CN112794377A - Rare earth doped transition metal sulfide/carbon composite material and preparation method and application thereof - Google Patents
Rare earth doped transition metal sulfide/carbon composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a rare earth doped transition metal sulfide/carbon composite material and a preparation method and application thereof, belonging to the technical field of lithium-sulfur batteries. The invention provides a preparation method of a rare earth doped transition metal sulfide/carbon composite material, which comprises the following steps: mixing a rare earth compound, a transition metal compound, a carbon source and a solvent, and drying to obtain precursor powder; carbonizing the precursor powder to obtain the rare earth doped transition metalA carbon composite; oxidizing the rare earth doped transition metal/carbon composite material to obtain a rare earth doped transition metal oxide/carbon composite material; and mixing the rare earth doped transition metal oxide/carbon composite material with sulfur, and vulcanizing under a protective atmosphere to obtain the rare earth doped transition metal sulfide/carbon composite material. Doping transition metal sulfide with rare earth metal ions to further improve Li content of transition metal sulfide2SnCatalytic decomposition of (1).
Description
Technical Field
The invention relates to the technical field of lithium-sulfur batteries, in particular to a rare earth doped transition metal sulfide/carbon composite material and a preparation method and application thereof.
Background
In recent years, lithium-sulfur batteries have attracted much attention because of their advantages such as high theoretical specific capacity, high theoretical specific energy, and environmental friendliness. However, lithium sulfur batteries produce soluble long chain lithium polysulfide Li during charging and discharging2Sn(2<n<8)，Li2SnThe problems of poor conductivity of the sulfur positive electrode, corrosion and pulverization of the lithium negative electrode and the like caused by the shuttle effect between the positive electrode and the negative electrode cause low coulombic efficiency, fast capacity attenuation and short cycle life of the lithium-sulfur battery, and finally limit the practical application of the lithium-sulfur battery.
To suppress Li2SnThe shuttle effect of the lithium ion battery can improve the cycle utilization rate of the anode material, and the main modification measures at present comprise Li2SnCoating of (2), Li2SnAdsorption of (2) and Li2SnCatalytic decomposition of (3). Wherein Li2SnBy using metals, metal oxides or metalsSulfide pair Li2SnElectrocatalysis of redox reaction to promote long-chain Li in charge-discharge process2SnTo short chain Li2S or Li2S2Thereby inhibiting Li2SnShuttling effects of, in particular, scandium, zinc oxide, copper oxide and molybdenum disulfide, but metals, metal oxides or metal sulfides of the prior art to Li2SnThe catalytic decomposition of (2) has a problem of low efficiency.
Disclosure of Invention
In view of the above, the present invention aims to provide a rare earth doped transition metal sulfide/carbon composite material, and a preparation method and an application thereof. The rare earth doped transition metal sulfide/carbon composite material prepared by the invention is Li2SnThe catalytic decomposition efficiency is high.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a rare earth doped transition metal sulfide/carbon composite material, which comprises the following steps:
mixing a rare earth compound, a transition metal compound, a carbon source and a solvent, and drying to obtain precursor powder;
carbonizing the precursor powder to obtain a rare earth doped transition metal/carbon composite material;
oxidizing the rare earth doped transition metal/carbon composite material to obtain a rare earth doped transition metal oxide/carbon composite material;
and mixing the rare earth doped transition metal oxide/carbon composite material with sulfur in a protective atmosphere for vulcanization to obtain the rare earth doped transition metal sulfide/carbon composite material.
Preferably, the molar ratio of the rare earth element in the rare earth compound to the transition metal element in the transition metal compound is 0.01-0.1: 1.
Preferably, the rare earth element in the rare earth compound comprises one or more of europium, dysprosium, cerium, yttrium and gadolinium.
Preferably, the transition metal element in the transition metal compound includes one or more of nickel, cobalt, and iron.
Preferably, the mass ratio of the total mass of the rare earth compound and the transition metal compound to the carbon source is 1: 10-100.
