CN115763816A - Ion conductive agent for multifunctional thermal battery and preparation and application thereof - Google Patents
Ion conductive agent for multifunctional thermal battery and preparation and application thereof Download PDFInfo
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- CN115763816A CN115763816A CN202211619352.6A CN202211619352A CN115763816A CN 115763816 A CN115763816 A CN 115763816A CN 202211619352 A CN202211619352 A CN 202211619352A CN 115763816 A CN115763816 A CN 115763816A
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- 239000006258 conductive agent Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 21
- 150000002367 halogens Chemical class 0.000 claims abstract description 21
- 238000002844 melting Methods 0.000 claims abstract description 19
- 230000008018 melting Effects 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 230000005496 eutectics Effects 0.000 claims abstract description 10
- 238000012937 correction Methods 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 230000007704 transition Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 150000002500 ions Chemical class 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- 239000007791 liquid phase Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
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- 238000000034 method Methods 0.000 claims description 13
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- 125000002091 cationic group Chemical group 0.000 claims description 2
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 16
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- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 6
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- 229910001508 alkali metal halide Inorganic materials 0.000 description 5
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 2
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- -1 oxysalt and the like Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- 239000011575 calcium Substances 0.000 description 1
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a multifunctional thermal battery ion conductive agent and application thereof, wherein the multifunctional thermal battery ion conductive agent is an ionic bond eutectic salt with uniform chemical components, which is composed of Ni element with a monomer voltage correction function, li element with high ionic conductivity and F, cl and Br halogens, wherein the mass ratio of the solvated nickel element in a high-temperature liquid state is 1-10%. The ion conductivity of the multifunctional thermal battery ion conductive agent is 0.1-5S/cm, the melting point is 440-650 ℃, and the multifunctional thermal battery ion conductive agent can be used as a thermal battery anode additive, a transition layer between an anode and a diaphragm, and an isolation layer between the anode layer and a heating layer.
Description
Technical Field
The invention belongs to the technical field of chemical power thermal batteries, and particularly relates to an ionic conductive agent for a multifunctional thermal battery, and preparation and application thereof.
Background
The thermal battery is a special chemical power supply, and is widely applied to the field of aerospace due to excellent power output performance and long storage life. Common thermal battery anode materials (such as sulfide) have large interface resistance at high temperature and are easy to thermally decompose, so that a molten salt material with high-temperature phase change needs to be added as an ion conductive agent, the interface resistance is improved, and high-temperature thermal shock is resisted. Common ionic conductive agents are binary electrolytes (LiCl-KCl) and ternary full lithium electrolytes (LiF-LiCl-LiBr). However, with the rise of a novel long-time terminal heavy-current load thermal battery, the research on a thermal battery anode material with high voltage in the initial stage and strong load capacity in the later stage and an accessory technology thereof becomes one of the current thermal battery technology development trends.
Since the electrolyte can act as an ion conductor of the positive electrode material, the current ion conductor is mainly a binary electrolyte, a ternary all-lithium electrolyte and other alkali metal halides (Masset Patrick, guidotti Ronald A. Thermal activated) battery technology: part II. Molten salt electrolytes [ J ]]Journal of Power Sources,2007,164 (1): 397-414). The alkali metal halide electrolyte not only maintains high ionic conductivity and improves the contact wettability with the anode, but also cannot effectively regulate and control the anode potential and provide electronic conductivity, so that the later current load capacity of the tail end large pulse load thermal battery is limited. CN202011570678.5 reports LiCl-Li with high pressure resistance and decomposition resistance 2 CO 3 -Li 2 SO 4 Electrolytes are mainly aimed at high electricityThe electrolyte developed by the anode pressing material is low in electromigration speed and ionic conductivity due to the existence of oxygen-containing acid radicals such as carbonate, sulfate and the like, and is not suitable for being used as an ionic conductive agent of a high-power thermal battery. CN202011488418.3 prepares 10% -40% of ternary full-lithium electrolyte as an ion conductive agent, 10% -30% of alumina anti-overflow agent and 50% -80% of nickel chloride anode material, and obtains the solid-phase nickel chloride anode material molten and infiltrated by solid-phase alumina adsorption liquid-phase ternary full-lithium electrolyte.
