CN112563489A - Preparation method of nickel chloride anode for novel thermal battery - Google Patents
Preparation method of nickel chloride anode for novel thermal battery Download PDFInfo
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Abstract
The invention relates to a preparation method of a novel nickel chloride anode for a thermal battery, which comprises the following steps: step 1: adopting NiCl2 & 6H2O containing crystal water as an initial raw material, and performing forced air drying and vacuum drying, and crushing to obtain yellow anhydrous nickel chloride powder; step 2: carrying out vacuum drying treatment on the molten salt electrolyte; and step 3: respectively weighing anhydrous nickel chloride powder and dried molten salt electrolyte according to the mass ratio of nickel chloride to the molten salt electrolyte in the nickel chloride cathode material, uniformly mixing, melting in a muffle furnace at 450-650 ℃ for 2-3 h, cooling to room temperature, and crushing by a crusher to obtain a nickel chloride cathode precursor; and 4, step 4: respectively weighing precursor powder and nano-alumina according to the mass percentages of nickel chloride, molten salt electrolyte and alumina in the anode material, uniformly mixing, and placing in a muffle furnace for melting at 450-650 ℃ for 2-3 h; and 5: and cooling the mixture obtained after melting to room temperature, then crushing in a crusher, and drying in vacuum to obtain the cathode material. The nickel chloride anode prepared by the method has the characteristics of high voltage, good conductivity, good formability, long storage life and the like.
Description
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a preparation method of a novel nickel chloride anode material for a thermal battery.
Background
The traditional lithium alloy-metal disulfide electrochemical system has the characteristics of stable voltage, high specific power, large specific energy, high mechanical strength and the like, and is most widely applied to thermal batteries. However, the cell voltage of this type of system is low (about 2 v), the cathode is easily polarized during heavy current discharge, and the thermal stability is poor (about 550 ℃ for FeS2 and about 650 ℃ for CoS 2), and the capacity loss is large during high temperature operation. Meanwhile, the initial voltage spike is insufficient in the initial discharge period. Therefore, it is a continuous object to find a positive electrode material having a discharge capacity matching that of a lithium alloy anode, good thermal stability and a high decomposition temperature.
Compared with an iron disulfide anode, the nickel chloride serving as the anode material of the lithium thermal battery has the advantages of high theoretical capacity, high discharge current density, positive electrode potential (the voltage of a single battery reaches 2.6V) and the like, and is an ideal anode material matched with the excellent performance of a lithium alloy anode.
However, the following problems also exist in the conventional nickel chloride positive electrode battery:
1) the nickel chloride has compact structure, small specific surface area and poor electrochemical performance before high temperature or sublimation treatment. In order to improve the performance of the nickel chloride powder, sublimation treatment is required to be carried out, so that the structure of the nickel chloride powder is loose, the specific surface area is large, but the sublimation temperature is high, special equipment needs to be designed, the equipment is complex, the operation is difficult, and the formability of the nickel chloride powder subjected to sublimation treatment is also poor;
2) the nickel chloride has poor conductivity and electrochemical activity, so that the thermal battery has longer activation time and certain voltage delay, and a conductive agent must be added in the preparation process to enhance the conductivity of the positive electrode, reduce polarization and improve the voltage delay phenomenon. The common conductive agents of the nickel chloride anode are graphite and nickel carbonyl powder, wherein the addition of the graphite can reduce the formability of nickel chloride anode powder and influence the strength of a single battery, the nickel carbonyl powder has an obvious effect only when the addition amount is 20%, but the battery capacity is seriously reduced due to the excessively high addition ratio of the nickel carbonyl powder, and the nickel carbonyl powder is extremely toxic, has great potential safety hazard in practical application and does not meet the requirements of green chemical production;
3) the nickel chloride battery is easy to overflow when working at high temperature, which causes short circuit of the battery and seriously shortens the service life of the battery. The problems restrict the application of the thermal battery.
Disclosure of Invention
The invention aims to provide a preparation method of a novel nickel chloride positive electrode for a thermal battery, which is used for solving the problems in the prior art.
