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
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Abstract

The application discloses composite electrode slice of high specific energy for thermal battery among the thermal battery technical field, composite electrode slice are the basic unit who constitutes monomer thermal battery, and the performance of composite electrode slice is the final performance of deciding the unit cell, and composite electrode slice mainly comprises diaphragm material, RSEI material and halide composite anode material, and wherein RSEI material is 70 ~ 95 by carbon nanotube and electrolyte according to the weight ratio: 5-30, and drying in inert gas at 100-600 ℃, wherein the electrolyte is 9.56 +/-1% LiF and 22 +/-1% LiCl2And 68.44 +/-1% of LiBr. The composite electrode plate has higher specific capacity compared with the conventional CoS2The specific capacity of the composite sheet is improved by 15%; compared with the conventional halide composite sheet, the specific capacity of the composite sheet is improved by 50 percent.

Description

High specific energy composite electrode plate for thermal battery and preparation method thereof
Technical Field
The invention belongs to the technical field of thermal batteries, and particularly relates to a high specific energy composite electrode plate for a thermal battery 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 solid-state salt electrolyte 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, is widely applied to weapon systems and the like, and is also emphasized to be applied in the civil field, so that the thermal battery has been reported to be used 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, the requirements on the working time of the thermal battery are longer and longer, and the requirements on the output power and the high specific property are higher and higher. The thermal battery mainly comprises a substrate, a positive plate, a negative plate, a diaphragm plate, a sheet current collecting plate, a heating system (an electric ignition head or a fire, ignition paper and a heating plate), a heat-insulating gasket, a battery shell and a battery cover with a binding post, wherein the positive plate and the diaphragm plate are combined together to form a composite electrode plate. The composite electrode sheet needs to have the following characteristics: (1) electromotive force is 2v (vs li) greater; (2) thermal stability>800 ℃; (3) the conductivity is high, and large current discharge can be realized; (4) good dynamic characteristics (high rate capacity); (5) good compatibility with molten salts (no or as little fusion to molten salts as possible); (6) low molecular weight (high coulomb/mole ratio, i.e., high electrochemical capacity); (7) non-embedded (multi-phase) discharge; (8) the reaction product is not fused in molten salt, and has high conductivity (preventing the internal resistance from increasing in the discharging process) and thermal stability; (9) high thermal conductivity, facilitating rapid activation; (10) the heat capacity is low, minimizing the heat input required from the heating fins; (11) stably exist in the storage temperature range (-50 ℃ to 70 ℃), and are not easy to react with water, oxygen and CO2And the like.
The influence of the material of the composite electrode plate on the electrochemical properties such as output capacity, specific power and the like is the most critical, and at present, FeS2、CoS2Is the most widely used anode material of thermal batteries, but the working voltages of the two single batteries are below 2V, and the high-power output is very influencedThe specific capacity reaches a certain limit (theoretical specific capacity 1206As/g (333mAh/g)), which is not beneficial to the development of miniaturization and lightweight thermal batteries, and the halide in the conventional halide positive electrode composite electrode plate has compatibility with molten salt and does not have long-time working capability. Therefore, it is necessary to develop a novel positive electrode technology with both high potential and high specific capacity and develop a composite electrode sheet with high potential and high specific capacity.
At present, the thermal battery has strict requirements on the composite electrode plate, and only FeS which can realize engineering application at present2、CoS2The working voltage of the single battery of the composite sheet made of the anode material is below 2V; the halide in the conventional halide cathode composite sheet has compatibility with molten salt and does not have long-time working capability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention prepares the high specific energy composite electrode plate for the thermal battery.
The invention aims to provide a high-specific-energy composite electrode plate for a thermal battery, which is mainly prepared from a diaphragm material, an RSEI material and a halide composite positive electrode material, wherein the RSEI material is prepared from a carbon nano tube and an electrolyte according to the weight ratio of 70-95: 5-30, and drying in an inert gas environment at 100-600 ℃, wherein the electrolyte comprises 9.56 +/-1 weight percent LiF and 22 +/-1 weight percent LiCl2And 68.44 +/-1% of LiBr.
Specifically, the halide composite positive electrode material comprises the following raw materials of anhydrous halide, electrolyte, adsorbent and carbon nano tube, wherein the anhydrous halide: electrolyte: adsorbent: 70-90% of carbon nanotubes: 3-10: 3-10: 1 to 5.