Preferably, the carbonization temperature is 500-1500 ℃, and the carbonization time is 2-10 h.
Preferably, the heating rate of the temperature rise to the carbonization temperature is 2-20 ℃/min.
Preferably, the vulcanizing temperature is 300-500 ℃ and the time is 4-40 h.
The invention also provides the rare earth doped transition metal sulfide/carbon composite material prepared by the preparation method in the technical scheme, which comprises the rare earth doped transition metal sulfide and an amorphous carbon substrate, wherein the rare earth doped transition metal sulfide is loaded in the amorphous carbon substrate.
The invention also provides the application of the rare earth doped transition metal sulfide/carbon composite material in the technical scheme in the field of lithium-sulfur batteries.
The invention provides a preparation method of a rare earth doped transition metal sulfide/carbon composite material, which comprises the following steps: mixing a rare earth compound, a transition metal compound, a carbon source and a solvent, and drying to obtain precursor powder; carbonizing the precursor powder to obtain a rare earth doped transition metal/carbon composite material; oxidizing the rare earth-doped transition metal/carbon composite material to obtain a rare earth-doped transition metal oxide/carbon composite material; and mixing the rare earth doped transition metal oxide/carbon composite material with sulfur, and vulcanizing under a protective atmosphere to obtain the rare earth doped transition metal sulfide/carbon composite material.
The invention also provides the rare earth doped transition metal sulfide/carbon composite material prepared by the preparation method in the technical scheme. The invention utilizes rare earth metal ions to dope transition metal sulfides, and the rare earth-containing compound shows unique catalytic performance due to the special electronic configuration and various electronic energy levels of rare earth elements, and the rare earth doping of the transition metals can further realize the purpose of doping the transition metalsIncrease its Li content2SnCatalytic decomposition of (1), acceleration of soluble Li2SnTo insoluble Li2S or Li2S2The conversion of (2) accelerates the reaction kinetics of the lithium-sulfur battery and reduces long-chain Li2SnThereby significantly suppressing Li2SnThe transition metal sulfide can effectively adsorb Li formed in the charging and discharging process2SnAnd catalytically accelerating Li2SnReduction to form insoluble Li2S or Li2S2Further improve the Li content of transition metal sulfide2SnCatalytic decomposition of (1). In addition, the network carbon distributed among the transition metal sulfide particles can increase the transmission of electrons and ions, improve the conductivity of the composite material, facilitate the transmission of electrons and further improve the cycle stability. The examples show that the composite material prepared by the invention can reduce Li when being used as a carrier material of a sulfur positive electrode of a lithium-sulfur battery2SnThe shuttle effect of the lithium sulfur battery improves the specific capacity of the lithium sulfur battery and improves the cycling stability of the lithium sulfur battery.
Drawings
FIG. 1 is a flow chart of a process for preparing a rare earth doped transition metal sulfide/carbon composite according to an embodiment of the present invention;
FIG. 2 shows Ni prepared in example 2 of the present invention0.95Eu0.05The S/carbon composite material is at 1600 mA.g-1Cycling performance curve under charge and discharge current density.
Detailed Description
The invention provides a preparation method of a rare earth doped transition metal sulfide/carbon composite material, which comprises the following steps:
mixing a rare earth compound, a transition metal compound, a carbon source and a solvent, and drying to obtain precursor powder;
carbonizing the precursor powder to obtain a rare earth doped transition metal/carbon composite material;
oxidizing the rare earth doped transition metal/carbon composite material to obtain a rare earth doped transition metal oxide/carbon composite material;
and mixing the rare earth doped transition metal oxide/carbon composite material with sulfur, and vulcanizing under a protective atmosphere to obtain the rare earth doped transition metal sulfide/carbon composite material.
In the present invention, the starting materials used are all commercial products in the art unless otherwise specified.
The invention mixes and dries rare earth compound, transition metal compound, carbon source and solvent to obtain precursor powder. In the present invention, the rare earth element in the rare earth compound preferably includes one or more of europium, dysprosium, cerium, yttrium and gadolinium; the europium is preferably provided by europium nitrate, europium carbonate or europium oxide; the dysprosium is preferably provided by dysprosium nitrate, the cerium is preferably provided by cerium nitrate, cerium oxide or cerium carbonate, the yttrium is preferably provided by yttrium nitrate, and the gadolinium is preferably provided by gadolinium nitrate.
In the present invention, the transition metal element in the transition metal compound is preferably one or more of nickel, cobalt and iron, the nickel is preferably provided by nickel nitrate, nickel oxide or nickel carbonate, the cobalt is preferably provided by cobalt nitrate, and the iron is preferably provided by iron nitrate, iron carbonate or iron acetate.
In a specific embodiment of the present invention, when the rare earth element in the rare earth compound is europium, the transition metal element in the transition metal compound is preferably nickel or cobalt; when the rare earth element in the rare earth compound is cerium, the transition metal element in the transition metal compound is preferably cobalt.
In the present invention, the carbon source is preferably an organic carbon source, and the organic carbon source preferably includes one or more of sucrose, soluble starch, glucose, melamine, citric acid, polyethylene glycol, polyvinyl alcohol, and phenol resin.
In the invention, the molar ratio of the rare earth element in the rare earth compound to the transition metal element in the transition metal compound is preferably 0.01-0.1: 1, and more preferably 1:19
In the invention, the mass ratio of the total mass of the rare earth compound and the transition metal compound to the carbon source is preferably 1: 10-100, and more preferably 1: 13-35.
In the present invention, the solvent preferably includes one or more of deionized water, 10 wt% nitric acid solution, ethanol, ethylene glycol and acetone, and more preferably a mixture of ethanol and deionized water, and the mass ratio of ethanol to deionized water in the mixture is preferably 1: 1.
In the invention, the mass ratio of the total mass of the rare earth compound, the transition metal compound and the carbon source to the solvent is preferably 1: 1-20, and more preferably 1: 10-15.
The preparation method preferably comprises the steps of mixing the rare earth compound, the transition metal compound and the carbon source, adding the solvent, mechanically stirring for 2-6 hours to obtain a mixed solution, and drying the mixed solution to obtain precursor powder. In the invention, the drying is preferably vacuum drying or spray drying, and the temperature of the vacuum drying is preferably 110-130 ℃, more preferably 120-125 ℃; the temperature of the air inlet of the spray drying is preferably 220-300 ℃, and more preferably 250-280 ℃; in the present invention, the drying time is not particularly limited, and the solvent can be completely removed.
In the present invention, the particle size of the precursor powder is preferably 2 to 10 μm.
After precursor powder is obtained, the precursor powder is carbonized to obtain the rare earth doped transition metal/carbon composite material.
In the invention, the carbonization temperature is preferably 500-1500 ℃, more preferably 900-1000 ℃, and the time is preferably 2-10 h, more preferably 3-4 h.
In the present invention, the rate of temperature increase from room temperature to the carbonization temperature is preferably 2 to 20 ℃/min, more preferably 5 to 15 ℃/min, and most preferably 10 ℃/min.
In the present invention, the carbonization is preferably performed in a protective atmosphere, which is preferably nitrogen.
After the carbonization, the invention preferably naturally cools the obtained carbonized product to room temperature to obtain the rare earth doped transition metal/carbon composite material.
After the rare earth doped transition metal/carbon composite material is obtained, the rare earth doped transition metal/carbon composite material is oxidized to obtain the rare earth doped transition metal oxide/carbon composite material.
In the invention, the oxidizing oxidant is preferably hydrogen peroxide, and the concentration of the hydrogen peroxide is preferably 30 wt%; the oxidation is preferably: adding hydrogen peroxide into the rare earth doped transition metal/carbon composite material, carrying out ultrasonic oscillation for 2-4 hours, and then standing for 20-40 hours.
In the invention, the ultrasonic oscillation time is preferably 3 hours, the temperature is preferably room temperature, the oscillation frequency is preferably 10 megahertz, and the standing time is preferably 24-36 hours.