The invention relates to a preparation method of a nickel chloride anode for a novel thermal battery, which comprises the following steps: step 1: adopting NiCl2 & 6H2O containing crystal water as an initial raw material, and performing forced air drying and vacuum drying, and crushing to obtain yellow anhydrous nickel chloride powder; step 2: carrying out vacuum drying treatment on the molten salt electrolyte; and step 3: respectively weighing anhydrous nickel chloride powder and dried molten salt electrolyte according to the mass ratio of nickel chloride to the molten salt electrolyte in the nickel chloride cathode material, uniformly mixing, melting in a muffle furnace at 450-650 ℃ for 2-3 h, cooling to room temperature, and crushing by a crusher to obtain a nickel chloride cathode precursor; and 4, step 4: respectively weighing precursor powder and nano-alumina according to the mass percentages of nickel chloride, molten salt electrolyte and alumina in the anode material, uniformly mixing, and placing in a muffle furnace for melting at 450-650 ℃ for 2-3 h; and 5: and cooling the mixture obtained after melting to room temperature, then crushing in a crusher, and drying in vacuum to obtain the cathode material.
One embodiment of the method for preparing the nickel chloride positive electrode for the novel thermal battery according to the invention is that the preparation environment is a dew point of not more than-32 ℃.
According to one embodiment of the preparation method of the nickel chloride anode for the novel thermal battery, the anode material comprises the following components in percentage by mass: 50-80% of nickel chloride, 10-40% of molten salt electrolyte and 10-30% of alumina.
One embodiment of the method for preparing the nickel chloride positive electrode for the novel thermal battery according to the present invention is that the nickel chloride is dehydrated anhydrous nickel chloride.
According to an embodiment of the method for preparing the nickel chloride positive electrode for the novel thermal battery, the molten salt electrolyte system is as follows: LiF-LiCl-LiBr eutectic salt system or LiCl-KCl eutectic salt system.
According to one embodiment of the preparation method of the nickel chloride anode for the novel thermal battery, disclosed by the invention, a LiF-LiCl-LiBr eutectic salt system comprises the following components in percentage by mass: 9.6% LiF-22.0% LiCl-68.4% LiBr; the LiCl-KCl eutectic salt system comprises the following components in percentage by mass: 45.0% LiCl-55.0% KCl.
One embodiment of the method for preparing the nickel chloride positive electrode for the novel thermal battery according to the invention is that the alumina is nano alumina.
According to one embodiment of the preparation method of the nickel chloride anode for the novel thermal battery, the nano-alumina is gamma-phase alumina, the particle size is 10-50 nm, the specific surface area is 180-250 m2/g, and the purity is more than 99.99%.
According to one embodiment of the method for preparing the nickel chloride anode for the novel thermal battery, the single battery is pressed by taking a mixture of LiF-LiCl-LiBr molten salt electrolyte and electrolyte binder magnesium oxide as an isolating layer and LiB alloy as a single battery cathode.
According to one embodiment of the preparation method of the nickel chloride anode for the novel thermal battery, a mixture of LiCl-KCl molten salt electrolyte and electrolyte binder magnesium oxide is used as an isolation layer, LiSi alloy is used as a single battery cathode, and the single battery is pressed.
The invention provides a preparation method of a nickel chloride anode for a thermal battery, which removes a complicated and difficult sublimation process in the traditional process, and can achieve the purposes of enhancing the conductivity of the anode, reducing polarization and improving voltage hysteresis without additionally adding a conductive agent and a depolarizer. Meanwhile, the problem that the nickel chloride battery is easy to overflow during high-temperature discharge is effectively solved. The positive electrode prepared by the preparation method has the characteristics of high voltage, good conductivity, good formability and the like, and the preparation method has the characteristics of simple process, no sublimation, no addition of a conductive agent and a depolarizer, no complex post-treatment and suitability for industrial large-scale production.
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Detailed Description
In order to make the objects, contents, and advantages of the present invention clearer, the following detailed description of the embodiments of the present invention will be given in conjunction with examples.
In order to solve the technical problems in the prior art, a preparation method of a novel nickel chloride anode for a thermal battery is provided, and the anode material comprises the following components in percentage by mass: 50-80% of nickel chloride, 10-40% of molten salt electrolyte and 10-30% of alumina.
