CN114843704B - Manganese-containing fluoride thermal battery - Google Patents
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Abstract
The invention discloses a manganese-containing fluoride thermal battery, which consists of a positive electrode containing manganese fluoride as an active substance, a multi-layer diaphragm, a lithium alloy negative electrode, a heating component and other accessory components, wherein the multi-layer diaphragm is of a multi-layer structure at least consisting of a first functional transition layer and a second mass transfer conductive layer which are different in chemical composition. The first functional transition layer consists of a high-temperature fluorine-fixing conversion anode functional agent, a carbonaceous conductive agent, a high-temperature ion conductive agent and a high-temperature chemical inert oxide according to a certain proportion, and the second mass transfer conductive layer consists of a high-temperature chemical inert oxide and a high-temperature ion conductive electrolyte. The no-load monomer voltage of the manganese-containing fluoride thermal battery can reach 3.0-3.7V.
Description
Technical Field
The invention belongs to the technical field of thermal batteries, and particularly relates to a manganese-containing fluoride thermal battery.
Background
The thermal battery is a reserve type high-temperature molten salt battery that is activated by melting molten salt as an electrolyte using a heat source. The thermal battery can discharge in a large current pulse or constant current, has the characteristics of higher specific energy and specific power, wide use environment temperature, long storage time, no need of maintenance, quick and reliable activation, simple and convenient process, strong environmental adaptability and the like, and rapidly develops into an ideal power supply of a modern weapon.
The core component of the thermal battery is a single battery consisting of a diaphragm, a negative electrode and a positive electrode. The diaphragm material is solid molten salt and binder, namely, is used as a conductive medium and also plays a role in isolating anode and cathode materials, and is commonly used as a eutectic salt electrolyte based on lithium-halogen compounds. The negative electrode material mainly adopts alkali metal, alkaline earth metal and alloy thereof with negative electrode potential, wherein LiB alloy gradually becomes the latest generation negative electrode material of the thermal battery. The positive electrode material of the thermal battery mainly comprises transition metal disulfide, chloride, oxide and the like, and is a key for restricting the improvement of the performance of the thermal battery at present.
F is the element with the strongest electronegativity in the atomic periodic table, and has the highest bonding polarity with metal ions, so that the fluoride positive electrode thermal battery has higher theoretical discharge voltage. Among them, manganese-containing fluoride is a candidate material with great potential because of its stable properties and strong thermal stability. Patent CN111244425B proposes a method of preparing a ceramic powder by MnF 3 The single-body voltage of the positive electrode material for the thermal battery is up to 4V. It should be noted that manganese-containing fluorides undergo partial thermal decomposition at high temperatures, releasing trace amounts of fluorine gas. This not only reduces the operating time and theoretical capacity of the thermal battery, but also increases the internal pressure of the battery, even causing the thermal battery to burst and terminate discharge, causing safety problems.
On the other hand, since fluoride itself has a wide band gap due to its high ionic property, it basically behaves as an insulator, and thus there is a problem that fluoride is poor in conductivity. The adoption of different conductive agents to improve the electron conduction rate and the ion migration rate is an effective means for improving the electrochemical performance of the material. Patent CN103855389a proposes a method for preparing an iron trifluoride/carbon composite material by ball milling, which utilizes a carbon material with high electron conductivity to improve the conductivity of fluoride. Patent CN109841821B proposes adding LiF-NaF-LiCl or LiF-KF-LiCl eutectic molten salt with high ionic conductivity to the positive electrode material, thereby improving the ionic conductivity of the fluoride. Although the conductivity of the fluoride anode material is improved to a certain extent by the composite method, the realization of high-efficiency conductivity between the anode and the cathode of the thermal battery is still an important problem to be solved.
Therefore, how to further enhance the conductivity between the anode and the cathode of the manganese-containing fluoride thermal battery and to properly treat the fluorine gas generated during the operation of the thermal battery is a key step in the manganese-containing fluoride thermal battery becoming a high-power weapon device. At present, no description of a multi-layer diaphragm is seen in the manganese-containing fluoride thermal battery, and no description of a high-temperature fluorine-fixing conversion positive electrode functional agent is seen in the manganese-containing fluoride thermal battery.
Disclosure of Invention
The invention aims to provide a manganese-containing fluoride thermal battery, which provides a choice for the design of a novel thermal battery.
