HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-viologen hybrid and application of HF-free wide-temperature-range battery fire extinguishing material in battery fire extinguishing agent

Abstract

The invention discloses an HF-free wide-temperature-range battery fire extinguishing material based on a fluorosilane grafted MXene-viologen hybrid and application of the HF-free wide-temperature-range battery fire extinguishing material in a battery fire extinguishing agent. The HF-free wide-temperature-range battery fire extinguishing material comprises the following raw materials in percentage by weight: 8-12% of a Ti3C2TX-viologen hybrid, 80-85% of a carrier, 5-7% of a SnF2 / SbF5 composite coolant and 1-3% of a graphdiyne intercalation agent, the carrier is perfluoropolyether ester or perfluoroalkyl polyether; and the molar ratio of SnF2 to SbF5 in the SnF2 / SbF5 composite coolant is 3: 1. Through grafting modification of fluorosilane, a hydrolysis path of MXene is thoroughly blocked, HF generation is avoided, a rapid response chain of electron capture (lt, 0.2 ms)-free radical quenching (lt, 300 ms)-endothermic explosion suppression (lt, 0.5 s) is achieved, the viscosity at-50 DEG C is smaller than or equal to 40 cP, and the thermal storage stability at 70 DEG C is gt; therefore, the application requirement of a wide temperature range is met.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of new energy battery safety, more specifically, to a HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene- viologen hybrid and its application in battery fire extinguishing agent. BACKGROUND

[0002] In recent years, new energy represented by lithium batteries has developed rapidly, and the rise of electric vehicle industry is particularly rapid. Electric vehicles are favored for their high energy efficiency, diversification, simple structure, easy maintenance, and low pollution and noise. However, in recent years, safety accidents caused by power supply of electric vehicles have raised concerns about the safety of electric vehicles, and the safety of electric vehicles has been increasingly valued. Although various battery internal management technologies are becoming more mature, factors affecting battery safety are still difficult to accurately control, and the potential danger of explosion accidents cannot be completely ruled out.

[0003] The existing lithium battery fire extinguishing materials and related technologies have many defects, which limit their application in the field of new energy battery safety. The specific defects are as follows: 1. MXene hydrolysis risk: traditional Ti3C2T X materials are easy to generate HF (concentration often > 500 ppm) when meeting water, which can seriously corrode battery components (reference: Nature Mater. 2020, 19: 894).

[0004] 2. Insufficient flowability in wide temperature range: mainstream fire extinguishing medium (such as perfluorohexanone) has a sharp increase in viscosity at low temperature, for example, viscosity > 500 cP at -30℃, which cannot meet the rapid diffusion requirement in extreme low temperature environment.

[0005] 3. Cooling agent safety hazard: Some cooling agents (such as borohydride) release toxic B2H6 when thermally decomposed, and its OSHA safety limit is < 50 ppb, which poses a serious safety risk (reference: J. Hazard. Mater. 2023, 458: 132000).

[0006] 4. Response speed bottleneck: conventional electron capture agents (such as quinones) have a response time > 200 ms, which is difficult to quickly suppress the chain reaction in the initial stage of battery thermal runaway (reference: ACS Energy Lett. 2023, 8: 123).

[0007] In view of this, we propose a HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene- viologen hybrid and its application in battery fire extinguishing agent. SUMMARY

[0008] To address the shortcomings of existing technologies, one of the objectives of this invention is to provide an HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-violet hybrid. Through fluorosilane grafting modification, the hydrolysis pathway of MXene is completely blocked, avoiding HF generation and achieving a rapid response chain of "electron capture (<0.2ms) → free radical quenching (<300ms) → endothermic explosion suppression (<0.5s)". The viscosity is ≤40cP at -50℃ and the thermal storage stability is >99.7% at 70℃, meeting the requirements for wide-temperature-range applications.

