CN110993924A - Preparation method of stannous oxide nano micro sheet and nitrogen-containing carbon nano box composite material - Google Patents
Preparation method of stannous oxide nano micro sheet and nitrogen-containing carbon nano box composite material Download PDFInfo
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- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 title claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000007772 electrode material Substances 0.000 claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 230000020477 pH reduction Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 33
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229920001690 polydopamine Polymers 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 6
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000007853 buffer solution Substances 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- 239000002113 nanodiamond Substances 0.000 claims 1
- 239000002064 nanoplatelet Substances 0.000 claims 1
- 239000002135 nanosheet Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 10
- 239000000872 buffer Substances 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 229910001887 tin oxide Inorganic materials 0.000 description 6
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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 belongs to the technical field of electrode material preparation, and particularly relates to a preparation method of a stannous oxide nano microchip and nitrogen-containing carbon nano box composite material. Synthesizing a carbon nano box substrate by a template method, and synthesizing a stannous oxide nano microchip and a nitrogen-containing carbon nano box composite electrode material by an acidification and hydrothermal method. The composite structure of the invention fully exerts the characteristics of high specific surface area, high active sites and high specific capacity of the stannous oxide nanosheets, and can well buffer the problem of large volume expansion of the stannous oxide in the charging and discharging processes among nanosheets, the large specific surface area of the nanosheets not only can improve the contact area with the electrolyte, but also can reduce the transmission path of electrons and ions, and the advantages can effectively improve the cycle performance and the rate capability of the electrode material.
Description
The technical field is as follows:
the invention belongs to the technical field of electrode material preparation, and particularly relates to a preparation method of a stannous oxide nano microchip and nitrogen-containing carbon nano box composite material.
Background art:
because the graphite negative electrode belongs to an intercalation material, the theoretical specific capacity is lower, and the requirement of people on the energy density of the lithium ion battery is not enough, so that the research and development of a negative electrode material with higher specific capacity are needed. The metal-based negative electrode material with alloy or conversion reaction has higher theoretical specific capacity due to multi-electron reaction in the energy storage process, and has attracted extensive attention in recent years. Among many metal conversion materials, tin oxide has received extensive attention from researchers because of its high specific capacity, low cost, and simple synthesis method. However, tin oxide undergoes large volume expansion during lithium intercalation or sodium intercalation, and a pulverization phenomenon can occur under the action of stress to fall off from a current collector, so that loss of active substances and structural damage of an electrode material are caused, and the cycle life and the actual specific capacity of the electrode material are influenced. In addition, the low conductivity of tin oxide is another drawback that limits its development, and the low conductivity limits the rate capability of the electrode material.
The invention content is as follows:
the invention aims to solve the technical problems that tin oxide can generate large volume expansion in the process of lithium intercalation or sodium intercalation, and can generate pulverization phenomenon to fall off from a current collector under the action of stress, so that the loss of active substances and the damage of an electrode material structure are caused, and the cycle life and the actual specific capacity of the tin oxide are influenced. In addition, the lower conductivity of tin oxide is another drawback that limits its development.
In order to solve the problems, the invention firstly synthesizes the carbon nano box substrate by a template method, and then synthesizes the stannous oxide nano microchip and the nitrogen-containing carbon nano box composite electrode material by an acidification and hydrothermal method.
In order to achieve the purpose, the invention is realized by the following technical scheme that the preparation method of the composite material of the stannous oxide nano micro-sheet and the nitrogen-containing carbon nano-box comprises the steps of synthesizing a carbon nano-box substrate by a template method, and synthesizing the composite electrode material of the stannous oxide nano-micro-sheet and the nitrogen-containing carbon nano-box by an acidification and hydrothermal method.
Further, the method for preparing the iron oxide nano small blocks comprises the following steps: slowly pouring NaOH solution into FeCl prepared in advance3Stirring the solution, and then putting the brown colloid solution into a drying oven at 100 ℃ for standing; and centrifugally cleaning and drying the obtained red precipitate to obtain the ferric oxide nano small square. Obtaining the iron oxide nano small blocks as templates for synthesizing the carbon nano box.
Further, 50mL of 5.4M NaOH solution was slowly poured into 50mL of 2.0M FeCl prepared in advance in a thermostatic water bath at 75 deg.C3In solution; the red precipitate was dried at 70 ℃. The constant temperature water bath can ensure that the temperature of the whole reaction is kept constant in the process of carrying out the reaction.