In the present invention, the solid-to-liquid ratio of the oxidation system at the time of oxidation is preferably 20% to 40%, more preferably 30% to 35%.
After the oxidation is finished, the oxidation product is preferably sequentially filtered and dried to obtain the rare earth doped transition metal oxide/carbon composite material. In the invention, the drying is preferably vacuum drying, the temperature of the vacuum drying is preferably 80-120 ℃, more preferably 100-110 ℃, and the time is preferably enough to completely remove the water.
After the rare earth doped transition metal oxide/carbon composite material is obtained, the rare earth doped transition metal oxide/carbon composite material is mixed with sulfur and then vulcanized under a protective atmosphere to obtain the rare earth doped transition metal sulfide/carbon composite material.
In the present invention, the protective atmosphere is preferably nitrogen.
In the invention, the mass ratio of the rare earth doped transition metal oxide/carbon composite material to sulfur is preferably 2: 1-1: 2, more preferably 1:1, and the sulfur is preferably elemental sulfur.
In the present invention, the mixing is preferably performed mechanically for 0.5 to 3 hours. In the invention, the vulcanizing temperature is preferably 300-500 ℃, and more preferably 350-450 ℃; the time is preferably 4 to 40 hours, and more preferably 24 to 30 hours.
After the vulcanization, the obtained vulcanization product is preferably naturally cooled, then carbon disulfide with the solid-to-liquid ratio of 1: 5-20 is added, the mixture is stirred for 4-6 hours, redundant elemental sulfur is removed, and the mixture is filtered and dried at the temperature of 60-80 ℃ to obtain the rare earth doped transition metal sulfide/carbon composite material.
The invention also provides the rare earth doped transition metal sulfide/carbon composite material prepared by the preparation method in the technical scheme, which comprises the rare earth doped transition metal sulfide and an amorphous carbon substrate, wherein the rare earth doped transition metal sulfide is loaded in the amorphous carbon substrate, and the mass fraction of the amorphous carbon substrate is preferably 0-100%, and more preferably 80-90%.
The invention also provides the application of the rare earth doped transition metal sulfide/carbon composite material in the technical scheme in the field of lithium-sulfur batteries.
In the present invention, the application is preferably to use the rare earth doped transition metal sulfide/carbon composite material as a positive electrode material of a lithium sulfur battery.
According to the invention, the rare earth doped transition metal sulfide/carbon composite material is preferably mixed with sublimed sulfur and then heated to obtain the active substance sulfur-loaded cathode material.
In the present invention, the mass ratio of the rare earth-doped transition metal sulfide/carbon composite to sublimed sulfur is preferably 1: 4.
In the present invention, the heating temperature is preferably 155 ℃ for 12 hours. In the present invention, the heating is preferably performed in a hydrothermal reactor.
In order to further illustrate the present invention, the rare earth doped transition metal sulfide/carbon composite material provided by the present invention, the preparation method and the application thereof are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
FIG. 1 is a flow chart of the preparation process for preparing rare earth doped transition metal sulfide/carbon composite material according to the present invention. Mixing a rare earth compound, a transition metal compound, a carbon source and a solvent, and drying to obtain precursor powder; and sequentially carbonizing, oxidizing and vulcanizing the precursor powder to obtain the rare earth doped transition metal sulfide/carbon composite material.
Example 1
Weighing 0.223g Eu (NO)3)3·6H2O、2.762g Ni(NO3)2·6H2Adding 500g of deionized water into O and 40g of glucose, mechanically stirring for 2 hours, and then carrying out vacuum drying at 110 ℃ to obtain precursor powder;
heating the precursor powder to 1500 ℃ at the speed of 2 ℃/min under the protection of nitrogen, preserving the heat for 4 hours, and cooling to obtain Ni0.95Eu0.05A carbon composite;
weighing 3gNi0.95Eu0.05Adding 10 ml of 30 wt% hydrogen peroxide aqueous solution into the carbon/carbon composite material, ultrasonically oscillating for 2 hours, standing for 24 hours, filtering, and drying in vacuum at 100 ℃ to obtain Ni0.95Eu0.05An O/carbon composite;
mixing Ni0.95Eu0.05Mixing an O/carbon composite material and elemental sulfur according to the mass ratio of 1:1, preserving heat for 24 hours at 500 ℃ under the protection of nitrogen, cooling, adding carbon disulfide with the solid-to-liquid ratio of 1:5, stirring for 4 hours, filtering, and drying at 60 ℃ to obtain the rare earth doped transition metal sulfide/carbon composite material, wherein the mass fraction of the amorphous carbon substrate is 80%, and is marked as Ni0.95Eu0.05An S/carbon composite material. Obtained Ni0.95Eu0.05And mixing the S/carbon composite material and sublimed sulfur according to the mass ratio of 1:4, and preserving the mixture in a hydrothermal kettle at 155 ℃ for 12 hours to obtain the active substance sulfur-loaded cathode material.
The battery performance test of the anode material adopts a CR2025 button cell battery, and the assembly is carried out in a glove box filled with inert atmosphere. The negative electrode adopts a metal lithium sheet, and the electrolyte adopts 1 mol.L-1LiPF6DMC (volume ratio 1:1), where EC is ethylene carbonate and DMC is dimethyl carbonate. The preparation process of the positive plate comprises the following steps: prepared Ni0.95Eu0.05The S/carbon-loaded sulfur active material, conductive agent acetylene black and binder PVDF (polyvinylidene fluoride) are uniformly mixed according to the mass ratio of 90:5:5, NMP (N-methyl pyrrolidone) with the mass ratio of 10:1 to PVDF is added and uniformly ground in an agate mortar to form a viscous colloidal mixture, then the viscous colloidal mixture is uniformly coated on an aluminum foil with the thickness of 0.02mm, and the aluminum foil is placed in vacuum at 80 DEG CDrying for 10 h. The assembled blue battery test system for the battery carries out constant current charge and discharge test at 1600 mA.g-1At current density, Ni0.95Eu0.05The initial specific discharge capacity of the S/carbon-loaded sulfur active material is 167 mAh.g-1The capacity is maintained at 156mAh g after 40 times of circulation-1。
Example 2
Weighing 0.223g Eu (NO)3)3·6H2O、2.762g Ni(NO3)2·6H2Adding 400g of deionized water into O and 40g of glucose, mechanically stirring for 2 hours, and then carrying out spray drying, wherein the temperature of an air inlet is 220 ℃, so as to obtain precursor powder; heating the precursor powder to 1000 ℃ at a speed of 20 ℃/min under the protection of nitrogen, preserving heat for 3 hours, and cooling to obtain Ni0.95Eu0.05A carbon composite; weighing 3gNi0.95Eu0.05Adding 10 ml of 30 wt% hydrogen peroxide aqueous solution into the carbon/carbon composite material, ultrasonically oscillating for 2 hours, standing for 24 hours, filtering, and drying in vacuum at 100 ℃ to obtain Ni0.95Eu0.05An O/carbon composite; mixing Ni0.95Eu0.05Mixing an O/carbon composite material and elemental sulfur according to the mass ratio of 1:1, preserving heat for 24 hours at 450 ℃ under the protection of nitrogen, cooling, adding carbon disulfide with the solid-to-liquid ratio of 1:10, stirring for 4 hours, filtering, and drying at 80 ℃ to obtain the rare earth doped transition metal sulfide/carbon composite material, wherein the mass fraction of the amorphous carbon substrate is 85%, and is marked as Ni0.95Eu0.05An S/carbon composite material.
