CN110459752B - Sodium-ion battery negative electrode material and preparation method and application thereof - Google Patents
Sodium-ion battery negative electrode material and preparation method and application thereof Download PDFInfo
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- CN110459752B CN110459752B CN201910806554.3A CN201910806554A CN110459752B CN 110459752 B CN110459752 B CN 110459752B CN 201910806554 A CN201910806554 A CN 201910806554A CN 110459752 B CN110459752 B CN 110459752B
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 79
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 89
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 67
- 239000002135 nanosheet Substances 0.000 claims abstract description 42
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 34
- 239000011733 molybdenum Substances 0.000 claims abstract description 34
- 239000010406 cathode material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000011065 in-situ storage Methods 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 29
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 27
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 23
- 238000005245 sintering Methods 0.000 claims description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 17
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000009831 deintercalation Methods 0.000 abstract description 2
- 238000009830 intercalation Methods 0.000 abstract description 2
- 230000002687 intercalation Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 238000001816 cooling Methods 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000001035 drying Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 16
- 239000012300 argon atmosphere Substances 0.000 description 14
- 238000001878 scanning electron micrograph Methods 0.000 description 14
- 238000005406 washing Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 8
- 238000010000 carbonizing Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- 238000011068 loading method Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- -1 tin oxide Chemical class 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
Images
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- 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
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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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
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of electrode materials, in particular to a sodium ion battery cathode material and a preparation method thereof. The sodium ion battery cathode material provided by the invention comprises sponge carbon and a molybdenum-doped tin dioxide nanosheet array growing on a sponge carbon skeleton structure in situ; the molybdenum-doped tin dioxide nanosheet array accounts for 30-45% of the negative electrode material of the sodium-ion battery by mass. The sponge carbon is used as a conductive framework, and is also helpful for relieving volume expansion of the tin dioxide in the circulation process. Meanwhile, molybdenum is doped in the tin dioxide to improve the conductivity of the tin dioxide and accelerate the transmission of sodium ions in the negative electrode material of the sodium ion battery. The nano-sheet increases the contact area of the composite material and the electrolyte, so that the intercalation and deintercalation of sodium ions are more sufficient. According to the description of the embodiment, the negative electrode material of the sodium-ion battery has good cycle performance and rate capability.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a sodium ion battery cathode material and a preparation method and application thereof.
Background
With the continuous development of global economy and the continuous improvement of the living standard of people, the energy and environmental problems are increasingly prominent. As a carrier for storing electric energy, lithium ion secondary batteries have been widely used in the fields of mobile phones, digital portable products, and the like, due to their advantages of high energy density, long cycle life, small self-discharge effect, environmental friendliness, and the like. However, due to the limited resources of lithium on earth, new energy batteries that can replace lithium ion batteries are being sought. In such a background, sodium ions are considered as a potential substitute for lithium ions due to their physical and chemical properties similar to those of lithium ions, their large earth reserves and their low cost.
Since the radius of the sodium ions is larger than that of the lithium ions, the conventional graphite negative electrode cannot accommodate the sodium ions at all. Therefore, it is very important to find a suitable sodium ion battery negative electrode material. In recent years, metal oxides, particularly tin oxide, have received much attention due to their higher specific capacity. However, tin dioxide has low conductivity and is accompanied by large volume expansion in the charge-discharge cycle process, so that the application of the tin dioxide in batteries is greatly limited.
In order to solve the above problems, the methods of constructing a nano-structured negative electrode material, compounding and doping with carbon or a conductive polymer having strong conductivity, and the like are mainly used to alleviate the problems. However, the negative electrode material obtained by the above-described mitigation method needs to be coated on a current collector as a negative electrode to be able to participate in charge and discharge.
Disclosure of Invention
The invention aims to provide a sodium ion battery negative electrode material, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a sodium ion battery cathode material which comprises sponge carbon and a molybdenum-doped tin dioxide nanosheet array growing on a sponge carbon skeleton structure in situ;
the molybdenum-doped tin dioxide nanosheets account for 30-45% of the negative electrode material of the sodium-ion battery by mass.
Preferably, the atomic percent of molybdenum in the negative electrode material of the sodium-ion battery is 0.5-1.5%.