In the preparation method of the ion conductive agent, except traditional molten salts such as alkali metal halide electrolyte and the like and modified molten salts such as oxysalt and the like, reports of introducing heavy metal particles to regulate and control the properties of the ion conductive agent are not seen, and reports of halide co-molten salts utilizing solvated nickel ions at high temperature and application of the halide co-molten salts in thermal batteries are also not seen.
Disclosure of Invention
The invention provides an ionic conductive agent for a multifunctional thermal battery and preparation and application thereof, aiming at the characteristics of high heat, easy decomposition of an anode and large late resistance of the long-time tail heavy-current load thermal battery. Firstly, introducing a heavy metal element nickel into a molten salt system with high ion migration speed, improving the melting point of molten salt, reducing the thermal shock influence of a heating material on an anode material at the initial activation stage, and preventing the decomposition of an anode active substance; and secondly, the viscosity of the material is changed by introducing a heavy metal element nickel, the high-temperature fluidity of the ion conductive agent is reduced, and the binding force with an active substance interface is improved. Particularly, the uniform distribution of the metal nickel ions is realized by utilizing the high-temperature solvation effect of F, cl and Br ions on the heavy metal nickel ions, and a nickel-containing solvation combination body with a monomer voltage regulation function is constructed, so that the multifunctional ionic conductive agent not only has the basic function of ionic conductivity, but also can provide correction voltage in the initial low-current or no-load operation, and utilizes weak electrochemical action or self-discharge effect to generate high-conductivity metal nickel, thereby providing a high-activity electronic conductive agent for the later electrochemical process of the battery and realizing the later large battery load output.
The purpose of the invention is realized by the following technical scheme:
the invention relates to an ion conductive agent (for a multifunctional thermal battery), which is an ionic bond eutectic salt with uniform chemical components and composed of a Ni element with a monomer voltage correction function, a Li element with high ionic conductivity and halogen, wherein 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.
Firstly, the ionic bond eutectic salt is a chemical component uniform molten salt containing elements such as Ni, li, F, cl, br and the like formed by high-temperature eutectic melting. Secondly, the nickel element in the ionic conductive agent is solvated in the high-temperature liquid-phase melt, no solid-phase nickel-containing substance exists, and the solvated nickel has a voltage correction and regulation function. The mass ratio of the nickel element is 1-10%, when the mass ratio of the nickel element is lower than 1%, the nickel element is slightly different from the alkali metal halide electrolyte, and the nickel element has influence on the large-current load capacity in the later period. When the proportion of nickel element is more than 10%, niF is formed 2 ，NiCl 2 ，NiBr 2 When the solid phase substance is used, the melting point and the viscosity of the ionic conduction agent are improved, and when the proportion of nickel element is too large, a muddy melt can be formed, so that the ionic conduction agent is not suitable for being used as the ionic conduction agent.
As an embodiment, the element F to Br molar ratio is about 22a 47b, and the Cl element molar ratio n is determined by the cationic Ni element molar ratio m, with values of n =31c + m × 2, a, b, c ranging from 0.95 to 1.05, respectively, and values of m ranging from 1 to 10. The values of a, b and c are lower in this range and higher in the absence of this range. When the nickel element proportion m is less than 1, the electrolyte has small difference with alkali metal halide electrolyte and has influence on the large current load capacity of the battery in the later period. When the ratio m of nickel element is larger than 10, niF is formed 2 ，NiCl 2 ，NiBr 2 When the proportion of nickel element is too large, a muddy melt can be formed, and the ionic conductive agent is not suitable for being used as the ionic conductive agent.
