CN114464807A - Oxygen-deficient metal oxide catalyst, in-situ preparation method thereof and lithium-sulfur battery - Google Patents
Oxygen-deficient metal oxide catalyst, in-situ preparation method thereof and lithium-sulfur battery Download PDFInfo
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 50
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 50
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- 239000001301 oxygen Substances 0.000 title claims abstract description 41
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 41
- 230000002950 deficient Effects 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 7
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- 238000001354 calcination Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 27
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 22
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- 239000011593 sulfur Substances 0.000 claims abstract description 22
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
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- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 3
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- 239000011888 foil Substances 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
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- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 238000002484 cyclic voltammetry Methods 0.000 description 2
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- 238000004090 dissolution Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910015189 FeOx Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 239000010416 ion conductor Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
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- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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Abstract
The invention discloses an oxygen-deficient metal oxide catalyst, an in-situ preparation method thereof and a lithium-sulfur battery. The method comprises the following steps: 1) preparing a precursor solution containing graphene oxide, a one-dimensional carbon material, a regulation ion source and a doping source; 2) carrying out hydrothermal reaction by using the precursor solution, and drying a hydrothermal product after the reaction is finished; 3) firstly, carrying out primary calcination in the atmosphere of protective gas, and then carrying out secondary calcination in the atmosphere containing reducing gas to obtain the oxygen-deficient metal oxide catalyst. The method solves the problems of uneven dispersion of the metal oxide and partial agglomeration and deactivation of the metal oxide possibly occurring along with battery cycle, and realizes high-efficiency utilization, high energy density and long cycle life of the sulfur anode when being applied to the lithium-sulfur battery.
Description
Technical Field
The invention relates to the field of electrochemical energy and materials, in particular to an oxygen-deficient metal oxide catalyst, an in-situ preparation method thereof and a lithium-sulfur battery.
Background
Due to their high volumetric and mass energy densities, lithium-sulfur batteries are most likely to find widespread use in large energy storage devices and in electrical networks, such as electric vehicles, in the future. However, the lithium-sulfur battery still has some problems such as insulation of electronic ions between sulfur as an active material and lithium sulfide, dissolution and diffusion of lithium polysulfide, volume expansion and contraction of an electrode during charge and discharge, and the like.
At present, the actual energy density of a lithium-sulfur battery in a research stage is far lower than the theoretical energy density, and the cycle life of the battery is short, which is mainly due to the problems of low utilization rate of a positive electrode material, slow electron ion transmission of a positive electrode phase and an electrode electrolyte interface, slow reversible conversion kinetics of an intermediate substance lithium polysulfide and the like, irreversible dissolution and shuttling of the polysulfide ions during charging and discharging, and electrode structure damage caused by repeated expansion and contraction of the volume of an electrode. During cycling, the positive electrode of the battery is mainly affected by electron conduction and ion migration. These problems largely hinder the progress of industrialization of lithium sulfur batteries.
Therefore, it is still necessary to further study how to improve the conduction kinetics of electrons and lithium ions and improve the conversion efficiency, specific capacity and cycle performance of polysulfide of a battery.
Due to poor electron ion conductors of sulfur and lithium sulfide, the good conductivity of the carbon material is expected to solve the conductivity problem of the lithium-sulfur battery. Among a plurality of carbon materials, graphene has unique advantages, and the prepared three-dimensional porous graphene network structure can effectively shorten an electron and ion transmission path, limit migration of polysulfide and greatly improve the cycle performance of the lithium-sulfur battery. However, three-dimensional graphene is very prone to stacking during synthesis, and graphene is a weak polar substance, so that the polysulfide adsorption capacity to polarity is weak.
The above problems can be solved to some extent by simply adding a metal oxide to the matrix of the carbon material, but there are some problems: if the preparation process is complex, the product structure is uncontrollable, and the preparation cost is high; polar metal oxides such as TiO2、MnO2The metal oxides have strong adsorption capacity to polysulfide, but the metal oxides are poor conductors of electrons and cannot be uniformly distributed in a positive electrode material, and partial agglomeration of the metal oxides can occur along with battery circulationThe activity of these polar oxides is lost, and moreover, the conversion of lithium polysulphides and the activation of the lithium sulphide, the discharge product, are also deficient, the active sites for catalytic conversion being far from sufficient. Therefore, the cycle performance at a high rate is difficult to achieve, and the industrialization process of the lithium sulfur battery is hindered.
Disclosure of Invention
In view of the above problems in the prior art, it is an object of the present invention to provide an oxygen-deficient metal oxide catalyst, an in-situ preparation method thereof, and a lithium-sulfur battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for the in situ preparation of an oxygen deficient metal oxide catalyst, characterised in that the method comprises the steps of:
(1) preparing a precursor solution containing graphene oxide, a one-dimensional carbon material, a regulation and control ion source and a doping source;
(2) carrying out hydrothermal reaction by using the precursor solution, and drying a hydrothermal product after the reaction is finished;
(3) firstly, carrying out primary calcination in the protective gas atmosphere, and then carrying out secondary calcination in the reducing gas-containing atmosphere to obtain the oxygen-deficient metal oxide catalyst.
According to the method, the excellent conductivity and large specific surface area of the one-dimensional carbon material and graphene oxide are utilized, the functional porous doped nano carbonaceous carrier of the metal oxide with the defect of ion regulation is prepared in the hydrothermal process, the conductivity of the carbonaceous carrier is improved through primary calcination, the metal oxide with the defect of oxygen enrichment is obtained through secondary calcination, the metal oxide is uniformly dispersed on the highly conductive porous doped nano carbonaceous carrier, the problem that the metal oxide is not uniformly dispersed and partially agglomerated and loses activity possibly along with battery circulation of the metal oxide is solved, and the method is applied to the lithium-sulfur battery to realize the efficient utilization of the sulfur anode, the high energy density and the long cycle life.
The oxygen-deficient metal oxide catalyst prepared by the method is suitable for the positive active material of the lithium-sulfur battery, and the excellent conductivity of the porous doped nano carbonaceous carrier can effectively solve the problem of low utilization rate of active substances in the lithium-sulfur battery. The carrier has high specific surface area, and is doped and has a porous structure, so that polysulfide (such as lithium polysulfide) is favorably adsorbed; the oxygen defect characteristics of the oxygen-deficient metal oxide effectively reduce the energy barrier of the lithium sulfide anode, improve the conduction of lithium ions in a solid phase and an electrolyte/electrode interface in an anode material and the conversion efficiency of polysulfide, enhance the adsorption capacity of polysulfide, and realize the efficient utilization, high energy density and long cycle life of the sulfur anode. Compared with other battery electrode materials, the electrode material disclosed by the invention has more excellent electrochemical performance, and has great guiding significance for accelerating the industrialization process of lithium-sulfur batteries.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
Preferably, the one-dimensional carbon material in step (1) includes at least one of carbon nanotubes, carbon nanofibers, and derivatives thereof.
Preferably, in the mixed solution a in the step (1), the mass ratio of the graphene oxide to the one-dimensional carbon material is (1-2.5): 1, for example, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.3:1, or 2.5: 1.
Preferably, the source of the modulated ion in step (1) comprises at least one of a niobium salt, an iron salt, a cobalt salt, a copper salt, a manganese salt, a nickel salt and an aluminum salt, preferably at least one of a niobium salt, an iron salt and a cobalt salt.
Preferably, the doping source of step (1) comprises a nitrogen source and/or a sulfur source.
Preferably, the nitrogen source comprises urea and/or ammonium salts.
Preferably, the sulfur source comprises a sulfide.
Preferably, the mass content of the sulfide, ammonium salt and urea is independently 1-20%, such as 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18% or 20%, etc., based on 100% of the total mass of dry substances in the precursor solution.
Preferably, the content of the niobium salt, iron salt, cobalt salt, copper salt, manganese salt, nickel salt and aluminum salt is independently 1 to 10%, for example 1%, 3%, 5%, 7%, 8% or 10%, etc., based on 100% of the total mass of the dry-based substances in the precursor solution.
Preferably, the process of formulating in step (1) comprises: respectively preparing a mixed solution A containing graphene oxide and a one-dimensional carbon material and a mixed solution B containing a control ion source and a doping source, and mixing the mixed solution A and the mixed solution B to obtain a precursor solution.
Preferably, the preparation process of the mixed solution a in the step (1) includes ultrasonic treatment, and the ultrasonic treatment time is preferably 30-50 min, such as 30min, 35min, 40min, 45min or 50 min. Better dispersion effect can be achieved through ultrasound, and graphene oxide lamella stripping is facilitated.
Preferably, the temperature of the hydrothermal reaction in the step (2) is 150 to 200 ℃, for example, 150 ℃, 160 ℃, 180 ℃, 185 ℃ or 200 ℃.
Preferably, the hydrothermal reaction time in the step (2) is 8-20 h, such as 8h, 9h, 10h, 12h, 15h, 18h or 20 h.
Preferably, the following steps are carried out after the reaction in the step (2) is finished and before the drying is carried out: cooled, filtered and washed.
Preferably, the drying of step (2) is freeze drying.
In a preferred embodiment of the method of the present invention, the atmosphere in the secondary calcination in step (3) is a mixed gas of a reducing gas and a protective gas.
Preferably, the protective gas for the primary and secondary calcinations is independently selected from He, Ar and N2At least one of (1).
Preferably, the reducing gas is H2；
Preferably, the volume ratio of the reducing gas in the mixed gas for the secondary calcination is 5 to 15%, for example, 5%, 8%, 12%, 13%, 15%, etc., preferably 10 to 12%.
Preferably, the temperature of the primary calcination is 300 to 800 ℃, such as 300 ℃, 400 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃, and the like, and preferably 600 to 700 ℃.
Preferably, the time of the primary calcination is 2-5 h, such as 2h, 2.5h, 3h, 4h or 5 h.
Preferably, the temperature of the secondary calcination is 200 to 1100 ℃, such as 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, or the like, preferably 350 to 450 ℃.
Preferably, the time of the secondary calcination is 0.5 to 1.5 hours, such as 0.5 hour, 0.8 hour, 1 hour, 1.2 hour or 1.5 hour.
By regulating and controlling the temperature and atmosphere of the secondary calcination, more oxygen defects can be generated, and the material performance is further improved.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) mixing a carbon nano tube and a graphene oxide solution, carrying out ultrasonic treatment for 45min to obtain a mixed solution A, dispersing a regulating ion source and a doping source in alcohol to obtain a mixed solution B, and dropwise adding the mixed solution B into the mixed solution A under the stirring condition to obtain a precursor solution;
(2) transferring the precursor solution which is fully and uniformly stirred into a reaction kettle, carrying out hydrothermal reaction for 8-20 h at the temperature of 150-200 ℃, cooling a hydrothermal product to room temperature, filtering, washing, and freeze-drying;
(3) calcining the product dried in the step (2) for 2-3H at 600-700 ℃ in an argon atmosphere, and then calcining in H2Calcining for 0.5-1 h at 350-450 ℃ in the mixed gas atmosphere of Ar to obtain an oxygen-deficient metal oxide catalyst;
said H2In a mixed gas of Ar and H2The volume ratio of (A) is 10-12%.
In a second aspect, the present invention provides an oxygen-deficient metal oxide catalyst prepared by the method of the first aspect, wherein the oxygen-deficient metal oxide catalyst comprises three-dimensional porous nanocomposite carbon doped with nitrogen and/or sulfur, and an oxygen-deficient metal oxide supported on the three-dimensional porous nanocomposite carbon.
In a third aspect, the present invention provides a positive electrode active material comprising the oxygen-deficient metal oxide catalyst according to the second aspect and nano-sulfur supported on the oxygen-deficient metal oxide catalyst.
In a fourth aspect, the present invention provides a lithium sulfur battery comprising the positive electrode active material according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the method, the one-dimensional carbon material and graphene oxide have excellent conductivity and large specific surface area, the functional porous doped nano carbonaceous carrier of the metal oxide with the defect of ion regulation and control is prepared in the hydrothermal process, the conductivity of the carbonaceous carrier is improved through primary calcination, the metal oxide rich in the oxygen defect is obtained through secondary calcination, and the metal oxide is uniformly dispersed on the highly conductive porous doped nano carbonaceous carrier, so that the problem that the metal oxide is not uniformly dispersed, and the problem that the metal oxide is partially agglomerated and loses activity along with the circulation of a battery is solved.
The oxygen-deficient metal oxide catalyst of the invention is suitable for the anode active material of the lithium-sulfur battery, can effectively solve the problem of low utilization rate of active substances in the lithium-sulfur battery, enhances the adsorption capacity to polysulfide,
the conduction of lithium ions in a solid phase and an electrolyte/electrode interface in the anode material and the conversion efficiency of polysulfide are improved, and the efficient utilization, high energy density and long cycle life of the sulfur anode are realized. Compared with other battery electrode materials, the electrode material disclosed by the invention has more excellent electrochemical performance, and can be used as a matrix material of a sulfur positive electrode to be applied to a lithium-sulfur secondary battery, so that the soft package battery can be charged and discharged at a high rate (such as 0.2C).
Drawings
FIG. 1 is a scanning electron micrograph of an oxygen deficient metal oxide catalyst prepared according to example 1.
FIG. 2 is a scanning electron micrograph of the oxygen deficient metal oxide catalyst prepared in example 1.
FIG. 3 is a thermogravimetric plot of sulfur adsorption for the sulfur-loaded samples prepared in example 3.
FIG. 4 is NbO prepared in example 6xA cyclic voltammogram of @ HHPC @ S positive electrode material.
FIG. 5 is FeO prepared in example 5xAnd a comparative graph of charging and discharging of the @ HHPC @ S positive electrode material under different multiplying factors.
FIG. 6 is a CoO prepared in example 4x@ HHPC @ S positive electrode material impedance analysis diagram.
FIG. 7 is NbO prepared in example 6x@ HHPC @ S cathode material soft package cycle stability analysis diagram.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1:
measuring a certain amount of low-concentration graphene oxide solution (4mg/mL), wherein the mass ratio of graphene oxide to carbon nano tubes is 2:1, weighing a certain mass of carbon nano tube, adding ultrapure water for dilution, and performing ultrasonic treatment for 45min to obtain a mixed solution A.
A niobium ion source (niobium chloride) and a nitrogen source (urea) were dispersed in ethanol to obtain a mixed solution B.
And dropwise adding the mixed solution B into the ultrasonically-treated mixed solution A while stirring to obtain a precursor solution (wherein the concentration of graphene oxide is 1.2mg/mL, the mass content of niobium ions is 5% and the mass content of nitrogen elements in urea is 3% based on 100% of the total mass of dry substances in the precursor solution), sufficiently and uniformly stirring, and transferring to a reaction kettle for hydrothermal reaction at 180 ℃ for 15 hours. Cooling the hydrothermal product to room temperature, filtering, washing, freeze drying, calcining at 600 deg.C for 2 hr in 10% H under argon atmosphere2Calcining at 400 ℃ for 1h under the atmosphere of/Ar mixed gas to obtain a sample, namely the oxygen-deficient metal oxide catalyst (NbO for short)x@ HHPC), the catalyst comprising a three-dimensional porous nanocomposite carbonAnd oxygen-deficient niobium oxide supported on the three-dimensional porous nanocomposite carbon, the three-dimensional porous nanocomposite carbon being nitrogen-doped. As can be seen from the scanning electron microscope in fig. 1, graphene sheets significantly interact with each other to form a three-dimensional porous structure.
Example 2:
measuring a certain amount of low-concentration graphene oxide solution (5mg/mL), wherein the mass ratio of graphene oxide to carbon nano tubes is 2:1, weighing a certain mass of carbon nano tube, adding ultrapure water for dilution, and performing ultrasonic treatment for 45min to obtain a mixed solution A.
And dispersing an iron ion source (ferric chloride) and a nitrogen source (urea) in ethanol to obtain a mixed solution B.
And dropwise adding the mixed solution B into the ultrasonically-treated mixed solution A while stirring to obtain a precursor solution (wherein the concentration of the graphene oxide is 1.5mg/mL, the mass content of iron ions is 7% and the mass content of nitrogen elements in urea is 2% based on 100% of the total mass of dry substances in the precursor solution), sufficiently and uniformly stirring, and transferring to a reaction kettle for hydrothermal reaction at 180 ℃ for 15 hours. Cooling the hydrothermal product to room temperature, filtering, washing, freeze drying, calcining at 600 deg.C for 2 hr in argon atmosphere, and calcining at 10% H2Calcining at 400 ℃ for 1h in an atmosphere of/Ar mixed gas to obtain a sample, namely the oxygen-deficient metal oxide catalyst (abbreviated as FeO)x@ HHPC) comprising three-dimensional porous nanocomposite carbon doped with nitrogen, and oxygen-deficient iron oxide supported on the three-dimensional porous nanocomposite carbon. As can be seen from the scanning electron microscope in fig. 2, the graphene sheets have significant interaction, continue to maintain a three-dimensional porous structure, and are loaded with iron oxides with many oxygen defects.
Example 3:
measuring a certain amount of low-concentration graphene oxide solution (4mg/mL), wherein the mass ratio of graphene oxide to carbon nano tubes is 2:1, weighing a certain mass of carbon nano tube, adding ultrapure water for dilution, and performing ultrasonic treatment for 45min to obtain a mixed solution A.
And dispersing a cobalt ion source (cobalt chloride) and a nitrogen source (urea) in ethanol to obtain a mixed solution B.
And dropwise adding the mixed solution B into the ultrasonically-treated mixed solution A while stirring to obtain a precursor solution (wherein the concentration of the graphene oxide is 1.3mg/mL, the mass content of cobalt ions is 5% and the mass content of nitrogen elements in urea is 1.5% based on 100% of the total mass of dry-based substances in the precursor solution), sufficiently and uniformly stirring, and transferring to a reaction kettle for hydrothermal reaction at 180 ℃ for 15 hours. Cooling the hydrothermal product to room temperature, filtering, washing, freeze drying, calcining at 600 deg.C for 2 hr in 10% H under argon atmosphere2Calcining at 400 ℃ for 1h in the atmosphere of/Ar mixed gas, and cooling to room temperature to obtain the oxygen-deficient metal oxide catalyst (abbreviated as CoO)x@ HHPC) comprising three-dimensional porous nanocomposite carbon doped with nitrogen, and oxygen-deficient cobalt oxide supported on the three-dimensional porous nanocomposite carbon.
The liquid-phase sulfur-carrying method is utilized to carry sulfur to the prepared oxygen-deficient metal oxide catalyst CoOxOn @ HHPC, a sulfur-carrying sample is obtained, and the test of figure 3 shows that the sulfur content of the sulfur-carrying sample is 75%.
Example 4:
using the oxygen deficient metal oxide catalyst prepared in example 3, a defined amount of CoO was weighedx@ HHPC, loading 75% of nano sulfur by mass percent by using a solution method to obtain a positive active material CoOx@HHPC@S。
Adding CoOx@ HHPC @ S, carbon black (conductive agent) and binder (PVDF) were mixed as follows 7: 2:1, preparing anode slurry, uniformly coating the anode slurry on an aluminum foil, drying at 50 ℃ in vacuum for 24 hours, punching into a sheet with the diameter of 10mm as an anode, taking metal lithium as a cathode, and adding 1 percent of LiNO3The electrolyte solution of LiTFSI in 1M DOL/DME (1: 1 by volume) was used to assemble a button cell with a 2025 type cell can.
FIG. 6 shows CoO prepared in this examplex@ HHPC @ S positive electrode material impedance analysis diagram.
Example 5:
using the oxygen deficient metal oxide catalyst prepared in example 2, a certain amount was weighedFeO in an amountx@ HHPC, loading 75 wt% of nano sulfur by solution method to obtain positive active material FeOx@HHPC@S。
FeO is addedx@ HHPC @ S, carbon black (conductive agent) and binder (PVDF) were mixed as follows 7: 2:1, preparing anode slurry, uniformly coating the anode slurry on an aluminum foil, drying at 50 ℃ in vacuum for 24 hours, punching into a sheet with the diameter of 10mm as an anode, taking metal lithium as a cathode, and adding 1 percent of LiNO3The electrolyte solution of 1M of LiTFSI in DOL/DME (1: 1 by volume) was used to assemble the button cell with a 2025 cell case.
FIG. 5 shows FeO prepared in this examplexAnd a comparative graph of charging and discharging of the @ HHPC @ S positive electrode material under different multiplying factors.
Example 6:
using the oxygen deficient metal oxide catalyst prepared in example 1, a certain amount of NbO was weighedx@ HHPC, loading 75% of nano sulfur by solution method to obtain positive active material NbOx@HHPC@S。
NbOx@ HHPC @ S, carbon black (conductive agent) and binder (PVDF) were mixed as follows 7: 2:1, preparing anode slurry, uniformly coating the anode slurry on an aluminum foil, drying at 50 ℃ in vacuum for 24 hours, punching into sheets with the diameter of 30mm x 40mm as an anode, using metal lithium as a cathode, and adding 1 percent of LiNO3The electrolyte solution of 1M LiTFSI in DOL/DME (1: 1 by volume) was assembled into a pouch cell.
FIG. 4 shows NbO prepared in this examplexA cyclic voltammogram of @ HHPC @ S positive electrode material.
FIG. 7 is a graph illustrating the soft-pack cycling stability analysis of the NbOx @ HHPC @ S cathode material prepared in this example.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for preparing an oxygen deficient metal oxide catalyst in situ, said method comprising the steps of:
(1) preparing a precursor solution containing graphene oxide, a one-dimensional carbon material, a regulation ion source and a doping source;
(2) carrying out hydrothermal reaction by using the precursor solution, and drying a hydrothermal product after the reaction is finished;
(3) firstly, carrying out primary calcination in the protective gas atmosphere, and then carrying out secondary calcination in the reducing gas-containing atmosphere to obtain the oxygen-deficient metal oxide catalyst.