The invention also provides a preparation method of the sodium-ion battery cathode material, which comprises the following steps:
mixing a tin source, a molybdenum source, concentrated hydrochloric acid, thioglycollic acid, urea and water to obtain a mixed solution;
and placing sponge carbon into the mixed solution, and sequentially carrying out hydrothermal reaction and sintering to obtain the sodium-ion battery cathode material.
Preferably, the molar ratio of the tin source to the molybdenum source is (1.0-1.6): (0.05-0.35);
the tin source is calculated as tin and the molybdenum source is calculated as molybdenum.
Preferably, the mass concentration of the concentrated hydrochloric acid is 37%;
the dosage ratio of the urea to the thioglycollic acid to the concentrated hydrochloric acid to the tin source to the water is (0.8-1.2) g: (18-22) μ L: (0.8-1.2) mL: (1.0-1.1) mmol: (75-85) mL;
the tin source is calculated as tin.
Preferably, the dosage ratio of the sponge carbon to the mixed solution is (1.2-5.6) g: (70-80) mL.
Preferably, the temperature of the hydrothermal reaction is 110-130 ℃, and the time of the hydrothermal reaction is 8-12 h.
Preferably, the sintering is carried out in a protective atmosphere;
the sintering temperature is 450-650 ℃, the heating rate is 1-2 ℃/min, and the sintering heat preservation time is 2-5 h.
Preferably, the preparation method of the sponge carbon comprises the following steps:
under the inert atmosphere, carrying out high-temperature carbonization on melamine sponge to obtain sponge carbon;
the temperature of the high-temperature carbonization is 750-850 ℃, the heating rate is 4.5-5.5 ℃/min, and the heat preservation time of the high-temperature carbonization is 1-3 hours;
and before the sponge carbon is placed in the mixed solution, carrying out hydrophilic treatment on the sponge carbon.
The invention also provides the application of the sodium-ion battery negative electrode material in the technical scheme or the sodium-ion battery negative electrode material prepared by the preparation method in the technical scheme in a sodium-ion battery.
The invention provides a sodium ion battery cathode material which comprises sponge carbon and a molybdenum-doped tin dioxide nanosheet array growing on a sponge carbon skeleton structure in situ; the molybdenum-doped tin dioxide nanosheet array accounts for 30-45% of the negative electrode material of the sodium-ion battery by mass. According to the invention, sponge carbon is used as a conductive framework, so that the sponge carbon can play a self-supporting role, and thus when the sponge carbon is used as an electrode material, the sponge carbon does not need to be coated on a current collector, and the sponge carbon is also helpful for relieving volume expansion of tin dioxide in a circulation process. Meanwhile, molybdenum is doped in the tin dioxide to improve the conductivity of the tin dioxide and accelerate the transmission of sodium ions in the negative electrode material of the sodium ion battery. The nano-sheet increases the contact area of the composite material and the electrolyte, so that the intercalation and deintercalation of sodium ions are more sufficient. According to the description of the embodiment, the negative electrode material of the sodium-ion battery has good cycle performance and rate capability.
Drawings
FIG. 1 is SEM images of sponge carbon prepared in example 1 at different magnification (a is SEM image at magnification of 10, b is SEM image at magnification of 20);
fig. 2 is SEM images of the negative electrode material of the sodium ion battery prepared in example 1 at different magnifications (a is SEM image at 10 magnifications, b is SEM image at 20 magnifications, and c is SEM image at 100 magnifications);
fig. 3 is TEM images of the sodium ion battery anode material prepared in example 1 under different magnification (a is TEM image under 200 magnification, b is TEM image under 1000 magnification, c is EDS image under 50 magnification of the test under TEM);
FIG. 4 XRD patterns of the negative electrode material of the sodium-ion battery prepared in example 1 under different times;
FIG. 5 shows the negative electrode material of the sodium-ion battery prepared in example 1 at 0.1 A.g-1、0.2A·g-1、0.5A·g-1、1A·g-1A rate performance plot at current density of (a);
FIG. 6 shows the negative electrode material of the sodium-ion battery prepared in example 1 at 0.1 A.g-1Current density of (c) and coulombic efficiency plot for 100 cycles of discharge capacity.
Detailed Description
The invention provides a sodium ion battery cathode material which comprises sponge carbon and a molybdenum-doped tin dioxide nanosheet array growing on a sponge carbon skeleton structure in situ;
the molybdenum-doped tin dioxide nanosheet array accounts for 30-45% of the negative electrode material of the sodium-ion battery by mass.