[0009] To solve the above-mentioned technical problems, the present invention provides the following technical solution: The HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-violet hybrid comprises the following raw materials by weight percentage: Ti3C2T X @8-12% Violet hybrid, 80-85% carrier, 5-7% SnF2 / SbF5 composite coolant, 1-3% Graphdiyne intercalating agent; The carrier is a perfluoropolyether ester or a perfluoroalkyl polyether; The SnF2:SbF5 molar ratio in the SnF2 / SbF5 composite coolant is 3:1; Ti3C2T X The preparation method of the purple sperm hybrid includes the following steps: (1) Fluorine-free molten salt etching of MXene: Ti3AlC2MAX phase was mixed and reacted with KCl / LiF mixed salt under a nitrogen protective atmosphere to prepare Ti3C2T X -OH; (2) Ti3C2T X -OH groups were dispersed in anhydrous toluene, and perfluorooctyltrimethoxysilane was added. The mixture was then refluxed to form a fluorosilane grafting layer. (3) Add aminovioletin and bond it through EDC / NHS catalytic condensation reaction to obtain Ti3C2T X -OHBV 2+ Hybrid.

[0010] Ti3C2T X The functional mechanism of the Violet hybrid (2nm thick fluorosilane grafting layer, contact angle >160°) is: electron capture (specific surface area >380m² / g) + high-efficiency thermal conductivity (thermal conductivity 25W / mK).

[0011] The functional mechanism of perfluoropolyether ester (Fluorolink PFPE, viscosity 38cP at -60℃) is as follows: wide temperature range carrier, surface tension 12mN / m, ensuring low-temperature fluidity and high-temperature stability.

[0012] The functional mechanism of the SnF2 / SbF5 composite coolant is: endothermic reaction: 4SnF2+O2→2SnO+4F・+285kJ; SbF5 fixes free HF to generate SbF6 - .

[0013] The functional mechanism of the graphdiyne intercalation agent (interlayer spacing 1.2nm, pore size 0.8nm) is: inhibiting the stacking of MXene layers, improving the ion permeability and dispersibility of the material.

[0014] The action mechanism of the perfluoroalkyl polyether is: solubility parameter δ=6.2cal 1 / 2 / cm 3 / 2 , improving the electrolyte compatibility.

[0015] Preferably, in step (1), the mixing reaction temperature is 600-700 DEG C, and the reaction time is 1.5-2.5h.

[0016] Preferably, in step (2), the temperature of the reflux reaction is 75-85 DEG C, and the reaction time is 11-13h.

[0017] Preferably, the graphdiyne intercalation agent is prepared by ultrasonic assisted impregnation treatment of graphdiyne, the ultrasonic frequency is 40kHz, and the treatment time is 2h.

[0018] Preferably, the graphdiyne has a particle size of 5nm.

[0019] The second object of the application is to provide a lithium ion battery extinguishing agent, comprising the above-mentioned HF-free wide temperature range battery extinguishing material based on fluorosilane grafted MXene- viologen hybrid, and the carrier of the extinguishing material is perfluoropolyether fat. X The preparation method of the lithium ion battery extinguishing agent is as follows: according to the proportion, Ti3C2T

[0020] The third object of the application is to provide a lithium metal battery extinguishing agent, comprising LiF coated graphdiyne and the above-mentioned HF-free wide temperature range battery extinguishing material based on fluorosilane grafted MXene- viologen hybrid, and the carrier of the extinguishing material is perfluoropolyether fat, and the mass ratio of the LiF coated graphdiyne and the extinguishing material is 2:98. XThe fire extinguishing agent for lithium metal batteries is prepared by dispersing and mixing the viologen hybrid, SnF2 / SbF5 composite coolant, graphdiyne intercalating agent, LiF coated graphdiyne and perfluoropolyether fat under the assistance of supercritical CO2, wherein the mixing pressure is 35 MPa, the mixing temperature is 50 DEG C, and the mixing time is 1 h.

[0021] The mechanism of the LiF coated graphdiyne is to promote uniform deposition of lithium ions and reduce the deposition overpotential by 70%.

[0022] The fourth object of the present application is to provide a fire extinguishing agent for sulfide solid-state batteries, which comprises a Li6PS5Cl coating layer and the HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-viologen hybrid as described above, wherein the carrier for the fire extinguishing material is perfluoropolyether fat, and the mass ratio of the Li6PS5Cl coating layer to the fire extinguishing material is 3:97. X @The fire extinguishing agent for sulfide solid-state batteries is prepared by dispersing and mixing the viologen hybrid, SnF2 / SbF5 composite coolant, graphdiyne intercalating agent, Li6PS5Cl coating layer and perfluoropolyether fat under the assistance of supercritical CO2, wherein the mixing pressure is 35 MPa, the mixing temperature is 50 DEG C, and the mixing time is 1 h.