In one embodiment, 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. The d value is lower in this range and higher in the absence of this range.
As one embodiment, the ionic conductivity of the ionic conductive agent is 0.1 to 5S/cm, the particle size is 1 to 200 μm, the melting point is 440 to 650 ℃, and the viscosity is 1 to 200 mPas.
The invention also relates to a preparation method of the ionic conductive agent, which comprises the following steps:
s1, pretreatment: will contain Ni 2+ ，Li + Cation and halogen X - Carrying out high-temperature vacuum drying on the anion raw material, transferring the anion raw material into a drying atmosphere, and weighing the anion raw material according to the proportion of anions and cations for later use;
s2, melting and roasting: will contain Li + Cation and halogen X - After the anion raw materials 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 - Anion raw materials are subjected to high-temperature melting roasting (transferred into a high-temperature furnace) 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.
The method utilizes the high-temperature solvation effect of F, cl and Br ions on heavy metal Ni ions to realize the uniform distribution of metal nickel ions, then utilizes a grid dispersion mode to realize high-temperature melt slitting, and adopts liquefied gas to carry out extremely-fast cooling to realize the fast shaping of high-temperature molten salt, thereby forming the uniform nickel ion-containing conductive agent.
As an embodiment, the Ni-containing raw material in step S1 is NiF 2 、NiCl 2 、NiBr 2 ，Li x NiX x+2 Any one or a combination of at least two of them. In the halide molten salt, nickel ions can be dissolved by high temperatureBy chemical conversion, in combination with halides to form complexes, the common nickel-containing starting material is NiF 2 ，NiCl 2 ，NiBr 2 ，Li x NiX x+2 。
As one embodiment, the Li x NiX x+2 Comprising Li 2 NiCl 4 、Li 2 NiCl 2 X’ 2 The derivative of the compound, X' can be one or more of F and Br. x has a value of 1 to 2, preferably 2, and a non-integer ratio is desirably eutectic, if x is less than 1, or greater than 2 x NiX x+2 All can be used as raw materials, and the properties of the raw materials are similar to those of NiX 2 Or LiX, but the material is not readily available.
As an embodiment, the vacuum drying temperature in step S1 is 60 to 300 ℃, preferably 150 to 250 ℃, and the drying time is 1 to 24 hours, preferably 4 to 12 hours. The temperature is higher than 300 ℃, the drying speed is high, the energy consumption is high, and the operation is complex. If the water content of the raw material is high, there is a risk of hydrolysis, the temperature is lower than 60 ℃, and the drying efficiency is low.
As an embodiment, the high-temperature roasting temperature in the step S2 is 450-800 ℃, the roasting time is 1-24 h, preferably the roasting temperature is 450-600 ℃, and the roasting time is 30 min-8 h. The high-temperature roasting temperature is lower than 450 ℃, a melt cannot be formed, the temperature is higher than 800 ℃, and the nickel-containing ionic conductive agent can be sublimated to cause the change of the nickel content and cause the quality reliability problem.
In step S3, an open container made of chemically inert materials such as stainless steel, quartz, corundum, graphite, ceramic, metal, etc. with a regular or irregular depth of 2-20 cm, such as a stainless steel plate, a pot, a bowl, a crucible, etc., is used as the container. The container mainly used holds liquid gas, keeps fused salt submergence formula cooling, and the degree of depth is less than 2cm, and is inefficient, probably causes the fuse-element can not cool off fast, and the degree of depth is greater than 20cm, also can guarantee to cool off, probably causes liquid gas extravagant.
As an embodiment, the grid type dispersion method in step S3 may adopt a high temperature grid to cut the melt into lines and points, so as to prevent the melt from entering the liquid gas in a block structure with a size greater than 1cm, and ensure the melt to be cooled rapidly.
In one embodiment, in step S4, the cryogenic 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 above. The liquefied gas is mainly used for rapid cooling, so that the molten salt components are ensured to be rapidly shaped and not to be segregated.