The nickel chloride is dehydrated anhydrous nickel chloride.
The molten salt electrolyte system is as follows: LiF-LiCl-LiBr eutectic salt system or LiCl-KCl eutectic salt system.
The LiF-LiCl-LiBr eutectic salt system comprises the following components in percentage by mass: 9.6% LiF-22.0% LiCl-68.4% LiBr; the LiCl-KCl eutectic salt system comprises the following components in percentage by mass: 45.0% LiCl-55.0% KCl.
The alumina is nano alumina.
The nano-alumina is gamma-phase alumina, the particle size is 10-50 nm, the specific surface area is 180-250 m2/g, and the purity is more than 99.99%.
The invention also provides a preparation method of the nickel chloride cathode material for the thermal battery, which comprises the following steps:
step 1: the method adopts NiCl2 & 6H2O containing crystal water as an initial raw material, and obtains yellow anhydrous nickel chloride powder after air-blast drying and vacuum drying and crushing treatment;
step 2: and carrying out vacuum drying treatment on the molten salt electrolyte at the dew point of not more than-32 ℃.
And step 3: under the condition that the dew point is not more than minus 32 ℃, according to the mass ratio of nickel chloride to molten salt electrolyte in the nickel chloride anode material, respectively weighing the anhydrous nickel chloride and the molten salt electrolyte treated in the step 1 and the step 2, uniformly mixing, melting in a muffle furnace at 450-650 ℃ for 2-3 h, cooling to room temperature, and crushing by a crusher to obtain the nickel chloride anode precursor.
And 4, step 4: under a dry environment with a dew point not greater than-32 ℃, respectively weighing the precursor powder obtained in the step (3) and the nano-alumina according to the mass percentages of the nickel chloride, the molten salt electrolyte and the alumina in the anode material, uniformly mixing, and placing in a muffle furnace for melting at 450-650 ℃ for 2-3 h;
and 5: and (3) under a drying environment with the dew point not more than-32 ℃, cooling the mixture obtained in the step (4) to room temperature, then crushing in a crusher, and carrying out vacuum drying to obtain the cathode material.
The cathode of the thermal battery is made of active lithium alloy, and the absorbed water may react with the lithium alloy at normal temperature, or when the thermal battery is activated, the water vapor and Li react with each other in an exothermic way to consume the Li cathode and reduce the battery capacity, so that the powder is prepared in a drying environment with the dew point not more than-32 ℃ by strictly controlling the dew point of the operating environment, and the absorbed water is removed by vacuum drying.
In the step 1, the blast drying condition is that the temperature is 160-180 ℃ and the time is 2-6 h; the vacuum drying condition is that the vacuum degree is below-0.08 MPa, the temperature is 150-200 ℃, and the time is 6-8 h.
The vacuum drying conditions in the step 2 and the step 5 are as follows: the vacuum degree is below-0.08 MPa, the drying time is 4h, and the temperature is 150 ℃ and 180 ℃.
The molten salt electrolyte in the step 3 comprises two eutectic salt systems, wherein the LiF-LiCl-LiBr eutectic salt system comprises the following components in percentage by mass: 9.6% LiF-22.0% LiCl-68.4% LiBr; in a LiCl-KCl eutectic salt system, the components in percentage by mass are as follows: 45.0% LiCl-55.0% KCl.
In the melting process in the step 3, the nickel chloride is soaked and dispersed in the molten salt electrolyte in the high-temperature melting process, the original compact structure of the nickel chloride is damaged, and the electrochemical activity of the nickel chloride is improved. Meanwhile, the molten salt electrolyte is used as a medium, so that a liquid environment can be provided in the discharge process of the battery, the ion diffusion speed is obviously accelerated, and an ion transmission channel is formed, thereby achieving the purposes of enhancing the conductivity of the anode, reducing polarization and improving the voltage hysteresis of the anode.
For the preparation method of the nickel chloride anode for the thermal battery, the anode material comprises the following components in percentage by mass: the cathode material comprises the following components in percentage by mass: 50-80% of nickel chloride, 10-40% of molten salt electrolyte and 10-30% of alumina.
