CN115763816A - Ion conductive agent for multifunctional thermal battery and preparation and application thereof - Google Patents

Abstract

The invention discloses a multifunctional thermal battery ion conductive agent and its application. The multifunctional thermal battery ion conductive agent is composed of Ni element with a single voltage correction function, Li element with high ion conductivity, and F, Cl, and Br halogens An ionic bond eutectic salt with uniform chemical composition, wherein the mass ratio of nickel element solvated in a high-temperature liquid state is 1% to 10%. The ion conductivity of the multifunctional thermal battery ion conductor is 0.1-5S/cm, and the melting point is 440-650°C. It can be used as an additive for the positive electrode of the thermal battery, a transition layer between the positive electrode and the separator, and an isolation layer between the positive electrode layer and the heating layer.

Description

A kind of ion conductive agent for multifunctional heat battery and its preparation and application

technical field

The invention belongs to the technical field of chemical power thermal batteries, and in particular relates to an ion-conducting agent for a multifunctional thermal battery and its preparation and application.

Background technique

Thermal battery is a kind of special chemical power source, which is widely used in aerospace field because of its excellent power output performance and long storage life. Common thermal battery cathode materials (such as sulfides) have high interface resistance at high temperatures and are easy to thermally decompose. Therefore, molten salt materials with high-temperature phase transitions need to be added as ion-conducting agents to improve interface impedance and resist high-temperature thermal shock. Common ion-conducting agents are binary electrolytes (LiCl-KCl) and ternary all-lithium electrolytes (LiF-LiCl-LiBr). However, with the rise of new long-term terminal high-current load thermal batteries, research on thermal battery anode materials with high initial voltage and strong later load capacity and their auxiliary technologies has become one of the current thermal battery technology development trends.

Since the electrolyte can act as an ion-conducting agent for positive electrode materials, the current ion-conducting agents are mainly binary electrolytes, ternary all-lithium electrolytes, and other alkali metal halides (Masset Patrick, Guidotti RonaldA. Thermal activated (thermal) battery technology: Part II . Molten saltelectrolytes [J]. Journal of Power Sources, 2007, 164 (1): 397-414). In addition to maintaining high ionic conductivity and improving contact wettability with the positive electrode, the alkali metal halide electrolyte cannot effectively regulate the positive electrode potential and cannot provide electronic conductivity, which in turn limits the later current carrying capacity of the terminal large pulse load thermal battery . CN202011570678.5 reports a LiCl-Li ₂ CO ₃ -Li ₂ SO ₄ electrolyte that is resistant to high pressure and resistance to decomposition. It is mainly developed for high-voltage positive electrode materials. Due to the presence of oxygen-containing acid groups such as carbonate and sulfate, the electromigration speed is slow , low ionic conductivity, not suitable for use as an ion conductive agent for high-power thermal batteries. CN202011488418.3 prepared 10% to 40% ternary all-lithium electrolyte as ion conductive agent, 10% to 30% alumina anti-overflow agent, 50% to 80% nickel chloride positive electrode material, and obtained solid Phase alumina adsorption liquid phase ternary all-lithium electrolyte melt-infiltrated positive electrode material of solid-phase nickel chloride, the research is essentially ternary all-lithium electrolyte as ion conductive agent, only suitable for short-term batteries, can not be used for long-term Terminal high current load thermal battery.

In the preparation method of ion-conducting agents, except for traditional molten salts such as alkali metal halide electrolytes and modified molten salts such as oxo-salts, there is no report on the introduction of heavy metal particles to regulate the properties of ion-conducting agents, and no high-temperature A report on halide eutectic salts utilizing solvated nickel ions and their application in thermal batteries.