[0023] The mechanism of the Li6PS5Cl coating layer is to reduce the interface impedance to <5 Omega cm 2 (bare interface impedance > 100 Omega cm 2 ).

[0024] The fifth object of the present application is to provide a fire extinguishing agent for flow batteries, which comprises the HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-viologen hybrid as described above, wherein the carrier for the fire extinguishing material is perfluoroalkyl polyether. X @The fire extinguishing agent for flow batteries is prepared by dispersing and mixing the viologen hybrid, SnF2 / SbF5 composite coolant, graphdiyne intercalating agent and perfluoroalkyl polyether under the assistance of supercritical CO2, wherein the mixing pressure is 35 MPa, the mixing temperature is 50 DEG C, and the mixing time is 1 h.

[0025] The sixth object of the present application is to provide a wide-temperature sodium battery fire extinguishing agent, which comprises Na3SbS4 solid-state electrolyte and the HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-viologen hybrid as described above, wherein the carrier for the fire extinguishing material is perfluoropolyether fat, and the mass ratio of the Na3SbS4 solid-state electrolyte to the fire extinguishing material is 1:99. XThe fire extinguishing agent for the wide-temperature sodium battery is prepared by dispersing and mixing a viologen hybrid, a SnF2 / SbF5 composite coolant, a graphdiyne intercalating agent, a Na3SbS4 solid-state electrolyte and a perfluoropolyether fat under the assistance of supercritical CO2, wherein the mixing pressure is 35 MPa, the mixing temperature is 50 DEG C, and the mixing time is 1 h.

[0026] The action mechanism of the Na3SbS4 solid-state electrolyte is to ensure that the ionic conductivity is greater than 0.1 mS / cm at-40 DEG C.

[0027] Compared with the prior art, the present application has the following beneficial effects: 1. The core structure of the HF-free wide-temperature battery fire extinguishing material based on the fluorosilane grafted MXene-viologen hybrid of the present application is a sandwich structure of "fluorocarbon hydrophobic layer-viologen electron capture layer-graphdiyne support layer", the fluorosilane coverage is greater than 20 chains / nm2 (verified by XPS characterization), and the interlayer spacing is 1.20+ / -0.05 nm (detected by XRD).

[0028] 2. The present application completely blocks the hydrolysis path of MXene through fluorosilane grafting modification, avoids the generation of HF, realizes the rapid response chain of "electron capture (<0.2 ms) -> free radical quenching (<300 ms) -> heat absorption and explosion suppression (<0.5 s)", and meets the application requirements in a wide temperature range with a viscosity of less than or equal to 40 cP at-50 DEG C and a thermal storage stability of greater than 99.7% at 70 DEG C.

[0029] 3. The present application first designs a SnF2 / SbF5 composite coolant, realizes the dual functions of "heat absorption and explosion suppression (285 kJ / mol)" and "HF fixation", the residual amount of HF is less than 0.1 ppm (lower than the detection limit), solves the toxicity problem of traditional coolants, eliminates the fluorine ion residue from the source through the fluorine-free molten salt etching process (Cl - The terminal ratio is greater than 90%), avoids the risk of intrinsic hydrolysis of MXene, and the supercritical CO2 dispersion process solves the problem of nanoparticle agglomeration and ensures that the particle size distribution D90 is less than 200 nm, thereby improving the uniformity of the material. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 The preparation flowchart of the HF-free wide-temperature battery fire extinguishing material based on the fluorosilane grafted MXene-viologen hybrid of the present application is shown in Figure 1. Figure 2 The structure diagram of the fluorosilane grafted MXene-viologen hybrid of the present application is shown in Figure 2. Figure 3 The reaction mechanism diagram of the SnF2 / SbF5 composite coolant of the present application is shown in Figure 3. DETAILED DESCRIPTION

[0031] In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0032] In the following examples, the test materials and reagents used, unless otherwise specified, can be obtained commercially. If specific techniques or conditions are not described in the examples, they can be performed according to the techniques or conditions described in the literature or according to the product instructions.