In the invention, the negative electrode material of the sodium-ion battery comprises sponge carbon; the sponge carbon has a three-dimensional conductive skeleton structure. In the invention, the mass percentage of the sponge carbon in the negative electrode material of the sodium-ion battery is preferably 55-70%, and more preferably 60-65%.
In the invention, the sodium-ion battery negative electrode material also comprises a molybdenum-doped tin dioxide nanosheet array growing on the sponge carbon skeleton structure in situ; the molybdenum-doped tin dioxide nanosheet array is formed by staggered arrangement of molybdenum-doped tin dioxide nanosheets (such as the structure shown in fig. 3). In the invention, the staggered molybdenum-doped tin dioxide nanosheets are more beneficial to increasing the contact area of the cathode material and the electrolyte, and the polymerization of tin is relieved to a certain extent. In the invention, the thickness of the molybdenum-doped tin dioxide nanosheet is preferably 10-15 nm, more preferably 11-14 nm, and most preferably 12-13 nm. The particle size of the molybdenum-doped tin dioxide nanosheet is preferably 15-40 nm, more preferably 18-35 nm, and most preferably 20-30 nm. In the invention, the mass percentage of the molybdenum-doped tin dioxide nanosheet array in the negative electrode material of the sodium-ion battery is preferably 30-45%, and more preferably 35-40%. According to the atomic percentage, in the molybdenum-doped tin dioxide nanosheet array, the percentage of molybdenum in the negative electrode material of the sodium-ion battery is preferably 0.5-1.5%, and more preferably 0.8-1.2%. The molybdenum is present in the form of substitutional sites for a portion of the tin atoms.
The invention also provides a preparation method of the sodium-ion battery cathode material, which comprises the following steps:
mixing a tin source, a molybdenum source, concentrated hydrochloric acid, thioglycollic acid, urea and water to obtain a mixed solution;
and placing sponge carbon into the mixed solution, and sequentially carrying out hydrothermal reaction and sintering to obtain the sodium-ion battery cathode material.
In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
Mixing a tin source, a molybdenum source, concentrated hydrochloric acid, thioglycollic acid, urea and water to obtain a mixed solution; in the present invention, the tin source is preferably stannous chloride, and the stannous chloride is preferably stannous chloride dihydrate and/or anhydrous stannous chloride, and is more preferably stannous chloride dihydrate.
In the invention, the molybdenum source is preferably one or more of sodium molybdate dihydrate, ammonium heptamolybdate and molybdenum chloride; when the molybdenum sources are more than two of the specific choices, the specific material proportion is not limited in any way, and the molybdenum sources can be mixed according to any proportion; when the molybdenum source is one of the above specific choices, the molybdenum source is more preferably sodium molybdate dihydrate. In the present invention, the mass concentration of the concentrated hydrochloric acid is preferably 37%.
In the present invention, the mixing is preferably carried out under stirring, and the stirring is not particularly limited in the present invention, and may be carried out by a stirring process known to those skilled in the art.
In the present invention, the tin source, the molybdenum source, the concentrated hydrochloric acid, the thioglycolic acid, the urea and the water are preferably mixed by adding the urea, the thioglycolic acid and the concentrated hydrochloric acid in sequence to the water until the mixture is uniform, and then adding the tin source and the molybdenum source in sequence.
In the present invention, the molar ratio of the tin source to the molybdenum source is preferably (1.0 to 1.6): (0.05-0.35), more preferably (1.1-1.5): (0.09-0.3), most preferably (1.2-1.3): (0.1 to 0.2); the tin source is preferably calculated as tin and the molybdenum source is preferably calculated as molybdenum. In the invention, the dosage ratio of the urea, the thioglycollic acid, the concentrated hydrochloric acid, the tin source and the water is preferably (0.8-1.2) g: (18-22) μ L: (0.8-1.2) mL: (1.0-1.1) mmol: (75-85) mL, more preferably (0.9-1.1) g: (19-21) μ L: (0.9-1.1) mL: (1.02-1.08) mmol: (78-82) mL, most preferably 1 g: 20 μ L of: 1mL of: 1.05 mmol: 80 mL.
In the invention, the urea has the function of providing amino, the thioglycolic acid has the function of reacting with the amino to generate an oxidizing group, and the concentrated hydrochloric acid has the function of adjusting the pH of the solution.
After the mixed solution is obtained, the sponge carbon is placed in the mixed solution, and hydrothermal reaction and sintering are sequentially carried out to obtain the sodium-ion battery cathode material.
In the present invention, the method for preparing the sponge carbon preferably comprises the steps of: and (3) carbonizing the melamine sponge at high temperature under inert atmosphere to obtain the sponge carbon. In the invention, the melamine sponge is preferably pretreated before high-temperature carbonization; the pretreatment is preferably to wash and dry the melamine sponge by using ethanol; in the invention, the cleaning is preferably carried out under the condition of ultrasonic treatment, and the ultrasonic treatment time is preferably 10-20 min, more preferably 12-18 min, and most preferably 15 min. In the present invention, the drying is preferably vacuum drying, and the vacuum drying conditions in the present invention are not limited in any way, and may be vacuum drying conditions well known to those skilled in the art.
In the invention, the inert atmosphere is preferably argon atmosphere or nitrogen atmosphere, and the high-temperature carbonization temperature is preferably 750-850 ℃, more preferably 780-820 ℃, and most preferably 800 ℃; the heating rate is preferably 4.5-5.5 ℃/min, more preferably 4.8-5.2 ℃/min, and most preferably 5.0 ℃/min; the heat preservation time is preferably 0.5 to 3 hours, more preferably 1.0 to 2.0 hours, and most preferably 1.0 hour.
In the present invention, before the obtained sponge carbon is placed in the mixed solution, the sponge carbon is preferably subjected to a hydrophilic treatment, and the hydrophilic treatment is preferably a plasma treatment. The plasma treatment is not particularly limited in the present invention, and may be performed by a process well known in the art. The specific process in the embodiment of the invention is preferably as follows: placing sponge carbon in a plasma instrument, and pumping to 1 × 10-5And then opening a plasma gas switch to start hydrophilic treatment, closing the plasma gas switch after 10-20 min of treatment, returning the gas in the cabin to the atmospheric pressure, and taking out the sample.
After the hydrophilic treatment is finished, the sponge carbon after the hydrophilic treatment is preferably fully soaked in a hydrochloric acid solution to remove redundant impurities; in the present invention, the concentration of the hydrochloric acid solution is preferably 1 mol/L; the dipping temperature is preferably 20-30 ℃, more preferably 22-28 ℃, and most preferably 25 ℃; the soaking time is preferably 20-30 h, more preferably 22-28 h, and most preferably 24-26 h.
In the invention, the dosage ratio of the sponge carbon to the mixed solution is preferably (1.2-5.6) g: (70-80) mL, more preferably (2.4-5.6) g: (70-80) mL, most preferably (4.8-5.6) g: (70-80) mL.
In the invention, the temperature of the hydrothermal reaction is preferably 110-130 ℃, more preferably 115-125 ℃, and most preferably 120 ℃, and the time of the hydrothermal reaction is preferably 10-15 h, more preferably 11-14 h, and most preferably 12-13 h. In the present invention, the hydrothermal reaction is preferably carried out in a hydrothermal reaction vessel, and the material of the inner liner of the reaction vessel is preferably tetrafluoroethylene.
After the hydrothermal reaction is finished, the product system after the hydrothermal reaction is cooled, and the cooling mode is preferably water cooling. After cooling, the product system obtained is preferably filtered, washed and dried by the present invention, and the filtration is carried out according to a process well known to those skilled in the art without any particular limitation; the cleaning is preferably to clean the filtered solid product by using deionized water and ethanol, and remove impurities by using 1mol/L sodium hydroxide solution for 10 hours at the temperature of 45 ℃; the drying process is not particularly limited, and may be performed by a drying process known to those skilled in the art.
In the invention, the hydrothermal reaction process is a process of growing the tin dioxide nanosheet array in situ and doping molybdenum, namely the two processes of growing in situ and doping in the hydrothermal process can be simultaneously realized.
In the present invention, the sintering is preferably performed in a protective atmosphere, and in the present invention, the protective atmosphere is preferably an argon atmosphere or a nitrogen atmosphere. In the invention, the sintering temperature is preferably 450-550 ℃, more preferably 480-520 ℃, and most preferably 500 ℃; the heating rate is preferably 0.8-1.2 ℃/min, more preferably 0.9-1.1 ℃/min, and most preferably 1.0 ℃/min; in the invention, the temperature rise process is preferably constant temperature rise; the sintering heat preservation time is preferably 2-5 h, more preferably 3-4 h, and most preferably 3 h.