The invention also relates to the application of the ionic conductive agent, wherein the ionic conductive agent is used as the thermal battery anode ionic conductive agent and is independently used as the anode diaphragm transition layer and/or the heating anode buffer layer.
The invention also relates to the use of an ionic conducting agent which is physically mixed or chemically combined with a metal or carbonaceous conducting agent to form an electronic and ionic dual conducting agent.
As one embodiment, the metal conductive agent includes a transition metal or main group metal simple substance or metal alloy such as gold, silver, platinum, manganese, iron, cobalt, nickel, copper, zinc, lead, tin, indium, antimony, bismuth, lithium, sodium, potassium, magnesium, calcium, aluminum, and the like.
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, fullerene, conductive graphite, or a combination of at least two thereof.
The invention contains solvated heavy metal element nickel, has the ability of preferentially accepting electrons, provides correction voltage, can generate high-conductivity metal nickel by utilizing weak electrochemical action or self-discharge effect, provides a high-activity electron conductive agent for the later electrochemical process of the battery, and realizes the later large battery load output. For example, the molten salt ion conductive agent composed of LiF, liCl, liBr, naCl or KCl, etc. can only provide high ion conductivity without a function of correcting voltage due to the absence of heavy metal ions, and does not contain a chemical product, and cannot provide metallic nickel with electronic conductivity for a later period.
Compared with the prior art, the invention has the following beneficial effects:
1) The method for preparing the nickel ion-containing conductive agent realizes the uniform distribution of metal nickel ions by utilizing the high-temperature solvation effect of F, cl and Br ions on heavy metal Ni ions, and realizes the rapid shaping of high-temperature molten salt by adopting the liquefied gas for extremely rapid cooling to form the uniform nickel ion-containing conductive agent; the nickel-ion-containing conductive agent prepared by the method has uniform components and high quality reliability;
2) The method has the advantages of simple related equipment, simple and clear process flow, high efficiency and low cost, and is suitable for large-scale production;
3) The nickel-ion-containing conductive agent prepared by the invention has the basic function of ionic conductivity, and can regulate and control the design voltage in the initial low current or no-load operation;
4) The nickel-ion-containing conductive agent prepared by the invention can also improve the melting point and viscosity of molten salt, reduce the thermal shock influence of a heating material on the anode material at the initial activation stage, prevent the decomposition of the anode active substance and improve the bonding force of the active substance interface;
5) The nickel-ion-containing conductive agent prepared by the invention can generate high-conductivity metallic nickel by utilizing weak electrochemical action or self-discharge effect, provides a high-activity electronic conductive agent for the later electrochemical process of the battery, and realizes the later large battery load output.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic diagram of the position of a positive heating buffer layer in a thermal battery;
FIG. 2 is a schematic diagram of the position of a transition layer of a positive separator in a thermal battery;
FIG. 3 is a schematic diagram of a conventional battery structure;
fig. 4 is a graph of long term end high current thermal battery discharge.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
Example 1
The embodiment relates to an ionic conductive agent for a multifunctional thermal battery, which is an ionic bond eutectic salt with uniform chemical components and composed of Ni element with a monomer voltage correction function, li element with high ionic conductivity and F, cl and Br halogens, wherein the mass ratio of the nickel element solvated in a high-temperature liquid state is about 3%. Wherein the molar ratio of halogen (F: cl: br) is about 22:37.6:47, metal molar ratio (Ni: li) 3.3. The multifunctional thermal battery ionic conductive agent has a melting point of about 460 ℃, a particle size of not more than 74 mu m, a viscosity of 40mPa & S at 500 ℃ and an ionic conductivity of about 2.5S/cm.
