CN108172757B - High-voltage thermal battery negative electrode material, high-voltage thermal battery and preparation method of high-voltage thermal battery negative electrode material - Google Patents
High-voltage thermal battery negative electrode material, high-voltage thermal battery and preparation method of high-voltage thermal battery negative electrode material Download PDFInfo
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Abstract
The invention discloses a high-voltage thermal battery cathode material and a high-voltage thermal battery. The thermal battery is composed of a positive electrode material, a negative electrode material and an electrolyte diaphragm material, wherein the positive electrode material is a manganese dioxide material, the negative electrode material is a lithium silicon alloy material coated by a lithium fast ion conductor lithium borate-lithium sulfate, and the electrolyte diaphragm material is a lithium nitrate-potassium nitrate-magnesium oxide material. According to the invention, the lithium silicon alloy is coated by the lithium fast ion conductor lithium borate-lithium sulfate, the interface composition of the negative electrode lithium silicon alloy and the electrolyte lithium nitrate-potassium nitrate and the transmission process of metal cations in the interface in the working process of the battery are changed, the diffusion rate and the ionic conductivity of lithium ions in the interface passivation film layer are greatly increased, and the working voltage of the thermal battery is further improved.
Description
Technical Field
The invention relates to the technical field of thermal batteries, in particular to a high-voltage thermal battery cathode material, a preparation method thereof and a high-voltage thermal battery adopting the high-voltage thermal battery cathode material.
Background
The thermal battery is a disposable reserve battery which adopts high-temperature molten salt as electrolyte and generally consists of a positive plate, a negative plate, an electrolyte diaphragm plate, a heating system and an activation system; the working principle is that the ignition paper is ignited by utilizing an activation system, and the electrolyte is heated by a heating system under the action of the ignition paper to be melted into an ion conductor and enter a working state; the thermal battery has the characteristics of high specific energy, high specific power, quick activation, long storage time and long-time maintenance-free property, and is widely applied to the military field and the high and new technology weapon field.
At present, most of the heatThe battery adopts lithium alloy/FeS2、CoS2In an electrochemical system, but the working voltages of the two single batteries are below 2V, so that high-power output is greatly limited; along with the updating and upgrading requirements of weapon systems, the requirement on the power output of the thermal battery is higher and higher, so that the development of the thermal battery of a high-voltage system has wide application prospect and practical significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a high-voltage thermal battery cathode material and a high-voltage thermal battery using the same, so as to solve the problem of low working voltage of the conventional thermal battery.
The technical scheme for solving the technical problems is as follows: provided is a high voltage thermal battery anode material, including: the lithium silicon alloy lithium borate-lithium sulfate fast ion conductor comprises a lithium silicon alloy and a lithium fast ion conductor lithium borate-lithium sulfate coated on the surface of the lithium silicon alloy; the addition amount of the lithium fast ion conductor lithium borate-lithium sulfate is 10-30% of the weight of the lithium silicon alloy.
The beneficial effects of adopting the above technical scheme are: the lithium silicon alloy is coated by the lithium fast ion conductor lithium borate-lithium sulfate, the interface composition of the negative electrode lithium silicon alloy and the electrolyte lithium nitrate-potassium nitrate and the transmission process of metal cations in the interface in the working process of the battery are changed, the diffusion rate and the ionic conductivity of lithium ions in the interface passivation film layer are greatly increased, and the working voltage of the thermal battery is further improved.
On the basis of the technical scheme, the invention can be further improved as follows:
further, the addition amount of the lithium fast ion conductor lithium borate-lithium sulfate is 20% of the weight of the lithium silicon alloy.
Further, the lithium fast ion conductor lithium borate-lithium sulfate is prepared by mixing lithium borate crystals and anhydrous lithium sulfate crystals, wherein the mass percentage of the lithium borate crystals is 30-40%; the mass percentage of the anhydrous lithium sulfate crystal is 60-70%.
Further, the preparation method of the lithium fast ion conductor lithium borate-lithium sulfate comprises the following steps:
(1) placing lithium hydroxide and boric acid in an alumina crucible, carrying out constant temperature treatment for 1 hour at 500 ℃, and then sintering at high temperature for 2 hours at 600 ℃ in an air atmosphere to obtain lithium borate crystals; the weight ratio of the lithium hydroxide to the boric acid is 1: 1;
(2) sintering the lithium sulfate at the high temperature of 300 ℃ for 2 hours in the argon atmosphere to obtain anhydrous lithium sulfate crystals;
(3) placing lithium borate crystals and anhydrous lithium sulfate crystals in ZrO2And (3) ball-milling for 50 hours in a ball-milling tank at 370rpm to obtain the lithium fast ion conductor lithium borate-lithium sulfate.
Another technical solution adopted by the present invention to solve the above technical problems is as follows: the high-voltage thermal battery is composed of a positive electrode material, a negative electrode material and an electrolyte diaphragm material, wherein the content of the positive electrode material is 30-50% by weight; the content of the negative electrode material is 10-30%; the content of the electrolyte diaphragm material is 20-40%; wherein the positive electrode material is manganese dioxide material, the negative electrode material is the high-voltage thermal battery negative electrode material as claimed in any one of claims 1 to 4, and the electrolyte diaphragm material is lithium nitrate-potassium nitrate-magnesium oxide material.
The beneficial effects of adopting the above technical scheme are: the modified negative electrode material, and the specific positive electrode material and the electrolyte diaphragm material which are matched with the modified negative electrode material are adopted, so that on one hand, the side reaction between the electrode material and the electrolyte solution is reduced, and the polarization effect in the discharging process is reduced; on the other hand, the diffusion channel of lithium ions can be greatly increased when the lithium ions are transmitted from the electrolyte solution to the electrode, and under the double action, the diffusion rate and the ionic conductivity of the lithium ions in the interface passivation film layer in the thermal battery of the system are greatly increased, so that the working voltage of the thermal battery is further improved.
On the basis of the technical scheme, the invention can be further improved as follows:
further, the high-voltage thermal battery is composed of a positive electrode material, a negative electrode material and an electrolyte diaphragm material, wherein the content of the positive electrode material is 44% by weight; the content of the negative electrode material is 21%; the content of the electrolyte separator material was 35%; wherein the positive electrode material is manganese dioxide material, the negative electrode material is the high-voltage thermal battery negative electrode material as claimed in any one of claims 1 to 4, and the electrolyte diaphragm material is lithium nitrate-potassium nitrate-magnesium oxide material.
Another technical solution adopted by the present invention to solve the above technical problems is as follows: the preparation method of the high-voltage thermal battery comprises the following steps:
and (3) pressing the positive electrode material, the negative electrode material and the electrolyte diaphragm material into the high-voltage lithium ion thermal battery in a composite mold process mode.
On the basis of the technical scheme, the invention can be further improved as follows:
further, mixing a manganese sulfate monohydrate solution with a potassium permanganate solution, reacting at 140 ℃ for 2 hours, naturally cooling to room temperature, washing an obtained product with deionized water and absolute ethyl alcohol, and drying at 80 ℃ for 10-12 hours to obtain a manganese dioxide material; the weight ratio of the manganese sulfate monohydrate to the potassium permanganate is 1: 2.
Further, the preparation method of the negative electrode material comprises the following steps:
coating lithium borate-lithium sulfate which is a fast lithium ion conductor on a lithium silicon alloy to obtain a lithium silicon alloy cathode material coated with the fast lithium ion conductor lithium borate-lithium sulfate on the surface;
the preparation method of the lithium fast ion conductor lithium borate-lithium sulfate comprises the following steps:
(1) placing lithium hydroxide and boric acid in an alumina crucible, carrying out constant temperature treatment for 1 hour at 500 ℃, and then sintering at high temperature for 2 hours at 600 ℃ in an air atmosphere to obtain lithium borate crystals; the weight ratio of the lithium hydroxide to the boric acid is 1: 1;
(2) sintering the lithium sulfate at the high temperature of 300 ℃ for 2 hours in the argon atmosphere to obtain anhydrous lithium sulfate crystals;
(3) placing lithium borate crystals and anhydrous lithium sulfate crystals in ZrO2And (3) ball-milling for 50 hours in a ball-milling tank at 370rpm to obtain the lithium fast ion conductor lithium borate-lithium sulfate.
Further, the preparation method of the electrolyte membrane material comprises the following steps:
respectively dissolving lithium nitrate and potassium nitrate in distilled water, uniformly dissolving and dispersing, adding 30-40% by mass of magnesium oxide as a flow inhibitor, heating, stirring, drying, placing in an inert atmosphere tube furnace, and melting at 400 ℃ for 4 hours to obtain an electrolyte diaphragm material; wherein the weight ratio of the lithium nitrate to the potassium nitrate is 1: 2.
The invention has the following beneficial effects:
the invention adopts the novel negative electrode material, changes the interface composition of the negative electrode lithium silicon alloy and the electrolyte and the transmission process of metal cations in the interface in the working process of the battery, and combines the negative electrode material with the specific positive electrode material and the electrolyte diaphragm material which are mutually matched to act so as to greatly increase the working voltage of the battery to form a high-voltage thermal battery system, thereby increasing the diffusion channel and the ionic conductivity of lithium ions in the negative electrode/electrolyte interface passivation film, further improving the discharge voltage of the single battery, further improving the specific discharge capacity, further meeting the characteristics of low-temperature and high-voltage working of the thermal battery, and having great application prospect.
Drawings
FIG. 1 shows a high voltage thermal battery prepared in example 1 of the present invention at 250 ℃ and 20mA/cm2And (3) measuring a discharge curve before and after the modification of the negative electrode material during constant current density discharge.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Example 1:
a high-voltage thermal battery cathode material consists of a lithium-silicon alloy and a lithium fast ion conductor lithium borate-lithium sulfate coated on the surface of the lithium-silicon alloy; the addition amount of the lithium fast ion conductor lithium borate-lithium sulfate is 20 percent of the weight of the lithium silicon alloy; the lithium fast ion conductor lithium borate-lithium sulfate is prepared by mixing lithium borate crystals and lithium crystals in anhydrous sulfuric acid, wherein the mass percentage of the lithium borate crystals is 40%; the mass percentage of the anhydrous lithium sulfate crystal is 60%.
The preparation method of the lithium fast ion conductor lithium borate-lithium sulfate comprises the following steps:
1) analyzing raw material to obtain pure-grade LiOH & H2O and H3BO3Respectively at Al2O3Performing constant temperature treatment at 500 ℃ for 1h in a crucible, and then sintering the crucible and the crucible at high temperature of 600 ℃ for 2h in air atmosphere to obtain Li3BO3A crystal; LiOH. H2O and H3BO3In a weight ratio of 1: 1;
2) raw material analysis pure grade Li2SO4·H2O is sintered at the high temperature of 300 ℃ for 2 hours in the argon atmosphere to obtain anhydrous Li2SO4A crystal;
3) finally, Li is added3BO3Crystalline and anhydrous Li2SO4Mechanical ball milling mixing of crystal to prepare lithium fast ion conductor Li3BO3－Li2SO4The method specifically comprises the following steps: mixing Li3BO3Crystalline and anhydrous Li2SO4The crystal mixture is put into ZrO2And in the ball milling tank, setting the rotation speed of 370rpm, and performing ball milling for 50h, wherein all ball milling processes and experimental operation processes are performed in an argon atmosphere.
Example 2:
a high-voltage thermal battery is composed of a positive electrode material, a negative electrode material and an electrolyte diaphragm material, wherein the content of the positive electrode material is 44% by weight; the content of the negative electrode material is 21%; the content of the electrolyte separator material was 35%; the anode material is a manganese dioxide material, the cathode material is a high-voltage thermal battery cathode material consisting of a lithium silicon alloy and a lithium fast ion conductor lithium borate-lithium sulfate coated on the surface of the lithium silicon alloy, and the electrolyte diaphragm material is a lithium nitrate-potassium nitrate-magnesium oxide material.
