CN113270578A - 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

Info

Publication number
CN113270578A
CN113270578A CN202110534397.2A CN202110534397A CN113270578A CN 113270578 A CN113270578 A CN 113270578A CN 202110534397 A CN202110534397 A CN 202110534397A CN 113270578 A CN113270578 A CN 113270578A
Authority
CN
China
Prior art keywords
halide
composite electrode
electrolyte
high specific
specific energy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110534397.2A
Other languages
Chinese (zh)
Other versions
CN113270578B (en
Inventor
唐军
冉岭
王毅
唐立成
赵文莉
潘志鹏
王京亮
赵洪楷
李云伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guizhou Meiling Power Supply Co Ltd
Original Assignee
Guizhou Meiling Power Supply Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guizhou Meiling Power Supply Co Ltd filed Critical Guizhou Meiling Power Supply Co Ltd
Priority to CN202110534397.2A priority Critical patent/CN113270578B/en
Publication of CN113270578A publication Critical patent/CN113270578A/en
Application granted granted Critical
Publication of CN113270578B publication Critical patent/CN113270578B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The application discloses high specific energy composite electrode slice for thermal battery in thermal battery technical field, the composite electrode slice is a basic unit for forming single thermal battery, the performance of the composite electrode slice finally determines the performance of the unit battery, the composite electrode slice mainly comprises diaphragm material, RSEI material and halide composite anode material, wherein the RSEI material comprises carbon nano tube and halide composite anode materialThe electrolyte is 70-95% by weight: 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 applied to civil fields.
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 collector, a heating system (an electric ignition head or a fire cap, ignition paper and a heating plate), a heat-insulating gasket, a battery shell and a battery cover with a connecting post, wherein the positive plate and the diaphragm plate are combined together to form a composite electrode plate. Compound medicineThe alloy 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 properties (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 existing in the storage temperature range (-50 ℃ to 70 ℃), and is 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、CoS2The electrode plate is a thermal battery anode material which is most widely applied, but the working voltage of the two single batteries is below 2V, the high-power output is greatly limited, meanwhile, the specific capacity reaches a certain limit (theoretical specific capacity 1206As/g (333mAh/g)), the development of miniaturization and lightweight thermal batteries is not facilitated, and the halide in the conventional halide anode composite electrode plate has compatibility with molten salt and does not have long-time working capacity. 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 and an RSEI materialAnd 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 particle size 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 longer than 24 hours.
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 the high specific energy composite electrode plate for the thermal battery, which comprises the steps of firstly pouring the dried diaphragm material into a mould frame, flattening, then adding the RSEI material, flattening, then adding the halide composite anode material, finally covering a mould, putting the mould on a press, applying pressure and pressing to form 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 negative electrode 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 electrical property test graphs 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 tests of the conventional halide composite electrode sheet 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 NiCl2·6H2O 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 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% LiF and 22% LiCl by weight2And 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, namely firstly 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 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, namely firstly removing the halide NiCl2·6H2Blowing O at 200 deg.C for drying, removing water, and adding 450 deg.C inert gasSintering in an environment of (argon and nitrogen), then crushing, sieving with 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 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 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 85: 6: 6: 3;
3) RSEI material preparation, carbon nano tube: electrolyte ratio according to 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 CuF2Blowing at 200 deg.C, drying to remove water, sintering in 450 deg.C inert gas (argon, nitrogen) environment, pulverizing, sieving with 100 mesh sieve, and bottling;
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 voltage platform. 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 foregoing is merely an example of the present invention and common general knowledge of known specific structures and features of the embodiments is not described herein in any greater detail. 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. The utility model provides a high specific energy composite electrode piece for thermal battery which characterized in that: the raw materials are mainly composed ofThe composite anode material comprises a diaphragm material, an RSEI material and a halide composite anode 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.
2. The high specific energy composite electrode sheet for thermal batteries 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: 70-90% of carbon nanotubes: 3-10: 3-10: 1 to 5.
3. The high specific energy composite electrode sheet for thermal batteries according to claim 2, wherein: the anhydrous halide is MnF3、NiCl2、CuF3、NiF2、FeF3And CoF3One or more of the components are compounded and then dried to obtain the product.
4. The high specific energy composite electrode sheet for thermal batteries according to claim 3, wherein: 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 high specific energy composite electrode sheet for thermal batteries according to claim 4, wherein: 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 high specific energy composite electrode sheet for thermal batteries 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 high specific energy composite electrode sheet for thermal batteries according to claim 6, wherein: the weight ratio of electrolyte to MgO in the diaphragm material is 50-70: 30 to 50 parts by weight.
8. 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. The method for preparing the high specific energy composite electrode sheet for the thermal battery according to claim 8, wherein the method comprises the following steps: firstly, pouring the dried 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 pressure and pressing to form the composite electrode plate.
10. An RSEI material for a thermal battery, characterized in that: the carbon nano tube and electrolyte are mixed according to the 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.
CN202110534397.2A 2021-05-17 2021-05-17 High specific energy composite electrode plate for thermal battery and preparation method thereof Active CN113270578B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110534397.2A CN113270578B (en) 2021-05-17 2021-05-17 High specific energy composite electrode plate for thermal battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110534397.2A CN113270578B (en) 2021-05-17 2021-05-17 High specific energy composite electrode plate for thermal battery and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113270578A true CN113270578A (en) 2021-08-17
CN113270578B CN113270578B (en) 2022-07-12