2. The method according to claim 1, wherein the one-dimensional carbon material of step (1) comprises at least one of carbon nanotubes, carbon nanofibers, and derivatives thereof;
preferably, the mass ratio of the graphene oxide to the one-dimensional carbon material in the step (1) is (1-2.5): 1;
preferably, the source of the modulated ion in step (1) comprises at least one of a niobium salt, an iron salt, a cobalt salt, a copper salt, a manganese salt, a nickel salt and an aluminum salt, preferably at least one of a niobium salt, an iron salt and a cobalt salt;
preferably, the doping source of step (1) comprises a nitrogen source and/or a sulfur source;
preferably, the nitrogen source comprises urea and/or ammonium salts;
preferably, the sulfur source comprises a sulfide;
preferably, the mass content of the sulfide, the ammonium salt and the urea is independently 1-20% calculated by the total mass of dry substances in the precursor solution as 100%;
preferably, the content of the niobium salt, the iron salt, the cobalt salt, the copper salt, the manganese salt, the nickel salt and the aluminum salt is independently 1-10% by the total mass of dry substances in the precursor solution as 100%.
3. The method of claim 1 or 2, wherein the formulating of step (1) comprises: respectively preparing a mixed solution A containing graphene oxide and a one-dimensional carbon material and a mixed solution B containing a regulating ion source and a doping source, and mixing the mixed solution A and the mixed solution B to obtain a precursor solution;
preferably, the preparation process of the mixed solution A in the step (1) comprises ultrasonic treatment, and the ultrasonic treatment time is preferably 30-50 min.
4. The method according to any one of claims 1 to 3, wherein the temperature of the hydrothermal reaction in the step (2) is 150 to 200 ℃;
preferably, the hydrothermal reaction time in the step (2) is 8-20 h;
preferably, the following steps are carried out after the reaction in the step (2) is finished and before the drying is carried out: cooling, filtering and washing;
preferably, the drying of step (2) is freeze drying.
5. The method according to any one of claims 1 to 4, wherein the atmosphere in the secondary calcination atmosphere in step (3) is a mixed gas of a reducing gas and a protective gas;
preferably, the protective gas for the primary and secondary calcinations is independently selected from He, Ar and N2At least one of;
preferably, the reducing gas is H2；
Preferably, the volume ratio of the reducing gas in the mixed gas for the secondary calcination is 5-15%, and preferably 10-12%.
6. The method according to claim 5, wherein the temperature of the primary calcination is 300 to 800 ℃, preferably 600 to 700 ℃;
preferably, the time of the primary calcination is 1-5 h, preferably 2-3 h;
preferably, the temperature of the secondary calcination is 200-1100 ℃, preferably 350-450 ℃;
preferably, the time of the secondary calcination is 0.5-1.5 h, preferably 0.5-1 h.
7. Method according to any of claims 1-6, characterized in that the method comprises the steps of:
(1) mixing a carbon nano tube and a graphene oxide solution, carrying out ultrasonic treatment for 45min to obtain a mixed solution A, dispersing a regulating ion source and a doping source in alcohol to obtain a mixed solution B, and dropwise adding the mixed solution B into the mixed solution A under the stirring condition to obtain a precursor solution;
(2) transferring the precursor solution which is fully and uniformly stirred into a reaction kettle, carrying out hydrothermal reaction for 8-20 h at the temperature of 150-200 ℃, cooling a hydrothermal product to room temperature, filtering, washing, and freeze-drying;
(3) calcining the product dried in the step (2) for 2-3H at 600-700 ℃ in an argon atmosphere, and then calcining in H2Calcining for 0.5-1 h at 350-450 ℃ in the mixed gas atmosphere of Ar to obtain an oxygen-deficient metal oxide catalyst;
said H2In a mixed gas of Ar and H2The volume ratio of (A) is 10-12%.
8. An oxygen-deficient metal oxide catalyst prepared according to the process of any one of claims 1 to 7, comprising a three-dimensional porous nanocomposite carbon doped with nitrogen and/or sulfur and an oxygen-deficient metal oxide supported on the three-dimensional porous nanocomposite carbon.
9. A positive electrode active material, comprising the oxygen-deficient metal oxide catalyst according to claim 8 and nano-sulfur supported on the oxygen-deficient metal oxide catalyst.
10. A lithium-sulfur battery, characterized in that it comprises the positive electrode active material according to claim 9.
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