Example 1 of a method for producing a nickel chloride positive electrode for a thermal battery of the present invention: a preparation method of the nickel chloride anode for the thermal battery comprises the following steps:
step 1: carrying out forced air drying and vacuum drying on NiCl2 & 6H2O, wherein the forced air drying temperature is 175 ℃, and the time is 4 hours; the vacuum drying condition is that the temperature is 180 ℃, the time is 4h, and the vacuum degree is below-0.08 MPa. Crushing to obtain yellow anhydrous nickel chloride powder;
step 2: and carrying out vacuum drying treatment on the LiF-LiCl-LiBr molten salt electrolyte and the nano aluminum oxide.
And step 3: and (2) weighing the anhydrous nickel chloride and the LiF-LiCl-LiBr molten salt electrolyte treated in the steps (1) and (2) respectively according to the mass percentages of 75% and 25% under the condition that the dew point is not more than-32 ℃, uniformly mixing, melting for 2 hours at 550 ℃ in a muffle furnace, cooling to room temperature, and crushing by a crusher to obtain the nickel chloride anode precursor.
And 4, step 4: under a drying environment with a dew point not greater than-32 ℃, respectively weighing the precursor powder obtained in the step 3 and the nano-alumina treated in the step 2 according to the mass percent of 85% and 15%, uniformly mixing, and placing in a muffle furnace for melting at 500 ℃ for 2.5 h;
and 5: and (3) under a drying environment with the dew point not more than-32 ℃, cooling the mixture obtained in the step (4) to room temperature, then crushing in a crusher, and carrying out vacuum drying to obtain the cathode material.
The vacuum drying conditions in the step 2 and the step 5 are that the temperature is 175 ℃, the time is 4 hours, and the vacuum degree is below-0.08 MPa.
The preparation method of the nickel chloride anode for the thermal battery of the invention, embodiment 2, comprises the following steps: a preparation method of the nickel chloride anode for the thermal battery comprises the following steps:
step 1: carrying out forced air drying and vacuum drying on NiCl2 & 6H2O, and crushing to obtain yellow anhydrous nickel chloride powder, wherein the conditions are the same as those in the step 1 in the example 1;
step 2: and (3) carrying out vacuum drying treatment on the LiCl-KCl molten salt electrolyte and the nano aluminum oxide.
And step 3: and (2) weighing the anhydrous nickel chloride and the LiCl-KCl molten salt electrolyte treated in the steps (1) and (2) respectively according to the mass percentage of 70% and 30% under the condition that the dew point is not more than-32 ℃, uniformly mixing, melting for 2 hours at 550 ℃ in a muffle furnace, cooling to room temperature, and crushing by a crusher to obtain the nickel chloride anode precursor.
And 4, step 4: respectively weighing the precursor powder obtained in the step (3) and the nano-alumina according to the mass percent of 83% and 17% in a drying environment with the dew point not more than-32 ℃, uniformly mixing, and placing in a muffle furnace for melting at 500 ℃ for 2.5 h; (ii) a
And 5: and (3) under a drying environment with the dew point not more than-32 ℃, cooling the mixture obtained in the step (4) to room temperature, then crushing in a crusher, and carrying out vacuum drying to obtain the cathode material.
The vacuum drying conditions in the step 2 and the step 5 are that the temperature is 175 ℃, the time is 4 hours, and the vacuum degree is below-0.08 MPa.
The preparation method of the nickel chloride anode for the thermal battery of the invention, embodiment 3, comprises the following steps: analysis of water content of the cathode materials described in examples 1 and 2:
the water content of the cathode material prepared by the method is below 1000ppm by using a trace moisture tester.
Embodiment 4 of a method for producing a nickel chloride positive electrode for a thermal battery according to the present invention; use of the positive electrode material described in example 1 in thermal batteries:
the nickel chloride positive electrode prepared in example 1 was used as a single cell positive electrode material, a mixture of LiF-LiCl-LiBr molten salt electrolyte and electrolyte binder magnesium oxide was used as an isolation layer, and LiB alloy was used as a single cell negative electrode, and a single cell was pressed. The single battery has good formability and high yield. Keeping the temperature at 500 ℃, and respectively testing the open-circuit voltage, the voltage of a load 3 omega and the voltage of a load 1.5 omega of the single battery, wherein the test results are as follows: the open circuit voltage is 2.6-2.7V, the voltage of load 1.5 omega is about 2.45-2.55V, and the voltage of load 3 omega is 2.60-2.65V. The anode powder is used in a thermal battery to simulate the storage life of the thermal battery, and the storage life of the prepared nickel chloride anode thermal battery can reach 20 years.