Specifically, the anhydrous halide is MnF3、NiCl2、CuF3、NiF2、FeF3And CoF3One or more of the components are compounded and then dried to obtain the product.
Specifically, the adsorbent is MgO or Al2O3Wherein the specific volume of the adsorbent is more than 20 mL/g-1, and the specific surface area is more than 60m2/g，The grain diameter is less than 100 nm.
Specifically, during preparation of the halide composite anode material, firstly, halide is subjected to forced air drying at 150-300 ℃ to remove water, then the halide is placed in inert gas at 400-600 ℃ for sintering, then the halide is crushed and sieved to obtain anhydrous halide for later use, the anhydrous halide is added into electrolyte according to a certain proportion and uniformly mixed, then adsorbent is added and uniformly mixed, and finally carbon nano tubes are added to obtain the halide composite anode material.
Specifically, the diaphragm material is a mixture of electrolyte and MgO, and is obtained by inert drying treatment, wherein the treatment temperature is 175-200 ℃, and the drying time is more than 24 h.
Specifically, the weight ratio of electrolyte to MgO in the diaphragm material is 50-70: 30 to 50 parts by weight.
Specifically, the inert gas is argon or nitrogen.
The second purpose of the invention is to provide a preparation method of a high specific energy composite electrode plate for a thermal battery, which comprises the steps of firstly pouring a dried diaphragm material into a mould frame, flattening, then adding an RSEI material, flattening, then adding a halide composite anode material, finally covering a mould, placing on a press, applying pressure, and pressing into the composite electrode plate.
The whole preparation process is completed in a dry environment with the humidity less than 3 percent.
The invention further aims to provide an RSEI material for a thermal battery, which is prepared from carbon nanotubes and an electrolyte in a weight ratio of 70-95: 5-30, and drying in an inert gas environment at 100-600 ℃, wherein the electrolyte is 9.56 +/-1% of LiF and 22 +/-1% of LiCl in percentage by weight2And 68.44 +/-1% of LiBr.
The working principle and the beneficial effects of the invention are as follows: 1. the composite electrode plate prepared by the method not only can exert the advantages of respective raw materials, but also meets the requirements of the composite electrode plate of a thermal battery with long time and high specific energy, has the advantages of good electrochemical performance, strong stability, good conductivity, good formability, high heat value, long storage time, quick activation, large output density of current, strong capability of resisting severe environment, high safety and the like, has a proper heating temperature range, can be well matched with a thermal battery system, has good compatibility with a negative electrode, and does not generate side reaction. Has better formability, and can be pressed into a composite electrode slice with the diameter of 10 mm-120 mm and the thickness of 0.5 mm-3 mm.
2. The composite electrode plate has a relative lithium boron alloy cathode electromotive force of more than 2.5V; thermal stability>800 ℃; high conductivity (avoiding increase of internal resistance during discharge) and thermal stability; high thermal conductivity, facilitating rapid activation; the heat capacity is low, minimizing the heat input required from the heating fins; stably existing in the storage temperature range (-50 ℃ to 70 ℃), and is not easy to react with water, oxygen and CO2And the like.
3. The composite electrode plate has higher specific capacity compared with the conventional CoS2The specific capacity of the composite electrode plate is improved by 15%; compared with the conventional halide composite electrode plate, the specific capacity of the electrode plate is improved by 50 percent.
4. 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 composite electrode plate, the novel composite electrode plate has better thermal shock resistance and can reduce the decomposition of electrode materials; compared with the unit battery prepared by the conventional composite electrode plate, the weight of the unit battery of the novel high specific energy composite electrode plate is reduced by more than 15%.
Drawings
FIG. 1 shows conventional CoS2Comparative graphs for electrical performance tests of the composite electrode sheet and the high specific energy halide composite electrode sheet of example 1;
fig. 2 is a graph comparing electrical performance testing of conventional halide composite electrode sheets with the high specific energy halide composite electrode sheet of example 1.