Family

ID=77231204

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110534397.2A Active CN113270578B (en) 2021-05-17 2021-05-17 High specific energy composite electrode plate for thermal battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113270578B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114464828A (en) * 2022-01-18 2022-05-10 贵州梅岭电源有限公司 Large-diameter electrode plate of thermal battery and preparation method thereof
CN115621479A (en) * 2021-12-23 2023-01-17 贵州梅岭电源有限公司 Thermal battery intermediate layer and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005194139A (en) * 2004-01-07 2005-07-21 Fujikura Ltd Method of manufacturing anhydrous nickel chloride
CN107978766A (en) * 2017-11-23 2018-05-01 上海空间电源研究所 A kind of three-decker formula single cell of thermo battery
CN110112431A (en) * 2019-04-28 2019-08-09 贵州梅岭电源有限公司 A kind of preparation method of coating type thermal cell compound electric pole piece
US20200358103A1 (en) * 2018-02-23 2020-11-12 Lg Chem, Ltd. Secondary Battery
CN112234162A (en) * 2020-10-19 2021-01-15 沈阳理工大学 Thermal battery nickel dichloride positive electrode film material and preparation method thereof
CN112563489A (en) * 2020-12-16 2021-03-26 北方特种能源集团有限公司西安庆华公司 Preparation method of nickel chloride anode for novel thermal battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005194139A (en) * 2004-01-07 2005-07-21 Fujikura Ltd Method of manufacturing anhydrous nickel chloride
CN107978766A (en) * 2017-11-23 2018-05-01 上海空间电源研究所 A kind of three-decker formula single cell of thermo battery
US20200358103A1 (en) * 2018-02-23 2020-11-12 Lg Chem, Ltd. Secondary Battery
CN110112431A (en) * 2019-04-28 2019-08-09 贵州梅岭电源有限公司 A kind of preparation method of coating type thermal cell compound electric pole piece
CN112234162A (en) * 2020-10-19 2021-01-15 沈阳理工大学 Thermal battery nickel dichloride positive electrode film material and preparation method thereof
CN112563489A (en) * 2020-12-16 2021-03-26 北方特种能源集团有限公司西安庆华公司 Preparation method of nickel chloride anode for novel thermal battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115621479A (en) * 2021-12-23 2023-01-17 贵州梅岭电源有限公司 Thermal battery intermediate layer and preparation method thereof
CN114464828A (en) * 2022-01-18 2022-05-10 贵州梅岭电源有限公司 Large-diameter electrode plate of thermal battery and preparation method thereof
CN114464828B (en) * 2022-01-18 2024-04-09 贵州梅岭电源有限公司 Large-diameter electrode plate of thermal battery and preparation method thereof

Also Published As

Publication number Publication date
CN113270578B (en) 2022-07-12

Similar Documents

Publication Publication Date Title
CN102522530B (en) Nano-sulfur composite cathode material for rare earth lithium-sulfur battery, and preparation method thereof
CN107895779B (en) High-capacity potassium ion battery negative electrode material and preparation method and application thereof
WO2016201979A1 (en) Preparation method for silicon-carbon composite anode material
CN106410164B (en) A kind of anode material and its preparation method and application
CN111029569A (en) Lithium ion battery lithium supplement additive, battery electrode and preparation method and application thereof
CN113270578B (en) High specific energy composite electrode plate for thermal battery and preparation method thereof
CN103050694B (en) A kind of positive electrode active materials and preparation method thereof, battery
CN107910502B (en) Manufacturing method of composite positive electrode of lithium battery and battery
CN104600296A (en) Preparation method of Se-C positive electrode composite material of lithium-selenium battery
CN102130359A (en) Lithium sulfur battery and preparation method thereof
CN105244474A (en) High-specific capacity lithium-sulfur secondary battery composite cathode and preparation method thereof
CN104810515A (en) Preparation method of doped Li4Ti5O12 anode material
CN106941171B (en) Lithium battery cathode composite material based on nano silicon carbon and preparation method thereof
CN110556537B (en) Method for improving electrochemical performance of anion-embedded electrode material
CN103000863B (en) Sn-Co/C alloy cathode material of lithium ion battery and preparation method thereof
CN104485443A (en) Preparation method for graphene polymer cladding niobium-doping cobalt and lithium aluminate composite anode material
CN111477859A (en) Composite positive electrode material, preparation method thereof and water-based secondary battery
CN111446450A (en) Functional material, positive plate containing functional material and lithium ion battery
CN110212171A (en) A kind of lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cell
CN104993148A (en) Synthesizing method for lithium-ion positive electrode material of LiCoO2/C
CN106972166A (en) A kind of lithium ion battery negative material and preparation method thereof
Shuai et al. An air-stable prelithiation technology for lithium ion-sulfurized polyacrylonitrile battery
CN109273707B (en) Nano carbon composite ternary material and preparation method thereof
CN109119607B (en) Polypyrrole nanotube coated lithium nickel manganese oxide positive electrode material and preparation method thereof
JP7256609B2 (en) All-solid-state battery with impurity scavenger

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant