CN112614996A - Ternary cathode material for NCF type thermal battery and preparation method thereof - Google Patents
Ternary cathode material for NCF type thermal battery and preparation method thereof Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
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Abstract
The invention relates to a ternary cathode material for an NCF type thermal battery and a preparation method thereof, belonging to the technical field of material chemistry. The invention aims to provide a ternary cathode material for an NCF type thermal battery and a preparation method thereof, wherein M (C) is prepared by a coprecipitation method2O4)·nH2The precursor of O (M: Ni, Co, Fe) solid solution is reduced by high pressure hydrogen-sulfur steam sulfurization to obtain cubic phase Ni0.1Co0.45Fe0.45S2The ternary positive electrode material is used for the type thermal battery. By adopting the preparation method provided by the invention, the obtained ternary cathode material has the characteristics of complete crystal structure, low self-loss rate, high capacity utilization rate and the like.
Description
Technical Field
The invention relates to a ternary cathode material for an NCF type thermal battery and a preparation method thereof, belonging to the technical field of material chemistry.
Background
MS2(M ═ Fe, Co) is the most widely used positive electrode material of the existing on-board thermal battery, among which FeS2The electrode potential for the Li negative electrode was 2.2V, the theoretical capacity was 1206As/g, the thermal decomposition temperature was 550 ℃ and CoS2The electrode potential of (A) was 2.1V, the theoretical capacity was 1045As/g, and the thermal decomposition temperature was 650 ℃. The application directions of the two anode materials are slightly different due to the performance difference, the working time of the thermal battery is continuously prolonged along with the continuous development of the on-bomb thermal battery technology, and the use requirements of the thermal battery are difficult to meet due to the defect of low utilization rate of the traditional anode materials.
The research focus of the high-utilization rate anode material for the thermal battery is the composite anode material, which can be widely applied because the utilization rate of the anode material can be greatly improved, such as Chinese patent CN105140485, Chinese patent CN107026256A, Proceedings of the 36th Power resources conference,1994, p.329, and the like.
The common anode material of the thermal battery is FeS2、NiS2Or CoS2Single positive electrode or FexCo1-xS2A binary composite positive electrode. Ni is similar in atomic structure to Fe and Co, so NiS2The positive electrode material is also paid attention by thermal battery researchers, and NiS is a common material2The anode material is prepared manually, and the performance of the anode material is compared with that of FeS2And CoS2The ratio of the single positive electrode is not obviously improved, so the single positive electrode is still in the experimental research stage. The research of ternary or more composite materials is rare, and especially NiS completely having theoretical feasibility2、FeS2And CoS2Reports of the base ternary composite cathode material do not appear yet.
Disclosure of Invention
Hair brushThe clear technical solution problem is as follows: overcomes the defects of the prior art, provides a ternary cathode material for an NCF type thermal battery and a preparation method thereof, and the method is used for NixCoyFezS2The development and research of the ternary cathode material provide certain basic support, and the cathode material with high utilization rate and low self-loss suitable for long-working-time thermal batteries is successfully developed.
The technical solution of the invention is as follows:
a ternary anode material for NCF type thermal battery comprises active substance, lithiating agent and ionic conductivity agent;
calculated by taking the total mass of the ternary cathode material as 100 percent, the mass percentage of each component is as follows:
78 to 82 percent of active substance
4 to 6 percent of lithium reagent
14 to 16 percent of ionic conductivity agent
The chemical formula of the active substance is as follows: ni0.1Co0.45Fe0.45S2；
The active material Ni0.1Co0.45Fe0.45S2The preparation method comprises the following steps:
step 3, placing the oxalate precursor into a tubular reduction furnace, reducing in a hydrogen atmosphere at the reduction temperature of 600-700 ℃ for 6-12h, cooling to room temperature after the reduction is finished, and passivating the reduction product to obtain metal powder;
step 4, placing the metal powder obtained by passivation in an argon atmosphere protective furnace, adding excessive sulfur powder, carrying out solid-phase reaction in the argon atmosphere at the reaction temperature of 250-300 ℃ for 4-8h, heating to 450-500 ℃ again, keeping the temperature for 2h, removing residual elemental sulfur powder, cooling to room temperature after the reaction is finished, crushing the obtained black solid to obtain the target product Ni0.1Co0.45Fe0.45S2。
The lithiating agent is Li2O, LiSi alloy, Li2At least one of S;
the ionic conduction agent is LiF-LiCl-LiBr electrolyte for a thermal battery;
in the step 2, the aging time is 2-12h, and the aging temperature is between room temperature and 50 ℃;
in the step 2, the drying temperature is 80-120 ℃;
in the step 3, the passivation operation method of the reduction product comprises the following steps: in a hydrogen atmosphere, the cooled reduction product is heated to 200 ℃ again, and the temperature is kept for 6-12 h.
A preparation method of a ternary positive electrode material for an NCF type thermal battery comprises the steps of mixing an active substance, a lithiating agent and an ion conductive agent, and carrying out lithiation treatment to obtain the ternary positive electrode material for the NCF type thermal battery.
Advantageous effects
(1) The invention provides ternary Ni for the first time0.1Co0.45Fe0.45S2NCF type positive electrode material and its preparation method, the material is in the existing mature FexCo1-xS2On the basis of the composite material, the utilization rate of the anode of the thermal battery with long working time is further improved by doping metal Ni element, the self-discharge rate of the material is less than 5%/h (550 ℃), and the capacity utilization rate exceeds 90% (the current density is 200 mA/cm)2Operating time 3600 s).
(2) The invention provides preparationNi produced0.1Co0.45Fe0.45S2The anode material product has single component and complete crystal structure, and forms a solid solution by utilizing the characteristic that atomic radii of three elements of Ni, Co and Fe are similar, so that the performance of the anode material prepared by mechanical mixing and other methods is obviously improved.
(3) The precipitation-reduction-vulcanization method provided by the invention has the advantages that the process is simple, the required raw materials are cheap and easily available, the production equipment is common anode material production equipment, the requirement of industrial mass production can be met, and the method has military and economic significance.
(4) The invention aims to provide a ternary cathode material for an NCF type thermal battery and a preparation method thereof, wherein M (C) is prepared by a coprecipitation method2O4)·nH2The precursor of O (M: Ni, Co, Fe) solid solution is reduced by high pressure hydrogen-sulfur steam sulfurization to obtain cubic phase Ni0.1Co0.45Fe0.45S2The ternary positive electrode material is used for the type thermal battery. By adopting the preparation method provided by the invention, the obtained ternary cathode material has the characteristics of complete crystal structure, low self-loss rate, high capacity utilization rate and the like.
Drawings
FIG. 1 is a schematic view of example 1, wherein Ni0.1Co0.45Fe0.45S2SEM photograph and XRD spectrogram of active ingredient;
FIG. 2 is a discharge capacity curve of the NCF type positive electrode material in example 1 (test conditions: a single cell was constructed using LiB as a negative electrode material and LiF-LiCl-LiBr as an electrolyte, and 200mA/cm2The working temperature is 550 ℃, the working time is 3600s, and the cut-off voltage is 1.5V);
FIG. 3 is a self-loss curve of the NCF type positive electrode material in example 1 (test conditions: constructing a single cell with LiB as a negative electrode material and LiF-LiCl-LiBr as an electrolyte, no-load discharge, operating temperature 550 ℃);
fig. 4 is an SEM photograph of the ternary cathode material for the NCF type thermal battery.
Detailed Description
The following provides 3 examples, for the first inventionSolid solution type Fe for thermal batteryxCo1-xS2The positive electrode material and the method for preparing the same are further described in detail.
Example 1
The NCF type ternary cathode material for the target product thermal battery comprises the following components in percentage by weight: ni0.1Co0.45Fe0.45S accounts for 80%, Li2O accounts for 5 percent, and LiF-LiCl-LiBr electrolyte accounts for 15 percent. Firstly, weighing NiSO according to stoichiometric ratio4·6H2O、CoSO4·7H2O and FeSO4·7H2O, preparing a solution with the total metal ion content of 1 mol/L; slowly dropwise adding 0.5mol/L (NH)4)2C2O4The solution is stirred and aged for 2 hours until the pH value is 12, the aging temperature is room temperature, and the solution is filtered, washed and dried to obtain a precursor, wherein the drying temperature is 80 ℃; placing the precursor in a tubular reduction furnace, reducing in hydrogen atmosphere at 600 ℃ for 12h, cooling to room temperature after reduction, reheating to 120 ℃, and preserving heat for 12h for passivation treatment; then placing the metal powder in an atmosphere protection furnace, adding excessive sulfur powder, carrying out solid-phase reaction in argon atmosphere at the reaction temperature of 250 ℃ for 8h, heating to 450 ℃ again and keeping the temperature for 2h, removing residual elemental sulfur powder, and cooling to room temperature after the reaction is finished to obtain Ni0.1Co0.45Fe0.45S2Pulverizing the active ingredients. Finally adding Ni0.1Co0.45Fe0.45S2Active ingredient and Li2And mixing O and LiF-LiCl-LiBr electrolyte, and then carrying out lithiation treatment to obtain the NCF type ternary cathode material.
The SEM photograph of the obtained NCF type ternary cathode material is shown in figure 4, and as can be seen from figure 4, the particle size distribution of the cathode material is uniform, and the consistency is good;
Ni0.1Co0.45Fe0.45S2the SEM picture and XRD spectrogram of the active ingredient are shown in figure 1, and the positive electrode material and the pyrite have the same crystal form by comparison with a card;
the discharge capacity curve of the NCF-type positive electrode material is shown in fig. 2, and the test conditions in fig. 2 are: using LiB as negative electrode materialThe material and LiF-LiCl-LiBr are used as electrolyte to construct a single battery, and 200mA/cm is used2The current density of the discharge is 550 ℃, the working time is 3600s, and the cut-off voltage is 1.5V; as can be seen from fig. 2, the discharge time is longer and the working capacity is larger than that of other common anode materials of the thermal battery;
the self-loss curve of the NCF-type positive electrode material is shown in fig. 3, and the test conditions in fig. 3 are: LiB is used as a negative electrode material, LiF-LiCl-LiBr is used as an electrolyte to construct a single battery, no-load discharge is carried out, the working temperature is 550 ℃, as can be seen from figure 3, the 3600s capacity fading rate is 6.1%, the working time of the thermal battery usually does not exceed 3600s, and the design capacity of the thermal battery has a margin of more than 20%, so that the positive electrode material can meet the use requirement of the thermal battery.
Example 2
The NCF type ternary cathode material for the target product thermal battery comprises the following components in percentage by weight: ni0.1Co0.45Fe0.45S accounts for 80%, Li2O accounts for 5 percent, and LiF-LiCl-LiBr electrolyte accounts for 15 percent. Firstly, weighing NiSO according to stoichiometric ratio4·6H2O、CoSO4·7H2O and FeSO4·7H2O, preparing a solution with the total metal ion content of 2 mol/L; slowly dropwise adding 0.5mol/L (NH)4)2C2O4The solution is stirred and aged for 12 hours until the pH value is 13, the aging temperature is 50 ℃, and the solution is filtered, washed and dried to obtain a precursor, wherein the drying temperature is 120 ℃; placing the precursor in a tubular reduction furnace, reducing in hydrogen atmosphere at 700 ℃ for 6h, cooling to room temperature after reduction, reheating to 200 ℃, and preserving heat for 6h for passivation treatment; then placing the metal powder in an atmosphere protection furnace, adding excessive sulfur powder, carrying out solid-phase reaction in argon atmosphere at the reaction temperature of 300 ℃ for 4 hours, heating to 500 ℃ again and keeping the temperature for 2 hours, removing residual elemental sulfur powder, and cooling to room temperature after the reaction is finished to obtain Ni0.1Co0.45Fe0.45S2Pulverizing the active ingredients. Finally adding Ni0.1Co0.45Fe0.45S2Active ingredient and Li2O and LiF-LiCl-LiBr electrolyte are mixedAnd carrying out lithiation treatment to obtain the NCF type ternary cathode material.
Example 3
The NCF type ternary cathode material for the target product thermal battery comprises the following components in percentage by weight: ni0.1Co0.45Fe0.45S accounts for 80%, Li2O accounts for 5 percent, and LiF-LiCl-LiBr electrolyte accounts for 15 percent. Firstly, weighing NiSO according to stoichiometric ratio4·6H2O、CoSO4·7H2O and FeSO4·7H2O, preparing a solution with the total metal ion content of 1 mol/L; slowly dropwise adding 0.5mol/L (NH)4)2C2O4The solution is stirred and aged for 6 hours to the pH value of 12, the aging temperature is room temperature, and the solution is filtered, washed and dried to obtain a precursor, wherein the drying temperature is 110 ℃; placing the precursor in a tubular reduction furnace, reducing in a hydrogen atmosphere at the reduction temperature of 650 ℃ for 8h, cooling to room temperature after the reduction is finished, reheating to 150 ℃, and preserving heat for 8h for passivation treatment; then placing the metal powder in an atmosphere protection furnace, adding excessive sulfur powder, carrying out solid-phase reaction in argon atmosphere at the reaction temperature of 250 ℃ for 8h, heating to 500 ℃ again and keeping the temperature for 2h, removing residual elemental sulfur powder, and cooling to room temperature after the reaction is finished to obtain Ni0.1Co0.45Fe0.45S2Pulverizing the active ingredients. Finally adding Ni0.1Co0.45Fe0.45S2Active ingredient and Li2And mixing O and LiF-LiCl-LiBr electrolyte, and then carrying out lithiation treatment to obtain the NCF type ternary cathode material.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to limit the present invention, and those skilled in the art can make variations and modifications of the present invention without departing from the spirit and scope of the present invention by using the methods and technical contents disclosed above.
Claims (10)
1. A ternary positive electrode material for an NCF type thermal battery is characterized in that: the composition of the ternary cathode material comprises an active substance, a lithiating agent and an ionic conductivity agent;
calculated by taking the total mass of the ternary cathode material as 100 percent, the mass percentage of each component is as follows:
78 to 82 percent of active substance
4 to 6 percent of lithium reagent
14 to 16 percent of ionic conductivity agent
The chemical formula of the active substance is as follows: ni0.1Co0.45Fe0.45S2。
2. The ternary positive electrode material for NCF-type thermal batteries according to claim 1, characterized in that: the active material Ni0.1Co0.45Fe0.45S2The preparation method comprises the following steps:
step 1, according to Ni0.1Co0.45Fe0.45S2In the stoichiometric ratio of three elements of Ni, Co and Fe, weighing NiSO4·6H2O、CoSO4·7H2O and FeSO4·7H2O, preparing a mixed sulfate solution with the total metal ion content of Ni, Co and Fe of 1-2 mol/L;
step 2, preparing (NH) with the concentration of (0.47-0.54) mol/L4)2C2O4Solution, then (NH)4)2C2O4Slowly adding the solution into the mixed sulfate solution prepared in the step 1 under the stirring condition until the pH value is 12-13, continuously stirring and aging, then filtering the precipitate, washing with deionized water and drying to obtain an oxalate precursor;
step 3, placing the oxalate precursor into a tubular reduction furnace, reducing in a hydrogen atmosphere at the reduction temperature of 600-700 ℃ for 6-12h, cooling to room temperature after the reduction is finished, and passivating the reduction product to obtain metal powder;
step 4, placing the metal powder obtained by passivation in an argon atmosphere protection furnace, and adding excessive sulfurCarrying out solid-phase reaction in an argon atmosphere at the reaction temperature of 250-300 ℃ for 4-8h, heating to 450-500 ℃ again, keeping the temperature for 2h, removing residual elemental sulfur powder, cooling to room temperature after the reaction is finished, and crushing the obtained black solid to obtain the target product Ni0.1Co0.45Fe0.45S2。
3. The ternary positive electrode material for NCF-type thermal batteries according to claim 1, characterized in that: the lithiating agent is Li2O, LiSi alloy, Li2At least one of S.