The cell was assembled and tested according to the method of example 1, and fig. 2 shows Ni prepared in example 2 of the present invention0.95Eu0.05The S/carbon composite material is at 1600 mA.g-1The cycle performance curve under the charge-discharge current density shows that Ni0.95Eu0.05S/carbon-supported sulfur active material 1600mA g-1Under the current density, the initial discharge specific capacity of the material is 248 mAh.g-1The circulation capacity is maintained at 249.8mAh g after 40 times-1。
Example 3
Weighing 0.045g Eu (NO)3)3·6H2O、2.878g Ni(NO3)2·6H2Adding 500g of ethanol and deionized water mixed solution (the mass ratio of ethanol to deionized water is 1:1) into O and 45g of glucose, mechanically stirring for 2 hours, and then carrying out vacuum drying at 110 ℃ to obtain precursor powder; heating the precursor powder to 1500 ℃ at the speed of 5 ℃/min under the protection of nitrogen, preserving the heat for 3 hours, and cooling to obtain Ni0.99Eu0.01A carbon composite; weighing 3gNi0.99Eu0.01Adding 10 ml of 30 wt% hydrogen peroxide aqueous solution into the carbon/carbon composite material, ultrasonically oscillating for 2 hours, standing for 24 hours, filtering, and drying in vacuum at 100 ℃ to obtain Ni0.99Eu0.01An O/carbon composite; mixing Ni0.99Eu0.01Mixing an O/carbon composite material and elemental sulfur according to the mass ratio of 1:1, preserving heat for 40 hours at 300 ℃ under the protection of nitrogen, cooling, adding carbon disulfide with the solid-to-liquid ratio of 1:20, stirring for 4 hours, filtering, and drying at 80 ℃ to obtain the rare earth doped transition metal sulfide/carbon composite material, wherein the mass fraction of the amorphous carbon substrate is 86.5 percent and is marked as Ni0.99Eu0.01An S/carbon composite material.
The cell was assembled and tested as in example 1, 1600mA g-1At current density, Ni0.99Eu0.01The initial discharge specific capacity of the S/carbon-supported sulfur electrode material is 188mAh g-1The circulation capacity is maintained at 179.8mAh g after 40 times-1。
Example 4
Weighing 0.223g Eu (NO)3)3·6H2O、2.765g Co(NO3)2·6H2Adding 1200g of ethanol and deionized water mixed solution (the mass ratio of ethanol to deionized water is 1:4) into O and 40g of soluble starch, mechanically stirring for 2 hours, and then carrying out vacuum drying at 110 ℃ to obtain precursor powder; heating the precursor powder to 1000 ℃ at a speed of 10 ℃/min under the protection of nitrogen, preserving heat for 3 hours, and cooling to obtain Co0.95Eu0.05A carbon composite; weighing 3g of Co0.95Eu0.05Adding 10 ml of 30 wt% hydrogen peroxide aqueous solution into the carbon/carbon composite material, ultrasonically oscillating for 2 hours, standing for 24 hours, filtering, and drying in vacuum at 100 ℃ to obtain Co0.95Eu0.05An O/carbon composite; mixing Co0.95Eu0.05Mixing an O/carbon composite material and elemental sulfur according to the mass ratio of 1:1, preserving heat for 30 hours at 450 ℃ under the protection of nitrogen, cooling, adding carbon disulfide with the solid-to-liquid ratio of 1:10, stirring for 6 hours, and drying at 80 ℃ to obtain the rare earth doped transition metal sulfide/carbon composite material, wherein the mass fraction of the amorphous carbon substrate is 81%, and is marked as Co0.95Eu0.05An S/carbon composite material.