The preparation method of the high-voltage thermal battery comprises the following steps:
(1) MnO as positive electrode material2Preparation of
Taking 1.5mmol of MnSO4·H2Dissolving O in deionized water, and taking 3mmol KMnO4Dissolving in deionized water, and dissolving KMnO4Transferring the solution into the solution system before adding the solutionReacting in a 50mL reaction kettle at 140 ℃ for 2h, naturally cooling to room temperature, washing the obtained product with deionized water and absolute ethyl alcohol for several times, and drying in a vacuum drying oven at 80 ℃ for 12 h to obtain a black product MnO2A material;
(2) preparation of cathode material
Lithium fast ion conductor Li3BO3－Li2SO4Mechanically mixing with the lithium-silicon alloy as the negative electrode material, loading the two materials into a ball milling tank under an inert environment to ensure uniform mixing and coating, and uniformly mixing and coating the materials on a planetary ball mill under the condition of not putting a grinding ball to finally obtain the Li coated on the surface3BO3－Li2SO4The lithium silicon alloy negative electrode material of (1); the addition amount of the lithium fast ion conductor lithium borate-lithium sulfate is 20 percent of the weight of the lithium silicon alloy; wherein, the lithium fast ion conductor Li3BO3－Li2SO4The preparation method comprises the following steps:
analyzing raw material to obtain pure-grade LiOH & H2O and H3BO3Respectively at Al2O3Performing constant temperature treatment at 500 ℃ for 1h in a crucible, and then sintering the crucible and the crucible at high temperature of 600 ℃ for 2h in air atmosphere to obtain Li3BO3A crystal; LiOH. H2O and H3BO3In a weight ratio of 1: 1;
raw material analysis pure grade Li2SO4·H2O is sintered at the high temperature of 300 ℃ for 2 hours in the argon atmosphere to obtain anhydrous Li2SO4A crystal; finally, Li is added3BO3Crystalline and anhydrous Li2SO4Mechanical ball milling mixing of crystal to prepare lithium fast ion conductor Li3BO3－Li2SO4The method specifically comprises the following steps: placing the mixture into ZrO2Setting the rotation speed of 370rpm in a ball milling tank, and performing ball milling for 50 hours, wherein all ball milling processes and experimental operation processes are performed in an argon atmosphere; li3BO3Crystalline and anhydrous Li2SO4The weight ratio of the crystals was 2: 3.
(3) Preparation of electrolyte separator Material
Will analytically pure LiNO3、KNO3Vacuum drying at 180 deg.C to completely dehydrate raw materials, grinding in dry environment, dissolving in distilled water, stirring, heating, ultrasonic vibrating to dissolve and disperse the components uniformly, adding 35% MgO as flow inhibitor, heating, stirring, evaporating most of water, oven drying until all water is completely evaporated, placing in a tube furnace in inert atmosphere, melting at 400 deg.C for 4 hr, pulverizing, and grinding to obtain final LiNO3－KNO3-MgO material, among which LiNO3And KNO3The weight ratio of (A) to (B) is 1: 2;
(4) high voltage thermal battery preparation
The anode material, the cathode material and the electrolyte diaphragm material are mixed and pressed into a single battery by adopting a three-in-one powder tabletting process, namely the high-voltage thermal battery.
Example 3
A high-voltage thermal battery cathode material consists of a lithium-silicon alloy and a lithium fast ion conductor lithium borate-lithium sulfate coated on the surface of the lithium-silicon alloy; the addition amount of the lithium fast ion conductor lithium borate-lithium sulfate is 10 percent of the weight of the lithium silicon alloy; the lithium fast ion conductor lithium borate-lithium sulfate is prepared by mixing lithium borate crystals and lithium crystals in anhydrous sulfuric acid, wherein the mass percentage of the lithium borate crystals is 30%; the mass percentage of the anhydrous lithium sulfate crystal is 70%.
The preparation method of the lithium fast ion conductor lithium borate-lithium sulfate comprises the following steps:
1) analyzing raw material to obtain pure-grade LiOH & H2O and H3BO3Respectively at Al2O3Performing constant temperature treatment at 500 ℃ for 1h in a crucible, and then sintering the crucible and the crucible at high temperature of 600 ℃ for 2h in air atmosphere to obtain Li3BO3A crystal; LiOH. H2O and H3BO3In a weight ratio of 1: 1;
2) raw material analysis pure grade Li2SO4·H2O is sintered at the high temperature of 300 ℃ for 2 hours in the argon atmosphere to obtain anhydrous Li2SO4A crystal;
3) finally, Li is added3BO3Crystalline and anhydrous Li2SO4Mechanical ball milling mixing of crystal to prepare lithium fast ion conductor Li3BO3－Li2SO4The method specifically comprises the following steps: mixing Li3BO3Crystalline and anhydrous Li2SO4The crystal mixture is put into ZrO2In the ball milling tank, the rotation speed is set to be 370rpm, the ball milling is carried out for 50h, and all the ball milling processes and the experimental operation processes are carried out in the argon atmosphere.
Example 4
A high-voltage thermal battery is composed of an anode material, a cathode material and an electrolyte diaphragm material, wherein the content of the anode material is 35% by weight; the content of the anode material is 28%; the content of the electrolyte separator material was 37%; the anode material is a manganese dioxide material, the cathode material is a high-voltage thermal battery cathode material consisting of a lithium silicon alloy and a lithium fast ion conductor lithium borate-lithium sulfate coated on the surface of the lithium silicon alloy, and the electrolyte diaphragm material is a lithium nitrate-potassium nitrate-magnesium oxide material.
The preparation method of the high-voltage thermal battery comprises the following steps:
(1) MnO as positive electrode material2Preparation of
Taking 1.5mmol of MnSO4·H2Dissolving O in deionized water, and taking 3mmol KMnO4Dissolving in deionized water, and dissolving KMnO4Transferring the solution into a 50mL reaction kettle before adding the solution, reacting at 140 ℃ for 2h, naturally cooling to room temperature, respectively washing the obtained product with deionized water and absolute ethyl alcohol for several times, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain a black product MnO2A material;
(2) preparation of cathode material
Lithium fast ion conductor Li3BO3－Li2SO4Mechanically mixing with the lithium-silicon alloy as the negative electrode material, loading the two materials into a ball milling tank under an inert environment to ensure uniform mixing and coating, and uniformly mixing and coating the materials on a planetary ball mill under the condition of not putting a grinding ball to finally obtain the Li coated on the surface3BO3－Li2SO4The lithium silicon alloy negative electrode material of (1); the addition amount of the lithium fast ion conductor lithium borate-lithium sulfate is 10 percent of the weight of the lithium silicon alloy; wherein, the lithium fast ion conductor Li3BO3－Li2SO4The preparation method comprises the following steps:
analyzing raw material to obtain pure-grade LiOH & H2O and H3BO3Respectively at Al2O3Performing constant temperature treatment at 500 ℃ for 1h in a crucible, and then sintering the crucible and the crucible at high temperature of 600 ℃ for 2h in air atmosphere to obtain Li3BO3A crystal; LiOH. H2O and H3BO3In a weight ratio of 1: 1;
raw material analysis pure grade Li2SO4·H2O is sintered at the high temperature of 300 ℃ for 2 hours in the argon atmosphere to obtain anhydrous Li2SO4A crystal; finally, Li is added3BO3Crystalline and anhydrous Li2SO4Mechanical ball milling mixing of crystal to prepare lithium fast ion conductor Li3BO3－Li2SO4The method specifically comprises the following steps: placing the mixture into ZrO2Setting the rotation speed of 370rpm in a ball milling tank, and performing ball milling for 50 hours, wherein all ball milling processes and experimental operation processes are performed in an argon atmosphere; li3BO3Crystalline and anhydrous Li2SO4The weight ratio of the crystal is 3: 7.
(3) preparation of electrolyte separator Material
Will analytically pure LiNO3、KNO3Vacuum drying at 180 deg.C to completely dehydrate raw materials, grinding in dry environment, dissolving in distilled water, stirring, heating, ultrasonic vibrating to dissolve and disperse the components uniformly, adding MgO with mass fraction of 40% as flow inhibitor, heating, stirring, transferring into oven after most water is evaporated until all water is completely evaporated, placing into tube furnace in inert atmosphere, melting at 400 deg.C for 4h, pulverizing, and grinding to obtain final LiNO3－KNO3-MgO electrolyte separator material, wherein LiNO3And KNO3The weight ratio of (A) to (B) is 1: 2;
(4) high voltage thermal battery preparation
The anode material, the cathode material and the electrolyte diaphragm material are mixed and pressed into a single battery by adopting a three-in-one powder tabletting process, namely the high-voltage thermal battery.
Example 5
A high-voltage thermal battery cathode material consists of a lithium-silicon alloy and a lithium fast ion conductor lithium borate-lithium sulfate coated on the surface of the lithium-silicon alloy; the addition amount of the lithium fast ion conductor lithium borate-lithium sulfate is 30 percent of the weight of the lithium silicon alloy; the lithium fast ion conductor lithium borate-lithium sulfate is prepared by mixing lithium borate crystals and lithium crystals in anhydrous sulfuric acid, wherein the mass percentage of the lithium borate crystals is 35%; the mass percentage of the anhydrous lithium sulfate crystal is 65%.
The preparation method of the lithium fast ion conductor lithium borate-lithium sulfate comprises the following steps:
1) analyzing raw material to obtain pure-grade LiOH & H2O and H3BO3Respectively at Al2O3Performing constant temperature treatment at 500 ℃ for 1h in a crucible, and then sintering the crucible and the crucible at high temperature of 600 ℃ for 2h in air atmosphere to obtain Li3BO3A crystal; LiOH. H2O and H3BO3In a weight ratio of 1: 1;
2) raw material analysis pure grade Li2SO4·H2O is sintered at the high temperature of 300 ℃ for 2 hours in the argon atmosphere to obtain anhydrous Li2SO4A crystal;
3) finally, Li is added3BO3Crystalline and anhydrous Li2SO4Mechanical ball milling mixing of crystal to prepare lithium fast ion conductor Li3BO3－Li2SO4The method specifically comprises the following steps: mixing Li3BO3Crystalline and anhydrous Li2SO4The crystal mixture is put into ZrO2In the ball milling tank, the rotation speed is set to be 370rpm, the ball milling is carried out for 50h, and all the ball milling processes and the experimental operation processes are carried out in the argon atmosphere.
Example 6
A high-voltage thermal battery is composed of a positive electrode material, a negative electrode material and an electrolyte diaphragm material, wherein the content of the positive electrode material is 40% by weight; the content of the negative electrode material is 20%; the content of the electrolyte separator material is 40%; the anode material is a manganese dioxide material, the cathode material is a high-voltage thermal battery cathode material consisting of a lithium silicon alloy and a lithium fast ion conductor lithium borate-lithium sulfate coated on the surface of the lithium silicon alloy, and the electrolyte diaphragm material is a lithium nitrate-potassium nitrate-magnesium oxide material.
The preparation method of the high-voltage thermal battery comprises the following steps:
(1) MnO as positive electrode material2Preparation of
Taking 1.5mmol of MnSO4·H2Dissolving O in deionized water, and taking 3mmol KMnO4Dissolving in deionized water, and dissolving KMnO4Transferring the solution into a 50mL reaction kettle before adding the solution, reacting at 140 ℃ for 2h, naturally cooling to room temperature, respectively washing the obtained product with deionized water and absolute ethyl alcohol for several times, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain a black product MnO2A material;
(2) preparation of cathode material
Lithium fast ion conductor Li3BO3－Li2SO4Mechanically mixing with the lithium-silicon alloy as the negative electrode material, loading the two materials into a ball milling tank under an inert environment to ensure uniform mixing and coating, and uniformly mixing and coating the materials on a planetary ball mill under the condition of not putting a grinding ball to finally obtain the Li coated on the surface3BO3－Li2SO4The lithium silicon alloy negative electrode material of (1); the addition amount of the lithium fast ion conductor lithium borate-lithium sulfate is 30 percent of the weight of the lithium silicon alloy; wherein, the lithium fast ion conductor Li3BO3－Li2SO4The preparation method comprises the following steps:
analyzing raw material to obtain pure-grade LiOH & H2O and H3BO3Respectively at Al2O3Performing constant temperature treatment at 500 ℃ for 1h in a crucible, and then sintering the crucible and the crucible at high temperature of 600 ℃ for 2h in air atmosphere to obtain Li3BO3A crystal; LiOH. H2O and H3BO3In a weight ratio of 1: 1;
raw material analysis pure grade Li2SO4·H2O is sintered at the high temperature of 300 ℃ for 2 hours in the argon atmosphere to obtain anhydrous Li2SO4A crystal; finally, Li is added3BO3Crystalline and anhydrous Li2SO4Mechanical ball milling mixing of crystal to prepare lithium fast ion conductor Li3BO3－Li2SO4The method specifically comprises the following steps: placing the mixture into ZrO2Setting the rotation speed of 370rpm in a ball milling tank, ball milling for 50h, wherein all ball milling processes and experimental operation processes are carried out in argon atmosphere; li3BO3Crystalline and anhydrous Li2SO4The weight ratio of the crystals is 7: 13.