The invention aims at realizing the following technical scheme:
the invention relates to a manganese-containing fluoride thermal battery, which consists of a positive electrode containing manganese fluoride as an active substance, a multi-layer diaphragm, a lithium alloy negative electrode, a heating component and other accessory components, wherein the multi-layer diaphragm at least consists of a first functional transition layer and a second mass transfer conductive layer which are different in chemical composition. The multi-layer film provided by the invention is particularly used for a manganese-containing fluoride thermal battery, and has the functions of conducting electricity, fixing fluorine, assisting in discharging and the like.
As one embodiment, the manganese-containing fluoride thermal battery has no-load monomer voltage of 3.0-3.7V and activation time of 0.5-0.8 s.
As one embodiment, the manganese-containing fluoride active material comprises MnF 2 、MnF 3 、MnF 4 、Mn 2 F 5 Such as one or more of physical mixing or chemical compounding, preferably MnF 2 、MnF 3 。
As one embodiment, the first functional transition layer of the multi-layered separator is adjacent to the positive electrode and the second mass transfer conductive layer is adjacent to the negative electrode. The multi-layer diaphragm can be provided with a layered interface or integrated (the integrated composite integration refers to that the multi-layer diaphragm or the multi-layer diaphragm and the anode and cathode materials are pressed and formed sequentially at one time or sprayed sequentially, as shown in fig. 1, and the multi-layer diaphragm is still in a layered structure basically). The layered interface and the composite integration depend on the battery manufacturing process, the powder pressing process is adopted to favor the layered monolithic structure under the condition that the powder amount is enough, the powder amount is less, the composite integration is adopted, the processes of coating, spraying and the like are adopted, and the composite integration is mainly adopted.
As one embodiment, the first functional transition layer is composed of a high temperature fluorine-fixing conversion positive electrode functional agent, a carbonaceous conductive agent, a high temperature ion conductive agent and a high temperature chemical inert oxide in a certain proportion.
As one embodiment, the ion conductive agent comprises a compound selected from the group consisting of LiF, liCl, liBr, naF, naCl, naBr, KF, KCl, KBr, csCl, liNO 3 、KNO 3 、Li 2 SO 4 、Na 2 SO 4 、Li 2 CO 3 、Na 2 CO 3 And LiOH, naOH, KOH, and a molten salt composed of two or more substances.
As one embodiment, the second mass transfer conductive layer is composed of a high temperature chemically inert oxide and a high temperature ion conductive electrolyte, wherein the electrolyte composition is different from the ion conductive agent in the first functional transition layer, including a composition of LiF, liCl, liBr, naF, naCl, naBr, KF, KCl, KBr, csCl, liNO 3 、KNO 3 、Li 2 SO 4 、Na 2 SO 4 、Li 2 CO 3 、Na 2 CO 3 The mass ratio of the high-temperature ion conductive electrolyte to the second mass transfer conductive layer is 30-70%
As one embodiment, the weight ratio of the high-temperature fluorine-fixing conversion anode functional agent, the carbonaceous conductive agent, the high-temperature ion conductive agent and the high-temperature chemical inert oxide in the first functional transition layer is 0.1-10:0-1:30-70:30-70.
As one embodiment, the high-temperature fluorine-fixing conversion anode functional agent can react with free fluorine at a high temperature of 200-1000 ℃ and be converted into fluoride with high-temperature stability. The manganese-containing fluoride will be partially thermally decomposed during high temperature operation and generate a minute amount of fluorine gas. The high-temperature fluorine-fixing conversion positive electrode functional agent can absorb fluorine gas, prevent the internal pressure of the battery from increasing, form different metal fluorides, and the formed metal fluorides can further participate in electrochemical reaction to become a conversion positive electrode.
As one embodiment, the high-temperature fluorine-fixing conversion positive electrode functional agent is metal powder with good electronic conductivity, and comprises one or more of lithium, sodium, potassium, aluminum, magnesium, calcium, iron, cobalt, nickel, copper, zinc, manganese, vanadium, chromium, tungsten, titanium, zirconium and other elements. The transition metal powder may be converted to a stable transition metal fluoride by reaction with fluorine gas. The fluoride can be used as an auxiliary positive electrode material, and after the reaction of the positive electrode manganese-containing fluoride positive electrode material is finished, the fluoride can be used as an auxiliary positive electrode material to continue the reaction, so that the secondary relay discharge of the thermal battery is realized, and the discharge life and specific capacity of the fluorine-based thermal battery are improved; the reaction product of the alkali metal powder and the fluorine gas can be used as a molten salt component, so that the wettability and the suitability of the anode material and the molten salt electrolyte are enhanced, and the overall stability and the discharge performance of the thermal battery are improved; the alkaline earth metal reaction product may also be used as an adsorbent.