Contents of the invention

The thermal battery with long-term terminal high-current load has the characteristics of small initial current of discharge and large load current at the later stage. The present invention provides a kind of Ionic conductive agent for multifunctional thermal battery and its preparation and application. First, by introducing the heavy metal element nickel into the molten salt system with fast ion migration speed, the melting point of the molten salt is increased, and the thermal impact of the heating material on the positive electrode material at the initial stage of activation is reduced to prevent the decomposition of the positive electrode active material; secondly, the material is changed by introducing the heavy metal element nickel The viscosity can reduce the high-temperature fluidity of the ion-conducting agent and improve the binding force with the interface of the active material. It is especially important that by utilizing the high-temperature solvation of heavy metal nickel ions by F, Cl, and Br ions, the uniform distribution of metal nickel ions is achieved, and a nickel-containing solvation complex with a single voltage regulation function is constructed, so the multifunctional In addition to the basic function of ionic conductivity, the ionic conductive agent can also provide a corrected voltage in the initial small current or no-load operation, and use weak electrochemical action or self-discharge effect to produce high-conductivity metal nickel, which can be used for the later electrochemical process of the battery. Provide highly active electronic conductive agent to achieve large battery load output in the later stage.

The purpose of the present invention is to be achieved through the following technical solutions:

The present invention relates to an ion-conducting agent (for multi-functional thermal batteries), the ion-conducting agent is composed of Ni element with monomer voltage correction function, Li element with high ion conductivity and halogen with uniform chemical composition and ionic bond. The molten salt, wherein the mass ratio of nickel solvated in a high-temperature liquid state is 1% to 10%, and the halogen is at least one of F, Cl, and Br.

First of all, the ionic bond eutectic salt is a molten salt containing Ni, Li, F, Cl, Br and other elements with uniform chemical composition formed by high temperature eutectic. Secondly, the nickel element in the ion-conducting agent is solvated in the high-temperature liquid phase melt, and there is no solid-phase nickel-containing substance, and the solvated nickel has the function of voltage correction and regulation. The mass ratio of the nickel element is 1% to 10%. When the ratio of the nickel element is lower than 1%, there is little difference in properties from the alkali metal halide electrolyte, and it will affect the large current load capacity in the later stage. When the proportion of nickel element is greater than 10%, it will form NiF ₂ , NiCl ₂ , NiBr ₂ and other solid phase substances, which will increase the melting point and viscosity of the ion conductive agent. When the proportion of nickel element is too large, it will form a muddy melt, not applicable Used as an ion-conducting agent.

As an embodiment, the molar ratio of element F to Br is about 22a:47b, and the molar ratio n of Cl element is determined by the molar ratio m of cationic Ni element, and its value n=31c+m×2, a, b, and c values are respectively 0.95~1.05, m value is 1~10. The values of a, b, and c have a lower melting point in this range, and the melting point will increase if they are not in the range. When the nickel element ratio m<1, there is little difference in properties from the alkali metal halide electrolyte, and it will affect the large current load capacity of the battery in the later stage. When the proportion of nickel element m>10, it will form NiF ₂ , NiCl ₂ , NiBr ₂ and other solid phase substances, which will increase the melting point and viscosity of the ion conductive agent. When the proportion of nickel element is too large, it will form a muddy melt, which is not applicable Used as an ion-conducting agent.

As an embodiment, the molar ratio of Ni element to Li element is about m:100d, and the value of d is 0.95˜1.05. The melting point of the d value is lower in this range, and the melting point will increase if it is not in the range.

As an embodiment, the ionic conductivity of the ion-conducting agent is 0.1-5 S/cm, the particle size is 1-200 μm, the melting point is 440-650° C., and the viscosity is 1-200 mPa·s.