Further, preparing nano-box Fe2O3The method of @ PDA is as follows: uniformly dispersing 80mg of iron oxide nano square blocks in 100ml of 10mM tris buffer solution by an ultrasonic method, then pouring 50mg of dopamine hydrochloride into the solution, continuously stirring for 4 hours, and centrifugally cleaning to obtain Polydopamine (PDA) -coated Fe2O3Nano box Fe2O3@ PDA, the amount of ferric oxide and dopamine hydrochloride in the coating process is adjustable. The pH of the 10mM Tirs buffer solution is 8.5, which can ensure that dopamine hydrochloride is polymerized in the atmosphere to form the polymerized dopamine PDA.
Further, Fe is produced3O4The method of @ C nanobubes is as follows: mixing Fe2O3Heat treatment of @ PDA for 3 hours in inert atmosphere, carbonization of PDA, Fe2O3Conversion to Fe3O4To obtain Fe3O4@ C nanometer square. Heat treatment of PDA carbonization of Fe2O3Carbothermic reduction to Fe3O4。
Further, the temperature of the heat treatment was 500 ℃.
Further, the steps for synthesizing the stannous oxide nano microchip and nitrogen-containing carbon nano box composite electrode material are as follows:
etching of Fe with 4M HCl solution3O4@ C, mechanically stirring for 3 hours, then centrifugally cleaning, and drying the obtained carbon box for later use;
activating the obtained carbon box in concentrated nitric acid and concentrated sulfuric acid to make the carbon box hydrophilic, centrifugally cleaning after activation, and drying for later use;
30mg of the activated carbon boxes were ultrasonically and uniformly dispersed in 70ml of deionized water, and then 8mmol of SnCl2Dissolving in the solution; then, adding 30 wt% ammonia water into the solution dropwise until the pH value is 5, wherein the process needs to be carried out by stirring;
placing the solution in a 100ml hydrothermal kettle, and standing at 200 ℃ for 10 hours; and (4) centrifugally cleaning the product, and drying to obtain the composite material of the stannous oxide nano micro-sheet and the nitrogen-containing carbon nano box.
Further, the above drying temperature was 70 ℃.
The composite material of the stannous oxide nano micro-sheet and the nitrogen-containing carbon nano box prepared by the method is shown in figures 1-3, wherein the stannous oxide nano-sheet uniformly grows on the surface of the nitrogen-containing carbon nano hollow box, and a cavity is arranged in the carbon box.
The composite structure gives full play to the characteristics of high specific surface area, high active sites and high specific capacity of the stannous oxide nanosheets, and can well buffer the problem of large volume expansion of the stannous oxide in the charging and discharging processes among nanosheets, the large specific surface area of the nanosheets can improve the contact area with electrolyte, and simultaneously reduce the transmission paths of electrons and ions, and the advantages can effectively improve the cycle performance and the rate capability of the electrode material. In addition, the matrix carbon box can not only improve the conductivity of the whole electrode material, but also improve the stability of the whole structure. The carbon box belongs to a flexible substrate material, particularly the existence of an internal cavity can better buffer the stress problem of the stannous oxide in the expansion process through the indent, and the cycle performance of the electrode material is improved.
The invention has the beneficial effects that:
(1) the composite stannous oxide nano thin sheet of the invention uniformly grows on the surface of the nitrogen-containing carbon nano hollow box. The matrix carbon box can improve the conductivity of the whole electrode material and the stability of the whole structure. The carbon box belongs to a flexible substrate material, particularly the existence of an internal cavity can better buffer the stress problem of the stannous oxide in the expansion process through the indent, and the cycle performance of the electrode material is improved.
(2) The composite structure of the invention fully exerts the characteristics of high specific surface area, high active sites and high specific capacity of the stannous oxide nanosheets, and can well buffer the problem of large volume expansion of the stannous oxide in the charging and discharging processes among nanosheets, the large specific surface area of the nanosheets not only can increase the contact area with the electrolyte, but also can reduce the transmission path of electrons and ions, and the advantages can effectively improve the cycle performance and the rate capability of the electrode material.
(3) A synthetic method for growing stannous oxide on a carbon nano-box is provided.
Drawings
FIG. 1 is a composite scanning electron microscope picture I of the present invention;
FIG. 2 is a composite scanning electron microscope picture II of the present invention;
FIG. 3 is a composite scanning electron microscope image III of the present invention.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of a stannous oxide nano microchip and nitrogen-containing carbon nano box composite material comprises the following steps:
(1) 50mL of 5.4M NaOH solution was slowly poured into the previously prepared 50mL of 2.0M FeCl3In solution, the above process is carried out in a thermostatic water bath at 75 ℃. After stirring for five minutes, the brown colloidal solution was placed in a 100 ℃ oven and allowed to stand for four days.
(2) And centrifugally washing the obtained red precipitate, and drying at 70 ℃ to obtain the iron oxide nano cube.