As one embodiment, the carbonaceous conductive agent includes a composite or mixed carbon material of one or more combinations of carbon nanotubes, carbon fibers, graphene oxide, acetylene black, carbon black, and the like. The carbonaceous conductive agent can accelerate interfacial electron conduction of the positive electrode active material, reduce the overall contact resistance in the electrode and reduce polarization.
As one embodiment, the high temperature chemically inert oxide is MgO, siO 2 ，Al 2 O 3 ，Y 2 O 3 Or a combination or mixed oxide of one or more thereof.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention provides a multi-layer diaphragm in a manganese-containing fluoride thermal battery, and a first functional transition layer is added on the basis of a traditional mass transfer conducting layer so as to reduce the internal resistance of the battery, stabilize the voltage of the battery, adjust the peak voltage and voltage precision of the thermal battery and prolong the working time of the battery;
2) The high-temperature fluorine-fixing conversion anode functional agent is introduced into the first functional transition layer, and can react with fluorine gas released by thermal decomposition to generate a fluoride auxiliary anode material when working at high temperature, and after the reaction of the manganese-containing fluoride anode material is finished, the fluoride auxiliary anode material is used as the auxiliary anode material to continue the reaction, so that the secondary relay discharge of the thermal battery is realized, and the discharge life and specific capacity of the fluorine-based thermal battery are improved;
2) According to the invention, the carbonaceous conductive agent and the high-temperature ionic conductive agent are introduced into the first functional transition layer, so that the overall conductivity of the thermal battery is improved, and the wettability and the suitability of the positive electrode material and the molten salt electrolyte are enhanced, thereby improving the overall stability and the discharge performance of the thermal battery;
3) The manganese-containing fluoride thermal battery prepared by the invention has the characteristics of high monomer voltage, quick activation and long working time, has higher application value, and is expected to be used in the fields of high-voltage thermal batteries and energy sources on a large scale.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is a schematic diagram of a manganese-containing fluoride thermal battery;
FIG. 2 is a graph of the discharge of the thermal battery of example 1;
FIG. 3 is a graph of internal resistance of the thermal battery of example 1;
FIG. 4 is a graph of comparative example 1 thermal battery discharge;
FIG. 5 is a graph of internal resistance of the thermal battery of comparative example 1;
FIG. 6 is a graph of comparative example 2 thermal battery discharge;
FIG. 7 is a graph of internal resistance of the thermal battery of comparative example 2;
FIG. 8 is a graph of comparative example 3 thermal battery discharge;
FIG. 9 is a graph of the internal resistance of the thermal battery of comparative example 3.
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 present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Example 1
By MnF 3 As a positive electrode active material, nickel, carbon nano tubes, liCl-KCl and magnesium oxide with a mass ratio of 5:1:55:39 are used as a first functional transition layer, and magnesium oxide, liF-LiCl-KF-LiNO with a mass ratio of 40:60 are used as a second functional transition layer 3 -Li 2 SO 4 -Li 2 CO 3 As a second mass transfer conductive layer, a manganese-containing fluoride thermal battery was prepared and assembled with a lithium-boron alloy as a negative electrode material, as shown in fig. 1 (reference numeral 5). The no-load monomer voltage is 3.46V, the activation time is 0.66s, and the 2.5V voltage is the cut-off voltage, 110mA/cm 2 The operating time was 152s, as shown in fig. 2. At 1A/cm 2 At current density, the internal resistance was about 18mΩ, as shown in fig. 3.
Example 2
By MnF 3 As the positive electrode active material, the mass ratio was 6:0.1:54.9:39 cobalt, graphene, liCl-LiCO 3 、SiO 2 As a first functional transition layer, mgO and LiF-LiCl-KBr-Li with the mass ratio of 45:55 2 SO 4 And as a second mass transfer conductive layer, preparing and assembling the manganese-containing fluoride thermal battery by taking the lithium-boron alloy as a negative electrode material. The no-load monomer voltage is 3.42V, the activation time is 0.59s, and the 2.5V voltage is the cut-off voltage, 110mA/cm 2 The operating time was 166s for the current density discharge case. At 1A/cm 2 At current density, the internal resistance is about 19mΩ.