The present invention also relates to a preparation method of an ion-conducting agent, said method comprising the steps of:

S1. Pretreatment: vacuum-dry the raw materials containing Ni ²⁺ , Li ⁺ cations and halogen X ^- anions at high temperature, transfer them into a dry atmosphere, and weigh them according to the ratio of anions and cations for later use;

S2, melting and roasting: After ball milling and mixing the raw materials containing Li ⁺ cations and halogen X ^- anions, they are transferred to a crucible, and the raw materials containing Ni ²⁺ cations and halogen X ^- anions are added thereon, (transferred into a high-temperature furnace) for High-temperature melting and roasting, so that the material forms a uniform melt;

S3, extremely rapid cooling: Pour the low-temperature liquefied gas into the container to form a liquid-phase gas pool, and then quickly disperse and drop the high-temperature melt obtained in step S2 into the liquid-phase gas pool by using a grid-type dispersion method;

S4. Post-processing: the molten salt crystal particles obtained after cooling in the liquid phase are quickly pulverized in a cold state, and sieved with 80-200 mesh to obtain the ion-conducting agent for the multifunctional thermal battery.

This method uses the high-temperature solvation of heavy metal Ni ions by F, Cl, and Br ions to achieve uniform distribution of metal nickel ions, and then uses grid dispersion to achieve high-temperature melt cutting, and uses liquefied gas for extremely rapid cooling. The high-temperature molten salt can be quickly set to form a uniform nickel-containing ion-conducting agent.

As an embodiment, the Ni-containing raw material in step S1 is any one or a combination of at least two of NiF ₂ , NiCl ₂ , NiBr ₂ , and Li _x NiX _x+2 . In halide molten salts, nickel ions can combine with halides to form complexes through high-temperature solvation, so common nickel-containing raw materials are NiF ₂ , NiCl ₂ , NiBr ₂ , Li _x NiX _x+2 .

As an embodiment, the Li _x NiX _x+2 includes Li ₂ NiCl ₄ , Li ₂ NiCl ₂ X' ₂ and their derivatives, and X' can be one or more of F and Br. The value of x is 1-2, preferably 2, non-integer ratio needs eutectic synthesis, if x is lower than 1, or higher than 2, Li _x NiX _x+2 can be used as raw material, its properties are similar to NiX ₂ or LiX, but Materials are not readily available.

As an embodiment, the vacuum drying temperature in step S1 is 60-300° C., preferably 150-250° C., and the drying time is 1-24 hours, preferably 4-12 hours. The temperature is higher than 300°C, the drying speed is fast, the energy consumption is high, and the operation is complicated. If the moisture content of the raw material is high, there is a risk of hydrolysis, the temperature is lower than 60°C, and the drying efficiency is low.

As an embodiment, the high-temperature calcination temperature in step S2 is 450-800° C., the calcination time is 1-24 hours, preferably the calcination temperature is 450-600° C., and the calcination time is 30 minutes-8 hours. If the high-temperature calcination temperature is lower than 450°C, a melt cannot be formed. If the temperature is higher than 800°C, the nickel-containing ion-conducting agent may sublimate, resulting in a change in the nickel content and causing quality and reliability problems.

As an embodiment, in step S3, the container is an open container with a regular or irregular depth of 2 to 20 cm of chemically inert materials such as stainless steel, quartz, corundum, graphite, ceramics, and metal, such as a stainless steel plate, a basin, Bowls, crucibles, etc. The container is mainly used to hold liquid gas and keep the molten salt immersion cooling. The depth is less than 2cm, and the efficiency is low, which may cause the melt to not be cooled quickly. The depth is greater than 20cm, which can also ensure cooling, which may cause waste of liquid gas.

As an implementation example, the grid-type dispersion method in step S3 can use a high-temperature grid to cut the melt into lines and points to prevent the melt from entering the liquid gas in a block structure with a size greater than 1 cm, ensuring The melt cools rapidly.

As an embodiment, in step S4, the low-temperature liquefied gas is any one or a combination of at least two of liquid nitrogen, liquid argon, liquefied carbon dioxide, liquefied oxygen, and liquefied air. The liquefied gas is mainly used for rapid cooling to ensure that the molten salt components are quickly shaped and segregated.

The present invention also relates to the use of an ion-conducting agent, which is used as a positive-electrode ion-conducting agent for a thermal battery, and is used alone as a positive-electrode diaphragm transition layer and/or as a heating positive-electrode buffer layer.