The cell was assembled and tested as in example 1, 1600mA g-1At current density, Co0.95Eu0.05The initial specific discharge capacity of the O/carbon-loaded sulfur electrode material is 368 mAh.g-1The circulation capacity is maintained at 359.2mAh g after 40 times-1。
Example 5
0.217g of Ce (NO) is weighed out3)3·6H2O、2.765g Co(NO3)2·6H2Adding 1200g of deionized water into O and 45g of glucose, mechanically stirring for 2 hours, and then carrying out spray drying, wherein the temperature of an air inlet is 220 ℃, so as to obtain precursor powder; heating the precursor powder to 1000 ℃ at a speed of 15 ℃/min under the protection of nitrogen, preserving heat for 3 hours, and cooling to obtain Co0.95Ce0.05A carbon composite; weighing 3g of Co0.95Ce0.05Adding 10 ml of 30 wt% hydrogen peroxide aqueous solution into the carbon/carbon composite material, ultrasonically oscillating for 2 hours, standing for 24 hours, filtering, and drying in vacuum at 100 ℃ to obtain Co0.95Ce0.05An O/carbon composite; mixing Co0.95Ce0.05Mixing an O/carbon composite material and elemental sulfur according to the mass ratio of 1:1, preserving heat for 24 hours at 450 ℃ under the protection of nitrogen, cooling, adding carbon disulfide with the solid-to-liquid ratio of 1:10, stirring for 4 hours, and drying at 60 ℃ to obtain the rare earth doped transition metal sulfide/carbon composite material, wherein the mass fraction of the amorphous carbon substrate is 86%, and is marked as Co0.95Ce0.05An S/carbon composite material.
The cell was assembled and tested as in example 1, 1600mA g-1Under the current density, the initial specific discharge capacity of the material is 412mAh g-1The circulating capacity is kept to 369.8mAh g after 40 times-1。
Example 6
Weighing 0.035g Eu2O3、2.849g Ni(NO3)2·6H2Adding 1200g of 10 wt% nitric acid solution into O and 100g of soluble starch, mechanically stirring for 2 hours, and then carrying out spray drying, wherein the temperature of an air inlet is 220 ℃, so as to obtain precursor powder; heating the precursor powder to 1000 ℃ at the speed of 2 ℃/min under the protection of nitrogen, preserving the heat for 3 hours, and cooling to obtain Ni0.98Eu0.02A carbon composite; weighing 3gNi0.98Eu0.02Adding 10 ml of 30 wt% hydrogen peroxide aqueous solution into the carbon/carbon composite material, ultrasonically oscillating for 2 hours, standing for 24 hours, filtering, and drying in vacuum at 100 ℃ to obtain Ni0.98Eu0.02An O/carbon composite; mixing Ni0.98Eu0.02Mixing an O/carbon composite material and elemental sulfur according to the mass ratio of 1:1, preserving heat for 24 hours at 450 ℃ under the protection of nitrogen, cooling, adding carbon disulfide with the solid-to-liquid ratio of 1:5, stirring for 6 hours, and drying at 60 ℃ to obtain the rare earth doped transition metal sulfide/carbon composite material, wherein the mass fraction of the amorphous carbon substrate is 90%, and is marked as Ni0.98Eu0.02An S/carbon composite material.
The cell was assembled and tested as in example 1, 1600mA g-1Under the current density, the initial specific discharge capacity of the material is 202.3 mAh.g-1The capacity is maintained at 171.8mAh g after 40 times of circulation-1。
Comparative example 1
2.907g of Ni (NO) were weighed out3)2·6H2Adding 400g of deionized water into O and 40g of glucose, mechanically stirring for 2 hours, and then carrying out spray drying, wherein the temperature of an air inlet is 220 ℃, so as to obtain precursor powder; preserving the heat of the precursor powder for 3 hours at 1000 ℃ under the protection of nitrogen, and cooling to obtain an undoped Ni/carbon composite material; weighing 3 gNi/carbon composite material, adding 10 ml of 30 wt% hydrogen peroxide aqueous solution, ultrasonically oscillating for 2 hours, standing for 24 hours, filtering, and vacuum drying at 100 ℃ to obtain NiO/carbon composite material; mixing the NiO/carbon composite material with elemental sulfur according to the mass ratio of 1:1, preserving heat for 24 hours at 450 ℃ under the protection of nitrogen, removing redundant elemental sulfur by using carbon disulfide after cooling, adding carbon disulfide with the solid-to-liquid ratio of 1:10, stirring for 4 hours to remove redundant elemental sulfur, filteringAnd drying at 60 ℃ to obtain the NiS/carbon composite material, wherein the mass fraction of carbon is 82.6%.
