CN112652759A - Preparation method of nano copper oxide high-potential positive electrode material for thermal battery - Google Patents
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Abstract
The invention relates to a preparation method of a nano copper oxide high-potential anode material for a thermal battery, wherein the preparation method comprises the following steps of 1: vacuum drying the raw materials, wherein LiCl, LiBr, LiF and KCl are dried and then subjected to ball milling and sieving treatment; step 2: respectively weighing the substances pretreated in the step 1 according to the mass ratio of each component in the molten salt electrolyte, uniformly mixing, melting in a muffle furnace, cooling to room temperature, and crushing by using a crusher to obtain the molten salt electrolyte; and step 3: respectively weighing the nano copper oxide and the molten salt electrolyte according to the mass percentage of the nano copper oxide and the molten salt electrolyte in the anode material, uniformly mixing, and placing in a muffle furnace for melting; and 4, step 4: and (4) cooling the mixture obtained in the step (3) to room temperature, then crushing in a crusher, and drying in vacuum to obtain the cathode material. The invention has the characteristics of simple process, low material cost, few constraint conditions, no need of complex post-treatment, good powder quality consistency and the like.
Description
Technical Field
The invention belongs to the technical field of thermal batteries, and particularly relates to a preparation method and application of a nano copper oxide high-potential positive electrode material for a thermal battery.
Background
The thermal battery is a thermal activation storage battery which uses a self heating system to heat and melt non-conductive solid salt electrolyte into an ion conductor to enter a working state, and has the unique properties of quick activation time, large current density, long storage life and wide use temperature.
With the upgrading and upgrading of weapon systems, the development tends to miniaturization and miniaturization, the power output requirement of thermal battery products is continuously increased, and the capacity loss is large when the traditional metal disulfide positive electrode material works at high temperature because of the limit of the decomposition temperature (about 550 ℃ for FeS2 and about 650 ℃ for CoS 2). The working voltage of both single batteries is less than or equal to 2v, and the high-power output is greatly limited. Therefore, a high-potential cathode material having high thermal stability has become one of the hot spots in the field of thermal batteries.
Copper oxide has gained more and more attention from researchers because of its characteristics such as high thermal stability (decomposition temperature about 1000 ℃), high lithium electromotive force (about 2.3V), good conductivity of reaction products, and high theoretical specific capacity (about 2400C/g).
Pas et al synthesized copper oxide in a bundle-like structure (Journal of Alloys and Compounds, 2009, 484: 322-. However, the copper oxide obtained by the method has high resistivity and poor power output capability.
Shuhaibo et al synthesized the MoS 2/copper oxide composite material (Chinese patent CN106732668A) by a hydrothermal method, and the composite material synthesized by the method has the characteristics of good dispersibility and high crystallinity. However, the hydrothermal method has low yield and is difficult to meet the requirement of large-scale industrial application.
Wang et al synthesized a copper oxide-graphene composite material (Journal of Materials Chemistry, 2010, 20: 10661-10664) by a solution precipitation method, and the composite material synthesized by the method had a high specific surface area and good rate capability. However, the composite material is limited by problems such as graphene preparation and performance consistency.
The copper oxide-based composite anode material (Chinese patent 107611389A) is prepared by the high-temperature decomposition of anhydrous copper oxalate by the Fengdan and the like, so that the anode material has better performance. However, the method is limited by the reaction conditions of the thermal decomposition of anhydrous copper oxalate, and the amount of anhydrous copper oxalate must be strictly calculated and the partial pressure ratio of CO2 and O2 in the reaction gas must be controlled to adjust the relative contents of copper oxide and Cu in the product. Meanwhile, the price of the raw material anhydrous cupric oxalate of the method is very high. Therefore, the method has the disadvantages of complex treatment process, high material cost, more constraint conditions and difficulty in ensuring the quality consistency of the anode powder.
Disclosure of Invention
The invention aims to provide a preparation method of a nano copper oxide high-potential anode material for a thermal battery, which is used for solving the problems that the conductivity of common copper oxide is insufficient, a copper oxide-based composite material is difficult to prepare, the treatment process is complex, the constraint conditions are multiple, the material cost is high, the consistency is poor, the industrial large-scale production is difficult to meet and the like.
The invention relates to a preparation method of a nano copper oxide high-potential anode material for a thermal battery, which comprises the following steps of 1: vacuum drying the raw materials, wherein LiCl, LiBr, LiF and KCl are dried and then subjected to ball milling and sieving treatment; step 2: respectively weighing the substances pretreated in the step 1 according to the mass ratio of each component in the molten salt electrolyte, uniformly mixing, melting in a muffle furnace at 450-650 ℃ for 3-5 h, cooling to room temperature, and crushing by using a crusher to obtain the molten salt electrolyte; and step 3: respectively weighing the nano copper oxide and the molten salt electrolyte according to the mass percentage of the nano copper oxide and the molten salt electrolyte in the anode material, uniformly mixing, and placing in a muffle furnace for melting for 2 hours at 450-650 ℃; and 4, step 4: and (4) cooling the mixture obtained in the step (3) to room temperature, then crushing in a crusher, and drying in vacuum to obtain the cathode material.
According to an embodiment of the method for preparing the nano copper oxide high-potential cathode material for the thermal battery, the vacuum drying conditions are as follows: the vacuum degree is below-0.08 MPa, the temperature is 150-180 ℃, and the drying time is 4 h.
According to an embodiment of the preparation method of the nano copper oxide high-potential cathode material for the thermal battery, in the step 2, the molten salt electrolyte comprises two eutectic salt systems, wherein the 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.
According to an embodiment of the method for preparing the nano copper oxide high-potential cathode material for the thermal battery, in the melting process in the step 3, the nano copper oxide is soaked and dispersed in the molten salt electrolyte at a high temperature, and an ion transmission channel is formed in the battery discharging process.
According to one embodiment of the preparation method of the nano copper oxide high-potential cathode material for the thermal battery, the screening is performed according to 80-120 meshes.
According to an embodiment of the preparation method of the nano copper oxide high-potential cathode material for the thermal battery, the step 2 specifically comprises the following steps: and (2) respectively weighing the substances pretreated in the step (1) according to the mass ratio of each component in the LiF-LiCl-LiBr molten salt electrolyte, uniformly mixing, melting for 2 hours at 550 ℃ in a muffle furnace, cooling to room temperature, crushing, and sieving with a 100-mesh sieve to obtain the LiF-LiCl-LiBr molten salt electrolyte.
According to an embodiment of the preparation method of the nano copper oxide high-potential cathode material for the thermal battery, the step 3 specifically comprises the following steps: under the condition that the dew point is not more than-32 ℃, respectively weighing nano copper oxide and LiF-LiCl-LiBr molten salt electrolyte, wherein the mass percentages of the nano copper oxide and the LiF-LiCl-LiBr molten salt electrolyte are respectively 75.5% and 24.5%, uniformly mixing, and placing in a muffle furnace for melting at 550 ℃ for 4 hours.
According to an embodiment of the preparation method of the nano copper oxide high-potential cathode material for the thermal battery, the cathode material comprises the following components in percentage by mass: 60 to 90 percent of nano copper oxide and 10 to 40 percent of molten salt electrolyte.
According to an embodiment of the method for preparing the nano copper oxide high-potential cathode material for the thermal battery, the copper oxide is nano copper oxide.
According to an embodiment of the preparation method of the nano copper oxide high-potential cathode material for the thermal battery, steps 2-4 are carried out under the condition that the dew point is not more than-32 ℃.
The invention provides a nano copper oxide high-potential anode material for a thermal battery, and a preparation method and application thereof, the anode material solves the problems that the conductivity of common copper oxide is insufficient, a copper oxide-based composite material is difficult to prepare, the treatment process is complex, the constraint conditions are more, the material cost is high, the consistency is poor, the industrial large-scale production is difficult to meet, and the like, and the preparation method has the characteristics of simple process, low material cost, few constraint conditions, no need of complex post-treatment, good powder quality consistency, and the like.
Drawings
Fig. 1 is a discharge curve diagram of a unit cell with a nano copper oxide positive electrode and iron disulfide as a positive electrode prepared in example 1 under the conditions of 550 ℃ and 3 Ω load.
Fig. 2 is a discharge curve diagram of the unit cell with the nano-copper oxide positive electrode and the iron disulfide positive electrode prepared in example 1 under the conditions of 550 ℃ and 1.5 omega load.
Fig. 3 is a discharge curve diagram of the unit cell with the nano-copper oxide positive electrode and the iron disulfide positive electrode prepared in example 2 under the conditions of 550 ℃ and 3 Ω load.
Fig. 4 is a discharge curve diagram of the unit cell with the nano-copper oxide positive electrode and the iron disulfide positive electrode prepared in example 2 under the conditions of 600 ℃ and 3 Ω load.