(3) preparation of electrolyte separator Material
Will analytically pure LiNO3、KNO3Vacuum drying at 180 deg.C to completely dehydrate raw materials, grinding in dry environment, dissolving in distilled water, stirring, heating, ultrasonic vibrating to dissolve and disperse the components uniformly, adding MgO with mass fraction of 40% as flow inhibitor, heating, stirring, transferring into oven after most water is evaporated until all water is completely evaporated, placing into tube furnace in inert atmosphere, melting at 400 deg.C for 4h, pulverizing, and grinding to obtain final LiNO3－KNO3-MgO electrolyte separator material, wherein LiNO3And KNO3The weight ratio of (A) to (B) is 1: 2;
(4) high voltage thermal battery preparation
The anode material, the cathode material and the electrolyte diaphragm material are mixed and pressed into a single battery by adopting a three-in-one powder tabletting process, namely the high-voltage thermal battery.
Test examples
The performance of the high voltage thermal battery prepared in example 2 was tested
FIG. 1 is a graph showing the operation temperature of a high voltage thermal battery prepared in example 2 of the present invention at 250 ℃ and a current density of 20mA/cm2The initial discharge voltage of the monomer high-voltage thermal battery after interface modification is 3.168V, the voltage is slowly reduced in the discharge process, and the specific discharge capacity is up to 2.0V886.5mAh/g, and the specific discharge capacity is 2072.4mAh/g when the voltage is cut off to 0.1V;
the initial discharge voltage of the monomer battery without interface modification is 3.166V, the specific discharge capacity is 474.2mAh/g when the battery is cut off to 2.0V, and the specific discharge capacity is 1639.2mAh/g when the battery is cut off to 0.1V; after the interface is modified, the discharge voltage and the discharge specific capacity of the monomer thermal battery are obviously improved in the whole discharge process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The high-voltage thermal battery cathode material is characterized by consisting of a lithium-silicon alloy and a lithium fast ion conductor lithium borate-lithium sulfate coated on the surface of the lithium-silicon alloy; the addition amount of the lithium fast ion conductor lithium borate-lithium sulfate is 10-30% of the weight of the lithium silicon alloy;
the lithium fast ion conductor lithium borate-lithium sulfate is prepared by mixing lithium borate crystals and anhydrous lithium sulfate crystals, wherein the mass percentage of the lithium borate crystals is 30-40%; the mass percentage of the anhydrous lithium sulfate crystal is 60-70%;
the preparation method of the lithium fast ion conductor lithium borate-lithium sulfate comprises the following steps:
(1) placing lithium hydroxide and boric acid in an alumina crucible, carrying out constant temperature treatment for 1 hour at 500 ℃, and then sintering at high temperature for 2 hours at 600 ℃ in an air atmosphere to obtain lithium borate crystals; the weight ratio of the lithium hydroxide to the boric acid is 1: 1;
(2) sintering the lithium sulfate at the high temperature of 300 ℃ for 2 hours in the argon atmosphere to obtain anhydrous lithium sulfate crystals;
(3) placing lithium borate crystals and anhydrous lithium sulfate crystals in ZrO2And (3) ball-milling for 50 hours in a ball-milling tank at 370rpm to obtain the lithium fast ion conductor lithium borate-lithium sulfate.
2. The high voltage thermal battery anode material according to claim 1, wherein the lithium fast ion conductor lithium borate-lithium sulfate is added in an amount of 20% by weight of the lithium silicon alloy.
3. A high-voltage thermal battery is characterized by comprising a positive electrode material, a negative electrode material and an electrolyte diaphragm material, wherein the content of the positive electrode material is 30-50% by weight; the content of the negative electrode material is 10-30%; the content of the electrolyte diaphragm material is 20-40%; wherein the positive electrode material is manganese dioxide material, the negative electrode material is the high-voltage thermal battery negative electrode material as claimed in any one of claims 1-2, and the electrolyte diaphragm material is lithium nitrate-potassium nitrate-magnesium oxide material.