The cell was assembled and tested as in example 1, with the NiS/carbon-supported sulfur active material at 1600mA g-1Under the current density, the initial specific discharge capacity of the material is 187.2 mAh.g-1The capacity is kept at 131.8mAh g after 40 times of circulation-1。
Comparative example 2
Weighing 0.223g Eu (NO)3)3·6H2O、2.765g Co(NO3)2·6H2Adding 200g of deionized water into the mixture, mechanically stirring the mixture for 2 hours, and then carrying out spray drying, wherein the temperature of an air inlet is 220 ℃, so as to obtain precursor powder; heating the precursor powder to 1200 ℃ at a speed of 15 ℃/min under the protection of nitrogen, preserving heat for 3 hours, and cooling to obtain Co0.95Eu0.05(ii) a Weighing 3g of Co0.95Eu0.05Adding 10 ml of 30 wt% hydrogen peroxide aqueous solution, ultrasonically oscillating for 2 hours, standing for 24 hours, filtering, and vacuum drying at 100 ℃ to obtain Co0.95Eu0.05An O material; mixing Co0.95Eu0.05Mixing O and elemental sulfur in a mass ratio of 1:1, preserving heat for 24 hours at 450 ℃ under the protection of nitrogen, cooling, adding carbon disulfide in a solid-to-liquid ratio of 1:10, stirring for 4 hours, filtering, and drying at 60 ℃ to obtain Co0.95Eu0.05And S, wherein the mass fraction of carbon is 0%. The cell was assembled and tested as in example 1, 1600mA g-1Under the current density, the initial discharge specific capacity of the material is 132 mAh.g-1The capacity is kept at 78.3mAh g after 40 times of circulation-1。
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. A preparation method of a rare earth doped transition metal sulfide/carbon composite material is characterized by comprising the following steps:
mixing a rare earth compound, a transition metal compound, a carbon source and a solvent, and drying to obtain precursor powder;
carbonizing the precursor powder to obtain a rare earth doped transition metal/carbon composite material;
oxidizing the rare earth doped transition metal/carbon composite material to obtain a rare earth doped transition metal oxide/carbon composite material;
and mixing the rare earth doped transition metal oxide/carbon composite material with sulfur in a protective atmosphere for vulcanization to obtain the rare earth doped transition metal sulfide/carbon composite material.
2. The production method according to claim 1, wherein the molar ratio of the rare earth element in the rare earth compound to the transition metal element in the transition metal compound is 0.01 to 0.1: 1.
3. The method of claim 1 or 2, wherein the rare earth element in the rare earth compound comprises one or more of europium, dysprosium, cerium, yttrium, and gadolinium.
4. The production method according to claim 1 or 2, wherein the transition metal element in the transition metal compound includes one or more of nickel, cobalt, and iron.
5. The method according to claim 1, wherein the mass ratio of the total mass of the rare earth compound and the transition metal compound to the carbon source is 1:10 to 100.
6. The method according to claim 1, wherein the carbonization is carried out at a temperature of 500 to 1500 ℃ for 2 to 10 hours.
7. The production method according to claim 6, wherein a temperature rise rate at which the temperature is raised to the carbonization temperature is 2 to 20 ℃/min.
8. The method according to claim 1, wherein the vulcanization is carried out at a temperature of 300 to 500 ℃ for 4 to 40 hours.
9. The rare earth-doped transition metal sulfide/carbon composite material prepared by the preparation method of any one of claims 1 to 8, comprising a rare earth-doped transition metal sulfide and an amorphous carbon substrate, wherein the rare earth-doped transition metal sulfide is supported in the amorphous carbon substrate.
10. Use of the rare earth doped transition metal sulfide/carbon composite of claim 9 in a lithium sulfur battery.
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| CN114243002A (en) * | 2021-11-11 | 2022-03-25 | 惠州锂威新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN115595468A (en) * | 2022-10-10 | 2023-01-13 | 中国核动力研究设计院（Cn） | Eu-containing nickel-based neutron absorber material and preparation method and application thereof |
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| CN114243002A (en) * | 2021-11-11 | 2022-03-25 | 惠州锂威新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
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