Detailed Description
The following is further detailed by way of specific embodiments:
example 1
The preparation method of the composite electrode plate of the high specific energy thermal battery comprises the following steps:
1) drying the halide, first of all the halide NiCl2·6H2Blowing O at 200 deg.C to dry and remove water, and adding 450 deg.C inert gas ((argon gas)Nitrogen), then crushing, sieving by a 100-mesh sieve and bottling for later use;
2) compounding of halides, first NiCl prepared in step (1)2Adding electrolyte, mixing uniformly, then adding adsorbent MgO, mixing uniformly, finally adding carbon nano tube and halide: electrolyte: adsorbent: carbon nanotubes 85: 6: 6: 3, obtaining a halide composite positive electrode material;
3) RSEI material preparation, carbon nano tube: the electrolyte is prepared from the following components in a weight ratio of 80: 20, uniformly mixing, and finally drying in an inert gas environment at 450 ℃, wherein the inert gas is argon or nitrogen;
4) the preparation of the diaphragm material comprises the steps of mixing electrolyte and MgO according to the weight ratio of 1:1, and drying in an inert gas environment at the processing temperature of 175-200 ℃ for more than 24 hours, wherein the inert gas is argon or nitrogen.
5) The preparation of the composite electrode plate comprises the steps of firstly pouring the prepared diaphragm material into a mould frame, flattening, then adding the RSEI material, flattening, then adding the halide composite anode material, finally covering the mould, putting the mould on a press, applying a certain pressure, and pressing to form the composite electrode plate.
Wherein, the electrolyte comprises 9.56 percent of LiF and 22 percent of LiCl by weight percentage2And 68.44% of LiBr.
Example 2
The preparation method of the composite electrode plate of the high specific energy thermal battery comprises the following steps:
1) removing impurities from the halide, i.e. first removing the halide NiCl2·6H2O is put into a blast drying furnace at 200 ℃ for removing water, then is put into an inert gas (argon and nitrogen) environment at 450 ℃ for sintering, and then is crushed, sieved by a 100-mesh sieve and bottled for standby;
2) compounding of halides, first the NiCl prepared in step (1)2Adding electrolyte, mixing uniformly, then adding adsorbent MgO, mixing uniformly, finally adding carbon nano tube and halide: electrolyte: adsorbent: carbon nanotubes 85: 6: 6: 3;
3) RSEI material preparation, carbon nano tube: electrolyte ratio according to 80: 20, uniformly mixing, and finally drying in inert gas at 200 ℃, wherein the inert gas is argon or nitrogen;
4) the preparation of the diaphragm material comprises the steps of mixing electrolyte and MgO according to the weight ratio of 7:3, and drying in an inert gas environment at the processing temperature of 175-200 ℃ for more than 24 hours, wherein the inert gas is argon or nitrogen.
5) The preparation of the composite electrode plate comprises the steps of firstly pouring the prepared diaphragm material into a mould frame, flattening, then adding the RSEI material, flattening, then adding the halide composite anode material, finally covering the mould, putting the mould on a press, applying a certain pressure, and pressing to form the composite electrode plate.
Wherein the electrolyte comprises 9.56 + -1% LiF and 22 + -1% LiCl in percentage by weight2And 68.44 +/-1% of LiBr.
Example 3
The preparation method of the composite electrode plate of the high specific energy thermal battery comprises the following steps:
1) removing impurities from the halide, i.e. first removing the halide NiCl2·6H2O is put into a blast drying furnace at 200 ℃ for removing water, then is put into an inert gas (argon and nitrogen) environment at 450 ℃ for sintering, and then is crushed, sieved by a 100-mesh sieve and bottled for standby;
2) compounding of halides, first NiCl prepared in step (1)2Adding electrolyte, mixing uniformly, then adding adsorbent MgO, mixing uniformly, finally adding carbon nano tube and halide: electrolyte: adsorbent: carbon nanotubes of 90: 4: 4: 2;
3) RSEI material preparation, carbon nano tube: electrolyte ratio according to 80: 20, uniformly mixing, and finally drying in inert gas at 200 ℃, wherein the inert gas is argon or nitrogen;
4) the preparation of the diaphragm material comprises the steps of mixing electrolyte and MgO according to the weight ratio of 3:2, and drying in an inert gas environment at the processing temperature of 175-200 ℃ for more than 24 hours, wherein the inert gas is argon or nitrogen.
5) The preparation of the composite electrode plate comprises the steps of firstly pouring the prepared diaphragm material into a mould frame, flattening, then adding the RSEI material, flattening, then adding the halide composite anode material, finally covering the mould, putting the mould on a press, applying a certain pressure, and pressing to form the composite electrode plate.