4. The high-voltage thermal battery as claimed in claim 3, which is composed of a positive electrode material, a negative electrode material and an electrolyte separator material, the content of the positive electrode material being 44% by weight; the content of the negative electrode material is 21%; the content of the electrolyte separator material was 35%; wherein the positive electrode material is manganese dioxide material, the negative electrode material is the high-voltage thermal battery negative electrode material as claimed in any one of claims 1 to 3, and the electrolyte diaphragm material is lithium nitrate-potassium nitrate-magnesium oxide material.
5. The method of manufacturing a high voltage thermal battery of claim 3 or 4, comprising:
and (3) pressing the positive electrode material, the negative electrode material and the electrolyte diaphragm material into the high-voltage lithium ion thermal battery in a composite mold process mode.
6. The method for preparing a high-voltage thermal battery according to claim 5, wherein the method for preparing the positive electrode material comprises the following steps:
mixing a manganese sulfate monohydrate solution with a potassium permanganate solution, reacting at 140 ℃ for 2 hours, naturally cooling to room temperature, washing an obtained product with deionized water and absolute ethyl alcohol, and performing vacuum drying at 80 ℃ for 10-12 hours to obtain a manganese dioxide material; the weight ratio of the manganese sulfate monohydrate to the potassium permanganate is 1: 2.
7. The method of claim 5, wherein the negative electrode material is prepared by:
coating lithium borate-lithium sulfate which is a fast lithium ion conductor on a lithium silicon alloy to obtain a lithium silicon alloy cathode material coated with the fast lithium ion conductor lithium borate-lithium sulfate on the surface;
the preparation method of the lithium fast ion conductor lithium borate-lithium sulfate comprises the following steps:
(1) placing lithium hydroxide and boric acid in an alumina crucible, carrying out constant temperature treatment for 1h at 500 ℃, and then sintering at 600 ℃ for 2h in an air atmosphere to obtain lithium borate crystals; the weight ratio of the lithium hydroxide to the boric acid is 1: 1;
(2) sintering the lithium sulfate at the high temperature of 300 ℃ for 2 hours in the argon atmosphere to obtain anhydrous lithium sulfate crystals;
(3) placing lithium borate crystals and anhydrous lithium sulfate crystals in ZrO2And (3) ball-milling for 50 hours in a ball-milling tank at 370rpm to obtain the lithium fast ion conductor lithium borate-lithium sulfate.
8. The method of manufacturing a high voltage thermal battery of claim 5 wherein the electrolyte separator material is prepared by:
respectively dissolving lithium nitrate and potassium nitrate in distilled water, uniformly dissolving and dispersing, adding 30-40% by mass of magnesium oxide as a flow inhibitor, heating, stirring, drying, placing in an inert atmosphere tube furnace, and melting at 400 ℃ for 4 hours to obtain an electrolyte diaphragm material; wherein the weight ratio of the lithium nitrate to the potassium nitrate is 1: 2.
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| CN109378460B (en) * | 2018-10-24 | 2021-09-10 | 上海空间电源研究所 | 5 Ah-level thermal battery single battery |
| CN109671929A (en) * | 2018-12-12 | 2019-04-23 | 福建翔丰华新能源材料有限公司 | The Li-Si alloy composite negative pole material and preparation method thereof of sulfide electrolyte cladding |
| JP7212327B2 (en) * | 2019-03-26 | 2023-01-25 | 国立大学法人 名古屋工業大学 | Solid electrolyte and method for producing solid electrolyte |
| JP7203200B2 (en) * | 2019-03-26 | 2023-01-12 | 日本碍子株式会社 | All-solid secondary battery |
| CN112349888B (en) * | 2019-08-07 | 2022-03-01 | 珠海冠宇电池股份有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
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| CN111640918A (en) * | 2020-05-11 | 2020-09-08 | 深圳新恒业电池科技有限公司 | Electrode material, preparation method thereof and electrode slice |
| CN114975901A (en) * | 2021-04-30 | 2022-08-30 | 广汽埃安新能源汽车有限公司 | Negative electrode material and preparation method thereof, lithium ion battery negative electrode, lithium ion battery and preparation method thereof, and lithium ion battery pack |
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