In the invention, the sintering process improves the crystallinity of the product, enhances the electrical conductivity of the product, and is beneficial to the shuttling of sodium ions in the electrochemical reaction process, thereby improving the rate capability of the battery.
After the sintering is completed, the sintered product is preferably cooled, and the cooling is not particularly limited in the present invention, and may be performed by a process well known to those skilled in the art.
The invention also provides the application of the sodium-ion battery negative electrode material in the technical scheme or the sodium-ion battery negative electrode material prepared by the preparation method in the technical scheme in a sodium-ion battery.
In the invention, the sodium ion battery cathode material is preferably directly used as a cathode and assembled with a sodium sheet to form a button cell with the model number of CR 2025; the electrolyte of the button cell is preferably 5 vol% of FEC, and the volume ratio of EC to DEC is 1: 1MNaClO4A solution; the separator of the button cell is preferably a commercial glass fiber filter paper (Whatman GF/F).
The following will describe the negative electrode material of sodium ion battery and its preparation method and application in detail with reference to the examples, but they should not be construed as limiting the scope of the invention.
Example 1
Under the condition of stirring, 1g of urea, 20 mu L of thioglycolic acid and 1mL of 37 wt% concentrated hydrochloric acid are sequentially added into 80mL of water until the mixture is uniform, and then 0.238g (0.00105mol) of stannous chloride dihydrate and 0.022g (0.00009mol) of sodium molybdate dihydrate are sequentially added to obtain a mixed solution;
under the ultrasonic condition, washing melamine sponge with ethanol for 15min, and then drying in vacuum; heating to 800 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, carbonizing at high temperature for 1h, and cooling; carrying out hydrophilic treatment on the cooled product in plasma gas, soaking the product in 1mol/L HCl solution for 24 hours at 35 ℃, and drying to obtain sponge carbon;
placing sponge carbon (5.6g) with the size of 4cm x 1cm x 0.5cm in 80mL of mixed solution, performing hydrothermal reaction (120 ℃,12h), sequentially performing water cooling and filtration, washing a filtered solid product with deionized water and ethanol, removing impurities with 1mol/L sodium hydroxide solution at 45 ℃ for 10h, and drying to obtain a molybdenum-doped tin dioxide nanosheet array in which the sponge carbon grows in situ;
in an argon atmosphere, sintering the molybdenum-doped tin dioxide nanosheet array grown in situ from the sponge carbon (raising the temperature to 500 ℃ at a heating rate of 1 ℃/min, and preserving the heat for 3 hours), and then cooling to room temperature to obtain the sodium-ion battery cathode material (the loading capacity of the nanosheet is 38%, and the doping amount of molybdenum is 1%).
SEM tests are carried out on the sponge carbon and the sodium-ion battery negative electrode material, and the test results are shown in fig. 1 and fig. 2, wherein fig. 1 is SEM images of the sponge carbon under different times (a is the SEM image under the 10 times, and b is the SEM image under the 30 times), and as can be seen from fig. 1, the sponge carbon is in a three-dimensional self-supporting network structure, and the surface of a framework is smooth; fig. 2 is SEM images of the sodium ion battery negative electrode material at different multiples (a is an SEM image at 10 multiples, b is an SEM image at 30 multiples, and c is an SEM image at 100 multiples), and it can be seen from fig. 2 that a molybdenum-doped tin dioxide nanosheet array in the sodium ion battery negative electrode material uniformly grows on a skeleton of sponge carbon, and the thickness of the molybdenum-doped tin dioxide nanosheet is 10 nm;
performing a TEM test on the sodium-ion battery anode material, wherein the test result is shown in FIG. 3(a is a TEM image at a magnification of 200, b is a TEM image at a magnification of 1000, and c is an EDS image at a magnification of 50 for the test under the TEM), wherein the image c is from left to right, and the upper left corner respectively represents an icon c, a carbon element, a tin element, an oxygen element and a molybdenum element; as can be seen from fig. 3, the molybdenum-doped tin dioxide nanosheets are staggered to form an array, and the interplanar spacing coincides with the interplanar spacing corresponding to tin dioxide;
XRD (X-ray diffraction) testing is carried out on the sodium ion battery negative electrode material, the testing result is shown in figure 4, and as can be seen from figure 4, the crystal plane diffraction peak of the sodium ion battery negative electrode material is identical with the crystal plane of tin dioxide.