4. The ternary positive electrode material for NCF-type thermal batteries according to claim 1, characterized in that: the ionic conduction agent is LiF-LiCl-LiBr electrolyte for a thermal battery.
5. The ternary positive electrode material for NCF-type thermal batteries according to claim 1, characterized in that: in the step 2, the aging time is 2-12 h.
6. The ternary positive electrode material for NCF-type thermal batteries according to claim 1, characterized in that: the aging temperature is from room temperature to 50 ℃.
7. The ternary positive electrode material for NCF-type thermal batteries according to claim 1, characterized in that: in the step 2, the drying temperature is 80-120 ℃.
8. The ternary positive electrode material for NCF-type thermal batteries according to claim 1, characterized in that: in the step 3, the passivation operation method of the reduction product comprises the following steps: in a hydrogen atmosphere, the cooled reduction product is heated to 200 ℃ again, and the temperature is kept for 6-12 h.
9. A preparation method of a ternary cathode material for an NCF type thermal battery is characterized by comprising the following steps: and mixing the active substance, the lithiating agent and the ion conductive agent, and lithiating to obtain the ternary cathode material for the NCF type thermal battery.
10. The method for preparing a ternary positive electrode material for an NCF-type thermal battery according to claim 1, wherein: calculated by taking the total mass of the ternary cathode material as 100 percent, the mass percentage of each component is as follows:
78 to 82 percent of active substance
4 to 6 percent of lithium reagent
14 to 16 percent of ionic conductivity agent.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107026256A (en) * | 2016-08-12 | 2017-08-08 | 中国科学院过程工程研究所 | A kind of thermal cell positive electrode FexCo1‑xS2Powder and preparation method thereof |
| CN108539195A (en) * | 2018-04-10 | 2018-09-14 | 上海空间电源研究所 | A kind of thermal cell solid solution FexCo1-xS2 positive electrodes and preparation method thereof |
| CN108675267A (en) * | 2018-06-14 | 2018-10-19 | 西南大学 | An a kind of step prepares the universal method of nano metal sulphide and its compound |
| CN110783540A (en) * | 2019-10-08 | 2020-02-11 | 贵州梅岭电源有限公司 | Ternary composite positive electrode material for thermal battery and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107026256A (en) * | 2016-08-12 | 2017-08-08 | 中国科学院过程工程研究所 | A kind of thermal cell positive electrode FexCo1‑xS2Powder and preparation method thereof |
| CN108539195A (en) * | 2018-04-10 | 2018-09-14 | 上海空间电源研究所 | A kind of thermal cell solid solution FexCo1-xS2 positive electrodes and preparation method thereof |
| CN108675267A (en) * | 2018-06-14 | 2018-10-19 | 西南大学 | An a kind of step prepares the universal method of nano metal sulphide and its compound |
| CN110783540A (en) * | 2019-10-08 | 2020-02-11 | 贵州梅岭电源有限公司 | Ternary composite positive electrode material for thermal battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| A. AWANO等: ""Li/Fe1-xCoxS2 SYSTEM THERMAL BATTERY PERFORMANCE"", 《1992 IEEE 35TH INTERNATIONAL POWER SOURCES SYMPOSIUM》 * |
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