The ionic conduction agent of the present example was prepared as follows:
s1, pretreatment: will contain NiCl 2 Vacuum drying raw materials of LiF, liCl and LiBr at the high temperature of 180 ℃ for 12 hours, transferring the raw materials into a drying atmosphere with the water oxygen value lower than 1ppm, and weighing the raw materials according to the proportion of anions and cations for later use. Wherein the molar halogen ratio (F: cl: br) is about 22:37.6:47, metal molar ratio (Ni: li) 3.3.
S2, melting and roasting: weighing LiF, liCl and LiBr as raw materials, loading the raw materials into the bottom of a crucible, and then adding NiCl 2 Transferring into a crucible, covering the upper part of the lithium-containing raw material, transferring into a high-temperature furnace, and carrying out high-temperature melting roasting at 550 ℃ for 4 hours to enable the material to form a uniform melt.
S3, extremely fast cooling: pouring liquid nitrogen into a stainless steel pot with a depth of 20cm to form a 10cm liquid phase gas pool, and passing the high temperature melt through about 0.5cm 2 The grid is dispersed and quickly dripped into a liquid phase gas pool.
S4, post-processing: and (3) crushing molten salt crystal particles obtained after liquid phase cooling in a cold state, and sieving by a 100-mesh sieve to obtain the nickel-ion-containing conductive agent.
The multifunctional ionic conductive agent of the embodiment can be applied to a positive electrode material. Under the condition of adopting a full lithium electrolyte (LiF-LiCl-LiBr) diaphragm and a lithium boron alloy negative electrode, a positive electrode material is compounded by 75 percent of iron disulfide and 25 percent of multifunctional ionic conductive agent, the no-load voltage is about 2.30V, and when the positive electrode material is compounded by 75 percent of iron disulfide and 25 percent of binary electrolyte (LiCl-KCl), the no-load voltage is 2.02V.
Example 2
The embodiment provides an ion conductive agent for a multifunctional thermal battery, which is an ionic bond eutectic salt with uniform chemical components and composed of a Ni element with a monomer voltage correction function, a Li element with high ionic conductivity and F, cl and Br halogens, wherein the mass ratio of the nickel element solvated in a high-temperature liquid state is about 1%. Wherein the molar halogen ratio (F: cl: br) is about 22:33.02:47, metal molar ratio (Ni: li) about 1.01. The multifunctional thermal battery ionic conductive agent has a melting point of about 450 ℃, a particle size of less than 50 mu m, a viscosity of 20mPa & S at 500 ℃ and an ionic conductivity of about 3S/cm.
The ionic conduction agent of the present example was prepared as follows:
s1, pretreatment: will contain NiCl 2 Vacuum drying raw materials of LiF, liCl and LiBr at the high temperature of 180 ℃ for 12 hours, transferring the raw materials into a drying atmosphere with the water oxygen value lower than 1ppm, and weighing the raw materials according to the proportion of anions and cations for later use. Wherein the molar ratio of halogen (F: cl: br) is about 22:33.02:47, metal molar ratio (Ni: li) about 1.01.
S2, melting and roasting: weighing LiF, liCl and LiBr as raw materials, loading the raw materials into the bottom of a crucible, and then adding NiCl 2 Transferring into a crucible, covering the upper part of the lithium-containing raw material, transferring into a high-temperature furnace, and carrying out high-temperature melting roasting at 550 ℃ for 4 hours to enable the material to form a uniform melt.
S3, extremely fast cooling: pouring liquid nitrogen into a stainless steel basin with a depth of 20cm to form a 10cm liquid phase gas pool, and passing the high temperature melt through a 1cm tank 2 The grid is dispersed and quickly dripped into a liquid phase gas pool.
S4, post-processing: and (3) crushing molten salt crystal particles obtained after liquid phase cooling in a cold state, and sieving by a 100-mesh sieve to obtain the nickel-ion-containing conductive agent.