Fig. 5 is a discharge curve diagram of the unit cell with the nano-copper oxide positive electrode and the iron disulfide positive electrode prepared in example 2 under the conditions of 650 ℃ and 3 Ω load.
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 made in conjunction with the accompanying drawings and examples.
The invention provides a preparation method of a nano copper oxide high-potential anode material for a thermal battery, which comprises the following steps:
step 1: all raw materials in the invention need vacuum drying treatment. Drying LiCl, LiBr, LiF and KCl, and then performing ball milling and sieving (80-120 meshes) treatment;
step 2: under the condition that the dew point is not more than-32 ℃, respectively weighing the medicines pretreated in the step 1 according to the mass ratio of each component in the molten salt electrolyte, uniformly mixing, melting in a muffle furnace at 450-650 ℃ for 3-5 h, cooling to room temperature, and crushing by a crusher to obtain the molten salt electrolyte.
And step 3: under the condition that the dew point is not more than-32 ℃, respectively weighing the nano copper oxide and the molten salt electrolyte according to the mass percentage of the nano copper oxide and the molten salt electrolyte in the cathode material, uniformly mixing, and placing in a muffle furnace for melting for 2 hours at 450-650 ℃;
and 4, step 4: and (3) cooling the mixture obtained in the step (3) to room temperature in a drying environment with the dew point not more than-32 ℃, 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.
The vacuum drying conditions in the above steps are all as follows: the vacuum degree is below-0.08 MPa, the temperature is 150-180 ℃, and the drying time is 4h to remove the crystal water.
The molten salt electrolyte in the step 2 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 nano copper oxide is soaked and dispersed in the molten salt electrolyte at high temperature, so that an ion transmission channel can be formed in the discharging process of the battery, and the ion diffusion speed is obviously accelerated. Compared with other preparation methods, the method does not need to synthesize copper oxide or prepare copper oxide-based composite materials through chemical reaction, effectively reduces preparation procedures, and has the advantages of less conditions to be controlled, low material cost, uniform particle size distribution of prepared powder, good consistency and good performance.
The invention provides a preparation method and application of a nano copper oxide high-potential anode material for a thermal battery, wherein the anode material comprises the following components in percentage by mass: 60 to 90 percent of nano copper oxide and 10 to 40 percent of molten salt electrolyte. The copper oxide is nano copper oxide. The particle size of the nano copper oxide is 40-50nm, the nano copper oxide has a spherical structure, and the purity is more than 99%. 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 invention relates to a nano copper oxide high-potential anode material for a thermal battery, which comprises the following components in percentage by mass: 60 to 90 percent of nano copper oxide and 10 to 40 percent of molten salt electrolyte. The nano copper oxide in the anode material has small particle size, large specific surface area and high reaction activity, the electrical property of the nano copper oxide is superior to that of common copper oxide, and meanwhile, the molten salt electrolyte is used as an ion conductor in the anode material, so that the electrical conductivity of the anode material can be improved.
Example 1: a preparation method of the nano-copper oxide high-potential positive electrode material for the thermal battery comprises the following steps:
step 1: carrying out vacuum drying on nano copper oxide, LiCl, LiBr and LiF, wherein the LiCl, LiBr and LiF are subjected to ball milling and sieving (80-120 meshes) after being subjected to vacuum drying;
step 2: and (2) under the condition that the dew point is not more than-32 ℃, respectively weighing the medicines pretreated in the step (1) according to the mass ratio of each component in the LiF-LiCl-LiBr molten salt electrolyte (9.6% LiF-22.0% LiCl-68.4% LiBr), uniformly mixing, melting for 2 hours at 550 ℃ in a muffle furnace, cooling to room temperature, crushing, and sieving with a 100-mesh sieve to obtain the LiF-LiCl-LiBr molten salt electrolyte.
And step 3: respectively weighing nano copper oxide and LiF-LiCl-LiBr molten salt electrolyte under the condition that the dew point is not more than-32 ℃, wherein the mass percentages of the nano copper oxide and the LiF-LiCl-LiBr molten salt electrolyte are respectively 75.5% and 24.5%, uniformly mixing, and placing in a muffle furnace for melting at 550 ℃ for 4 hours;
and 4, step 4: and (3) cooling the mixture obtained in the step (3) to room temperature in a drying environment with the dew point not more than-32 ℃, then crushing in a crusher, and carrying out vacuum drying to obtain the cathode material.