Example 3
By MnF 3 As the positive electrode active material, iron, liF-LiCl-LiBr, al in a mass ratio of 8:52:40 2 O 3 As a first functional transition layer, the mass ratio is 30:70, and preparing and assembling a manganese-containing fluoride thermal battery by taking MgO and LiF-NaF-KF-LiCl as a second mass transfer conductive layer and taking a lithium boron alloy as a negative electrode material. The no-load monomer voltage is 3.65V, the activation time is 0.71s, and the 2.5V voltage is the cut-off voltage, 110mA/cm 2 The operating time was 130s in the case of a current density discharge. At 1A/cm 2 At current density, the internal resistance is about 18mΩ.
Example 4
By MnF 2 As the positive electrode active material, zinc, graphene oxide, liCl-LiBr-KBr, mgO, and Al in a mass ratio of 3:1:56:40 2 O 3 As a first functional transition layer, mgO-Y with a mass ratio of 50:50 2 O 3 The mixture and LiF-LiCl-LiBr are used as a second mass transfer conductive layer, and the lithium silicon alloy is used as a negative electrode material to prepare and assemble the manganese-containing fluoride thermal battery. The no-load monomer voltage was 3.02V, the activation time was 0.69s, and the working time was 78s. At 1A/cm 2 At current density, the internal resistance is about 22mΩ.
Example 5
By MnF 2 Nickel and lithium in a mass ratio of 4:1:55:40, carbon black, liCl-Li as positive electrode active materials 2 SO 4 And SiO 2 As a first functional transition layer, al with a mass ratio of 60:40 2 O 3 LiCl-KCl-NaF is used as a second mass transfer conductive layer, and a lithium boron alloy is used as a negative electrode material to prepare and assemble the manganese-containing fluoride thermal battery. The no-load monomer voltage was 3.14V, the activation time was 0.57s, and the working time was 102s. At 1A/cm 2 At current density, the internal resistance is about 25mΩ.
Example 6
By MnF 3 As the positive electrode active material, iron and calcium, carbon nanotubes, liOH-LiCl, siO were mixed in a mass ratio of 8:0.5:53.5:38 2 As a first functional transition layer, the mass ratio is 70:30, and preparing and assembling a manganese-containing fluoride thermal battery by taking MgO and LiF-KF-NaF as a second mass transfer conductive layer and taking a lithium-boron alloy as a negative electrode material. The no-load monomer voltage is 3.41V, the activation time is 0.5s, and the 2.5V voltage is the cut-off voltage, 110mA/cm 2 The operating time was 133s in the case of current density discharge. At 1A/cm 2 At current density, the internal resistance is about 17mΩ.
Example 7
By MnF 2 As the positive electrode active material, copper, carbon black, liCl-KCl and MgO in a mass ratio of 7:1:52:40 were used as the first functional transition layer, and the mass ratio was 35:65 MgO, liNO 3 -KNO 3 And as a second mass transfer conductive layer, preparing and assembling the manganese-containing fluoride thermal battery by taking the lithium-boron alloy as a negative electrode material. No-load single-body electricityThe voltage is 3.0V, the activation time is 0.72s, and the voltage of 2.5V is cut-off voltage, 110mA/cm 2 The operating time was 78s for the current density discharge case. At 1A/cm 2 At current density, the internal resistance is about 25mΩ.
Comparative example 1
By MnF 2 As the positive electrode active material, the mass ratio was 35:65 MgO, liNO 3 -KNO 3 As a single-layer separator, a manganese-containing fluoride thermal battery was prepared and assembled with a lithium-boron alloy as a negative electrode material. The no-load monomer voltage was 2.4V, the activation time was 0.89s, and the 2.5V cut-off voltage was not reached during the test, as shown in fig. 4. At 1A/cm 2 At current density, the internal resistance was about 42mΩ, as shown in fig. 5.
Comparative example 2
By MnF 2 As the positive electrode active material, carbon black, liCl-KCl and MgO with a mass ratio of 1:52:40 were used as the first functional transition layer, and the mass ratio was 35:65 MgO, liNO 3 -KNO 3 And as a second mass transfer conductive layer, preparing and assembling the manganese-containing fluoride thermal battery by taking the lithium-boron alloy as a negative electrode material. The no-load monomer voltage is 2.8V, the activation time is 0.85s, and the 2.5V voltage is the cut-off voltage, 110mA/cm 2 The operating time was 15s as shown in fig. 6 for the current density discharge case. At 1A/cm 2 At current density, the internal resistance was about 31mΩ, as shown in fig. 7.