[0033] Example 1 The present embodiment provides a HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-viologen hybrid, which comprises the following raw materials by weight percentage: Ti3C2T X @viologen hybrid 10%, perfluoropolyether grease 82%, SnF2 / SbF5 composite coolant 6%, graphdiyne intercalation agent 2%; the molar ratio of SnF2 to SbF5 in the SnF2 / SbF5 composite coolant is 3:1; 1. The preparation method of the fire extinguishing material is as follows: (1) Preparation of Ti3C2T X @viologen hybrid: Ti3AlC2MAX phase is mixed with KCl / LiF mixed salt (molar ratio 7:3) under nitrogen protection atmosphere, the reaction temperature is 600°C, and the reaction time is 2h, to obtain Ti3C2T X -OH (oxygen terminal content >90%, to avoid fluorine source residue); Ti3C2T X -OH is dispersed in anhydrous toluene, perfluorooctyltrimethoxysilane (molar ratio 1:5 with Ti3C2T X -OH) is added, and reflux reaction is carried out at 80°C for 12h to form a fluorosilane grafted layer; amino viologen (-NH2-BV 2+ ) is added and bonded through EDC / NHS catalytic condensation reaction to obtain Ti3C2T X -OHBV 2+ hybrid.

[0034] (2) Graphdiyne (spherical diameter 5nm) is subjected to ultrasonic assisted impregnation treatment for 2h, and the ultrasonic frequency is 40kHz, to obtain a graphdiyne intercalation agent (intercalation rate >95%); (3) According to the proportion, Ti3C2T X@The HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-violet hybrid is prepared by dispersing and mixing MXene-violet hybrid, SnF2 / SbF5 composite coolant, graphyne intercalating agent and perfluoropolyether ester under supercritical CO2 assistance, with a mixing pressure of 35MPa, a mixing temperature of 50℃ and a mixing time of 1h.

[0035] 2. Comparative testing of the safety performance of SnF2 / SbF5 composite coolant and Mg(BH4)2: The test method was to detect the components of the thermal decomposition gas by GC-MS, and the test results are shown in Table 1.

[0036] Table 1. Comparison of safety performance test results between SnF2 / SbF5 composite coolant and Mg(BH4)2

[0037] Example 2 This embodiment provides a fire extinguishing agent for lithium-ion batteries, which is the HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-violet hybrid prepared in Example 1.

[0038] Performance verification of fire extinguishing agents for lithium-ion batteries: The 100Ah battery module was overcharged to 5.5V, and the battery performance parameters were tested at ambient temperatures of -50℃ and 70℃. The test results are shown in Table 2.

[0039] Table 2 Performance test results of fire extinguishing agents for lithium-ion batteries

[0040] Example 3 This embodiment provides a fire extinguishing agent for lithium metal batteries, comprising the following raw materials by weight percentage: 2% LiF-coated graphylene, Ti3C2T X The composition includes: 10% violet hybrid, 80% perfluoropolyether ester, 6% SnF2 / SbF5 composite coolant, and 2% graphyne intercalating agent. Among these, Ti3C2T... X The preparation method of the @violet hybrid and the treatment method of the graphyne intercalating agent are the same as in Example 1.

[0041] When the fire extinguishing agent for lithium metal batteries was used on lithium metal batteries, the dendrite penetration time was tested to be 15 hours at -50°C.

[0042] Example 4 This embodiment provides a fire extinguishing agent for sulfide solid-state batteries, comprising the following raw materials by weight percentage: 3% Li6PS5Cl coating layer, Ti3C2T XViologen hybrid 8%, perfluoropolyether grease 82%, SnF2 / SbF5 composite coolant 5%, graphdiyne intercalation agent 2%. Among them, Ti3C2T X The preparation method of the viologen hybrid and the treatment method of the graphdiyne intercalation agent are the same as in Example 1.

[0043] Verification of the permeability of the extinguishing agent for sulfide solid-state batteries: The TOF-SIMS depth profiling (pulse field assisted permeation) was used for testing, and the test results are shown in Table 3.

[0044] Table 3 Comparison results of permeability test of extinguishing agent for sulfide solid-state batteries and traditional viologen extinguishing material

[0045] Example 5 The present embodiment provides an extinguishing agent for flow batteries, which comprises the following raw materials by weight percentage: Ti3C2T X Viologen hybrid 10%, perfluoroalkyl polyether 82%, SnF2 / SbF5 composite coolant 6%, graphdiyne intercalation agent 2%. Among them, Ti3C2T X The preparation method of the viologen hybrid and the treatment method of the graphdiyne intercalation agent are the same as in Example 1.