(3) Uniformly dispersing 80mg of iron oxide nano square blocks in 100ml of 10mM tris buffer solution by an ultrasonic method, then pouring 50mg of dopamine hydrochloride into the solution, continuously stirring for 4 hours, and centrifugally cleaning to obtain Polydopamine (PDA) -coated Fe2O3Nano box Fe2O3@ PDA, the amount of ferric oxide and dopamine hydrochloride in the coating process is adjustable.
(4) Mixing Fe2O3@ PDA is heat treated at 500 deg.C for 3 hr in inert atmosphere, PDA is carbonized, Fe2O3Conversion to Fe3O4To obtain Fe3O4@ C nanometer square.
(5) Etching of Fe with 4M HCl solution3O4@ C, mechanically stirred for 3h and then centrifugally washed, and the resulting carbon boxes were dried at 70 ℃.
(6) Activating the obtained carbon box in concentrated nitric acid and concentrated sulfuric acid to make the carbon box hydrophilic, centrifugally cleaning after activation, and drying at 70 ℃.
(7) Uniformly dispersing 30mg of activated carbon boxes in 70ml of deionized water by ultrasonic treatment, and then dissolving 8mmol of SnCl2 in the solution; then, 30 wt% aqueous ammonia was added dropwise to the above solution to pH 5, with stirring.
(8) The solution was placed in a 100ml hydrothermal kettle and allowed to stand at 200 ℃ for 10 hours. The product was washed by centrifugation and dried at 70 ℃.
Claims (9)
1. The preparation method of the stannous oxide nanometer microchip and nitrogen-containing carbon nanometer box composite material is characterized by comprising the following steps: synthesizing a carbon nano box substrate by a template method, and synthesizing a stannous oxide nano microchip and a nitrogen-containing carbon nano box composite electrode material by an acidification and hydrothermal method.
2. A method of preparing a composite material according to claim 1, wherein: the method for preparing the ferric oxide nano small blocks comprises the following steps: slowly pouring NaOH solution into FeCl prepared in advance3Stirring the solution, and then putting the brown colloid solution into a drying oven at 100 ℃ for standing; and centrifugally cleaning and drying the obtained red precipitate to obtain the ferric oxide nano small square.
3. A method of preparing a composite material according to claim 2, wherein: in a thermostatic water bath at 75 ℃, 50mL of 5.4M NaOH solution is slowly poured into 50mL of 2.0M FeCl prepared in advance3In solution; the red precipitate was dried at 70 ℃.
4. A method of preparing a composite material according to claim 1 or 2, characterized in that: preparation of Nanobique Fe2O3The method of @ PDA is as follows: uniformly dispersing iron oxide nano-diamonds in a buffer solution by an ultrasonic method, then pouring dopamine hydrochloride into the solution, continuously stirring, and centrifugally cleaning to obtain polydopamine-coated Fe2O3Nano box Fe2O3@PDA。
5. A method of preparing a composite material according to claim 1 or 2, characterized in that: preparation of Fe3O4The method of @ C nanobubes is as follows: mixing Fe2O3Heat treatment of @ PDA at 500 ℃ for 3 hours in an inert atmosphere to obtain Fe3O4@ C nanometer square.
6. A method of preparing a composite material according to claim 1 or 2, characterized in that: the steps for synthesizing the stannous oxide nano microchip and nitrogen-containing carbon nano box composite electrode material are as follows:
etching of Fe with 4M HCl solution3O4@ C, mechanically stirring for 3 hours, then centrifugally cleaning, and drying the obtained carbon box for later use;
activating the obtained carbon box in concentrated nitric acid and concentrated sulfuric acid to make the carbon box hydrophilic, centrifugally cleaning after activation, and drying for later use;
ultrasonically and uniformly dispersing the activated carbon boxes in deionized water, and then SnCl2Dissolving in the solution; subsequently adjusting the solution to pH 5;
placing the solution in a hydrothermal kettle, and standing at 200 ℃ for 10 hours; and (4) centrifugally cleaning the product, and drying to obtain the composite material of the stannous oxide nano micro-sheet and the nitrogen-containing carbon nano box.
7. The method of preparing a composite material according to claim 6, wherein: the drying temperature was 70 ℃.
8. The method of preparing a composite material according to claim 6, wherein: the pH of the solution was adjusted by stirring.
9. A stannous oxide nanoplatelets and nitrogen-containing carbon nano-box composite prepared by the method of claim 1, which is characterized in that: wherein the stannous oxide nano thin sheet uniformly grows on the surface of the nitrogen-containing carbon nano hollow box, and a cavity is arranged in the carbon box.
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