CN113488623A - Thermal battery anode composite material and preparation method and application thereof - Google Patents

Thermal battery anode composite material and preparation method and application thereof Download PDF

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CN113488623A
CN113488623A CN202110771673.7A CN202110771673A CN113488623A CN 113488623 A CN113488623 A CN 113488623A CN 202110771673 A CN202110771673 A CN 202110771673A CN 113488623 A CN113488623 A CN 113488623A
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fef
thermal battery
composite material
graphene oxide
battery anode
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CN113488623B (en
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胡军
宋卫兵
谭远
薛静静
刘喻波
闫雷
尚筱萌
付小倩
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Northwest University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
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    • H01M4/00—Electrodes
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Abstract

The invention belongs to the technical field of thermal batteries, and provides a thermal battery anode composite material and a preparation method and application thereof. The thermal battery anode composite material comprises FeF3‑FeF2Micro-nano spheres and graphene oxide. Fluorine is the most electronegative element of the periodic table of elements, and has the highest polarity of bonding with metal ions. Therefore, metal fluorides have a higher discharge voltage than sulfides. Meanwhile, the strong polarity of Fe-F bond makes the ferric fluoride haveThe high electrode potential results in a large bandgap width (5.96 eV). Therefore, the conductivity of ferric trifluoride is poor, and the theoretical advantage of ferric trifluoride cannot be exerted when the ferric trifluoride is directly used as a thermal battery anode material. According to the invention, the graphene oxide is introduced into the thermal battery anode composite material, so that the thermal battery anode composite material has higher conductivity. The examples show that: the working voltage of the thermal battery anode composite material provided by the invention is 3.2V, and the normal-temperature conductivity is 1878S-cm‑1。

Description

Thermal battery anode composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of thermal batteries, in particular to a thermal battery anode composite material and a preparation method and application thereof.
Background
The thermal battery is a primary reserve battery which takes fused salt as electrolyte, the electrolyte is non-conductive solid inorganic salt under normal temperature storage, the non-conductive solid can be melted and transformed into liquid with high ionic conductivity under high temperature, and the working temperature is generally 350-550 ℃, so the thermal battery is generally applied to the military field, such as missile, torpedo, nuclear weapons and the like.
Currently, the common positive electrode material of thermal batteries is generally sulfide, such as FeS2And CoS2But FeS2Has an ordinary temperature conductivity of 27.7S cm-1，CoS2Has a normal temperature conductivity of 500S cm-1(ii) a Obviously, the sulfide has poor conductivity, which limits the application of the thermal battery. Meanwhile, the working voltage of the sulfide is low, usually about 2V, and in a high-power output mode, the low working voltage means that a large current density needs to be borne, and according to the Joule law, the large current density can enable the heat productivity of the circuit to rise sharply, so that the circuit is burnt, and great potential safety hazards and loss exist.
Disclosure of Invention
In view of the above, the present invention provides a positive electrode composite material for a thermal battery, and a preparation method and an application thereof. The thermal battery anode composite material provided by the invention has higher normal-temperature conductivity and higher working voltage.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a thermal battery anode composite material, which comprises FeF3-FeF2Micro-nanospheres, and coating on said FeF3-FeF2Graphene oxide on the micro-nanospheres;
the FeF3-FeF2FeF in micro-nanospheres3And FeF2In a molar ratio of 7: 3-5.5: 4.5;
the coating amount of the graphene oxide is 0.0001-4 wt%;
the specific surface area of the thermal battery anode composite material is 18-22 m2The porosity is 0.07-0.12 cm3/g。
Preferably, the FeF3-FeF2The particle size of the micro-nano sphere is 200-300 nm.
The invention also provides a preparation method of the thermal battery anode composite material, which comprises the following steps:
mixing absolute ethyl alcohol, polyethylene glycol, hydrofluoric acid and water-soluble ferric salt, and carrying out solvothermal reaction to obtain FeF3·0.33H2O nano material;
subjecting the FeF to3·0.33H2Mixing the O nano material, graphene oxide and water, and freeze-drying to obtain FeF3·0.33H2O/GO nanocomposites;
subjecting the FeF to3·0.33H2Carrying out water removal treatment on the O/GO nano composite material to obtain a precursor;
and calcining the precursor under a protective atmosphere to obtain the thermal battery anode composite material.
Preferably, the volume ratio of the absolute ethyl alcohol to the polyethylene glycol is 25: 15-15: 25; the amount ratio of the water-soluble ferric salt to the hydrofluoric acid is 1: (6-10).
Preferably, the temperature of the solvothermal reaction is 115-125 ℃, and the time is 11-13 h.
Preferably, the FeF3·0.33H2The mode of mixing the O nano material, the graphene oxide and the water is as follows: subjecting the FeF to3·0.33H2Dissolving O nano material and graphene oxide in water respectively to form FeF3·0.33H2O nano material dispersion liquid and graphene oxide dispersion liquid; dropwise adding the graphene oxide dispersion liquid to the FeF3·0.33H2O nano material dispersion liquid.
Preferably, the dropping speed is 0.8-1.2 mL/min.
Preferably, the water removal treatment mode is vacuum drying; the temperature of the vacuum drying is 140-160 ℃, and the time is 2-4 h.
Preferably, the calcining temperature is 380-420 ℃ and the calcining time is 1-2 h.
The invention also provides the application of the thermal battery anode composite material or the thermal battery anode composite material obtained by the preparation method in the technical scheme as an anode material in a thermal battery.
The invention provides a thermal battery anode composite material, which comprises FeF3-FeF2Micro-nanospheres, and coating on said FeF3-FeF2Graphene oxide on the micro-nanospheres; the FeF3-FeF2FeF in micro-nanospheres3And FeF2In a molar ratio of 7: 3-5.5: 4.5; the coating amount of the graphene oxide is 0.0001-4 wt%; the specific surface area of the thermal battery anode composite material is 18-22 m2The porosity is 0.07-0.12 cm3(ii) in terms of/g. In the present invention, fluorine is the most electronegative element in the periodic table of elements, and has the highest polarity of bonding with metal ions, so that metal fluorides have a higher discharge voltage than sulfides. Meanwhile, due to the strong polarity of Fe-F bonds, the ferric fluoride has high electrode potential, and the larger band gap width (5.96eV) is also caused; therefore, the conductivity of ferric trifluoride is poor, and the theoretical advantage of ferric trifluoride cannot be exerted when the ferric trifluoride is directly used as a thermal battery anode material. The invention is in the positive electrode composite material of the thermal batteryAnd the graphene oxide is introduced, so that the positive electrode composite material of the thermal battery has higher conductivity. Simultaneously, FeF3-FeF2The micro-nano sphere has small size and higher specific surface area and porosity, so that when the thermal battery anode composite material is applied to a thermal battery, the thermal battery anode composite material can be fully contacted with electrolyte, the utilization rate of the anode composite material can be improved, the electrochemical polarization in the discharging process of the battery can be reduced, and the discharging performance of the battery is obviously improved. The data of the examples show that: the working voltage of the thermal battery anode composite material provided by the invention is 3.2V, and the normal-temperature conductivity is 1878S-cm-1。
The invention also provides a preparation method of the thermal battery anode composite material, which comprises the following steps: mixing absolute ethyl alcohol, polyethylene glycol, hydrofluoric acid and water-soluble ferric salt, and carrying out solvothermal reaction to obtain FeF3·0.33H2O nano material; subjecting the FeF to3·0.33H2Mixing the O nano material, graphene oxide and water, and freeze-drying to obtain FeF3·0.33H2O/GO nanocomposites; subjecting the FeF to3·0.33H2Carrying out water removal treatment on the O/GO nano composite material to obtain a precursor; and calcining the precursor under a protective atmosphere to obtain the thermal battery anode composite material. The invention uses FeF with smaller size3·0.33H2FeF prepared by using O nano material as substrate and changing different solvent ratios3·0.33H2The O nano material has small size, so that the thermal battery composite material can be fully contacted with an electrolyte when being applied to a thermal battery, the utilization rate of the anode composite material can be improved, the electrochemical polarization in the discharge process of the battery can be reduced, and the discharge performance of the battery can be obviously improved; simultaneously, graphene oxide and FeF are subjected to freeze drying3·0.33H2The O nano-materials are compounded together to maintain FeF3·0.33H2The structure of O nano material, and then FeF is calcined3·0.33H2Crystal water in the O nano material is removed, the specific surface area and the porosity of the final thermal battery anode composite material are increased, and the final thermal battery anode composite material and the electrolyte are further improvedThe contact area of (2) improves the reaction activity.
Drawings
FIG. 1 shows FeF prepared by different solvent volume ratios3·0.33H2XRD pattern of O nano material;
FIG. 2 shows FeF prepared with different solvent volume ratios3·0.33H2SEM and Mapping graphs of O nano materials;
FIG. 3 shows FeF as a product before calcination at Fe: F molar ratios of 1:4, 1:8 and 1:12, respectively3·0.33H2XRD pattern of O nano material;
FIG. 4 shows the product FeF after calcination with Fe: F molar ratio of 1:4 and 1:83-FeF2XRD spectrum of the positive electrode composite material of the thermal battery;
FIG. 5 shows FeF3·0.33H2SEM images of O/GO nanocomposites;
FIG. 6 shows FeF obtained at different calcination temperatures3-FeF2XRD atlas of positive pole composite material of/rGO thermal battery;
FIG. 7 shows FeF obtained by calcination at 400 deg.C3-FeF2SEM and Mapping diagrams of/rGO thermal battery anode composite material;
FIG. 8 shows FeF obtained by calcination at 400 deg.C3-FeF2XPS diagram of/rGO thermal battery positive electrode composite material;
FIG. 9 shows FeF obtained by calcination at 400 deg.C3-FeF2Specific surface area diagram of/rGO thermal battery positive electrode composite material;
FIG. 10 shows FeF obtained by calcination at 400 deg.C3-FeF2The pore diameter distribution diagram of the/rGO thermal battery anode composite material;
FIG. 11 shows FeF obtained by calcination at 400 deg.C3-FeF2An empty discharge diagram of the/rGO thermal battery anode composite material;
FIG. 12 shows FeF obtained by calcination at 400 deg.C3-FeF2Sheet resistance and resistivity maps of/rGO thermal battery positive electrode composites;
FIG. 13 shows FeF obtained at different argon flows3-FeF2XRD atlas of/rGO thermal battery positive pole composite material.
Detailed Description
The present invention providesA composite anode material for thermal battery is composed of FeF3-FeF2Micro-nanospheres, and coating on said FeF3-FeF2Graphene oxide on the micro-nanospheres;
the FeF3-FeF2FeF in micro-nanospheres3And FeF2In a molar ratio of 7: 3-5.5: 4.5;
the coating amount of the graphene oxide is 0.0001-4 wt%;
the specific surface area of the thermal battery anode composite material is 18-22 m2The porosity is 0.07-0.12 cm3/g。
In the present invention, the FeF3-FeF2FeF in micro-nanospheres3And FeF2Preferably 6: 4.
in the present invention, the FeF3-FeF2The particle size of the micro-nano sphere is preferably 200-300 nm.
The invention also provides a preparation method of the thermal battery anode composite material, which comprises the following steps:
mixing absolute ethyl alcohol (EtOH), polyethylene glycol (PEG), hydrofluoric acid and water-soluble ferric salt, and carrying out solvothermal reaction to obtain FeF3·0.33H2O nano material;
subjecting the FeF to3·0.33H2Mixing the O nano material, graphene oxide and water, and freeze-drying to obtain FeF3·0.33H2O/GO nanocomposites;
subjecting the FeF to3·0.33H2Carrying out water removal treatment on the O/GO nano composite material to obtain a precursor;
and calcining the precursor under a protective atmosphere to obtain the thermal battery anode composite material.
In the present invention, the raw materials are preferably those commercially available, unless otherwise specified.
The invention mixes absolute ethyl alcohol, polyethylene glycol, hydrofluoric acid and water-soluble trivalent ferric salt, and carries out solvothermal reaction to obtain FeF3·0.33H2And (4) O nano material.
In the present invention, the polyethylene glycol is preferably polyethylene glycol 400. In the present invention, the water-soluble ferric salt is preferably ferric nitrate or ferric chloride, more preferably ferric nitrate, and even more preferably ferric nitrate nonahydrate.
In the present invention, the volume ratio of the absolute ethanol to the polyethylene glycol is preferably 25: 15-15: 25, more preferably 1: 1.
in the present invention, the ratio of the amounts of the substances of the water-soluble ferric salt and hydrofluoric acid is preferably 1: (6-10), more preferably 1: 8.
in the present invention, the mixing manner of the anhydrous ethanol, the polyethylene glycol, the hydrofluoric acid and the water-soluble ferric salt is preferably: mixing absolute ethyl alcohol and polyethylene glycol to obtain a mixed solvent, and then sequentially adding water-soluble trivalent ferric salt and hydrofluoric acid into the mixed solvent. In the present invention, the time for mixing the anhydrous ethanol and the polyethylene glycol is preferably 30 min. In the present invention, the mixing method of adding the water-soluble ferric salt is preferably stirring, and the stirring time is preferably 30 min. In the present invention, the hydrofluoric acid is preferably added and mixed by stirring, and the stirring time is preferably 1 hour. In the invention, the equipment for mixing the absolute ethyl alcohol, the polyethylene glycol, the hydrofluoric acid and the water-soluble ferric salt is preferably a polytetrafluoroethylene container.
In the invention, the temperature of the solvothermal reaction is preferably 115-125 ℃, and is further preferably 120 ℃; the time is preferably 11 to 13 hours, and more preferably 12 hours. In the present invention, the solvothermal reaction is preferably carried out in an oven.
After the solvothermal reaction, the invention preferably further comprises washing and drying the obtained solvothermal reaction system to obtain FeF3·0.33H2And (4) O nano material.
In the present invention, the washing reagent is preferably absolute ethanol; the number of washing is preferably 5; the washing can remove unreacted moisture and organic matter. In the invention, the drying temperature is preferably 70-90 ℃, and more preferably 80 ℃; the time is preferably 11-13 h, and more preferably 12 h; the drying is preferably carried out in a vacuum oven.
To obtain FeF3·0.33H2After the nanometer material is O, the FeF is treated by the invention3·0.33H2Mixing the O nano material, graphene oxide and water, and freeze-drying to obtain FeF3·0.33H2O/GO nanocomposites.
In the present invention, the water is preferably deionized water.
In the present invention, the FeF3·0.33H2The mass ratio of the O nanomaterial to the graphene oxide is preferably 500: 20. in the invention, the thickness of the graphene oxide is preferably 1-2 nm, and the single-layer sheet diameter is preferably 0.2-10 μm. In the present invention, the FeF3·0.33H2The grain diameter of the O nano material is preferably 200-1000 nm.
In the present invention, the FeF3·0.33H2The mode of mixing the O nano material, the graphene oxide and the water is preferably as follows: subjecting the FeF to3·0.33H2Dissolving O nano material and graphene oxide in water respectively to form FeF3·0.33H2O nano material dispersion liquid and graphene oxide dispersion liquid; dropwise adding the graphene oxide dispersion liquid to the FeF3·0.33H2O nano material dispersion liquid. In the present invention, the concentration of the graphene oxide dispersion is preferably 1mg/mL, and the FeF3·0.33H2The concentration of the O nanomaterial dispersion is preferably 25 mg/L. In the present invention, the dropping rate is preferably 0.8 to 1.2mL/min, and more preferably 1.0 mL/min. Dropwise adding the graphene oxide dispersion liquid to FeF3·0.33H2In the process of dropwise adding O nano-material dispersion liquid, FeF3·0.33H2FeF in O nano material dispersion liquid3·0.33H2The content of the O nano material is high, the content of the graphene oxide is low, and the FeF is well coated with the graphene oxide3·0.33H2O nanometer material.
In the present invention, the temperature of the freeze-drying is preferably 48 hours. In the present invention, the freeze-drying is preferably performed on a freeze-dryer. Compared with the heating and drying processes, the method has the advantages that,the freeze drying of the invention avoids the thermal movement of molecules and ensures that the FeF is coated with the graphene oxide3·0.33H2The structure of the O nano material is not affected, and the FeF is ensured3·0.33H2Good morphology and size of O/GO nanocomposites.
To obtain FeF3·0.33H2After the O/GO nano composite material is prepared, the FeF is prepared by the method3·0.33H2And (4) carrying out water removal treatment on the O/GO nano composite material to obtain a precursor.
In the invention, the dewatering treatment is preferably vacuum drying, and the temperature of the vacuum drying is preferably 140-160 ℃, and more preferably 150 ℃; the time is preferably 2 to 4 hours, and more preferably 3 hours. In the present invention, the water removal treatment is preferably provided in a vacuum drying oven. According to the invention, the water removal treatment can completely remove the water and residual organic matters on the surface of the material, and can prevent the material from being oxidized due to water evaporation in the subsequent high-temperature calcination process.
After the precursor is obtained, the precursor is calcined under the protective atmosphere to obtain the thermal battery anode composite material.
In the present invention, the protective atmosphere is preferably argon; the flow rate of the argon is preferably 1-2L/min. In the invention, the calcining temperature is preferably 380-420 ℃, and more preferably 400 ℃; the rate of heating to the calcining temperature is preferably 3-4 ℃/min; the time is preferably 1 to 2 hours, and more preferably 1.5 hours.
After the calcination, the present invention preferably further comprises naturally cooling the obtained calcination system to room temperature and taking out.
In the present invention, the calcination is capable of converting FeF3·0.33H2And crystal water in O is removed, so that the finally obtained thermal battery positive electrode composite material has higher specific surface area and porosity, and can be fully contacted with an electrolyte when applied to a thermal battery to provide more active sites.
The invention also provides the application of the thermal battery anode composite material in the technical scheme or the thermal battery anode composite material obtained by the preparation method in the technical scheme as an anode material in a thermal battery.
The invention does not specifically limit the way of applying the composite material as the anode material in the thermal battery, and can be realized by adopting the application way of the anode material of the thermal battery, which is well known to the technical personnel in the field.
The present invention provides a positive electrode composite material for a thermal battery, a method for preparing the same, and applications thereof, which are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Exploration of EtOH PEG different volume ratios FeF3·0.33H2Influence of O product Structure and morphology
The method comprises the following specific steps:
s1, preparing the absolute ethyl alcohol and the polyethylene glycol 400 into solvents with the volume ratio of 4:0, 3:1 and 1:1 respectively, and stirring in a polytetrafluoroethylene container for 30 min.
S2, mixing 2.02g Fe (NO)3)3·9H2And O is respectively added into the solvents, and stirred for 30min to be fully dissolved.
S3, respectively adding HF into the solvent according to the molar ratio of Fe to F of 1:4, fully stirring for 1h, and then putting into an oven to react for 12h at 120 ℃.
S4, washing the reacted precipitate for 5 times by using absolute ethyl alcohol to remove redundant water and unreacted organic matters, and then putting the precipitate into a vacuum oven to be dried for 12 hours at the temperature of 80 ℃ to obtain FeF with different shapes and sizes3·0.33H2And (4) O nano material.
FIG. 1 shows FeF prepared by different solvent volume ratios3·0.33H2XRD pattern of O nano material; FIG. 2 shows FeF prepared with different solvent volume ratios3·0.33H2SEM and Mapping graphs of O nano materials; wherein: a picture shows FeF obtained by the volume ratio of absolute ethyl alcohol to polyethylene glycol being 4:03·0.33H2SEM picture of O nano material, b picture is FeF obtained by anhydrous ethanol and polyethylene glycol with volume ratio of 4:03·0.33H2Partial SEM enlarged view and Mapping view of O nano material, wherein the c view is that the volume ratio of absolute ethyl alcohol to polyethylene glycol is 3:1FeF3·0.33H2SEM picture of O nano material, d picture is FeF obtained by anhydrous ethanol and polyethylene glycol with volume ratio of 3:13·0.33H2SEM partial enlarged view and Mapping view of the O nanometer material; e picture is FeF obtained by the volume ratio of absolute ethyl alcohol to polyethylene glycol being 1:13·0.33H2SEM picture of O nano material, wherein f picture is FeF obtained by volume ratio of absolute ethyl alcohol to polyethylene glycol of 1:13·0.33H2SEM partial enlarged view and Mapping view of O nanometer material.
As can be seen from fig. 1 and 2: when the volume ratio of the absolute ethyl alcohol to the polyethylene glycol is changed, the FeF is not influenced3·0.33H2Structure of O nanomaterial, FeF3·0.33H2The shape and size of the O nanometer material can be gradually changed. When the volume ratio of the absolute ethyl alcohol to the polyethylene glycol is 1:1 hour, FeF3·0.33H2The shape of the O nano material is a porous structure, and the size is the smallest; therefore, the specific surface area of the sample is the largest, and the volume ratio of the absolute ethyl alcohol to the polyethylene glycol is 1:1 subsequent experiments were performed.
Example 2
Different Fe were explored: the influence of the F molar ratio on the structure of the composite product of the positive electrode of the thermal battery.
The method comprises the following specific steps:
s1, preparing 3 parts of absolute ethyl alcohol and polyethylene glycol 400 by using a solvent with a volume ratio of 1:1, and stirring the mixture in a polytetrafluoroethylene container for 30min respectively.
S2, mixing 2.02g Fe (NO)3)3·9H2And O is added into the solvent respectively, and stirred for 30min to be fully dissolved.
S3, according to Fe: HF was added to the same solvent in the amounts of 1:4, 1:8 and 1:12, respectively, and the mixture was stirred for 1 hour, and then placed in an oven at 120 ℃ to react for 12 hours.
S4, washing the reacted precipitate with absolute ethyl alcohol for 5 times to remove excessive water and unreacted organic matters, and then putting the precipitate into a vacuum oven to be dried for 12 hours at the temperature of 80 ℃ to obtain FeF3·0.33H2And (4) O nano material.
S5, FeF with the Fe: F molar ratio of 1:4 and 1:83·0.33H2Calcining the O nano material in a tubular furnace at 400 ℃ for 1.5h, keeping the argon environment in the whole calcining process, wherein the argon flow is 1L/min, and taking out the O nano material after naturally cooling to room temperature to successfully prepare FeF3-FeF2A positive electrode composite material.
FIG. 3 shows FeF as a product before calcination at Fe: F molar ratios of 1:4, 1:8 and 1:12, respectively3·0.33H2XRD pattern of O nano material; as can be seen from fig. 3: FeF when the Fe: F molar ratio is increased from 1:4 to 1:83·0.33H2The crystal structure of the O material is not changed, but when the crystal structure of the O material is increased to 1:12, a plurality of mixed peaks appear in the crystal structure of the product, so that FeF with Fe: F molar ratios of 1:4 and 1:8 is adopted in the subsequent step3·0.33H2The O product is subjected to a subsequent calcination process.
FIG. 4 shows the product FeF after calcination with Fe: F molar ratio of 1:4 and 1:83-FeF2XRD pattern of the positive electrode composite material of the thermal battery. As can be seen from fig. 4: FeF when the molar ratio of Fe to F is 1:4 and 1:83·0.33H2The O material is calcined at 400 ℃ to obtain FeF3-FeF2The composite product, but the calcined product having a Fe: F molar ratio of 1:8, contains FeF3The content is more, and in order to improve the overall capacity of a subsequent battery, a subsequent graphene coating experiment is carried out by adopting the proportion of 1:8 of the molar ratio of Fe to F.
Example 3
The influence of the calcination temperature on the structure of the composite product of the anode of the thermal battery is explored
The method comprises the following specific steps:
s1, stirring the absolute ethyl alcohol and the polyethylene glycol 400 in a polytetrafluoroethylene container for 30min according to the volume ratio of 1: 1.
S2, mixing 2.02g Fe (NO)3)3·9H2O is added into the solvent and stirred for 30min to be fully dissolved.
S3, adding HF into the solvent according to the molar ratio of Fe to F of 1:8, fully stirring for 1h, and then putting into an oven to react for 12h at 120 ℃.
S4, washing the reacted precipitate with absolute ethanol for 5 times to remove excessive water and unreacted organic substances, and then drying in a vacuum oven at 80 deg.CDrying for 12h to obtain FeF3·0.33H2And (4) O nano material.
S5, collecting the above 0.5g FeF3·0.33H2Respectively ultrasonically dispersing O powder and 20mg graphene oxide powder (GO) in 20mL deionized water for about 10min, and then dropwise adding the graphene dispersion liquid into FeF in a dropwise adding mode (the dropwise adding speed is 1.0mL/min)3·0.33H2Dispersing O in the water solution, stirring for 1h to uniformly mix, and then putting into a freeze dryer to dry for 48h to obtain FeF with good appearance and size3·0.33H2O/GO nanocomposites.
S6, mixing the FeF3·0.33H2And drying the O/GO nano composite material in a vacuum oven at 150 ℃ for 3h to obtain a precursor.
S7, putting the precursor into a tube furnace for three times, setting the temperature to be 400 ℃, 450 ℃ and 500 ℃, the heating rate to be 4 ℃/min, the calcination time to be 1.5h, keeping the whole calcination process in an argon environment, setting the argon flow to be 1L/min, and taking out after naturally cooling to the room temperature to successfully prepare FeF3-FeF2the/rGO thermal battery anode composite material.
FIG. 5 shows FeF3·0.33H2SEM images of O/GO nanocomposites; as can be seen from fig. 5: FeF is uniformly coated with graphene oxide3·0.33H2Formation of FeF between and on the surface of O nanoparticles3·0.33H2The O/GO nano composite material forms a reticular coating structure beneficial to electronic conduction, and can improve the conductivity of the thermal battery anode composite material.
FIG. 6 shows FeF obtained at different calcination temperatures3-FeF2XRD atlas of positive pole composite material of/rGO thermal battery; as can be seen from fig. 6: when FeF3·0.33H2FeF in the thermal battery anode composite material after the O/GO nano composite material is subjected to different calcination temperatures3The content may also vary. FeF in the thermal battery anode composite material along with the calcination temperature being increased from 400 ℃ to 450 ℃ and then to 500 DEG C3Gradually decomposing into FeF2Result in FeF3The content gradually decreases, FeF2The content gradually increases. In order to improve the integrity of the thermal batteryVolume capacity, 400 ℃ calcination for preparing FeF3-FeF2the/rGO thermal battery anode composite material.
FIG. 7 shows FeF obtained by calcination at 400 deg.C3-FeF2SEM and Mapping diagrams of/rGO thermal battery anode composite material; as can be seen from fig. 7: the calcined graphene is well coated on the submicron spheres, and the iron element, the fluorine element and the carbon element are uniformly distributed in the positive composite material of the thermal battery.
In order to explore FeF after calcination at 400 DEG C3-FeF2FeF in/rGO thermal battery anode composite material3And FeF2In proportion of (A), the FeF obtained by calcination at 400 ℃ by XPS test3-FeF2The content of/rGO thermal battery positive electrode composite, results are shown in fig. 8. As can be seen from fig. 8: fe3+61% by weight, Fe 2+39% of the total content, namely the FeF calcined at 400 DEG C3-FeF2FeF in/rGO positive electrode composite material3And FeF2Is about 6: 4.
FIG. 9 shows FeF obtained by calcination at 400 deg.C3-FeF2Specific surface area diagram of/rGO thermal battery positive electrode composite material; FIG. 10 shows FeF obtained by calcination at 400 deg.C3-FeF2The pore diameter distribution diagram of the/rGO thermal battery anode composite material; from fig. 9 and 10, it can be seen that: FeF3-FeF2The specific surface area and the pore size of the/rGO thermal battery anode composite material are respectively 20.58m2At 19.35nm and/g, it can be seen that the FeF increases after calcination3-FeF2Specific surface area and pore size of/rGO thermal battery positive electrode composite material.
Calcination of the resulting FeF at 400 ℃ using the BET test3-FeF2Porosity of/rGO thermal battery positive electrode composite material, result is 0.095cm3/g。
FIG. 11 shows FeF obtained by calcination at 400 deg.C3-FeF2No-load discharge diagram of/rGO thermal battery positive electrode composite, as can be seen from fig. 11: FeF in the discharge interval of 900s3-FeF2the/rGO thermal battery anode composite material always has stable high voltage of about 3.2V, and provides a good foundation for high-power discharge of the thermal battery.
FIG. 12 is a graph of 400 deg.CCalcination of the resulting FeF3-FeF2Sheet resistance and resistivity maps of/rGO thermal battery positive electrode composites; the Rs is rho/w, where Rs is sheet resistance, rho is the resistivity of the material, and w is the thickness of the thin layer material; FeF by four-probe test3-FeF2The average sheet resistance Rs of the/rGO positive electrode composite material is 0.03550 omega/□, the average resistivity of the positive electrode composite material of the thermal battery can be calculated to be 0.0005325 omega cm from w being 0.15mm, and the average resistivity is converted into the conductivity of about 1878S cm-1Much higher than FeS used in the prior thermal battery2Normal temperature conductivity of 27.7 S.cm-1And CoS2Normal temperature conductivity of 500S cm-1Visible FeF3-FeF2the/rGO thermal battery positive electrode composite material has good electrical conductivity.
Example 4
Exploring argon flow during calcination to heat battery anode composite product FeF3-FeF2The specific steps of the structure of/rGO are as follows:
s1, stirring the absolute ethyl alcohol and the polyethylene glycol 400 in a polytetrafluoroethylene container for 30min according to the volume ratio of 1: 1.
S2, mixing 2.02g Fe (NO)3)3·9H2O is added into the solvent and stirred for 30min to be fully dissolved.
S3, adding HF according to the molar ratio of Fe to F of 1:8, fully stirring for 1h, and then putting into an oven to react for 12h at 120 ℃.
S4, washing the reacted precipitate with absolute ethyl alcohol for 5 times to remove excessive water and unreacted organic matters, and then drying in a vacuum oven at 80 ℃ for 12 hours to obtain FeF3·0.33H2And (4) O nano material.
S5, collecting the above 0.5g FeF3·0.33H2Respectively ultrasonically dispersing O powder and 20mg of Graphene Oxide (GO) in 20mL of deionized water for about 10min, and then dropwise adding the graphene dispersion liquid into FeF in a dropwise adding manner3·0.33H2Dispersing O in the water solution, stirring for 1h to uniformly mix, and then putting into a freeze dryer to dry for 48h to obtain FeF with good appearance and size3·0.33H2O/GO nanocomposites.
S6, mixing the FeF3·0.33H2And drying the O/GO nano composite material in a vacuum oven at 150 ℃ for 3h to obtain a precursor.
S7, putting the precursor into a tube furnace twice, controlling the temperature at 400 ℃, the heating rate at 4 ℃/min and the time at 1.5h, keeping the argon environment in the whole calcining process, respectively setting the argon flow at 0.5L/min and 1L/min, and taking out after naturally cooling to the room temperature to successfully prepare the FeF3-FeF2the/rGO thermal battery anode composite material.
FIG. 13 shows FeF obtained at different argon flows3-FeF2XRD pattern of/rGO thermal battery positive electrode composite material, known from FIG. 13: when the argon flow is 0.5L/min, FeF3·0.33H2Fe appears in the product after O/GO calcination3O4Diffraction peaks, which indicate insufficient argon flow during calcination and result in oxidation of iron fluoride by oxygen in the tube furnace, and FeF as the calcination product when the argon flow was increased to 1L/min3-FeF2The positive electrode composite material of the/rGO thermal battery adopts argon flow of 1L/min due to the consideration of cost.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The composite material for the positive electrode of the thermal battery is characterized by comprising FeF3-FeF2Micro-nanospheres, and coating on said FeF3-FeF2Graphene oxide on the micro-nanospheres;
the FeF3-FeF2FeF in micro-nanospheres3And FeF2In a molar ratio of 7: 3-5.5: 4.5;
the coating amount of the graphene oxide is 0.0001-4 wt%;
the specific surface area of the thermal battery anode composite material is 18-22 m2The porosity is 0.07-0.12 cm3/g。
2. The thermal battery positive composite of claim 1, wherein the FeF is3-FeF2The particle size of the micro-nano sphere is 200-300 nm.
3. The method for preparing a positive electrode composite material for a thermal battery according to claim 1 or 2, comprising the steps of:
mixing absolute ethyl alcohol, polyethylene glycol, hydrofluoric acid and water-soluble ferric salt, and carrying out solvothermal reaction to obtain FeF3·0.33H2O nano material;
subjecting the FeF to3·0.33H2Mixing the O nano material, graphene oxide and water, and freeze-drying to obtain FeF3·0.33H2O/GO nanocomposites;
subjecting the FeF to3·0.33H2Carrying out water removal treatment on the O/GO nano composite material to obtain a precursor;
and calcining the precursor under a protective atmosphere to obtain the thermal battery anode composite material.
4. The method according to claim 3, wherein the volume ratio of the absolute ethanol to the polyethylene glycol is 25: 15-15: 25; the amount ratio of the water-soluble ferric salt to the hydrofluoric acid is 1: (6-10).
5. The preparation method according to claim 3 or 4, wherein the temperature of the solvothermal reaction is 115-125 ℃ and the time is 11-13 h.
6. The method of claim 3, wherein the FeF is3·0.33H2The mode of mixing the O nano material, the graphene oxide and the water is as follows: subjecting the FeF to3·0.33H2Dissolving O nano material and graphene oxide in water respectively to form FeF3·0.33H2O nano material dispersion liquid and graphene oxide dispersion liquid; separating the graphene oxide intoDropwise adding the dispersion to the FeF3·0.33H2O nano material dispersion liquid.
7. The method according to claim 6, wherein the dropping is performed at a rate of 0.8 to 1.2 mL/min.
8. The method according to claim 3, wherein the water removal treatment is performed by vacuum drying; the temperature of the vacuum drying is 140-160 ℃, and the time is 2-4 h.
9. The preparation method of claim 3, wherein the calcining temperature is 380-420 ℃ and the calcining time is 1-2 h.
10. Use of the positive electrode composite material for a thermal battery according to claim 1 or 2 or the positive electrode composite material for a thermal battery obtained by the preparation method according to any one of claims 3 to 9 as a positive electrode material in a thermal battery.
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