[0046] The extinguishing agent for flow batteries is used on a full vanadium flow battery, and the electrolyte precipitation rate of 1000 cycles is 0%.

[0047] Example 6 The present embodiment provides an extinguishing agent for wide-temperature sodium batteries, which comprises the following raw materials by weight percentage: Na3SbS4 solid-state electrolyte 1%, Ti3C2T X Viologen hybrid 10%, perfluoroalkyl polyether 82%, SnF2 / SbF5 composite coolant 6%, graphdiyne intercalation agent 2%. Among them, Ti3C2T X The preparation method of the viologen hybrid and the treatment method of the graphdiyne intercalation agent are the same as in Example 1.

[0048] In summary, the core structure of the HF-free wide temperature range battery fire extinguishing material based on fluorosilane grafted MXene- viologen hybrid prepared by the application is a sandwich structure of "fluorocarbon hydrophobic layer-viologen electron capture layer-graphiteyne support layer", the fluorosilane coverage is > 20 chains / nm2 (verified by XPS characterization), the interlayer spacing is 1.20±0.05 nm (detected by XRD); the application completely blocks the hydrolysis path of MXene through fluorosilane grafting modification, avoids the generation of HF, realizes the rapid response chain of "electron capture (<0.2 ms) -> radical quenching (<300 ms) -> heat absorption and explosion suppression (<0.5 s)", the viscosity is ≤40 cP at-50℃, the thermal storage stability is >99.7% at 70℃, and the wide temperature range application requirement is met; the application first designs SnF2 / SbF5 composite coolant, realizes the dual functions of "heat absorption and explosion suppression (285 kJ / mol)" and "HF fixation", the residual amount of HF is <0.1 ppm (lower than the detection limit), the toxicity problem of the traditional coolant is solved, the fluorine ion residue (Cl - The terminal ratio is >90%), the risk of intrinsic hydrolysis of MXene is avoided, the supercritical CO2 dispersion process solves the problem of nanoparticle agglomeration, ensures that the particle size distribution D90 is <200 nm, and improves the uniformity of the material.

[0049] The application discloses preferred embodiments, but is not limited thereto, and those skilled in the art can easily understand the spirit of the application according to the above embodiments, and make different inferences and changes, as long as they do not deviate from the spirit of the application, they are within the protection scope of the application.

Claims

1. A HF-free, wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-violet hybrid, characterized in that, The raw materials include the following weight percentages: Ti3C2T X @8-12% Violet hybrid, 80-85% carrier, 5-7% SnF2 / SbF5 composite coolant, 1-3% Graphdiyne intercalating agent; The carrier is a perfluoropolyether ester or a perfluoroalkyl polyether; The SnF2:SbF5 molar ratio in the SnF2 / SbF5 composite coolant is 3:1; Ti3C2T X The preparation method of the purple sperm hybrid includes the following steps: (1) Fluorine-free molten salt etching of MXene: Ti3AlC2MAX phase was mixed and reacted with KCl / LiF mixed salt under a nitrogen protective atmosphere to prepare Ti3C2T X -OH; (2) Ti3C2T X -OH groups are dispersed in anhydrous toluene, and perfluorooctyltrimethoxysilane is added. The mixture is then refluxed to form a fluorosilane grafting layer, wherein the perfluorooctyltrimethoxysilane reacts with Ti3C2T X The molar ratio of -OH is 1:5; (3) Add aminovioletin and bond it through EDC / NHS catalytic condensation reaction to obtain Ti3C2T X -OHBV 2+ Hybrid.

2. The HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-violet hybrid as described in claim 1, characterized in that: In step (1), the mixing reaction temperature is 600-700℃ and the reaction time is 1.5-2.5h.

3. The HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-violet hybrid as described in claim 1, characterized in that: In step (2), the reflux reaction temperature is 75-85℃ and the reaction time is 11-13h.

4. The HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-violet hybrid as described in claim 1, characterized in that: The graphyne intercalating agent is prepared by ultrasonic-assisted impregnation of graphyne at a frequency of 40 kHz for 2 hours.