The present invention also relates to the use of an ion-conducting agent. The ion-conducting agent is physically mixed or chemically combined with a metal or carbonaceous conducting agent to form a dual-conducting agent for electrons and ions.

As an embodiment, the metal conductive agent includes gold, silver, platinum, manganese, iron, cobalt, nickel, copper, zinc, lead, tin, indium, antimony, bismuth, lithium, sodium, potassium, magnesium, calcium, aluminum Such as transition metals or main group metals or metal alloys.

As an embodiment, the carbonaceous conductive agent includes any one of carbon nanotubes, carbon nanofibers, graphene, carbon nanowires, Ketjen black, conductive carbon black Super P, porous carbon, fullerenes, and conductive graphite. one or a combination of at least two.

The invention contains solvated heavy metal element nickel, which has the ability to accept electrons preferentially, provides correction voltage, and can use weak electrochemical action or self-discharge effect to produce highly conductive metal nickel, which provides high activity for the later electrochemical process of the battery. Electronic conductive agent to realize the output of large battery load in the later stage. For example, molten salt ion conductors composed of LiF, LiCl, LiBr, NaCl or KCl, etc., can only provide high ion conductivity due to the absence of heavy metal ions, and do not have the function of correcting voltage, and have no electrochemical products. Electronically conductive metal nickel.

Compared with the prior art, the present invention has the following beneficial effects:

1) The method for preparing the nickel-ion-containing conductive agent of the present invention utilizes the high-temperature solvation of heavy metal Ni ions by F, Cl, and Br ions to realize uniform distribution of metal nickel ions, and uses liquefied gas for extremely rapid cooling to realize rapid shaping of high-temperature molten salts , forming a uniform nickel-containing ion-conducting agent; the nickel-containing ion-conducting agent prepared by the method has uniform composition and high quality and reliability;

2) The equipment involved in the method of the present invention is simple, the process flow is concise, the efficiency is high, the cost is low, and it is suitable for large-scale production;

3) In addition to the basic function of ion conductivity, the nickel-containing ion-conducting agent prepared by the present invention can also regulate and control the design voltage at the initial stage of small current or no-load operation;

4) The nickel-containing ion-conducting agent prepared by the present invention can also increase the melting point and viscosity of the molten salt, reduce the thermal impact of the heating material on the positive electrode material at the initial stage of activation, prevent the decomposition of the positive active material, and improve the binding force of the active material interface;

5) The nickel-containing ion-conducting agent prepared by the present invention can produce highly conductive metal nickel by weak electrochemical action or self-discharge effect, and provide a highly active electronic conducting agent for the later electrochemical process of the battery, so as to realize a large battery load output in the later stage.

Description of drawings

Other characteristics, objects and advantages of the present invention will become more apparent by reading the detailed description of non-limiting embodiments made with reference to the following drawings:

Figure 1 is a schematic diagram of the position of the positive electrode heating buffer layer in the thermal battery;

Figure 2 is a schematic diagram of the position of the transition layer of the positive electrode separator in the thermal battery;

Fig. 3 is a schematic diagram of a conventional battery structure;

Figure 4 is the discharge curve of the long-term terminal high-current thermal battery.

Detailed ways

The present invention will be described in detail below in conjunction with examples. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that those skilled in the art can make some adjustments and improvements without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

Example 1

This embodiment relates to a multi-functional ion-conducting agent for thermal batteries, which is an ion bond eutectic with uniform chemical composition composed of Ni element with monomer voltage correction function, Li element with high ion conductivity, and F, Cl, and Br halogens. Salt, wherein the mass ratio of nickel element solvated in high temperature liquid state is about 3%. Among them, the molar ratio of halogen (F: Cl: Br) is about 22:37.6:47, and the molar ratio of metal (Ni: Li) is 3.3:100. The melting point of the ion conductive agent for multifunctional thermal battery is about 460°C, the particle size is no more than 74μm, the viscosity is 40mPa·s at 500°C, and the ion conductivity is about 2.5S/cm.