The preparation method of the nickel chloride anode for the thermal battery of the invention, embodiment 5, comprises the following steps: application of the positive electrode material described in example 2 in thermal batteries:
the nickel chloride positive electrode prepared in example 2 was used as a single cell positive electrode material, a mixture of LiCl-KCl molten salt electrolyte and electrolyte binder magnesium oxide was used as an isolation layer, and a LiSi alloy was used as a single cell negative electrode to compact a single cell. The single battery has good formability and high yield. Keeping the temperature at 500 ℃, and respectively testing the open-circuit voltage, the voltage of a load of 1.5 omega and the voltage of a load of 3 omega of the single battery, wherein the test results are as follows: the open circuit voltage is 2.6-2.7V, the voltage of load 1.5 omega is about 2.4-2.5V, and the voltage of load 3 omega is 2.5-2.6V. The anode powder is used in a thermal battery to simulate the storage life of the thermal battery, and the storage life of the prepared nickel chloride anode thermal battery can reach 25 years.
The nickel chloride anode prepared by the method has the characteristics of high voltage, good conductivity, good formability, long storage life and the like. Meanwhile, the preparation method provided by the invention overcomes the problems of complex sublimation process, poor material formability, easiness in overflow of the anode and the like of the traditional preparation method, and has the following advantages:
(1) the anode material has high potential (no-load voltage is 2.5-2.6V), is higher than the potential of the traditional metal disulfide anode (no-load voltage is 1.9-2.0V), and can more easily meet the requirement of high-power output of a thermal battery;
(2) according to the anode prepared by the preparation method, the electrical property of nickel chloride can be improved without adding conductive agents such as graphite, nickel carbonyl powder and the like, the material formability is improved, the effective capacity of the anode is ensured, the toxic nickel carbonyl powder is avoided, and the anode is safer and more environment-friendly;
(3) according to the preparation method, the nickel chloride is soaked and dispersed in the molten salt electrolyte at high temperature, so that the original compact structure of the nickel chloride is damaged, the electrochemical activity of the nickel chloride is improved, and meanwhile, an ion transmission channel can be formed in the discharge process of a battery, so that the ion diffusion speed is remarkably accelerated, and the purposes of enhancing the conductivity of the positive electrode, reducing polarization and improving the voltage lag of the positive electrode are achieved;
(4) according to the preparation method, the co-melt of the nickel chloride and the molten salt electrolyte and the nano-alumina are subjected to secondary high-temperature melting, and the overflow problem of the anode powder in the working process of the battery is effectively inhibited by utilizing the high specific surface area and the strong adsorption capacity of the nano-alumina;
(5) compared with other known preparation methods, the preparation method of the invention can obtain the anode with good electrical property only through a simple high-temperature co-melting process. The complex sublimation process and the process of adding the conductive agent and the depolarizer in the conventional nickel chloride anode preparation process are avoided. The preparation process is effectively reduced, the process is simplified, the effective capacity of the anode is guaranteed, the prepared powder has good consistency and good performance, and the method is more suitable for large-scale industrial production.