Example 2
Under the condition of stirring, 1g of urea, 20 mu L of thioglycollic acid and 1mL of 37 wt% concentrated hydrochloric acid are sequentially added into 80mL of water until the mixture is uniform, and then 0.357g (0.00158mol) of stannous chloride dihydrate and 0.022g (0.00009mol) of sodium molybdate dihydrate are sequentially added to obtain a mixed solution;
under the ultrasonic condition, washing melamine sponge with ethanol for 15min, and then drying in vacuum; heating to 800 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, carbonizing at high temperature for 1h, and cooling; carrying out hydrophilic treatment on the cooled product in plasma gas, soaking the product in 1mol/L HCl solution for 24 hours at 35 ℃, and drying to obtain sponge carbon;
placing sponge carbon (5.2g) with the size of 4cm x 1cm x 0.5cm in 80mL of mixed solution, performing hydrothermal reaction (120 ℃,12h), sequentially performing water cooling and filtration, washing a filtered solid product with deionized water and ethanol, removing impurities with 1mol/L sodium hydroxide solution at 45 ℃ for 10h, and drying to obtain a molybdenum-doped tin dioxide nanosheet array in which the sponge carbon grows in situ;
in an argon atmosphere, sintering the molybdenum-doped tin dioxide nanosheet array grown in situ from the sponge carbon (raising the temperature to 500 ℃ at a heating rate of 1 ℃/min, and preserving the heat for 3 hours), and then cooling to room temperature to obtain the sodium-ion battery cathode material (the loading capacity of the nanosheet is 43.5%, and the doping capacity of molybdenum is 0.8%).
Example 3
Under the condition of stirring, 1g of urea, 20 mu L of thioglycolic acid and 1mL of 37 wt% concentrated hydrochloric acid are sequentially added into 80mL of water until the mixture is uniform, and then 0.238g (0.00105mol) of stannous chloride dihydrate and 0.022g (0.00009mol) of sodium molybdate dihydrate are sequentially added to obtain a mixed solution;
under the ultrasonic condition, washing melamine sponge with ethanol for 15min, and then drying in vacuum; heating to 800 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, carbonizing at high temperature for 1h, and cooling; carrying out hydrophilic treatment on the cooled product in plasma gas, soaking the product in 1mol/L HCl solution for 24 hours at 35 ℃, and drying to obtain sponge carbon;
placing sponge carbon (5.6g) with the size of 4cm x 1cm x 0.5cm in 80mL of mixed solution, performing hydrothermal reaction (120 ℃,8h), sequentially performing water cooling and filtration, washing a filtered solid product with deionized water and ethanol, removing impurities with 1mol/L sodium hydroxide solution at 45 ℃ for 10h, and drying to obtain a molybdenum-doped tin dioxide nanosheet array in which the sponge carbon grows in situ;
in an argon atmosphere, sintering the molybdenum-doped tin dioxide nanosheet array grown in situ from the sponge carbon (raising the temperature to 500 ℃ at a heating rate of 1 ℃/min, and preserving the heat for 3 hours), and then cooling to room temperature to obtain the sodium-ion battery cathode material (the loading capacity of the nanosheet is 36%, and the doping amount of molybdenum is 1.2%).
Example 4
Under the condition of stirring, 1g of urea, 20 mu L of thioglycolic acid and 1mL of 37 wt% concentrated hydrochloric acid are sequentially added into 80mL of water until the mixture is uniform, and then 0.238g (0.00105mol) of stannous chloride dihydrate and 0.08g (0.00035mol) of sodium molybdate dihydrate are sequentially added to obtain a mixed solution;
under the ultrasonic condition, washing melamine sponge with ethanol for 15min, and then drying in vacuum; heating to 800 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, carbonizing at high temperature for 1h, and cooling; carrying out hydrophilic treatment on the cooled product in plasma gas, soaking the product in 1mol/L HCl solution for 24 hours at 35 ℃, and drying to obtain sponge carbon;
placing sponge carbon (5.6g) with the size of 4cm x 1cm x 0.5cm in 80mL of mixed solution, performing hydrothermal reaction (120 ℃,12h), sequentially performing water cooling and filtration, washing a filtered solid product with deionized water and ethanol, removing impurities with 1mol/L sodium hydroxide solution at 45 ℃ for 10h, and drying to obtain a molybdenum-doped tin dioxide nanosheet array in which the sponge carbon grows in situ;
in an argon atmosphere, sintering the molybdenum-doped tin dioxide nanosheet array grown in situ from the sponge carbon (raising the temperature to 500 ℃ at a heating rate of 1 ℃/min, and preserving the heat for 3 hours), and then cooling to room temperature to obtain the sodium-ion battery cathode material (the loading capacity of the nanosheet is 35%, and the doping amount of molybdenum is 3%).