Wherein the electrolyte comprises 9.56 + -1% LiF and 22 + -1% LiCl in percentage by weight2And 68.44 +/-1% of LiBr.
Example 4
The preparation method of the composite electrode plate of the high specific energy thermal battery comprises the following steps:
1) removing impurities from the halide, namely firstly removing the halide NiCl2·6H2O is put into a blast dryer at 200 ℃ to remove water, then is put into an inert gas (argon and nitrogen) environment at 450 ℃ to be sintered, and then is crushed, sieved by a 100-mesh sieve and bottled for standby;
2) compounding of halides, first NiCl prepared in step (1)2Adding electrolyte, mixing uniformly, then adding adsorbent MgO, mixing uniformly, finally adding carbon nano tube and halide: electrolyte: adsorbent: carbon nanotube 85: 6: 6: 3;
3) RSEI material preparation, carbon nano tube: electrolyte proportions were as follows 90: 10, uniformly mixing, and finally drying at 175 ℃ in inert gas, wherein the inert gas is argon or nitrogen;
4) the preparation of the diaphragm material comprises the steps of mixing electrolyte and MgO according to the weight ratio of 1:1, and drying in an inert gas environment at the processing temperature of 175-200 ℃ for more than 24 hours, wherein the inert gas is argon or nitrogen.
5) The preparation of the composite electrode plate comprises the steps of firstly pouring the prepared diaphragm material into a mould frame, flattening, then adding the RSEI material, flattening, then adding the halide composite anode material, finally covering the mould, putting the mould on a press, applying a certain pressure, and pressing to form the composite electrode plate.
Wherein the electrolyte comprises 9 wt% LiF and 22.5 wt% LiCl2And 68.5 percent of LiBr.
Example 5
The preparation method of the composite electrode plate of the high specific energy thermal battery comprises the following steps:
1) drying the halide by first drying the halide CuF2Drying at 200 deg.C by blowingAdding water, sintering in an inert gas (argon and nitrogen) environment at 450 ℃, crushing, sieving with a 100-mesh sieve, and bottling for later use;
2) complexing of halides, CuF prepared first in step (1)2Adding electrolyte, mixing uniformly, then adding adsorbent MgO, mixing uniformly, finally adding carbon nano tube and halide: electrolyte: adsorbent: carbon nanotubes 85: 6: 6: 3, obtaining a halide composite positive electrode material;
3) RSEI material preparation, carbon nano tube: the electrolyte is prepared from the following components in a weight ratio of 80: 20, uniformly mixing, and finally drying in an inert gas at 450 ℃, wherein the inert gas is argon or nitrogen;
4) the preparation of the diaphragm material comprises the steps of mixing electrolyte and MgO according to the weight ratio of 7:3, and drying in an inert gas environment at the processing temperature of 175-200 ℃ for more than 24 hours, wherein the inert gas is argon or nitrogen.
5) The preparation of the composite electrode plate comprises the steps of firstly pouring the prepared diaphragm material into a mould frame, flattening, then adding the RSEI material, flattening, then adding the halide composite anode material, finally covering the mould, putting the mould on a press, applying a certain pressure, and pressing to form the composite electrode plate.
Wherein the electrolyte comprises 10% LiF and 22% LiCl in percentage by weight2And 68% of LiBr.
Test examples
Preparation of 16 composite electrode sheets according to the preparation method of example 1 to assemble a unit cell for performing the same operation as conventional CoS2The discharge comparison is carried out on the composite sheet and the unit cells equipped with the conventional halide composite sheet, and the preparation methods of the three unit cells are completely the same except that the preparation methods of the composite electrode plate are different; conventional CoS2The dosage of the positive electrode material of the composite sheet and the dosage of the conventional halide composite sheet are completely the same as the dosage of the diaphragm material of the composite electrode plate. FIG. 1 shows conventional CoS2Test chart of the electrical properties of the composite sheet and the composite electrode sheet of example 1, two batteries were used at the same current density of 100mA/cm2Lower discharge with CoS2Compared with the composite sheet, the composite electrode sheet of the embodiment 1 has longer working time and higher performanceA voltage plateau. FIG. 2 is an electrical property test chart of the conventional halide composite sheet and the composite electrode sheet of example 1, with two batteries at the same current density of 100mA/cm2Lower discharge, compare with conventional composite sheet, the operating time of the composite electrode slice of embodiment 1 improves by a wide margin, has avoided positive pole material and diaphragm material to dissolve each other, promotes the specific energy of thermal battery.