Comparative example 3
By MnF 2 As the positive electrode active material, copper, liCl-KCl and MgO with a mass ratio of 7:52:40 were used as the first functional transition layer, and the mass ratio was 35:65 MgO, liNO 3 -KNO 3 And as a second mass transfer conductive layer, preparing and assembling the manganese-containing fluoride thermal battery by taking the lithium-boron alloy as a negative electrode material. The no-load monomer voltage is 2.9V, the activation time is 0.77s, and the 2.5V voltage is the cut-off voltage, 110mA/cm 2 The operating time was 21s, as shown in fig. 8. At 1A/cm 2 At current density, the internal resistance was about 29mΩ, as shown in fig. 9.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (9)
1. The manganese-containing fluoride thermal battery is characterized by comprising a positive electrode containing manganese fluoride as an active substance, a multi-layer diaphragm, a lithium alloy negative electrode and a heating component, wherein the multi-layer diaphragm is of a multi-layer structure at least comprising a first functional transition layer and a second mass transfer conductive layer which contain molten salts with different chemical compositions; the first functional transition layer of the multi-layer diaphragm is adjacent to the positive electrode, and the second mass transfer conductive layer is adjacent to the negative electrode; the first functional transition layer consists of a high-temperature fluorine-fixing conversion anode functional agent, a carbonaceous conductive agent, a high-temperature ion conductive agent and a high-temperature chemical inert oxide in a certain proportion; the high-temperature fluorine-fixing conversion anode functional agent is metal powder with good electronic conductivity.
2. The manganese-containing fluoride thermal battery of claim 1, wherein the manganese-containing fluoride active material comprises MnF 2 、MnF 3 、MnF 4 、Mn 2 F 5 Is formed by physically mixing or chemically compounding one or more of the above materials.
3. The manganese-containing fluoride thermal battery of claim 1, wherein the multi-layered separator has a layered interface or is an integral composite integration.
4. The manganese-containing fluoride thermal battery of claim 1, wherein the high temperature ion conductive agent comprises a metal selected from the group consisting of LiF, liCl, liBr, naF, naCl, naBr, KF, KCl, KBr, csCl, liNO 3 、KNO 3 、Li 2 SO 4 、Na 2 SO 4 、Li 2 CO 3 、Na 2 CO 3 And LiOH, naOH, KOH, and a molten salt consisting of at least two substances.
5. The manganese-containing fluoride thermal battery according to claim 4, wherein the weight ratio of the high-temperature fluorine-fixing conversion positive electrode functional agent, the carbonaceous conductive agent, the high-temperature ion conductive agent and the high-temperature chemical inert oxide in the first functional transition layer is 0.1-10:0.1-1:30-70:30-70.
6. The manganese-containing fluoride thermal battery of claim 4, wherein the electronically conductive metal powder comprises one or more of lithium, sodium, potassium, aluminum, magnesium, calcium, iron, cobalt, nickel, copper, zinc, manganese, vanadium, chromium, tungsten, titanium, zirconium.
7. The manganese-containing fluoride thermal battery of claim 4, wherein the carbonaceous conductive agent comprises a composite or mixed carbon material of one or more of carbon nanotubes, carbon fibers, graphene oxide, acetylene black, carbon black.
8. The manganese-containing fluoride thermal battery of claim 1, wherein the second mass transfer conductive layer is comprised of a high temperature chemically inert oxide and a high temperature ion conductive electrolyte, wherein the electrolyte composition is distinct from the ion conductive agent in the first functional transition layer, comprising a metal oxide selected from the group consisting of LiF, liCl, liBr, naF, naCl, naBr, KF, KCl, KBr, csCl, liNO 3 、KNO 3 、Li 2 SO 4 、Na 2 SO 4 、Li 2 CO 3 、Na 2 CO 3 The high-temperature ion conductive electrolyte accounts for 30-70% of the mass of the second mass transfer conductive layer.
9. The manganese-containing fluoride thermal battery of claim 4 or 8, wherein the high temperature chemically inert oxide is MgO, siO 2 、Al 2 O 3 、Y 2 O 3 A composite or mixed oxide of one or more of the above.
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