The above examples illustrate: the nickel chloride anode material for the thermal battery prepared by the preparation method has the characteristics of high voltage, good forming, long storage life and the like. The preparation method has simple process and convenient operation, and avoids the complex sublimation process and the process of adding the conductive agent and the depolarizer in the conventional nickel chloride anode preparation process. The preparation process is effectively reduced, the process is simplified, the effective capacity of the anode is guaranteed, the prepared powder has good consistency and good performance, and the method is more suitable for large-scale industrial production.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a novel nickel chloride anode for a thermal battery is characterized by comprising the following steps:
step 1: adopting NiCl2 & 6H2O containing crystal water as an initial raw material, and performing forced air drying and vacuum drying, and crushing to obtain yellow anhydrous nickel chloride powder;
step 2: carrying out vacuum drying treatment on the molten salt electrolyte;
and step 3: respectively weighing anhydrous nickel chloride powder and dried molten salt electrolyte according to the mass ratio of nickel chloride to the molten salt electrolyte in the nickel chloride cathode material, uniformly mixing, melting in a muffle furnace at 450-650 ℃ for 2-3 h, cooling to room temperature, and crushing by a crusher to obtain a nickel chloride cathode precursor;
and 4, step 4: respectively weighing precursor powder and nano-alumina according to the mass percentages of nickel chloride, molten salt electrolyte and alumina in the anode material, uniformly mixing, and placing in a muffle furnace for melting at 450-650 ℃ for 2-3 h;
and 5: and cooling the mixture obtained after melting to room temperature, then crushing in a crusher, and drying in vacuum to obtain the cathode material.
2. The method of preparing a nickel chloride positive electrode for a novel thermal battery as claimed in claim 1, wherein the preparation environment is a dew point of not more than-32 ℃.
3. The method for preparing the nickel chloride anode for the novel thermal battery according to claim 1, wherein the anode material comprises the following components in percentage by mass: 50-80% of nickel chloride, 10-40% of molten salt electrolyte and 10-30% of alumina.
4. The method for preparing a nickel chloride positive electrode for a novel thermal battery according to claim 1, wherein the nickel chloride is dehydrated anhydrous nickel chloride.
5. The method for preparing a nickel chloride positive electrode for a novel thermal battery according to claim 1, wherein the molten salt electrolyte system is: LiF-LiCl-LiBr eutectic salt system or LiCl-KCl eutectic salt system.
6. The method for preparing the nickel chloride anode for the novel thermal battery as claimed in claim 5, wherein the LiF-LiCl-LiBr eutectic salt system comprises the following components in percentage by mass: 9.6% LiF-22.0% LiCl-68.4% LiBr; the LiCl-KCl eutectic salt system comprises the following components in percentage by mass: 45.0% LiCl-55.0% KCl.
7. The method of claim 1, wherein the alumina is nano alumina.
8. The preparation method of the novel nickel chloride anode for the thermal battery as claimed in claim 7, wherein the nano-alumina is gamma-phase alumina, the particle size is 10-50 nm, the specific surface area is 180-250 m2/g, and the purity is more than 99.99%.
9. The method of claim 6, wherein the cell is pressed by using a mixture of LiF-LiCl-LiBr molten salt electrolyte and electrolyte binder magnesium oxide as a separator and LiB alloy as a cell cathode.
10. The method of claim 6, wherein the single cell is pressed by using a mixture of LiCl-KCl molten salt electrolyte and magnesium oxide as electrolyte binder as a separator and LiSi alloy as a negative electrode of the single cell.
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| CN113130840A (en) * | 2021-04-19 | 2021-07-16 | 中国工程物理研究院电子工程研究所 | Thermal battery anode material with high performance and preparation method thereof |
| CN113270578A (en) * | 2021-05-17 | 2021-08-17 | 贵州梅岭电源有限公司 | High specific energy composite electrode plate for thermal battery and preparation method thereof |
| CN114388756A (en) * | 2021-12-27 | 2022-04-22 | 武汉理工大学 | High-performance thermal battery composite positive electrode material and preparation method thereof |
| CN114835176A (en) * | 2022-05-30 | 2022-08-02 | 金川集团镍盐有限公司 | Preparation method of spherical anhydrous nickel chloride product |
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| CN113130840A (en) * | 2021-04-19 | 2021-07-16 | 中国工程物理研究院电子工程研究所 | Thermal battery anode material with high performance and preparation method thereof |
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| CN113270578B (en) * | 2021-05-17 | 2022-07-12 | 贵州梅岭电源有限公司 | High specific energy composite electrode plate for thermal battery and preparation method thereof |
| CN114388756A (en) * | 2021-12-27 | 2022-04-22 | 武汉理工大学 | High-performance thermal battery composite positive electrode material and preparation method thereof |
| CN114835176A (en) * | 2022-05-30 | 2022-08-02 | 金川集团镍盐有限公司 | Preparation method of spherical anhydrous nickel chloride product |
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