The vacuum drying conditions in the above steps are all as follows: the vacuum degree is below-0.08 MPa, the temperature is 150-180 ℃, and the drying time is 4h to remove the crystal water. Preferably, the temperature is 175 ℃.
Example 2:
step 1: carrying out vacuum drying on the nano copper oxide, LiCl and KCl, wherein the LiCl and KCl are subjected to ball milling and sieving (80-120 meshes) after vacuum drying;
step 2: under the condition that the dew point is not more than minus 32 ℃, according to the mass ratio of each component in the LiCl-KCl molten salt electrolyte (45.0 percent LiCl-55.0 percent KCl), respectively weighing the medicines pretreated in the step 1, uniformly mixing, melting for 4 hours at 500 ℃ in a muffle furnace, cooling to room temperature, crushing and sieving by a 100-mesh sieve to obtain the LiCl-KCl molten salt electrolyte.
And step 3: respectively weighing nano copper oxide and LiCl-KCl molten salt electrolyte at the dew point of not more than-32 ℃, wherein the percentages of the nano copper oxide and the LiCl-KCl molten salt electrolyte are 65% and 35%, respectively, uniformly mixing, and placing in a muffle furnace for melting at 500 ℃ for 2 hours; (ii) a
And 4, step 4: and (3) crushing the mixture in the step (3) in a crusher in a drying environment with a dew point not more than-32 ℃, and performing vacuum drying to obtain the cathode material.
The vacuum drying conditions in the above steps are all as follows: the vacuum degree is below-0.08 MPa, the temperature is 150-180 ℃, and the drying time is 4h to remove the crystal water. Preferably, the temperature is 175 ℃.
Example 3: the positive electrode materials of example 1 and example 2 were tested for thermal stability
The thermal stability of the positive electrode materials of examples 1 and 2 was tested by a german staka 409PC differential scanning calorimeter, and copper oxide did not decompose or react with the molten salt electrolyte at 25-800 ℃.
Example 4: use of the positive electrode material described in example 1 in a thermal battery.
The nano-copper oxide anode prepared in example 1 and conventional iron disulfide were used as anode materials of the single cell, 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 cathode of the single cell, and the single cell was pressed. And (3) carrying out the electrical property test of the single battery under the conditions of constant temperature of 550 ℃ and load of 3 omega and 1.5 omega respectively. As shown in fig. 1 and 2, under the load conditions of 3 Ω and 1.5 Ω, the single cell using the nano-copper oxide cathode material prepared in example 1 as the cathode has a longer operation time and a higher voltage plateau than the single cell using iron disulfide as the cathode.
Example 5: use of the positive electrode material described in example 2 in a thermal battery.
The nano-copper oxide positive electrode prepared in example 2 and the conventional iron disulfide were used as the positive electrode materials of the single cell, the mixture of the LiCl-KCl molten salt electrolyte and the electrolyte binder magnesium oxide was used as the separator, and the LiSi alloy was used as the negative electrode of the single cell, and the single cell was pressed. The electrical performance test of the single battery is carried out under the conditions of 550 ℃, 600 ℃ and 650 ℃ and the load of 3 omega respectively. As shown in fig. 3, 4 and 5, the discharge curves of the unit cells using the nano copper oxide cathode material prepared in example 2 as the anode have significantly longer operation time and much higher voltage plateau than the unit cells using iron disulfide as the anode at three different operation temperatures of 550 ℃, 600 ℃ and 650 ℃.
The above examples illustrate that the positive electrode material of the present invention has high voltage, large capacity, good thermal stability, long working time, and electrical properties significantly better than iron disulfide positive electrode materials.