The above description is only an example of the present invention, and the common general knowledge of the known specific structures and characteristics in the schemes is not described herein. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.

Claims (10)

1. A preparation method of a high specific energy composite electrode plate for a thermal battery is characterized by comprising the following steps: the raw materials mainly comprise a diaphragm material, an RSEI material and a halide composite anode material, wherein the RSEI material comprises a carbon nano tube and an electrolyte according to the weight ratio of 70-95: 5-30, and then drying in an inert gas environment at the temperature of 100-600 ℃ to obtain the electrolyte, wherein the electrolyte is a ternary molten salt consisting of 9.56 +/-1% of LiF, 22 +/-1% of LiCl and 68.44 +/-1% of LiBr in percentage by weight; the preparation method comprises the steps of firstly pouring the dried diaphragm material into a die frame, flattening, then adding the RSEI material, flattening, then adding the halide composite positive electrode material, finally covering the die, putting the die on a press, applying pressure, and pressing to form the composite electrode plate.
2. The preparation method of the high specific energy composite electrode sheet for the thermal battery according to claim 1, characterized in that: the halide composite positive electrode material comprises the following raw materials of anhydrous halide, electrolyte, adsorbent and carbon nano tubes, wherein the anhydrous halide: electrolyte: adsorbent: carbon nanotube = 70-90: 3-10: 3-10: 1 to 5.
3. The preparation method of the high specific energy composite electrode sheet for the thermal battery according to claim 2, characterized in that: the anhydrous halide is MnF3、NiCl2、CuF2、NiF2、FeF3And CoF3One or more of the components are compounded and then dried to obtain the product.
4. The preparation method of the high specific energy composite electrode sheet for the thermal battery according to claim 3, characterized in that: the adsorbent is MgO or Al2O3Wherein the specific volume of the adsorbent is more than 20 mL.g-1, and the specific surface area is more than 60m2(g) the particle size is less than 100 nm.
5. The preparation method of the high specific energy composite electrode sheet for the thermal battery according to claim 4, characterized in that: when the halide composite anode material is prepared, firstly, halide is subjected to forced air drying at the temperature of 150-300 ℃ to remove water, then the halide is placed in inert gas at the temperature of 400-600 ℃ to be sintered, then the anhydrous halide is crushed and sieved to obtain anhydrous halide for later use, the anhydrous halide is added into electrolyte according to a proportion and is uniformly mixed, then, adsorbent is added and is uniformly mixed, and finally, carbon nano tubes are added to obtain the halide composite anode material.
6. The preparation method of the high specific energy composite electrode sheet for the thermal battery according to claim 1, characterized in that: the diaphragm material is a mixture of electrolyte and MgO, and is obtained by inert drying treatment, the treatment temperature is 175-200 ℃, and the drying time is more than 24 h.
7. The preparation method of the high specific energy composite electrode sheet for the thermal battery according to claim 6, characterized in that: the weight ratio of electrolyte to MgO in the diaphragm material is 50-70: 30 to 50 parts by weight.
8. The preparation method of the high specific energy composite electrode sheet for the thermal battery according to any one of claims 1 to 6, characterized in that: the inert gas is argon or nitrogen.
9. A high specific energy composite electrode sheet for a thermal battery prepared by the method of claim 8.
10. An RSEI material for a thermal battery, characterized in that: the RSEI material is prepared from a carbon nano tube and an electrolyte according to the weight ratio of 70-95: 5-30%, drying in an inert gas environment at 100-600 ℃, and obtaining the electrolyte, wherein the electrolyte is ternary molten salt consisting of 9.56 +/-1% of LiF, 22 +/-1% of LiCl and 68.44 +/-1% of LiBr in percentage by weight, when the high-specific-energy composite electrode plate for the thermal battery is prepared, firstly, the dried diaphragm material is poured into a die frame, the diaphragm material is flattened, then, the RSEI material is added, the diaphragm material is flattened, then, the halide composite positive electrode material is added, finally, the die is covered, the die is placed on a press, pressure is applied, and the composite electrode plate is pressed.
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