The preparation steps of the ion-conducting agent of the present embodiment are as follows:

S1. Pretreatment: vacuum-dry the raw materials containing NiCl ₂ , LiF, LiCl, and LiBr at 180°C for 12 hours, transfer them into a dry atmosphere with water and oxygen values lower than 1ppm, and weigh them according to the ratio of anions and cations for later use. Among them, the molar ratio of halogen (F: Cl: Br) is about 22:37.6:47, and the molar ratio of metal (Ni: Li) is 3.3:100.

S2. Melting and roasting: put the weighed LiF, LiCl and LiBr raw materials into the bottom of the crucible, then transfer _NiCl2 into the crucible, cover the upper part of the lithium-containing raw materials, transfer them into a high-temperature furnace, and perform high-temperature melting and roasting at 550 ° C for 4 hours , so that the material forms a homogeneous melt.

S3. Extremely rapid cooling: Pour liquid nitrogen into a stainless steel basin with a depth of 20cm to form a 10cm liquid-phase gas pool, then disperse the high-temperature melt through a grid of about ^0.5cm2 , and quickly drip into the liquid-phase gas pool .

S4. Post-processing: the molten salt crystal particles obtained after cooling in the liquid phase are crushed in a cold state, and sieved with 100 meshes to obtain a nickel-containing ion-conducting agent.

The multifunctional ion-conducting agent of this embodiment can be applied to positive electrode materials. In the case of using an all-lithium electrolyte (LiF-LiCl-LiBr) separator and a lithium-boron alloy anode, the cathode material is composed of 75% iron disulfide and 25% multifunctional ion conductor, and the no-load voltage is about 2.30V , when the positive electrode material is composed of 75% iron disulfide and 25% binary electrolyte (LiCl-KCl), the no-load voltage is 2.02V.

Example 2

This embodiment provides a multi-functional ion-conducting agent for thermal batteries, which is an ionic bond eutectic with uniform chemical composition composed of Ni element with monomer voltage correction function, Li element with high ion conductivity, and F, Cl, and Br halogens. Salt, wherein the mass ratio of nickel element solvated in high temperature liquid state is about 1%. Among them, the molar ratio of halogen (F: Cl: Br) is about 22:33.02:47, and the molar ratio of metal (Ni: Li) is about 1.01:100. The melting point of the ion-conducting agent for multifunctional thermal batteries is about 450°C, the particle size is below 50μm, the viscosity is 20mPa·s at 500°C, and the ion conductivity is about 3S/cm.

The preparation steps of the ion-conducting agent of the present embodiment are as follows:

S1. Pretreatment: vacuum-dry the raw materials containing NiCl ₂ , LiF, LiCl, and LiBr at 180°C for 12 hours, transfer them into a dry atmosphere with water and oxygen values lower than 1ppm, and weigh them according to the ratio of anions and cations for later use. Among them, the molar ratio of halogen (F: Cl: Br) is about 22:33.02:47, and the molar ratio of metal (Ni: Li) is about 1.01:100.

S2. Melting and roasting: put the weighed LiF, LiCl and LiBr raw materials into the bottom of the crucible, then transfer _NiCl2 into the crucible, cover the upper part of the lithium-containing raw materials, transfer them into a high-temperature furnace, and perform high-temperature melting and roasting at 550 ° C for 4 hours , so that the material forms a homogeneous melt.

S3. Rapid cooling: Pour liquid nitrogen into a stainless steel basin with a depth of 20cm to form a 10cm liquid-phase gas pool, and then disperse the high-temperature melt through a 1cm ² grid, and quickly drip into the liquid-phase gas pool.

S4. Post-processing: the molten salt crystal particles obtained after cooling in the liquid phase are crushed in a cold state, and sieved with 100 meshes to obtain a nickel-containing ion-conducting agent.