The multifunctional ionic conducting agent of the embodiment can be applied to a positive electrode material, under the condition that a full lithium electrolyte (LiF-LiCl-LiBr) diaphragm and a lithium boron alloy negative electrode are adopted, when the positive electrode material is compounded by 75% of cobalt disulfide, 24% of the multifunctional ionic conducting agent and 1% of a silver-carbon nano material, the no-load voltage is about 2.35V, and when the positive electrode material is compounded by 75% of cobalt disulfide, 25% of binary electrolyte (LiCl-KCl) and 1% of a silver-carbon nano material, the no-load voltage is 2.05V.
Example 3
The embodiment provides an ion conductive agent for a multifunctional thermal battery, which is an ionic bond eutectic salt with uniform chemical components, wherein the ionic bond eutectic salt comprises a Ni element with a monomer voltage correction function, a Li element with high ionic conductivity and F, cl and Br halogens, and the mass ratio of the nickel element solvated in a high-temperature liquid state is about 5%, and the molar ratio of the nickel element to the lithium element (Ni: li) is about 5.7. Wherein the molar halogen ratio (F: cl: br) is about 22:42.4:47.
the ionic conduction agent of the present example was prepared as follows:
s1, pretreatment: will contain Li 2 NiCl 4 And (3) carrying out vacuum drying on the raw materials of LiF, liCl and LiBr at the high temperature of 200 ℃ for 8 hours, transferring the raw materials into a dry atmosphere with the water oxygen value lower than 1ppm, and weighing the raw materials according to the proportion of anions and cations for later use. Wherein the molar halogen ratio (F: cl: br) is about 22:42.4:47, metal molar ratio (Ni: li) 5.7.
S2, melting and roasting: weighing LiF, liCl and LiBr as raw materials, loading the raw materials into the bottom of a crucible, and then putting Li into the crucible 2 NiCl 4 Transferring into a crucible, covering the upper part of the lithium-containing raw material, transferring into a high-temperature furnace, and roasting at 600 ℃ for 8h to form a uniform melt.
S3, extremely fast cooling: pouring liquid nitrogen into a ceramic container with a depth of 15cm to form a liquid-phase gas pool of 10cm, and passing the high-temperature melt through a 1 cm-deep ceramic container 2 The grid is dispersed and quickly dripped into a liquid phase gas pool.
S4, post-processing: and (3) crushing molten salt crystal particles obtained after liquid phase cooling in a cold state, and sieving by a 200-mesh sieve to obtain the nickel ion-containing conductive agent.
The multifunctional ionic conductive agent of the embodiment can be used as a positive electrode heating buffer layer (figure 1) and can also be applied to a positive electrode diaphragm transition layer (figure 2). As shown in fig. 1, the thermal battery includes a negative electrode current collector layer, a negative electrode layer, a separator layer, a positive electrode heating buffer layer, a positive electrode current collector layer, and a heating layer in this order. The thermal battery of fig. 2 includes, in order, a negative current collector layer, a negative electrode layer, a positive diaphragm transition layer, a positive electrode layer, a positive current collector layer, and a heating layer. Fig. 3 is a schematic structural diagram of a conventional thermal battery, which sequentially comprises a negative current collecting layer, a negative electrode layer, a diaphragm layer, a positive electrode layer, a positive current collecting layer and a heating layer.
In the case of using a full lithium electrolyte (LiF-LiCl-LiBr) diaphragm and a lithium boron alloy negative electrode, the positive electrode material consists of 18 mass percent of LiCl-KCl binary electrolyte and 80 mass percent of positive electrode active material FeS 2 1% of carbon nanotubes and an additive Li 2 The O is formed by high-temperature melting and roasting, the no-load monomer voltages of the heating anode buffer layer thermal battery (figure 1), the anode diaphragm transition layer thermal battery (figure 2) and the conventional battery (figure 3) are respectively 2.41V,2.24V and 2.05V, the pulse load capacities of the heating anode buffer layer thermal battery and the anode diaphragm transition layer thermal battery are strong, and the conventional battery can not load large current (figure 4).
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the 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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