Example 5
Under the condition of stirring, 1g of urea, 20 mu L of thioglycolic acid and 1mL of 37 wt% concentrated hydrochloric acid are sequentially added into 80mL of water until the mixture is uniform, and then 0.238g (0.0015mol) of stannous chloride dihydrate and 0.022g (0.00009mol) of sodium molybdate dihydrate are sequentially added to obtain a mixed solution;
under the ultrasonic condition, washing melamine sponge with ethanol for 15min, and then drying in vacuum; heating to 600 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, carbonizing at high temperature for 3h, and cooling; carrying out hydrophilic treatment on the cooled product in plasma gas, soaking the product in 1mol/L HCl solution for 24 hours at 35 ℃, and drying to obtain sponge carbon;
placing sponge carbon (4.8g) with the size of 4cm x 1cm x 0.5cm in 80mL of mixed solution, performing hydrothermal reaction (120 ℃,12h), sequentially performing water cooling and filtration, washing a filtered solid product with deionized water and ethanol, removing impurities with 1mol/L sodium hydroxide solution at 45 ℃ for 10h, and drying to obtain a molybdenum-doped tin dioxide nanosheet array in which the sponge carbon grows in situ;
in an argon atmosphere, sintering the molybdenum-doped tin dioxide nanosheet array grown in situ from the sponge carbon (raising the temperature to 500 ℃ at a heating rate of 1 ℃/min, and preserving the heat for 3 hours), and then cooling to room temperature to obtain the sodium-ion battery cathode material (the loading capacity of the nanosheet is 36%, and the doping amount of molybdenum is 1%).
Example 6
Under the condition of stirring, 1g of urea, 20 mu L of thioglycolic acid and 1mL of 37 wt% concentrated hydrochloric acid are sequentially added into 80mL of water until the mixture is uniform, and then 0.238g (0.0015mol) of stannous chloride dihydrate and 0.022g (0.00009mol) of sodium molybdate dihydrate are sequentially added to obtain a mixed solution;
under the ultrasonic condition, washing melamine sponge with ethanol for 15min, and then drying in vacuum; heating to 800 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, carbonizing at high temperature for 1h, and cooling; carrying out hydrophilic treatment on the cooled product in plasma gas, soaking the product in 1mol/L HCl solution for 24 hours at 35 ℃, and drying to obtain sponge carbon;
placing sponge carbon (5.4g) with the size of 4cm x 1cm x 0.5cm in 80mL of mixed solution, performing hydrothermal reaction (120 ℃,12h), sequentially performing water cooling and filtration, washing a filtered solid product with deionized water and ethanol, removing impurities with 1mol/L sodium hydroxide solution at 45 ℃ for 10h, and drying to obtain a molybdenum-doped tin dioxide nanosheet array in which the sponge carbon grows in situ;
in an argon atmosphere, sintering the molybdenum-doped tin dioxide nanosheet array grown in situ from the sponge carbon (raising the temperature to 600 ℃ at a heating rate of 2 ℃/min, and keeping the temperature for 2h), and then cooling to room temperature to obtain the sodium-ion battery cathode material (the loading capacity of the nanosheet is 38%, and the doping amount of molybdenum is 1%).