The multifunctional ion-conducting agent of the present embodiment can be applied in positive electrode material, under the situation of adopting all-lithium electrolyte (LiF-LiCl-LiBr) diaphragm and lithium-boron alloy negative pole, positive electrode material is made of 75% cobalt disulfide, 24% When the multifunctional ionic conductive agent is combined with 1% silver-carbon nanomaterials, the no-load voltage is about 2.35V, and the positive electrode material is composed of 75% cobalt disulfide, 25% binary electrolyte (LiCl-KCl) and 1% When the silver-carbon nanomaterials are composited, the no-load voltage is 2.05V.

Example 3

This embodiment provides a multi-functional ion-conducting agent for thermal batteries, which is an ionic bond eutectic with uniform chemical composition composed of Ni element with monomer voltage correction function, Li element with high ion conductivity, and F, Cl, and Br halogens. Salt, wherein the mass ratio of nickel element solvated in a high-temperature liquid state is about 5%, and the molar ratio of lithium element (Ni:Li) is about 5.7:100. The halogen molar ratio (F: Cl: Br) is about 22:42.4:47.

The preparation steps of the ion-conducting agent of the present embodiment are as follows:

S1. Pretreatment: Vacuum dry the raw materials containing Li ₂ NiCl ₄ , LiF, LiCl, and LiBr at 200°C for 8 hours, transfer them into a dry atmosphere with a water oxygen value lower than 1 ppm, and weigh them according to the ratio of anions and cations for later use. Among them, the molar ratio of halogen (F: Cl: Br) is about 22:42.4:47, and the molar ratio of metal (Ni: Li) is 5.7:100.

S2. Melting and roasting: put the weighed LiF, LiCl and LiBr raw materials into the bottom of the crucible, then transfer Li ₂ NiCl ₄ into the crucible, cover the upper part of the lithium-containing raw materials, transfer them into a high-temperature furnace, and perform high-temperature roasting at 600°C 8h, the material forms a homogeneous melt.

S3. Rapid cooling: Pour liquid nitrogen into a ceramic container with a depth of 15cm to form a 10cm liquid-phase gas pool, then disperse the high-temperature melt through a 1cm ² grid, and quickly drop into the liquid-phase gas pool.

S4. Post-processing: the molten salt crystal particles obtained after cooling in the liquid phase are crushed in a cold state, and sieved with 200 meshes to obtain a nickel-containing ion-conducting agent.

The multifunctional ion-conducting agent of this embodiment can be used as a positive electrode heating buffer layer (FIG. 1), and can also be applied to a positive electrode separator transition layer (FIG. 2). It can be seen from Figure 1 that the thermal battery sequentially includes a negative electrode current collector layer, a negative electrode layer, a separator layer, a positive electrode layer, a positive electrode heating buffer layer, a positive electrode current collector layer and a heating layer. The thermal battery in FIG. 2 sequentially includes a negative electrode current collector layer, a negative electrode layer, a positive electrode separator transition layer, a positive electrode layer, a positive electrode current collector layer and a heating layer. Fig. 3 is a schematic structural diagram of a conventional thermal battery, which sequentially includes a negative electrode current collector layer, a negative electrode layer, a separator layer, a positive electrode layer, a positive electrode current collector layer and a heating layer.

In the case of using an all-lithium electrolyte (LiF-LiCl-LiBr) separator and a lithium-boron alloy negative electrode, the positive electrode material consists of 18% by mass of LiCl-KCl binary electrolyte, 80% of positive electrode active material FeS ₂ , and 1% of carbon nanotubes And the additive Li ₂ O is melted and roasted at high temperature, and the no-load cell voltage of the positive electrode buffer layer thermal battery (Figure 1), the positive electrode diaphragm transition layer thermal battery (Figure 2), and the conventional battery (Figure 3) are respectively 2.41V , 2.24V, 2.05V, heating the positive electrode buffer layer thermal battery and the positive electrode diaphragm transition layer thermal battery has a strong pulse load capacity, and conventional batteries cannot carry large currents (Figure 4).

Specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art may make various changes or modifications within the scope of the claims, which do not affect the essence of the present invention.

Claims (10)

1. The ionic conduction agent is an ionic bond eutectic salt with uniform chemical components, wherein the ionic conduction agent is composed of a Ni element with a monomer voltage correction function, a Li element with high ionic conductivity and halogen, the mass ratio of the nickel element solvated in a high-temperature liquid state is 1% -10%, and the halogen is at least one of F, cl and Br.

2. The ionic conduction agent as claimed in claim 1, wherein the molar ratio of F to Br is about 22a to 47b, and the molar ratio of Cl element n is determined by the molar ratio of cationic Ni element m, and has values of n =31c + m × 2, values of a, b, c being respectively 0.95 to 1.05, and values of m being 1 to 10.

3. The ionic conduction agent as claimed in claim 1, wherein the molar ratio of the Ni element to the Li element is about m:100d, and the d value is 0.95 to 1.05.

4. The ionic conduction agent as claimed in claim 1, wherein the ionic conduction agent has an ionic conductivity of 0.1 to 5S/cm, a particle size of 1 to 200 μm, a melting point of 440 to 650 ℃, and a viscosity of 1 to 200 mPas.

5. A method for producing the ion conductive agent according to any one of claims 1 to 4, comprising the steps of:

s1, pretreatment: will contain Ni ²⁺ ，Li ⁺ Cation and halogen X ^- Vacuum drying the anion raw material at high temperature, transferring into dry atmosphere, weighing according to the ratio of anions and cations for use, and X ^- Is F ^- 、Cl ^- 、Br ^- At least one of (1);

s2, melting and roasting: will contain Li ⁺ Cation and halogen X ^- After the raw materials of anions are ball-milled and mixed uniformly, the mixture is transferred into a crucible, and Ni-containing materials are added on the crucible ²⁺ Cation and halogen X ^- Carrying out high-temperature melting roasting on anion raw materials to form a uniform melt;

s3, extremely fast cooling: pouring the low-temperature liquefied gas into a container to form a liquid-phase gas pool, and then quickly dispersing and dripping the high-temperature melt obtained in the step S2 into the liquid-phase gas pool by adopting a grid type dispersion method;

s4, post-processing: and (3) crushing molten salt crystal particles obtained after liquid phase cooling in a quick cold state, and sieving the crushed molten salt crystal particles by a sieve of 80-200 meshes to obtain the ionic conductive agent for the multifunctional thermal battery.

6. The method for producing an ion conductive agent according to claim 5, wherein Ni is contained in the step S2 ²⁺ Cation and halogen X ^- The anion is made of NiF ₂ 、NiCl ₂ 、NiBr ₂ ，Li _x NiX _x+2 Any one or a combination of at least two of them, and the value of x is 1 to 2.

7. The method for preparing an ion conductive agent according to claim 5, wherein the vacuum drying temperature in step S1 is 60 to 300 ℃ and the drying time is 1 to 24 hours; in the step S2, the high-temperature roasting temperature is 450-800 ℃, and the roasting time is 1-24 h.

8. The method for preparing an ionic conduction agent according to claim 5, wherein in step S4, the low-temperature liquefied gas is any one of liquid nitrogen, liquid argon, liquefied carbon dioxide, liquefied oxygen and liquefied air or a combination of at least two of the liquid nitrogen, the liquid argon, the liquefied carbon dioxide and the liquefied air.

9. Use of the ionic conduction agent according to any one of claims 1 to 4 as a thermal battery positive ionic conduction agent, as a positive separator transition layer or a heating positive buffer layer alone.

10. Use of the ionic conduction agent according to any one of claims 1 to 4, wherein the ionic conduction agent is physically mixed or chemically combined with a metal or carbonaceous conduction agent to form a dual electron and ion conduction agent.

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