5. The HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-violet hybrid as described in claim 4, characterized in that: The diameter of the graphyne spheres is 5 nm.

6. A fire extinguishing agent for lithium-ion batteries, characterized in that: The fire extinguishing material for HF-free wide-temperature range batteries based on fluorosilane grafted MXene-violet hybrids as described in any one of claims 1-5, wherein the carrier used in the fire extinguishing material is perfluoropolyether ester; the specific preparation method of the fire extinguishing agent for lithium-ion batteries is as follows: according to the formula, Ti3C2T X Fire extinguishing agent for lithium-ion batteries can be prepared by dispersing and mixing viologen hybrid, SnF2 / SbF5 composite coolant, graphylene intercalator and perfluoropolyether ester under supercritical CO2 assistance, with a mixing pressure of 35MPa, a mixing temperature of 50℃ and a mixing time of 1h.

7. A fire extinguishing agent for lithium metal batteries, characterized in that: The fire extinguishing agent includes LiF-coated graphylene and the HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-violet hybrid as described in any one of claims 1-5, wherein the carrier used in the fire extinguishing material is perfluoropolyether ester, and the mass ratio of LiF-coated graphylene to the fire extinguishing material is 2:98; the specific preparation method of the lithium metal battery fire extinguishing agent is as follows: according to the ratio, Ti3C2T X Fire extinguishing agent for lithium metal batteries can be prepared by dispersing and mixing violet hybrid, SnF2 / SbF5 composite coolant, graphyne intercalating agent, LiF-coated graphyne and perfluoropolyether ester under supercritical CO2 assistance, with a mixing pressure of 35MPa, a mixing temperature of 50℃ and a mixing time of 1h.

8. A fire extinguishing agent for sulfide solid-state batteries, characterized in that: The fire extinguishing material includes a Li6PS5Cl coating layer and the HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-violet hybrid as described in any one of claims 1-5, wherein the carrier used for the fire extinguishing material is perfluoropolyether ester, and the mass ratio of the Li6PS5Cl coating layer to the fire extinguishing material is 3:97; the specific preparation method of the sulfide solid-state battery fire extinguishing agent is as follows: according to the ratio, Ti3C2T X Fire extinguishing agent for sulfide solid-state batteries can be prepared by dispersing and mixing viologen hybrid, SnF2 / SbF5 composite coolant, graphylene intercalating agent, Li6PS5Cl coating layer and perfluoropolyether ester under supercritical CO2 assistance, with mixing pressure of 35MPa, mixing temperature of 50℃ and mixing time of 1h.

9. A fire extinguishing agent for flow batteries, characterized in that: The fire extinguishing material for HF-free wide-temperature range batteries based on fluorosilane grafted MXene-violet hybrids as described in any one of claims 1-5, wherein the carrier used in the fire extinguishing material is a perfluoroalkyl polyether; the preparation method of the fire extinguishing agent for the flow battery specifically comprises: according to the ratio, mixing Ti3C2T... X Fire extinguishing agent for flow batteries can be prepared by dispersing and mixing viologen hybrid, SnF2 / SbF5 composite coolant, graphyne intercalator and perfluoroalkyl polyether under supercritical CO2 assistance, with a mixing pressure of 35MPa, a mixing temperature of 50℃ and a mixing time of 1h.

10. A fire extinguishing agent for wide-temperature sodium batteries, characterized in that: The fire extinguishing agent includes a Na3SbS4 solid electrolyte and the HF-free wide-temperature-range battery fire extinguishing material based on fluorosilane grafted MXene-violet hybrid as described in any one of claims 1-5, wherein the carrier used for the fire extinguishing material is perfluoropolyether ester, and the mass ratio of the Na3SbS4 solid electrolyte to the fire extinguishing material is 1:99; the specific preparation method of the wide-temperature sodium battery fire extinguishing agent is as follows: according to the ratio, Ti3C2T X Fire extinguishing agent for wide-temperature sodium batteries can be prepared by dispersing and mixing viologen hybrid, SnF2 / SbF5 composite coolant, graphynylene intercalating agent, Na3SbS4 solid electrolyte and perfluoropolyether ester under supercritical CO2 assistance, with a mixing pressure of 35MPa, a mixing temperature of 50℃ and a mixing time of 1h.

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