Application example
The sodium ion battery cathode material described in example 1 was directly used as a cathode and sodium sheets were assembled into a button cell type CR 2025 (electrolyte was 1m naclo containing 5 vol% FEC, EC: DEC volume ratio 1: 1)4The solution, the membrane was a commercial glass fiber filter paper (Whatman GF/F)), and was tested for electrochemical performance:
FIG. 5 shows the button cell at 0.1A g-1、0.2A·g-1、0.5A·g-1、1A·g-1As can be seen from fig. 5, the button cell has a better rate performance because the capacity of the cell is only reduced to a small extent as the current density increases. At 0.1 A.g-1、0.2A·g-1、0.5A·g-1、1A·g-1The battery capacity was 1143mAh g, respectively, at the current density of (1)-1,570mAh·g-1,451mAh·g-1,336mAh·g-1。
FIG. 6 shows the button cell at 0.1A g-1The discharge capacity and coulombic efficiency at 100 cycles under the current density of (1) are shown in figure 6, and the initial discharge capacity of the button cell is 1017.11mAh g-1The discharge capacity after 100 cycles was 575mAh g-1The coulombic efficiency is kept at 99.3%, the battery capacity is not reduced basically, and even slight activation is carried out, so that the good cycle performance is realized.
Respectively carrying out a structural test and an electrochemical performance test on the sodium ion battery negative electrode materials of the embodiments 2-6, wherein the structure of the sodium ion battery negative electrode material is consistent with that of the sodium ion battery negative electrode material of the embodiment 1; the electrochemical performance is similar to the test result of the sodium-ion battery negative electrode material in example 1, and the battery negative electrode material has good cycle performance and rate performance.
According to the embodiment, the negative electrode material of the sodium-ion battery provided by the invention has good cycle performance and rate capability.
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 sodium ion battery negative electrode material is characterized by comprising sponge carbon and a molybdenum-doped tin dioxide nanosheet array growing on a sponge carbon skeleton structure in situ;
the molybdenum-doped tin dioxide nanosheets account for 30-45% of the negative electrode material of the sodium-ion battery by mass percent;
the preparation method of the sodium-ion battery negative electrode material comprises the following steps:
mixing a tin source, a molybdenum source, concentrated hydrochloric acid, thioglycollic acid, urea and water to obtain a mixed solution;
and placing sponge carbon into the mixed solution, and sequentially carrying out hydrothermal reaction and sintering to obtain the sodium-ion battery cathode material.
2. The negative electrode material of the sodium-ion battery as claimed in claim 1, wherein the atomic percent of molybdenum in the negative electrode material of the sodium-ion battery is 0.5-1.5%.
3. The preparation method of the negative electrode material of the sodium-ion battery as claimed in claim 1 or 2, characterized by comprising the following steps:
mixing a tin source, a molybdenum source, concentrated hydrochloric acid, thioglycollic acid, urea and water to obtain a mixed solution;
and placing sponge carbon into the mixed solution, and sequentially carrying out hydrothermal reaction and sintering to obtain the sodium-ion battery cathode material.
4. The production method according to claim 3, wherein the molar ratio of the tin source to the molybdenum source is (1.0 to 1.6): (0.05-0.35);
the tin source is calculated as tin and the molybdenum source is calculated as molybdenum.
5. The method according to claim 3, wherein the concentrated hydrochloric acid has a mass concentration of 37%;
the dosage ratio of the urea to the thioglycollic acid to the concentrated hydrochloric acid to the tin source to the water is (0.8-1.2) g: (18-22) μ L: (0.8-1.2) mL: (1.0-1.1) mmol: (75-85) mL;
the tin source is calculated as tin.
6. The method according to claim 3, wherein the ratio of the amount of the sponge carbon to the amount of the mixed solution is (1.2 to 5.6) g: (70-80) mL.
7. The preparation method according to claim 3, wherein the temperature of the hydrothermal reaction is 110 to 130 ℃ and the time of the hydrothermal reaction is 8 to 12 hours.
8. The method of claim 3, wherein the sintering is performed in a protective atmosphere;
the sintering temperature is 450-650 ℃, the heating rate is 1-2 ℃/min, and the sintering heat preservation time is 2-5 h.
9. The method of claim 3, wherein the sponge carbon is prepared by the steps of:
under the inert atmosphere, carrying out high-temperature carbonization on melamine sponge to obtain sponge carbon;
the temperature of the high-temperature carbonization is 750-850 ℃, the heating rate is 4.5-5.5 ℃/min, and the heat preservation time of the high-temperature carbonization is 1-3 hours;
and before the sponge carbon is placed in the mixed solution, carrying out hydrophilic treatment on the sponge carbon.
10. The sodium-ion battery negative electrode material as defined in claim 1 or 2 or the sodium-ion battery negative electrode material prepared by the preparation method as defined in any one of claims 3 to 9 is applied to a sodium-ion battery.
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