The nano copper oxide high-potential anode material for the thermal battery has high potential and good thermal stability, and the preparation method solves the problems that the common copper oxide has insufficient conductivity, the copper oxide based composite material is difficult to prepare, the treatment process is complex, the constraint conditions are multiple, the consistency is poor, the industrial large-scale production is difficult to meet and the like, and has the following advantages:
(1) the anode material has high potential (no-load voltage is 2.5-2.6V), and the potential is higher than that of a traditional metal disulfide anode (no-load voltage is 1.9-2.0V) and a common copper oxide or copper oxide-based composite anode (no-load voltage is 2.2-2.3V), so that the requirement of high-power output of a thermal battery is more easily met;
(2) the anode material has good thermal stability, and can not generate decomposition and side reaction within the temperature range of 25-800 ℃;
(3) the positive electrode material comprises the nano copper oxide and the molten salt electrolyte, the specific surface area and the reaction activity of the copper oxide positive electrode material can be improved by adopting the nano copper oxide, the contact area of an electrode and the electrolyte is large, the electrode reaction is more complete, and the battery discharge capacity is large;
(4) according to the preparation method, the nano copper oxide is soaked and dispersed in the molten salt electrolyte at high temperature, so that an ion transmission channel can be formed in the discharge process of the battery, and the ion diffusion speed is remarkably accelerated;
(5) compared with other preparation methods, the preparation method provided by the invention can obtain the positive electrode with good consistency only by a simple high-temperature melting process. The copper oxide is not required to be synthesized or the copper oxide-based composite material is not required to be prepared through chemical reaction, the preparation procedures are effectively reduced, the material cost is low, and the prepared powder has uniform particle size distribution, good consistency and good performance, and 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 nano copper oxide high-potential anode material for a thermal battery is characterized in that,
step 1: vacuum drying the raw materials, wherein LiCl, LiBr, LiF and KCl are dried and then subjected to ball milling and sieving treatment;
step 2: respectively weighing the substances pretreated in the step 1 according to the mass ratio of each component in the molten salt electrolyte, uniformly mixing, melting in a muffle furnace at 450-650 ℃ for 3-5 h, cooling to room temperature, and crushing by using a crusher to obtain the molten salt electrolyte;
and step 3: respectively weighing the nano copper oxide and the molten salt electrolyte according to the mass percentage of the nano copper oxide and the molten salt electrolyte in the anode material, uniformly mixing, and placing in a muffle furnace for melting for 2 hours at 450-650 ℃;
and 4, step 4: and (4) cooling the mixture obtained in the step (3) to room temperature, then crushing in a crusher, and drying in vacuum to obtain the cathode material.
2. The method for preparing a nano copper oxide high-potential positive electrode material for a thermal battery according to claim 1, wherein the vacuum drying conditions are as follows: the vacuum degree is below-0.08 MPa, the temperature is 150-180 ℃, and the drying time is 4 h.
3. The method for preparing a nano copper oxide high-potential cathode material for a thermal battery according to claim 1, wherein the molten salt electrolyte in the step 2 comprises two eutectic salt systems, and the eutectic salt system LiF-LiCl-LiBr 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.
4. The method for preparing a nano copper oxide high-potential cathode material for a thermal battery as claimed in claim 1, wherein the nano copper oxide is dispersed in the molten salt electrolyte by soaking at a high temperature during the melting process in the step 3, and an ion transport channel is formed during the discharging process of the battery.
5. The method for preparing a nano copper oxide high-potential positive electrode material for a thermal battery according to claim 1, wherein the nano copper oxide high-potential positive electrode material is sieved and processed by 80-120 meshes.
6. The method for preparing the nano-copper oxide high-potential cathode material for the thermal battery according to claim 1, wherein the step 2 specifically comprises the following steps: and (2) respectively weighing the substances pretreated in the step (1) according to the mass ratio of each component in the LiF-LiCl-LiBr molten salt electrolyte, uniformly mixing, melting for 2 hours at 550 ℃ in a muffle furnace, cooling to room temperature, crushing, and sieving with a 100-mesh sieve to obtain the LiF-LiCl-LiBr molten salt electrolyte.
7. The method for preparing the nano-copper oxide high-potential positive electrode material for the thermal battery according to claim 1, wherein the step 3 specifically comprises the following steps: under the condition that the dew point is not more than-32 ℃, respectively weighing nano copper oxide and LiF-LiCl-LiBr molten salt electrolyte, wherein the mass percentages of the nano copper oxide and the LiF-LiCl-LiBr molten salt electrolyte are respectively 75.5% and 24.5%, uniformly mixing, and placing in a muffle furnace for melting at 550 ℃ for 4 hours.
8. The preparation method of the nano-copper oxide high-potential cathode material for the thermal battery as claimed in claim 1, wherein the cathode material comprises the following components in percentage by mass: 60 to 90 percent of nano copper oxide and 10 to 40 percent of molten salt electrolyte.
9. The method for preparing a nano copper oxide high-potential cathode material for a thermal battery as claimed in claim 1, wherein the copper oxide is nano copper oxide.
10. The method for preparing a nano copper oxide high-potential cathode material for a thermal battery according to claim 1, wherein the steps 2 to 4 are all carried out under the condition that the dew point is not more than-32 ℃.
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